JPS60229918A - Polyurethane resin and polyester polyol therefor - Google Patents

Abstract

PURPOSE:A polyol to give a polyurethane resin having improved strength, heat- resistant stability, weather resistance and oil resistance, obtained by subjecting a specific butylethylpropanediol and a polycarboxylic acid to polycondensation. CONSTITUTION:A polyester polyol obtained by subjecting 2-n-butyl-2-ethyl-1,3- propanediol and a polycarboxylic acid to polycondensation. Phthalic acid, adipinic acid, dimerized linolenic acid, or maleic acid is used as the polycarboxylic acid. The polyester is reacted with a polyisocyanate, to give a polyurethane resin. Methylenebisphenyl isocyanate, tolylene diisocyanate, 1,5-naphthalene diisocyanate, etc. are used as the polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane resin and a polyester polyol for the resin. More specifically, the polyester polyol obtained by polycondensing a novel 2-n-butyl-2-ethyl-1,3-propanediol with a polycarboxylic acid as a polyol component, and the polyurethane obtained by reacting this polyester polyol with a polyincyanate. Regarding resin.

Polyurethane resin is one of the so-called polycondensation plastics obtained by polycondensing a specific polymeric polyol and polyinsyanate, and has relatively good heat resistance, hydrolysis resistance, oil resistance, etc. in practical terms. It has the physical properties of However, there is room for further improvement in these physical property values, and if the physical property values are improved, the practicality of the polyurethane resin may further increase.

Conventionally, polyester polyols used as raw materials for polyurethane include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, Glycols such as neopentyl glycol, trimethylolpropane, hexanetriol, glycerin,
Those obtained by dehydration polycondensation of polyols such as trimethylolethane or pentaerythritol have been used. The polyurethane resin obtained by subjecting the polyester polyol produced as described above to a condensation reaction with a polyisocyanate is used in applications such as paints, adhesives, fiber raw materials, urethane foams, and urethane elastomers.

However, as mentioned above, there is room for improvement in the practical physical properties of the resin, such as heat resistance, #hydrolyzability, oil resistance, and other physical properties.

The present inventors have conducted intensive research to solve the above-mentioned technical problem, in order to find a polyurethane resin with better practical physical properties than conventionally known polyurethane resins, and a new polyester polyol for polyurethane resins that makes it possible to manufacture the resin. Ta. As a result, 2-n-butyl-
It was discovered that by using 2-ethyl-1,3-propanediol (formula C), it was finally possible to produce the above-mentioned polyurethane resin with excellent practical physical properties,
We have arrived at the present invention.

4 Hs HOH20-C-CH2OH v Hs As is clear from the above description, the object of the present invention is to provide a polyester polyol that can produce a polyurethane resin with excellent practical physical properties, and a polyester polyol that can be obtained by reacting the polyester polyol with a polyincyanate. Another object of the present invention is to provide the above-mentioned polyurethane resin. Another object is to improve the performance of polyurethane resins in various applications.

The present invention (second invention) has the following main configurations (1) or (3) and the embodiment configurations (2) or (4) and (5).

(1) A polyester polyol for polyurethane resin, which is obtained by polycondensing 2-n-butyl-2-ethyl-1,3-propanediol with polycarboxylic acid.

(2) The polyester polyol according to item (1) above, which uses phthalic acid, adipic acid, luin forging or maleic acid as the polycarboxylic acid.

(3) A polyurethane resin obtained by reacting a polyester polyol obtained by polycondensing 2-n-butyl-2-ethyl-1,3-propanediol with a polycarboxylic acid and a polyisocyanate.

(4) The polyurethane resin according to the above item (3), wherein the polycarboxylic acid is phthalate-resistant, adipic acid, dimerization/rain forging, or maleic acid.

(5) As the polyisocyanate, methylene bisphenyl inocyanate, tolylene diisocyanate,! , 5
- The polyester polyol according to item (3), which uses naphthalene diisocyanate, triphenylmethane triisocyanate, toridine diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, dichlorohexylmethane diisocyanate or inphorone diisocyanate.

The structure and effects of the present invention will be explained in detail below.

Polyester polyol for polyurethane resin of the present invention (
2-n-butyl-2-ethyl-1,3-propanediol (hereinafter abbreviated as n-butyl-ethyl-1,3PC), which is essential as a raw material for the production of It is synthesized by a known method as a raw material. The purity required for n-butyl-ethyl-1,3PC is comparable to that of known polyols used for polyester polyols.

The polycarboxylic acids used in the production of the polyester polyol of the present invention are those conventionally known for use in polyurethane resins, such as phthalic acid (including anhydrides), adipic acid, phosphoric acid (containing anhydrides), or maleic acid (including anhydrides). )
These can be used alone or in combination of two or more.

The polyester polyol of the present invention can be produced by subjecting the aforementioned n-butyl-ethyl-1,3PC to a polycondensation reaction with the aforementioned polycarboxylic acid under reaction conditions similar to those of known methods. n-butyl-ethyl-1,3 used at this time
It is also possible to replace less than 50 mole percent of the PG with other known polyols. However, the substitution ratio is preferably 30 mol% or less. this! Specific examples of such polyols include glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, or neopentyl glycol, and those having three or more hydroxyl groups in one molecule such as trimethylolpropane and hexanetriol. .

Glycerin, trimethylolethane, pentaerythritol, etc. are used.

Practical physical properties of the polyester polyol according to the present invention, such as color number (APHA), hydroxyl value (mgKOH/g)
, water content (wt %), average molecular weight, etc., except for the number of colors, can be produced by known methods with no major differences from known polyester polyols.

Regarding the above-mentioned color value, a considerably high color value can be obtained when the product is produced under polycondensation and purification conditions in which other physical property values are at the same level. However, this fact does not mean that the reaction conditions for the polyester polyol and polyisocyanate used to produce the polyurethane resin of the present invention, which will be described later, require specific reaction conditions different from known reaction conditions. . The target molecular weight of the polyester polyol differs depending on the end use, as in the case of production of known polyurethane resins, but for the general use as mentioned above, i.e.
1,000 to 3,0 for manufacturing paints, adhesives, TAM, urethane foam or urethane elastomer.
00, preferably about 1,500 to 2,500. Therefore, the conditions for polycondensation of polyol and polycarboxylic acid (temperature: 2 hours) may vary depending on the desired molecular weight.

The thus obtained polyester polyol of the present invention is
Next, the reaction conditions (ratio of raw materials, temperature and time, etc.) for reacting with the above-mentioned polycarboxylic acid to form a polyurethane resin are the same as those in the known case, and are determined according to the purpose of use.

In order to facilitate the reaction for producing the polyurethane resin and to facilitate the processing of the resulting resin, a reaction solvent (for example, N,N-dimethylformamide) can be used as in known methods. Other auxiliaries, such as chain extenders, can also be used as in known methods.

The thus obtained polyurethane resin of the present invention is subjected to secondary processing depending on the purpose of use, but especially when made into a thermoplastic resin molded product, it has various strengths of heat resistance stability, weather resistance, and oil resistance compared to known products. It has a significantly superior effect. The reason for this is unknown, but n-butyl-ethyl-
This is thought to be due to the chemical structure of 1,3PC.

The present invention will be explained below with reference to Examples.

Example 1. Comparative Example 1.2 (Synthesis of polyester polyol) 2-n-butyl-2-ethyl-1,3- used in the present invention
Propanediol (Example 1) and, for comparison, neopentyl glycol (Comparative Example 1) 1,4-butanediol
(Comparative Example 2) were respectively subjected to dehydration polycondensation with adipic acid to obtain polyester polyols.

Table 1 shows the physical properties of each polyester polyol.

Table 1 Test Method Color Number (APHA) JIS-Ni-89014, 2, 1,
In accordance with

Hydroxyl value JIS-00'? 0 2.5. In accordance with

Acid value: Conforms to JIS-00702.1.

Water: Conforms to JIS-00682, 1.

Example 2. Comparative Examples 3 and 4 (Preparation of polyurethane film) In N,N-dimethylformamide, the above-mentioned Example 1,
Each polyester polyol obtained in Comparative Example 1 or Comparative Example 2 and chain extender were dissolved, methylene bisphenyl incyanate was added, and the viscosity of the solvent (30°C) was 600±.
The reaction end point is when 200 poise is reached. (The polyester polyols used are referred to as Example 2, Comparative Example 3, or Comparative Example 4 in the order of the polyester polyols used.) The obtained polyurethane was applied onto release paper, placed in a dryer, and heated at 120'C! Let the solvent evaporate for 5 minutes at -day!
A film was prepared by leaving it at room temperature overnight. Table 2 shows the room temperature properties of these films.

Table 2 Measurement conditions autograph lS-500 (manufactured by Shimadzu Corporation) Tensile speed 200mm/min Film thickness 100-200 Shape Tensile...JISK-E1301 No. 3 test piece Tensile...JTS K-6301B type test Figure 1 shows the temperature change in 100% modulus of these films at a measurement temperature of 25°, and Figure 2 shows the temperature change in 200% modulus. Symbol 1 in the figure is polyurethane produced from 2-n-butyl-2-ethyl-1,3-propanediol of the present invention, 2 is neopentyl glycol of comparison-i, and 3 is 1.4
A polyurethane made from butanediol is shown. (Same for each figure below).

The measurement conditions in the case of Figure 1.2 are as follows.

Autograph lS-500 (manufactured by Shimadzu Corporation) Tensile speed 200mm/win Film thickness 100-200l Shape JIS K-63013 type test piece measurement temperature
-20~25°C Example 3. Comparative Examples 5 and 6 (Measurement of heat resistance) Example 2. The upper end of each polyurethane film prepared in Comparative Example 3 or Comparative Example 4 was fixed, and a
1"0/m in a gear oven with a load of Kg/cm"
The temperature was increased at a rate of in, and the temperature at which the elongation rapidly increased was defined as the softening point.

As a result, as shown in Table 3, the polyurethane film using 2-n-butyl-2-ethyl-1,3-propanediol of the present invention showed better heat resistance than the film of the comparative example.

3rd N Example 4. Comparative Examples 7 and 8 (Hydrolysis Resistance) Example 2. The temperature of the polyurethane film prepared in Comparative Example 3 or Comparative Example 4? 0'C! After being kept in an atmosphere with a humidity of 95% or higher for 7, 14, 21, and 28 days, the test pieces were air-dried at room temperature and punched out using dumbbells of a predetermined shape. The measurement conditions are the same as for the film of Example 2. Table 4 shows the hydrolysis resistance test of polyurethane films.

Figure 3 shows the change in breaking strength of the same film, and Figure 4 shows the change in breaking strength retention. It shows superior hydrolysis resistance to the films on each side of the comparison.

Table 4 Example 5. Comparative Examples 9 and 10 (Weather resistance (light) resistance) Example 2. The polyurethane film prepared in Comparative Example 3 or Comparative Example 4 was weather-resistant (light) for 100 hours in 20-hour intervals using sunshine carbon at a panel temperature of 63°C.
A color change test was conducted. As a result, the polyurethane film produced from 1.4-butanediol of Comparative Example 10 was deeply discolored, but the polyurethane film produced from 2-n-butyl-2-ethyl 1,3-propanediol of the present invention and neopentyl glycol of Comparative Example 9 was The discoloration of the polyurethane film was slight and no difference was observed.

Example 6. Comparative Example 11.12 (Oil resistance) Example 2. The polyurethane film prepared in Comparative Example 3 or Comparative Example 4 was tested according to JIS K8301.12 with ASTM No.
70±1℃ using ASTM No. 1 oil and ASTM No. 3 oil.
After immersion in water for 72 hours, 100% modulus, 200% modulus, breaking strength, and breaking elongation were measured. The measurement conditions were the same as for the film of Example 2.

The oil resistance test using ASTM No. 1 oil is shown in Table 5.
Table 6 shows the oil resistance test using ASTM No. 3 oil.
Figure 6: I regret it. In Figures 5 and 6, (1) is 100% modulus (rath change), and (2) is 100% modulus change retention rate.

(3) is the break strength change, and (4) is the break strength change retention rate.

As is clear from Table 5, FIG. 5, Table 6, and FIG. In comparison, it shows good oil resistance.

[Brief explanation of the drawing]

Figures 81 to 6 show the relationship between the physical property values of the polyurethane resin film according to the present invention and the processing conditions (temperature 9 hours or days). In each figure, ←−＋−1.Curves showing examples. - Curve when neopentyl glycol is used as the polyol component of polyester polyol as a raw material for polyurethane resin as a comparative example. ->-- As a comparative example, a curve is shown in which 1,4-butanediol was used instead of neopentyl glycol. Measured physical property values are shown in Figure 1.2...100% or 200% modulus Figures 3 and 4...Breaking strength or breaking strength retention rate 5
Figures (1), (2)...100% modulus or 1
00% Modulus Change Retention Rate Figure 5 (3), (4)... Breaking Strength or Breaking Strength Retention Rate Figure 6 (1), (2)... 100% Modulus or io. % Modulus change retention rate Figure 6 (3), (4)... Breaking strength or breaking strength retention rate or higher Patent applicant Chisso Corporation Same as above Dainichiseika Kagyo Co., Ltd. Mockery (-

Claims (5)

[Claims] (1) A polyester polyol for polyurethane resin, which is obtained by polycondensing 2-n-butyl-2-ethyl-1,3-propanediol with polycarboxylic acid. (2) The polyester polyol according to claim (1), which uses phthalic acid, adipic acid, trimerized lyluic acid, or maleic acid as the polycarboxylic acid. (3) A polyurethane resin obtained by reacting a polyester polyol obtained by polycondensing 2-n-butyl-2-ethyl-1,3-propanediol with a polycarboxylic acid and a polyisocyanate. . (4) The polyurethane resin according to claim (3), which uses phthalic acid, adipic acid, trimerized lyluic acid, or maleic acid as the polycarboxylic acid. (5) As polyinsyanate, methylene bisphenyl inocyanate, tolylene diisocyanate, 1,5
- The polyester polyol according to claim 3, which uses naphthalene diisocyanate, triphenylmethane triisocyanate, toridine diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or inphorone diincyanate.