KR100205699B1 - Organic ti-p catalyst method of its preparation and process for perparing polyester imide using it - Google Patents

Abstract

The present invention relates to a catalyst for synthesizing polyester imide, Ti _n PO ₁₁ C ₁₄ H ₄₅ (where n is an integer of 1 to 3), a method for preparing the same, and a method for preparing polyester imide using the same.

The catalyst of the present invention and its manufacturing method are novel, and the polyester imide prepared using the catalyst according to the present invention is excellent in transparency and color as a basic resin of magnet wire coating in high heat-resistant electrical insulating paint. In addition to excellent heat resistance, flexibility and wear resistance.

Description

Organic Ti-P catalyst, preparation method thereof and preparation method of polyester imide using same

The present invention relates to an organic Ti-P catalyst, a method for producing the same, and a method for producing a polyesterimide using the same.

The organic Ti-P catalyst according to the present invention not only lowers the reaction temperature and shortens the reaction time but also minimizes side reactions that cause decomposition, color development, and the like. It is useful for producing polyesterimide resins having excellent heat resistance, flexibility and wear resistance as well as excellent transparency and color.

Polyester, polyimide or polyesterimide resins have been used as basic resins for high heat resistance magnet wire coating. In US Patent No. 3,342,780, a polyester resin was synthesized as a base resin for magnet wire coating, and in the polycondensation of dimethyl terephthalate and ethylene glycol, tris (2-hydroxyethyl), which is a trifunctional cyclic compound, was partially used. It is described that heat resistance can be improved by substituting with isocyanurate. U.S. Patent No. 3,426,098 also discloses dissolving trimellitic anhydride, methylene dianiline, ethylene glycol and tris (2-hydroxyethyl) isocyanurate in N-methyl pyrrolidinone solvent as a base wire for magnet wires and coatings. It was said that the heat resistance was improved by synthesizing the polyester imide which introduced the imide structure in the polymer chain by polycondensation. US Pat. No. 3,697,471 also synthesized a polyesterimide resin through condensation polymerization using trimellitic anhydride, methylene dianiline, ethylene glycol and tris (2-hydroxyethyl) isocyanurate as raw materials. It is described that polyesterimide can be obtained in one reaction by using m-cresol as a solvent instead of a lolidinone solvent.

Such conventional resins for high heat-resistant magnet wire coating base resin synthesis method does not consider the catalyst for promoting the polymerization reaction, the polymerization temperature is as high as 220 ~ 230 ℃ and the reaction time requires a long time as 14 hours or more. Since the polycondensation reaction is a reversible reaction, if the reaction temperature is high and the reaction time is long, problems such as discoloration of the polyester or polyesterimide resin synthesized due to increased side reactions such as reverse reaction, decomposition, and color development rather than forward reaction may occur. .

Titanium alkoxides are known to catalyze the synthesis of polyesters (US Pat. No. 4,007,218). However, titanium alkoxide has the disadvantage of changing the color of the produced polyester to brown because it promotes both the forward reaction and the decomposition reaction as well as the forward reaction of the polycondensation reaction.

When the magnet wire is coated with the additives necessary for coating in the resin thus prepared, pin holes are generated due to the accumulation of side reactions, difficulty of color control of the coated magnet wire, deterioration of heat resistance and deterioration of flexibility, etc. It causes problems.

The present inventors have conducted a study to solve the above problems, the fact that by using a specific organic Ti-P-based catalyst can lower the reaction temperature and shorten the reaction time to produce a polyesterimide excellent in heat resistance, flexibility and wear resistance It has been found that the present invention has been completed.

Conventionally, methods for synthesizing polyester or polyesterimide as a basic resin for high heat resistance magnet wire coating cannot avoid deterioration of physical properties without considering the polycondensation catalyst. Therefore, in the synthesis of polyester or polyesterimide base resin, it is important to advance the reaction at a lower temperature and to shorten the reaction time.

Accordingly, an object of the present invention is to provide an organic Ti-P-based catalyst for advancing the reaction at a lower temperature and shortening the reaction time in the synthesis of polyester or polyesterimide basic resin.

The organic Ti-P based catalyst according to the present invention is represented by Ti _n PO ₁₁ C ₁₄ H ₄₅ where n is an integer of 1 to 3.

It is another object of the present invention to agitate titanium chloride (titinitum (IV) chloride) with organic phosphate phosphoric acid or phosphate ester in a catalyst of CCl ₄ or n-hexene at 20-30 ° C. for 30 minutes, and then again with ethanol for 30 minutes. Reaction and then adding ethylene glycol to provide a method for producing an organic Ti-P-based catalyst represented by the general formula Ti _n PO ₁₁ C ₁₄ H ₄₅ (where n is an integer of 1 to 3). Preferred examples of organophosphates are trimethyl, triethyl or triphenyl phosphate.

It is still another object of the present invention to synthesize diacid diimide by reacting trimellitic anhydride and methylene dianiline in a m-cresol solvent, followed by ethylene glycol and tris (2-hydroxyethyl) isocyanurate. To provide a method for producing a polyesterimide by addition and polycondensation of an organic Ti-P-based catalyst represented by the general formula Ti _n PO ₁₁ C ₁₄ H ₄₅ (where n is an integer of 1 to 3).

The organic Ti-P catalyst of the present invention is distinguished from other titanium catalysts in that titanium chloride is reacted with triethyl phosphate and ethanol to introduce a phosphate group having a function of a heat stabilizer as a ligand, thereby making the catalyst excellent in heat resistance. In fact, triethyl phosphate is used as a thermal stabilizer in the synthesis of polyester or polyester imitate, and the polyester or polyester imitate synthesized by adding it is known to have excellent whiteness due to suppression of decomposition or reverse reaction. In the present invention, by synthesizing a catalyst capable of simultaneously catalyzing and acting as a thermal stabilizer by forming a new organic Ti-P compound by reacting triethyl phosphate having a function of the thermal stabilizer with titanium chloride together with ethanol It is characteristic.

Hereinafter, although an Example demonstrates this invention in more detail, the scope of the present invention is not limited only to an Example.

Example 1

Synthesis of Organic Ti-P Based Catalysts

0.05 mole of titanium chloride substituted with nitrogen at room temperature was added to a 100 ml nitrogen-substituted three-necked flask under no contact with air, and 0.017 mole of triethyl phosphate was slowly added dropwise over 30 minutes to remove the gas. It was. After the reaction was completed and the reaction heat was cooled to room temperature, 0.15 mole of ethanol was added dropwise with stirring over 30 minutes, followed by the addition of 24 g of ethylene glycol and an organic Ti- element having a Ti: 1 phosphorus ratio of 3: 1. P-based catalyst was prepared.

Example 2

Synthesis of Resin of Polyester Imide 1

115.7 g of trimellitic anhydride, 59.7 g of methylene dianiline, 36.9 g of ethylene glycol, and tris (2-hydroxyethyl) isocyanate in a 1L resin synthesis reactor equipped with a mechanical stirrer, a separation column, a condenser and a temperature controller at room temperature 70.5 g of anurate and 424.2 g of m-cresol were added thereto. Next, the organic Ti-P catalyst synthesized above was added to 0, 200, 400, and 800 ppm relative to the solids of the reactants, and the reactor was replaced with nitrogen. Heat was applied to the heating mantle surrounding the reactor and when the reactant melted, stirring was started and the temperature of the reactant was raised to 150 ° C. over 30 minutes. Thereafter, the speed of the stirrer was fixed at 250 rpm, and the temperature of the reactant was raised to 10 ° C. by 30 ° C. every 30 minutes to remove water as a side reaction. The side reactant water began to flow through the condenser when the temperature of the reactant was 160 ° C. The reactant, which was dark yellow, changed to a viscous transparent solution at 210 ° C through a pale yellow slurry. The polymerization time until the reactant is obtained as a transparent pale yellow viscous liquid phase at 210 ° C. shows that it takes 3 hours and 50 minutes without the addition of the organic Ti-P catalyst as shown in Table 1, or as the input amount of the catalyst increases. It can be seen that the reaction time is significantly shortened. In Table 1, the polyesterimide base resin prepared using the organic Ti-P catalyst was obtained in a clear pale yellow color, but when the catalyst was not added, an opaque dark brown color was obtained.

Note) * PEI = polyester imide

Example 3

Synthesis of Polyester Imide Resin 2

115.7 g of trimellitic anhydride, 59.7 g of methylene dianiline, and 424.2 g of m-cresol were introduced into a 1 L reactor at room temperature, and the reactor was replaced with nitrogen. When the reactor was heated to dissolve the reaction, stirring was started and the temperature of the reaction was raised to 150 ° C. over 30 minutes and stirred at 150 ° C. for 1 hour. Thereafter, the temperature of the reactants was increased by 10 ° C. over 30 minutes while removing the water, which was a side reaction product, to obtain a diacid diimide, an intermediate of polyesterimide resin, in a yellow slurry at 180 ° C. 36.9 g of ethylene glycol, 70.5 g of tris (2-hydroxyethyl) isocyanurate, and an organic Ti-P catalyst were added at 0, 200, 400, and 600 ppm relative to the solids of the reactant, and the reaction was heated to 190 ° C. Every 30 minutes thereafter, the temperature was raised to 210 ° C by 10 ° C. Table 2 shows the results of measuring the time at which the reactants change into a clear pale yellow solution while the reaction is continued at 210 ° C. The introduction of the organic Ti-P catalyst in Table 2 not only shortens the polymerization time of polyesterimide, which is a basic resin used for magnet wire coating, but also shows that the synthesized polyesterimide resin is obtained in pale yellow, which has excellent transparency and light color. Could know.

As can be seen by the above embodiment, first, the effect of the present invention is to use the organic Ti-P-based catalyst that is more reactive than the catalyst used in the synthesis of conventional polyesterimide resin, shortening the reaction time and lowering the reaction temperature Second, since there is a phosphate group that acts as a thermal stabilizer in the organic Ti-P catalyst, side reactions can be suppressed during the synthesis of polyesterimide resin, and third, the organic Ti-P resin in the synthesized polyesterimide resin Since the catalyst remains, the polyesterimide base resin can be mixed with other additives to serve as a heat stabilizer that can withstand high heat of about 450 ° C. even when coating the magnet wire. Fourth, titanium metal is included in the polyesterimide resin. There is good wear resistance.

Claims (4)

Organic Ti-P type catalyst for polyesterimide synthesis represented by the following formula: Ti _n PO ₁₁ C ₁₄ H ₄₅ wherein n is an integer of 1 to 3. Titanium chloride (titi) (IV) chloride triethyl organic phosphate phosphoric acid or phosphate ester in a catalyst of CCl ₄ or n- hexene was stirred for 30 minutes at 20 to 30 ℃, then reacted with ethanol for 30 minutes and then ethylene glycol A method for producing an organic Ti-P catalyst for synthesizing polyesterimide represented by the following formula: Ti _n PO ₁₁ C ₁₄ H ₄₅ wherein n is an integer of 1 to 3. The trimellitic anhydride and methylene dianiline were reacted in m-cresol solvent to synthesize diacidimide, followed by organic Ti-P system represented by the following formula together with ethylene glycol and tris (2-hydroxyethyl) isocyanurate. Process for producing polyesterimide by adding a catalyst and condensation polymerization: Ti _n PO ₁₁ C ₁₄ H ₄₅ wherein n is an integer of 1-3. The process according to claim 3, wherein the content of the organic Ti-P catalyst is 200 to 800 ppm based on the solids of the reactants.