KR100628036B1 - A metal organic compound and its manufacturing methods - Google Patents

Abstract

The present invention relates to a metal organic compound composite agent added to a polymeric material and used as a crystallizing or compatibilizing agent and a method for producing the same.

The metal organic compound complex of the present invention may be selected from metal compounds including metal alkoxides, metal acetates and metal acid compounds, ethylene glycol, propanediol and derivatives thereof, butanediol and derivatives thereof, pentanediol and derivatives thereof, and hexanol. Diols containing are mixed or reacted in a constant molar ratio, and trimethyl phosphate (TMP), triethyl phosphate (TEP), and triphenyl phosphate (TPP) are solid and liquid metal organic compounds prepared using additives. In addition, a method of producing a metal oxide having a uniform crystal grains of nano-sized by a separate heat treatment of the metal-organic compound composite according to the present invention.

Since the metal organic compound composite of the present invention has a hydroxyl group (-OH), when used as a crystallizing agent, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene or A product can be obtained in a single phase through the reaction with a hydroxyl group (-OH) or a carboxyl group (-COOH) of a polymer material such as phthalate (PEN). Through this action, the metal-organic compound composite prepared by the preferred embodiment of the present invention increases the crystallinity and crystallization rate of PET, PTT, PBT, PEN, etc., and acts as a crystallization agent, and is also applied to various polymer blends and commercialized. It has the effect of acting as a priest.

Metal organic compounds, crystallizers, compatibilizers, metal oxides, titanium dioxide

Description

Metal organic compound complex and its manufacturing method {A METAL ORGANIC COMPOUND AND ITS MANUFACTURING METHODS}             

1 is an infrared absorption spectroscopy (FT-IR) spectrum of a metal organic compound composite according to the present invention.

2 is a differential scanning calorimetry (DSC) result of titanium dioxyethanol as a metal organic compound composite according to the present invention.

3 is a thermogravimetric analysis (TGA) result of titanium dioxyethanol as a metal organic compound composite according to the present invention.

4 is a differential differential scanning calorimetry (DSC) diagram when a titanium dioxyethanol, which is a metal organic compound composite according to the present invention, is added to PET.

5 is a cooling differential scanning calorimetry (DSC) diagram when titanium dioxyethanol, which is a metal organic compound composite according to the present invention, is added to PET.

6 is a thermal differential scanning calorimetry (DSC) analysis when the titanium oxypropanol, which is a metal organic compound composite according to the present invention, is added to PET,

7 is a differential scanning calorimetry (DSC) analysis of the addition of titanium oxypropanol as a metal organic compound composite according to the present invention to PET.

8 is a heating DSC analysis diagram when titanium dioxyethanol, a metal organic compound composite according to the present invention, is added to a PTT / PC blend.

9 is a differential scanning calorimetry (DSC) result of heating when 0.1 ml of the liquid metal organic compound composite according to the present invention is added to a PTT / PET (90/10) blend.

10 is a heating differential scanning calorimetry (DSC) result of adding titanium dioxyethanol, which is a metal organic compound composite according to the present invention, to a PBT / PC blend.

11 is a morphology when 0.2 w% of titanium dioxyethanol, a metal organic compound composite according to the present invention, is added to a PET / LCP (90/10) blend.

12 is a morphology when 0.2 w% of titanium dioxyethanol, a metal organic compound composite according to the present invention, is added to a PTT / LCP (95/5) blend.

FIG. 13 is a morphology when 0.2 w% of titanium dioxyethanol, which is a metal organic compound composite according to the present invention, is added to a PBT / LCP (95/5) blend. FIG.

FIG. 14 and FIG. 15 are observing morphologies when and when titanium dioxyethanol, which is a metal organic compound composite according to the present invention, is added to a PET / PS (50/50) blend and is not added.

14 is a morphology of a PET / PS (50/50) blend,

FIG. 15 is a morphology when 2 w% of titanium dioxyethanol is added to a PET / PS (50/50) blend.

FIG. 16 and FIG. 17 show morphologies when and when titanium dioxyethanol, which is a metal organic compound composite according to the present invention, was added to a PTT / PS (50/50) blend and was not added.

16 is the morphology of the PTT / PS (50/50) blend,

FIG. 17 is a morphology when 2 w% of titanium dioxyethanol is added to a PTT / PS (50/50) blend.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite agent of a metal compound and an organic compound that acts as a compatibilizer and a crystallizing agent in the preparation of a polymer material. The present invention relates to a metal compound comprising a metal alkoxide, a metal acetate, a metal acid compound, ethylene glycol, propanediol, The present invention relates to a metal organic compound, which is a compound of a derivative thereof, butanediol, a derivative thereof, a pentandiol, a derivative thereof, and a diol including hexanol.

Generally, polyethylene terephthalate (PET, hereinafter called PET) has high strength, high elasticity, and excellent heat resistance, but has a problem of slow crystallization, touch and hydrolysis resistance, which are important factors in molding. There were efforts. Japanese Patent Application Laid-Open No. 56-141347, Korean Laid-Open Patent Publication No. 93-0012978 and the like disclose alkali or alkaline earth metals of organic sulfonic acid and higher fatty acid alkali metal salts having more than 26 carbon atoms, calcium salts, and the like in order to improve the crystallization rate of PET. Sodium salts or potassium salts of organic polymers having sodium carbonate or pentencarboxyl groups having 7 to 25 carbon atoms were added as nucleating agents. In U.S. Patent No. 4,368,283 and U.S. Patent No. 4,215,032, ester compounds (neopentyl glycol dibenzoate, etc.), ether compounds (sorbitan derivatives), epoxy compounds, etc. are added as plasticizers or copolymerized with a flexible component to increase crystal growth rate. In order to reduce the glass transition temperature (Tg), the crystallization rate at the low temperature is increased, and the crystallization rate of the whole is also increased. However, in the method of copolymerization, the melting point is enhanced and the physical properties are lowered. In addition, since the copolymerization of a compound having a nucleating agent effect and a plasticity function has been patented a method for improving the crystallization rate during molding while maintaining mechanical properties or heat resistance.

Korean Patent Publication No. 96-17779 discloses a method for adding boronite and phosphorus compounds as a nucleating agent of polybutylene terephthalate (PBT, hereinafter referred to as PBT), and registered Korean Patent No. 0175204 and European Patent No. 0,186,456. In this issue, studies have been conducted to improve crystallinity by adding metal salts, diols, titanium compounds, and phosphorus compounds to PBT. In addition, U.S. Patent No. 5,350,829 describes the crystallization rate and compatibility of polymer materials, which are the biggest disadvantages of polymer materials, such as glycol-soluble magnesium, zinc, nitrogen, phosphorus compounds, and the like in polyethylene naphthalate (PEN, hereinafter referred to as PEN). Various studies have been conducted to improve the problem.

However, in these methods, the miscibility between the added nucleating agent or the plasticizer and the polymer materials becomes a problem, and there is a problem that the mechanical properties are degraded due to the decrease in compatibility.

In addition, copolymerization with monomers having different chemical structures or blends between polymers are widely used as a method for compensating and improving the disadvantages of polymer materials. For example, PET-P is used to increase the crystallization rate of PET by using properties of PBT. In order to make PBT block copolymers or to use them as processing aids, studies are being conducted to improve mechanical properties such as blending liquid crystal polymers (LCP, hereinafter referred to as LCP) with thermoplastic molecules. However, polyester-based blends can react between the two components and add, decompose alcohols, and exchange during the melting process, resulting in the formation of new copolymers and undesirable properties. There was this.

Accordingly, the present invention is to solve the above-mentioned disadvantages and problems of the prior art, and to increase the degree of crystallization and crystallization rate of the polymer material and the metal organic compound composite agent that can improve the compatibility between the components during melt blending of the polymer and It is an object of the present invention to provide a preparation method thereof.

The object of the present invention is a metal compound comprising a metal alkoxide, metal acetate, metal acid compound and ethylene glycol, propanediol and derivatives thereof, butanediol and derivatives thereof, pentanediol and derivatives thereof, hexanol Diols are mixed in various molar ratios and trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP) are used as additives to achieve solid and liquid metal organic compound complexes prepared.

Since the metal-organic compound composite of the present invention has a hydroxyl group (-OH), hydroxyl groups such as PET, polytrimethylene terephthalate (PTT, hereinafter PTT), PBT, PEN, etc. when used as a crystallizing agent ) Or a carboxyl group (-COOH) to give a single product. Through this action, the metal organic compound composite prepared by the preferred embodiment of the present invention increases the crystallinity and crystallization rate of PET, PTT, PBT, PEN, etc., and acts as a crystallization agent, and is applied to various polymer blends to be used as a compatibilizer. Includes acting as a

In addition, a metal oxide having a nano-sized crystal grain may be manufactured by separately heat treating the metal organic compound composite agent of the present invention.

Details of the above object and technical configuration and the effects thereof according to the present invention will be more clearly understood by the following detailed description through preferred embodiments of the present invention.

The method for preparing a metal organic compound composite of the present invention and a method for verifying the effect thereof have a first step of preparing a metal organic compound composite of a metal compound and a diol in a nitrogen atmosphere, and the metal prepared in the first step. The second step of increasing the crystallization rate by adding the organic compound composites to PET, PTT, PBT, PEN, etc., and the metal organic compound composites prepared in the first step to the blend of the polymer material It comprises a third step of improving, and additionally comprises a four step of producing a nano-sized metal oxide by heat-treating the metal organic compound composite prepared in the first step.

The step of preparing the metal organic compound composite of the first step is divided into the step of selecting a starting material, the production of the solid phase and liquid phase production method and the analysis of the components and properties of the prepared metal organic compound composite. .

The starting material of the metal organic compound composite of the first step is selected according to the following Reaction Scheme (1), the corresponding metals and ligands are shown in Table 1.

M (OR) n + M R '(OH) 2 → M (OR'OH) m + ROH

(Wherein M = metal, R = alkyl group, M = mole, R ′ = alkyl group, n and m are positive integers.)

Element of metal alkoxide Metal alkoxide Metal element (M) Ligand (OR) MOR M (OR) 2 M (OR) 3 M (OR) 4 M (OR) 5 M (OR) 6 Li, Be, Na, K. Rb, Cs, Ca, Sr, Ba, Sc, Ln, Ti, Zr, Hl, V, Nb, Ta, Cr, Mn, Fe, Co, Rh, Ni, Pb, Pt, Cu, Zn, Ch, B, Al, Ga, In, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te, La, Ce, Th, Pr, Nd, Eu, Gd, Tb, Ho, Yb, Lu CH3 CH2CH3 (CH2) 2CH3 CH3CH2CH2CH2 CH3 (CH2) 7 (CH3) 2CH (C2H5) 2CH (CH3) 3C C2H5 (CH3) 2C CH3 (CH2) 4 (CH3) 2CH (CH2) 2 (CH3C2H5) CH2CH2 (CH3) ) 3CCH2 (CH3) 2C2H5C

More specifically, the molar ratio of the metal compound and the diol, which is the starting material of the solid metal organic compound composite, is 1: 1 to 1:10 (1: 1, 1: 1.5, 1: 2, 1: 3, 1: 4, 1: 5, 1: 6, 1:10), and the molar ratio of the metal compound and diol, which is the starting material of the liquid metal organic compound composite, is 1: 1000-1: 4000. The metal compound which is a starting material of the metal organic compound composite agent is at least one of metal alkoxide, metal acetate, metal sulfur compound, and metal acid compound, and diol is ethylene glycol (EG, HOCH2CH2OH), 1,3-propanediol (PDO, HO (CH2) 3OH), 1,2-propanediol (1,2-PDO, HOCH2CH (OH) CH3), 1,4-butanediol (BG, HO (CH2) 4OH), 1, 2-butanediol (1,2-BG, CH2CH5CH (OH) CH2OH), 1.3-butanediol (1,3-BG, CH3CH (OH) CH2CH2OH), 2,3-butanediol (2,3- BG, (CH3CH (OH) CH (OH) CH3), 1,5-pentanediol (PO, HO (CH2) 5OH), 1,2-pentanediol (1,2-PO, CH3CH2CH2CH (OH) CH2OH ), 1,4-pentanediol (1,4-PO, CH3CH (OH) (CH2) 3OH), 2,4-pentanediol (2,4-PO, CH3CH (OH) CH2CH (OH) CH3) , 1,6-hexanol (HO, HOCH2CH2CH2CH2CH2CH2OH), 1,2-hexanol (1,2-HO, CH3CH2CH2CH2CH (OH) CH2OH), 1,5-hexanol (1,5-HO, CH3CH (OH) CH 2 CH 2 CH (OH) CH 3), 2,5-hexanol (2,5-HO (CH 3 CH (OH) CH 2 CH 2 CH (OH) CH 3)) is reacted.

The method for preparing a metal organic compound composite of the first step may be classified into a solid phase and a liquid phase production method. The method for preparing a solid metal organic compound composite may be selected from the first to third processes after selecting a metal compound and a diol according to Scheme 1. Contains one process.

The first process is a mixing step in which the metal compound and the diol are mixed in a constant molar ratio, and a heating step in which a white precipitate is formed, which is heated in the range of 100-300 ° C. while stirring at a constant stirring speed in a nitrogen gas atmosphere, and further 10 minutes is generated. After heating, the reactants are cooled, followed by a cold washing step which is repeatedly washed several times with methyl alcohol and a drying step where the white precipitate is vacuum dried at 100 ° C for 12 hours.

The second process is a mixing step in which a metal compound and a diol are mixed at a constant molar ratio in a two-necked glass reactor, trimethyl phosphate (TMP, hereinafter referred to as TMP) and triethyl phosphate (TEP) of 0.1-2 times the mass of the metal compound. (Hereinafter referred to as TEP) and triphenylphosphate (TPP, hereinafter referred to as TPP), each of which is added, a heating step of heating in the range of 100-300 ° C. while stirring, and further heating for 10 minutes when a white precipitate starts to be produced. Then, the reactant containing the white precipitate is cooled and consists of a cold washing step which is repeatedly washed several times with methyl alcohol and a drying step in which the white precipitate is vacuum dried at 100 ° C. for 12 hours.

The third process is followed by a stage in which the product is cooled under the same conditions as the first process, a cooling device capable of cooling the product, and a vent line capable of applying vacuum, followed by a vacuum of 500 × 10 −3 Mbar and a reaction if the product no longer exits. It consists of a step of stopping.

Next, the liquid metal organic compound composite is prepared by selecting a starting material according to Scheme 1 and then including one of the following fourth to sixth processes.

The fourth process is a process in which a metal compound and a diol are mixed in a constant molar ratio in a two-necked glass reactor and then heated at 20-150 ° C.,

The fifth process is prepared in the same manner as the fourth process and is heated in the range of 100-300 ℃ and when the mixed solution becomes transparent, the heating is stopped to recover the transparent liquid compound.

In the sixth process, TMP, TEP, and TPP, each of which is 0.1-2 times the mass of the metal compound, are dissolved in diol in a two-neck glass reactor, and the metal compound is mixed in a constant molar ratio. It is composed of the step of heating in the range and the step of stopping the heating and recovering the transparent liquid compound when the mixed solution becomes transparent.

In this study, the solid metal organic compound composite reacts titanium butoxide (dibutyl tin dilaurate) with dibutyl tin dilaurate as a metal compound and ethylene glycol (EG, hereinafter referred to as EG) as a diol. Titanium dioxy ethanol (TOE, hereinafter referred to as TOE) and titanium oxypropanol (TPOE, TPOE) obtained from the reaction of a titanium compound (titanium (IV) isopropoxide) with diol EG. For example, as a liquid composite agent, one obtained through the reaction between titanium butoxide and ethylene glycol was obtained through the reaction between titanium oxyethylene glycol (TBOEG) and titanium isopropoxide and ethylene glycol. Ethylene glycol (TPPOEG), dibutyltin dilaurate obtained through the reaction of ethylene glycol and tinoxyethylene glycol (DTOEG), titanium Titanium oxypropanediol (TBOPDO) obtained through the reaction of the toxoxide and propanediol, titanium isopropoxydipanol (TPPPDO), dibutyltindiol obtained through the reaction of titanium isopropoxide and propanediol What was obtained through the reaction of the rate and propanediol has been described using tinoxypropanediol (DTDPDO) as an example, but the scope and effect of the present invention is not limited thereto and includes all materials shown in Scheme 1 and Table 1. .

1 is a spectrum obtained by analyzing the components of the metal organic compound composite using a FT-IR spectrophotometer (FT-IR spectrophotometer; Simadzu0 FT-IR 8700) manufactured through the first to third processes. The synthesis of the metal organic compound can be confirmed by confirming the hydroxyl group (—OH) peak in the 3100 cm −1 region, the ethylene (CH 2 CH 2) in the 2900 cm −1 region, and the CH 2 peak in the 1050 cm −1 and 1370 cm −1 regions.

2 and 3 show the results of differential scanning calorimetry (DSC, hereinafter referred to as DSC) and thermogravimetric analysis (TGA, hereinafter referred to as TGA) to measure the thermal properties of the TOE, a metal-organic compound composite. The highest decomposition temperature is 377.97. ℃, the heat of decomposition was 170.7 J / g as a result it was confirmed that the organic compound. Referring to the TGA results of FIG. 3, the TOE rapidly decomposed from above 300 ° C., but there was almost no weight loss at about 50% of the weight loss, and the decomposition temperature range in DSC and the decomposition process in TGA were consistent. The above results show that the TOE has excellent thermal stability as the temperature gets higher. In addition, the particle size analysis of the solid-state organic compound composite TOE by Gaussian Analysis showed that the particle size was 100-1000 nm and the particle distribution was very uniform.

In the step of increasing the crystallization rate of PET, PTT, PBT, PEN by adding the present metal organic compound in the second step, it was confirmed that the present metal organic compound plays a role as a crystallizer through the following examples.

Example 1 is to examine the effect of adding the metal organic compound composite according to the present invention to PET, 0.5-10w% metal organic compound in general-purpose PET using an extruder and a high pressure reactor with a single and double screw attached The composite agent was added and mixed for 5-10 minutes at a rotational speed of 40-50 rpm at a melting temperature of 260-290 ° C. and then recovered.

4 and 5 are heating / cooling DSC analysis results for comparing thermal properties and recrystallization according to PET secondary melting behavior when the TOE is added to PET, and FIGS. 6 and 7 illustrate that TPOE is added to PET. Table 2 shows the analysis results of FIGS. 4 to 7 as heating / cooling DSC analysis results for comparing thermal properties and recrystallization according to PET secondary melting behavior.

Thermal Properties of TOE and TPOE Added to PET Weight% T _g (℃) T _lc (℃) T _m (℃) T _c (℃) ΔH _m (J / g) ΔH _c (J / g) PET (100) 80.92 146.06 255.04 173.76 37.29 15.02 PET (100) -TOE 0.5 phr - - - 184.07 - 35.35 PET (100) -TOE 2 phr 80.48 139.00 255.37 205.79 42.21 41.71 PET (100) -TPOE 2phr 80.09 140.81 256.52 201.23 45.29 44.11 PET (100) -TOE 5 phr 79.98 135.89 256.24 209.58 41.79 38.41 PET (100) -TOE 10 phr 79.48 128.46 257.01 218.65 43.18 41.05

In Table 2, the glass transition temperature (Tg) and melting temperature (Tm) were constant regardless of the amount of metal organic compounds added, and when the TOE was added, heat of fusion (ΔHm), heat of crystallization (ΔHlc) and recrystallization at low temperatures were added. The heat of fire (ΔHc) and recrystallization temperature (Tc) increased as the amount of addition increased, but the crystallization temperature (Tlc) at lower temperature decreased as the amount of TOE increased, which increased the flexibility of the PET chain due to the addition of TOE. Because. When TPOE was added, the heat of crystallization at lower temperature was lower than when TOE was added, and heat of fusion and heat of crystallization was high.

In addition, TGA analysis of PET when pure PET and metal organic compounds were added showed that the pure PET was slightly more stable at a decomposition temperature of 400 ° C., but above 450 ° C., TOE and TPOE were added due to the thermal stability of the metal organic compound according to the present invention. PET was more stable.

Example 2 is to determine the effect of the metal organic compound according to the present invention to the PTT, and the same conditions as in Example 1, but mixed at a melting temperature of 250 ℃, the secondary of the PTT through DSC and TGA analysis Thermal properties and recrystallization according to melting behavior were compared. Table 3 shows the result of adding 0.5w% of TOE to PTT.

Thermal Properties of TOE Added to PTT TOE weight% T _g (℃) T _lc (℃) T _m (℃) T _c (℃) ΔH _m (J / g) ΔH _c (J / g) PTT (100) 45.64 71.12 226.43 159.66 60.27 42.87 PTT (100) -TOE 0.5% 45.10 71.36 226.38 173.75 60.27 48.22

In Table 3, glass transition temperature (Tg), crystallization temperature (Tlc) at low temperature, melting temperature (Tm), heat of crystallization (ΔHlc) and heat of melting (ΔHm) at low temperature were constant regardless of the amount of TOE. The recrystallization heat (ΔHc) increased with addition of TOE, and the recrystallization temperature (Tc) increased with addition of TOE. As a result, it can be seen that the flexibility of the chain increases due to the addition of the metal organic compound.

Example 3 is to investigate the effect of the metal organic compound according to the present invention to the PBT, and the same conditions as in Example 1, but mixed at a melting temperature of 250 ℃, the secondary of the PBT through DSC and TGA analysis Thermal properties and recrystallization according to melting behavior were compared. Table 4 shows the results when the TOE is added to the PBT.

Thermal Properties According to the Amount of TOE Added to the PBT TOE weight% T _g (℃) T _lc (℃) T _m (℃) T _c (℃) ΔH _m (J / g) ΔH _c (J / g) PBT (100) 39.32 - 223.93 178.79 52.83 42.64 PBT (100) -TE 0.5% - - - 189.90 - 50.74 PBT (100) -TE 2% 40.15 - 224.21 194.71 54.30 51.82 PBT (100) -TE 5% 38.74 - 222.94 189.80 48.90 46.28 PBT (100) -TE 10% 38.48 - 223.04 188.72 49.22 50.52

In Table 4, the glass transition temperature (Tg) and melting temperature (Tm) were constant regardless of the amount of TOE, and the heat of fusion (ΔHm) was higher than pure PBT at 2w% of TOE, but was lower than above. The recrystallization heat (ΔHc) and recrystallization temperature (Tc) increased as the amount of TOE increased. As a result, it can be seen that the recrystallization heat and the recrystallization temperature change due to the addition of TOE are due to the increased flexibility of the PBT chain due to the addition of metal organic compounds.

Thermal Properties According to the Amount of TOE Added to PEN TOE weight% T _c (℃) ΔH _c (J / g) PEN (100) 194.50 13.76 PEN (100) -TOE 0.5% 196.92 15.48 PEN (100) -TOE 2% 199.25 24.96 PEN (100) -TOE 5% 200.65 25.74

In Table 5, the recrystallization heat (ΔHc) and recrystallization temperature (Tc) increased as the amount of TOE increased. As a result, it can be seen that the recrystallization heat and the recrystallization temperature change due to the addition of the TOE due to the flexibility of the PEN chain due to the addition of the organic metal compound and the TOE as a nucleating agent.

Step 3 is a step of preparing a polymer composite material in a melt blend by adding the present metal organic compound composite,

In order to examine the effect of adding the metal organic compound composite according to the present invention to the melt blending of the polymer material, here, typically, PTT / polycarbonate (PC, hereinafter referred to as PC), PTT / PET, PBT / PC, PET , Any one of PTT and PBT, liquid crystal polymer (LCP, hereinafter referred to as LCP), PET, PTT and polystyrene (PS, hereinafter referred to as PS) are melt-blended to add the present metal organic compound, followed by DSC and TGA. The behavior was analyzed through.

In order to perform the third step, the following implementation method was performed. The melt blend uses a polymerization reactor, a single screw and a double screw compressor in a nitrogen atmosphere. The mixing temperature is 270 ° C for PET, 260 ° C for PTT and PBT, and the temperature of the extruder is 275 ° C-265 ° C-255 ° C for PET. PTT was 260 ° C-240 ° C-230 ° C, PBT was 250 ° C-240 ° C-225 ° C, the rotation speed was 40-50 rpm, and the mixing time was 5-10 minutes. The amount of additive was 0.2w% for PC and LCP, 2w% for PS, and 0.1ml for liquid additive. LCP used Estman Kodak's X7G, Smitimo's EKONOL, Dartco's XYDER, Celanese's VECTRA, Mitsubishi's NOVACURRATER, Unitika's RODRAN and outgoing petrochemicals LCP (PET (40) / PHB (60)). ) Was used as a representative, and the LCP used in the experiment was used by condensation polymerization at a condensation polymerization temperature of 270 ° C in a laboratory.

Example 4 is to investigate the behavior by adding a metal organic compound to the melt blend of the PTT / PC, according to the above-described method was melt-blended PTT and PC and added the TOE, a metal organic compound. 8 is a DSC graph according to the TOE addition amount, and the results are summarized in Table 5.

Thermal Properties of PTT / PC Blends Weight% T _g1 (℃) T _g2 (℃) T _lc (℃) ΔH _lc (J / g) T _m (℃) ΔH _m (J / g) PTT / PC (100/0) 44.12 - 71.2 34.09 227.44 57.37 PTT / PC (30/70) 45.41 139.74 77.81 6.985 224.56 15.83 PTT / PC (30/70) -TOE 2% 49.95 134.45 85.31 5.969 223.13 15.17 PTT / PC (0/100) - 150.98 - - - -

When the TOE was not added in Table 6, the glass transition temperature (Tg) of PTT was not changed, the glass transition temperature of PC decreased by about 10 ℃, and the crystallization temperature (Tlc) that appeared at low temperature increased by about 6 ℃. When the TOE was added, the glass transition temperature (Tg) of PTT increased by about 6 ℃ and the glass transition temperature of PC decreased by about 16 ℃. However, the heat of crystallization (ΔHlc) and heat of fusion (ΔHm) at low temperatures were the same regardless of the addition of TOE, and the melting temperature was lower in both cases. The change in the glass transition temperature was due to the compatibility by the transesterification reaction between the ester group of PTT and PC, and when TEO was added, the compatibility was increased by the transesterification reaction. In addition, since the melting temperature is lower without changing the heat of melting, it can be seen that the workability is improved.

Example 5 is to investigate the behavior by adding a metal organic compound to the PTT / PET melt blend, melt blending PTT and PET according to the above-described method, and here the titanium metal ethylene glycol (TBOEG) as a liquid metal organic compound composite ), 0.1 ml of titanium isopropyl ethylene glycol (TPPOEG), tinoxy ethylene glycol (DTOEG), titanium oxypropanediol (TBOPDO), titanium isopropyl propanediol (TPPPDO), and tinoxypropanediol (DTDPDO) After that, the secondary melting behavior was examined. As can be seen in Figure 9 and Table 7, it has a single glass transition temperature it can be seen that the liquid additives in all melt blends act as a compatibilizer.

Thermal Properties According to Additives in PTT / PET Blends additive T _g (℃) ΔT _lc (J / g) T _m (℃) ΔH _m (J / g) TBOEG 49.57 82.65 216.27 51.88 TPPOEG 48.85 82.52 215.77 53.56 DTDEG 49.80 83.54 216.34 50.55 TBOPDO 49.09 82.21 216.38 54.15 TPPPDO 49.28 82.45 217.37 53.32 DTDPDO 49.15 82.76 216.21 52.61

Example 6 is to investigate the behavior of the metal organic compound by adding to the PBT / PC melt blend, the TOE is added to the PBT and PC melt blend in accordance with the method described above and the results of the DSC analysis are shown in FIGS. Indicated.

Thermal Properties of PBT / PC Blends Weight% T _g (℃) T _lc (℃) ΔH _lc (J / g) T _m (℃) ΔH _m (J / g) PBT / PC (100/0) 39.22 - - 223.93 54.28 PBT / PC (30/70) 109.02 158.47 5.370 220.11 15.02 PBT / PC (30/70) -TOE 2% 99.72 182.20 3.672 216.31 7.851 PBT / PC (0/100) 150.98 - - - -

In Table 8, single glass transition temperature (Tg) appeared regardless of TOE addition, melting temperature and heat of fusion decreased, and exothermic phenomenon due to crystallization before melting due to interference of amorphous PC. When the TOE was added, the glass transition temperature (Tg) of the PBT was lowered by 9 ℃, the crystallization temperature at lower temperature was increased, and the heat of fusion was reduced by half than before the TOE was added. As a result, the transesterification reaction between the ester group of PBT and PC increased due to the addition of TOE, which reduced the heat of fusion as the degree of randomization increased. Therefore, by adjusting the TOE amount and mixing time, the mechanical properties can be improved due to the compatibility by the transesterification reaction.

Example 7 is to examine the secondary melting behavior according to the presence or absence of the addition of the metal organic compound when any one of PET, PTT, PBT and LCP is melt blended, PET / LCP, PTT / LCP After adding the TOE to the PBT / LCP melt blend, the thermal properties were analyzed by DSC (Table 9), and the morphology was observed by scanning electron microscopy (SEM, hereinafter referred to as SEM) (Figs. 11, 12, and 13).

Thermal Properties of Melt Blends with PET, PTT, PBT and LCP Weight% T _g (℃) T _lc (℃) ΔH _lc (J / g) T _m (℃) ΔH _m (J / g) ΔHc (J / g) PET / LCP (100/0) 80.92 146.06 32.21 255.04 37.30 15.02 PET / LCP (95/5) -TOE 0.2% 80.26 128.73 32.08 249.03 40.45 35.62 PTT / LCP (100/0) 44.12 71.22 34.09 227.44 57.37 42.87 PTT / LCP (95/5) -TOE 0.2% 46.99 73.02 29.60 227.16 51.03 45.33 PBT / LCP (100/0) 39.32 - - 223.93 54.28 42.64 PBT / LCP (95/5) -TOE 0.2% 42.27 - - 224.41 47.12 46.18

First, PET / LCP (90/10) is melt blended and the secondary melt and crystallization behaviors of the melt blend with and without 0.2w% of TOE are added (Table 9). In the case of blends, the glass transition temperature did not change regardless of the presence of the TOE. In the presence of the TOE, the crystallization temperature and melting temperature of the lower temperature were lowered, and the heat of melting increased. The decrease in melting temperature is due to the compatibility by the transesterification reaction between PET and LCP, and the increase in heat of crystallization can be seen as a result of the increase in crystallinity when the TOE is added to PET. The crystallization rate was higher than that of pure PET but lower than the sample to which 0.5w% of TOE was added. Figure 11 shows the morphology of the PET / LCP (90/10) -TOE 0.2w% blend, which looks like a rounded domain with LCP, and several rounded domains are pulled out like fibers. It can be seen that compatibility exists.

Next, look at the secondary melt and crystallization behavior of the melt blend with and without 0.2w% of TOE in the PTT / LCP (95/5) melt blend (Table 9). The crystallization temperature at the glass transition temperature and low temperature was higher than that of pure PTT, and the heat of crystallization and melting at lower temperature were decreased. This may be due to the compatibility between the PTT and the LCP by the transesterification reaction of the TOE, and the heat of crystallization and the rate of crystallization were higher than those of the pure PTT, but lower than the sample to which the TOE was added 0.5w%. 12 shows the morphology of the PTT / LCP (95/5) -TOE 0.2w% blend. It is LCP that looks like a rounded domain, and some rounded domains are pulled out like fibers, indicating that compatibility exists as the TOE acts as a catalyst in PTT and LCP blends.

As a final example of Example 7, the secondary melt behavior and crystallization behavior of the melt blend with and without 0.2w% of TOE in the PBT / LCP (95/5) melt blend were examined (Table 9). . In the case of PBT / LCP, the glass transition temperature was higher than that of pure PBT, the melting heat decreased, and the crystallization of PBT, which could not crystallize due to the rigid LCP, was found near 201 ℃. This may be due to the compatibility between the PBT and the LCP by the TOE as a catalyst, and due to the interchangeability of the transesterification reactions. FIG. 13 shows the morphology of PBT / LCP (95/5) -TOE 0.2w% blend. It is LCP that looks like a rounded domain, and some rounded domains are pulled out like fibers, indicating that compatibility exists as the TOE acts as a catalyst in PBT and LCP blends.

Therefore, the results of Example 7 are expected to reduce the melt viscosity due to the reduction of the interfacial tension and to improve the mechanical properties by the rigid LCP.

Example 8 is to examine the secondary melt behavior according to the presence or absence of the addition of the metal organic compound when any one of the PET and PTT melt blended, PET / PS, PTT / PS melt blend according to the above-described method After the TOE was added, thermal properties were analyzed by DSC (Table 10), and the morphology was observed by scanning electron microscope (SEM, hereinafter referred to as SEM) (Figs. 14, 15, 16, and 17).

Thermal Properties of Melt Blends with PET, PTT, and PS Weight% T _g1 (℃) T _g2 (℃) T _lc (℃) ΔH _lc (J / g) T _m (℃) ΔH _m (J / g) PET / PS (100/0) 80.90 - 146.06 32.21 255.04 37.30 PET / PS (50/50) 79.13 95.56 142.35 14.74 254.34 20.50 PET / PS (50/50) -TOE 2% 80.15 98.02 142.83 13.90 254.61 18.95 PTT / PS (100/0) 44.12 - 71.22 34.09 227.44 57.37 PTT / PS (50/50) 45.35 96.95 70.96 13.73 226.76 28.46 PTT / PS (50/50) -TOE 2% r 43.95 97.04 72.04 14.04 224.31 30.72 PTT / PS (0/100) - 98.76 - - - -

In order to examine the secondary melt behavior of PET / PS-TOE 2w% melt blend, the behavior of PET / PS melt blend without the addition of TOE (Table 10) shows that the glass transition temperature of PET is not changed. The glass transition temperature on the PS side was 3 ℃, and the crystallization temperature at the lower temperature was about 4 ℃ and the melting temperature did not change. PS is amorphous, impedes the crystallization of PET and increases the crystallization temperature appearing at low temperature. On the contrary, due to the thermal decomposition of PET and PS, the glass transition temperature of PS side and crystallization temperature appearing at low temperature are decreased. , PET and PS are incompatible. When 2w% of TOE is added, the glass transition temperature of PET and PS is not changed, and the crystallization temperature at low temperature is lowered.The heat of crystallization and melting at lower temperature is about 1J than without TOE 2w%. / g was lowered. The presence of 2w% of the TOE lowered the glass transition temperature due to the decomposition of PS, but there was no thermal decomposition of the PS due to the presence of the TOE. 14 and 15 are morphologies of PET / PS (50/50) and PET / PS (50/50) -TOE 2w% blends. The surface is PET, the round domain is PS, and in FIG. 14, the hole formed when the PS is pulled out can be seen, and there is a gap between the PET and the PS interface. The presence of a gap between the hole and the two interfaces makes the two polymers incompatible. However, in the case of FIG. 15, when the PS exits around the hole that does not exist in FIG. 14, the PET is pulled up. This makes the TOE compatible by inducing a reaction between PET and PS.

Next, it is necessary to examine the behavior of the PTT / PS melt blend when the TOE is not added to investigate the secondary melt behavior of the PTT / PS (50/50) -TOE 2w% melt blend. In Table 10, the glass transition temperature of PTT side, the crystallization temperature of melting temperature and low temperature did not change, and the glass transition temperature of PS side was lowered by 2 ℃. PTT and PS are incompatible because there is a change in the glass transition temperature on the PS side but no other thermal properties. When 2w% of TOE was added, the glass transition temperature of PTT side did not change, and the glass transition temperature of PS side decreased by 2 ℃. In addition, the crystallization temperature at lower temperature was higher, the melting temperature was lower, and the heat of melting was about 2J / g lower than without 2w% of TOE. The presence of TOE increased the heat of fusion due to the increased crystallinity, and the change in the crystallization temperature and melting temperature at low temperatures was due to the compatibility between PTT and PS. 16 and 17 show the morphology of the PTT / PS (50/50) and PTT / PS (50/50) -TOE 2w% blend. The surface is PTT and the rounded domain is PS. In FIG. 16, the hole formed when the PS is drawn can be seen, and there is a gap between the PTT and the PS interface. The presence of a gap between the hole and the two interfaces makes the two polymers incompatible. However, in FIG. 17, it can be seen that a surface in which two phases exist and a surface in which a single phase exists coexist. This makes the TOE compatible by inducing a reaction between the PTT and the PS.

In order to explain the second step and the third step, the effects on some of the polymer blends were representatively shown through Examples, but the metal organic compound complex of the present invention used as the crystallization agent and the compatibilizer is not limited thereto. Without PET, PTT, PBT, PEN, Polystyrene (PS), Polycarbonate (PC), Polyvinyl Chloride (PVC), Nylon (NYLON, NYLON 6, NYLON 66), Polymaleic Acronil (PMMA), Male Rickmea Chronyl (MMA), Polyethylene (PE), Polypropylene (PP), Acronyl Butane Styrene (ABS), Styrene Butadiene Styrene (SBS), Acryl-based Polymer (NBS, AN, SAN), Liquid Crystal Polymer ( LCP) and their waste materials, used for the production of various polymers including waste tire powder, and also for blends of at least two of these polymer materials.

The fourth step is a step of producing a nano-sized metal oxide by heat-treating the metal organic compound prepared in the first step, it is completed by heat treatment of the metal organic compound prepared by the first step in an electric furnace.

FIG. 18 is a particle size analysis result of a metal oxide obtained by heating the TOE to 700 ° C. at a heating rate of 10 ° C./min, showing a uniform distribution of 7 to 50 nm. Analysis of the components of the heat-treated metal oxides by XRD showed peaks of typical titanium dioxide (TiO2) with 2θ values of 27.3, 35.9, 41.0, 54.2, 56.5, and 68.9, and the energy dispersive X-ray spectroscopy (EDX) of the metal oxides. As a result of analysis, the purity of the starting material titanium alkoxide was 95%, while Ti was 98.5%. Table 11 shows the particle size before and after heat treatment of TPOE and TOP.The particle size before heat treatment was almost the same as 100-1000nm, but the particle size after heat treatment was 7-100nm and 5-50nm for TPOE. appear. Among the methods for producing high-purity nano-sized metal oxides, only three representative examples of the method and result of the production of high-purity nano-sized titanium dioxide are shown, but are not limited to titanium dioxide, but are used in the materials prepared through the first step. All apply.

Particle Size Before and After Heat Treatment of Solid Metal Organic Compound Kinds Before heat treatment (nm) After heat treatment (nm) TPOE 100-1000 7-100 TOP 100-1000 5-50

Therefore, when the metal-organic compound composite agent according to the present invention is added to the polymer materials such as PET, PTT, PBT, PEN, and the like universally, it is completely mixed to form a single phase, and thus is incompatible with the polymers. It increases the compatibility and at the same time has the effect of increasing the crystallinity without changing the thermal properties, that is, the glass transition temperature or the melting temperature. Organic compounds or inorganic compounds added to the existing polymer materials have disadvantages of poor thermal properties, mechanical properties, and compatibility, but the metal organic compounds according to the present study have excellent effects even when only a small amount is added. It can be used universally. In addition, since the metal oxide compound having high purity nano size crystal grains can be manufactured by heat-treating the metal organic compound composite agent according to the present invention, there is an advantage that it can be used in the precision industry.

Claims (21)

It is added to the polymer material and used as crystallization or compatibilizer of the polymer material. The metal compound and the diol are represented by the reaction formula of M (OR) _n + M R '(OH) ₂ → M (OR'OH) _m + ROH. Mixed or reacted to produce solid or liquid And wherein M is a metal, R is an alkyl group, M is a mole, R is an alkyl group, and n and m are positive integers. The metal organic compound composite according to claim 1, wherein the metal compound is at least one of metal alkoxides, metal acetates, metal sulfur compounds, and metal acid compounds. The method of claim 1, wherein the diol is ethylene glycol (EG, HOCH2CH2OH), 1,3-propanediol (PDO, HO (CH2) 3OH), 1,2-propanediol (1,2-PDO, HOCH2CH (OH) CH3), 1,4-butanediol (BG, HO (CH2) 4OH), 1,2-butanediol (1,2-BG, CH2CH5CH (OH) CH2OH), 1,3-butanedi Ol (1,3-BG, CH3CH (OH) CH2CH2OH), 2,3-butanediol (2,3-BG, (CH3CH (OH) CH (OH) CH3), 1,5-pentanediol (PO , HO (CH2) 5OH), 1,2-pentanediol (1,2-PO, CH3CH2CH2CH (OH) CH2OH), 1,4-pentanediol (1,4-PO, CH3CH (OH) (CH2) 3OH), 2,4-pentanediol (2,4-PO, CH3CH (OH) CH2CH (OH) CH3), 1,6-hexanol (HO, HOCH2CH2CH2CH2CH2CH2OH), 1,2-hexanol (1,2 -HO, CH3CH2CH2CH2CH (OH) CH2OH), 1,5-hexanol (1,5-HO, CH3CH (OH) CH2CH2CH (OH) CH3), 2,5-hexanol (2,5-HO (CH3CH (OH) ) CH2CH2CH (OH) CH3) at least one or more metal organic compound composite. The metal organic compound composite according to claim 1, wherein the solid metal organic compound composite is a nano-sized grain of 100-1000 nm. The metal organic compound composite according to claim 1, wherein the metal organic compound composite includes a hydroxyl group (-OH). The metal organic compound composite according to claim 1, wherein the solid metal organic compound composite is mixed or reacted with a metal compound and a diol in a molar ratio of 1: 1 to 1:10. The metal organic compound composite according to claim 1, wherein the liquid metal organic compound composite is mixed or reacted with a metal compound and a diol in a molar ratio of 1: 1000 to 1: 4000. delete A mixing step in which a metal compound and a diol are mixed by a reaction scheme of M (OR) _n + M R '(OH) ₂ → M (OR'OH) _m + ROH; A heating step in which the mixed metal compound and diol are heated in a range of 100-300 ° C. while being stirred in a nitrogen gas atmosphere; After the white precipitate starts to form a further 10 minutes cooling and cooling to wash repeatedly with methyl alcohol several times; And The washed white precipitate is made comprising a drying step of vacuum drying at 100 ℃ for 12 hours, The M = metal, R = alkyl group, M = mole, R '= alkyl group, n, m is a positive integer, characterized in that the manufacturing method of the metal organic compound composite. The method of claim 9, wherein between the mixing step and the heating step, trimethyl phosphate (TMP), triethyl phosphate (TEP) and triphenyl phosphate (TPP) corresponding to 0.1-2 times the mass of the metal compound are metal compounds. Method for producing a metal organic compound composite, characterized in that the addition step is added to the mixture of diol and diol. 10. The method of claim 9, further comprising, after the mixing and heating steps, further heating for 10 minutes and then cooling after the white precipitate starts to form; And Applying 500 × 10 ⁻³ Mbar of vacuum to the white precipitate and stopping if the product no longer exits Method for producing a metal-organic compound composite comprising a. As a method for producing a liquid metal organic compound composite which is added as a crystallizing or compatibilizing agent of a polymer material, A mixing step in which a metal compound and a diol are mixed by a reaction scheme of M (OR) _n + M R '(OH) ₂ → M (OR'OH) _m + ROH; The heating step of heating the mixed metal compound and diol at 20-150 ℃ It is made, including The M = metal, R = alkyl group, M = mole, R '= alkyl group, n, m is a positive integer, characterized in that the manufacturing method of the metal organic compound composite. A mixing step in which a metal compound and a diol are mixed by a reaction scheme of M (OR) _n + M R '(OH) ₂ → M (OR'OH) _m + ROH; A heating step of heating the mixed metal compound and diol at 100-300 ° C .; Recovering the transparent liquid compound by stopping heating when the mixed solution of the metal compound and the diol becomes transparent It is made, including The M = metal, R = alkyl group, M = mole, R '= alkyl group, n, m is a positive integer, characterized in that the manufacturing method of the metal organic compound composite. delete delete delete delete delete delete 14. The method of any one of claims 1, 9, 12 and 13, wherein the metal is lithium (Li), beryllium (Be), sodium (Na), potassium (K). Rubidium (Rb), Cesium (Cs), Calcium (Ca), Strontium (Sr), Barium (Ba), Scandium (Sc), Lanthanum (Ln), Titanium (Ti), Zirconium (Zr), Vanadium (V) , Niobium (Nb), tantalum (Ta), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), rhodium (Rh), nickel (Ni), lead (Pb), platinum (Pt) ), Copper (Cu), zinc (Zn), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), arsenic (As) ), Antimony (Sb), bismuth (Bi), selenium (Se), tellurium (Te), lanthanum (La), cerium (Ce), thorium (Th), preseodymium (Pr), neodymium (Nd), At least one of europium (Eu), gadolinium (Gd), ternium (Tb), holmium (Ho), ytterbium (Yb), lutetium (Lu), and thallium (Tl). The compound according to any one of claims 1, 9, 12 and 13, wherein the alkyl group is CH ₃ , CH ₂ CH ₃ , (CH ₂ ) ₂ CH ₃ , CH ₃ CH ₂ CH ₂ CH ₂ , CH ₃ (CH ₂ ) ₇ , (CH 3) ₂ CH, (C ₂ H ₅ ) ₂ CH, (CH ₃ ) ₃ C, C ₂ H ₅ (CH ₃ ) ₂ C, CH ₃ (CH ₂ ) ₄ , ( CH ₃ ) ₂ CH (CH ₂ ) ₂ , (CH ₃ C ₂ H ₅ ) CH · CH ₂ , (CH ₃ ) ₃ C · CH ₂ , (CH ₃ ) ₂ C ₂ H ₅ C Metal organic compound composite manufacturing method.

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