KR100966193B1 - Nano-composite comprising poss and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a PET nanocomposite comprising a POSS and a method of manufacturing the same. The nanocomposite of the present invention uses PET grafted with POSS as a compatibilizer to improve the compatibility of PET and POSS, which are nano-level organic and inorganic composite particles. The nanocomposite of the present invention is very excellent in heat resistance and modulus, and can be widely applied to various fields such as tire cords, sheets, or packaging containers, which are industrial fibers.

POSS, nanocomposites, polyethylene terephthalate, PET, compatibility

Description

Nanocomposite containing POSS and its manufacturing method {NANO-COMPOSITE COMPRISING POSS AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a polymer nanocomposite, and more particularly, to a PET nanocomposite including POSS which can be used for tire cords, sheets or packaging containers which are industrial fibers.

Polyethylene terephthalate (PET) has been widely used in the non-fiber field of textiles since the mid-20th century due to its excellent properties such as high strength, high heat resistance and transparency, processing characteristics, and price competitiveness. Efforts have been made to produce composites with better performance PET.

Nanocomposites are composites in which polymer, inorganic or metal particles having a size of 1 to 100 nanometers are dispersed in a polymer resin. The nanocomposite has a large surface area, that is, an interfacial area, and greatly reduces the distance between particles. As a result, strength and stiffness, barrier properties, abrasion resistance, and high temperature stability are greatly improved without damaging the impact resistance, toughness, and transparency of the polymer, and are very advantageous in terms of performance and cost.

As a nanocomposite using PET, there has been an attempt to manufacture a PET / clay nanocomposite including clay. PET / clay nanocomposites are characterized in that the polymer resin is made to penetrate between layers of clay mineral having a layered structure of silicates. However, plate silicates, which are the basic units of clay minerals, are very difficult to peel and disperse by polymer resin due to the strong attraction between the plates. In order to solve this problem, PET / clay nanocomposites have been developed in which clays are treated with organic substances having 8 or more alkyl groups. However, since the polymerization temperature of PET is high at about 280 to 290 ° C, most of the organicized parts at high temperatures are decomposed. There was a problem that is difficult to react with the polymer.

In recent years, the development of nanocomposites using Polyhedral Oligomeric Silsesquioxanes (Polyhedral Oligomeric Silsesquioxanes) has attracted attention. POSS is expected to improve the physical properties of the polymer resin when a nanocomposite is formed with a polymer resin such as PET because the organic reactive group at the terminal is maintained at a high temperature and has a uniform distribution of 100 nm or less.

However, since the nanocomposite is a composite material manufactured by combining heterogeneous materials, there is a problem in that phase separation due to heterogeneous components occurs and easily reaches the limit physical properties. Therefore, in order to form a stable composite system, it is very important to increase the affinity of two phases to extremely lower the interfacial tension between the phases, and to stabilize the system and not to cause aggregation or separation.

Therefore, in order to overcome the problems of phase separation that may appear in the nanocomposites and the disadvantages of the resulting physical properties, there is an urgent need for the development of nanocomposites with improved compatibility using additives such as compatibilizers.

In order to solve the above problems, an object of the present invention is to provide a nanocomposite having excellent heat resistance, high temperature modulus and mechanical properties by improving the dispersibility of PET and POSS.

The present invention provides a nanocomposite including PET (Polyethyleneterephthalate, polyethylene terephthalate), POSS (Polyhedral Oligomeric Silsesquioxanes, polyhedral oligomeric silsesquioxanes) dispersed in the PET, and a POSS grafted PET as a compatibilizer.

It is preferable to use the modified PET represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is hydrogen or C 1 -C 10 linear or cyclic alkyl group.

The content of the modified PET is preferably 0.1 parts by weight to 1 part by weight based on 100 parts by weight of the PET.

It is preferable to use the modified PET obtained by reacting terephthalate substituted with POSS with ethylene glycol.

Terephthalate substituted with POSS is preferably used as represented by the following formula (2).

[Formula 2]

R ₂ in Formula 2 is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

The terephthalate substituted with POSS may be obtained by reacting diethyl 2,5-dihydroxyterephthalate with POSS represented by the following formula (4). Formula 3 below shows a structural formula of diethyl 2,5-dihydroxyterephthalate.

(3)

[Formula 4]

R ₄ in Formula 4 is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

POSS dispersed in the PET is preferably used to those represented by the following formula (5), formula (6) or formula (7).

[Chemical Formula 5]

In Formula 5, R ₅ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

[Formula 6]

In the formula 6 R ₆ is hydrogen or C 1 -C 10 linear or cyclic alkyl group.

[Formula 7]

In Formula 7, R ₇ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

The content of POSS dispersed in the PET is preferably 1 part by weight to 10 parts by weight with respect to 100 parts by weight of PET.

In another aspect, the present invention provides a method for producing a nanocomposite comprising the step of preparing a modified PET grafted POSS (S1), adding the modified PET and POSS to the PET.

The modified PET is preferably represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

In the step (S1), the modified PET may be obtained by reacting terephthalate and ethylene glycol substituted with POSS.

In the reaction of terephthalate substituted with POSS and ethylene glycol, the mixing molar ratio of terephthalate substituted with POSS and ethylene glycol is preferably 1: 2 to 1: 3.

Terephthalate substituted with POSS is preferably used as represented by the following formula (2).

[Formula 2]

R ₂ in Formula 2 is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

The terephthalate substituted with POSS is preferably obtained by reacting diethyl 2,5-dihydroxy terephthalate with POSS represented by the following formula (4).

[Formula 4]

R ₄ in Formula 4 is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

In the reaction of the diethyl 2,5-dihydroxy terephthalate and the POSS represented by the formula (4), the mixing molar ratio of the diethyl 2,5-dihydroxy terephthalate and the POSS represented by the formula (4) is 1: 2 to It is preferable that it is 1: 3.

POSS of the step (S2) is preferably used to those represented by the following formula (5), formula (6) or formula (7).

[Chemical Formula 5]

In Formula 5, R ₅ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

[Formula 6]

In Formula 6, R ₆ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

[Formula 7]

In Formula 7, R ₇ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

The amount of POSS added in the step (S2) is preferably 1 part by weight to 10 parts by weight with respect to 100 parts by weight of PET.

The amount of the modified PET added in the step (S2) is preferably 0.1 parts by weight to 1 part by weight relative to 100 parts by weight of PET.

The step (S2) is preferably made by melt mixing PET, modified PET and POSS.

Hereinafter, the present invention will be described in detail.

PET nanocomposites of the present invention include PET, POSS and modified PET grafted POSS as compatibilizer.

The nanocomposite can be prepared by adding and mixing POSS and modified PET to PET. As a method of dispersing by adding, mixing, and dispersing POSS and modified PET to the PET, a polymerization method, a solution method, a melting method, etc. may be used. It is preferable to use the melting method to synthesize | combine.

In general, the particle is a POSS nano-sized functional groups that are connected to the somatic Si-O backbone, if in a set of nanostructures having the empirical formula RSiO _{1 .5,} R is a hydrogen, siloxy or cyclic group, or a reactive functional group Linear aliphatic or aromatic groups which may further contain. POSS has the advantages of excellent thermal stability, particle size of less than 100nm, organic and inorganic functionalities and various reactivity. Therefore, it can be used to increase the thermal stability, wear resistance and mechanical strength of the polymer resin by mixing with a polymer resin such as PET.

POSS dispersed in the PET is preferably used to those represented by the following formula (5), (6) or (7).

[Chemical Formula 5]

In Formula 5, R ₅ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

[Formula 6]

In the formula 6 R ₆ is hydrogen or C 1 -C 10 linear or cyclic alkyl group.

[Formula 7]

In the general formula 7 R ₇ is hydrogen or C 1 -C 10 linear or cyclic alkyl group.

The content of POSS dispersed in the PET is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the PET. When the content of POSS is less than 1 part by weight, the content of POSS is small and the effect of improving heat resistance and modulus is insignificant. When the content of the POSS is more than 10 parts by weight, the content of POSS is increased so that dispersibility is lowered and mechanical strength is lowered. Disadvantages occur.

When preparing the nanocomposite of the present invention, in order to produce a stable nanocomposite that does not occur phase separation when the POSS is dispersed in PET, a POSS-grafted modified PET grafted as a compatibilizer is added together to prepare a nanocomposite. .

In general, a pre-made block copolymer or a free graft copolymer may be used or an in-situ reaction may be performed depending on a method of introducing a compatibilizer during the mixing process of the polymer blend. And a type compatibilizer. The nanocomposite of the present invention is prepared as a compatibilizer using a modified PET prepared by graft polymerization of PET as a free graft copolymer as a POSS as a compatibilizer.

Compatibilizer used in the preparation of the nanocomposite in the present invention is represented by the formula (1), POSS is preferably grafted modified PET.

[Formula 1]

In Formula 1, R ₁ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

The content of the modified PET is preferably 0.1 parts by weight to 1 part by weight with respect to 100 parts by weight of PET, and more preferably 0.5 parts by weight with respect to 0.1 parts by weight. If less than 0.1 part by weight modified PET is not effective to improve the dispersibility of the POSS, if greater than 1 part by weight will lower the intrinsic viscosity affects the physical properties.

The modified PET can be prepared through the following manufacturing method.

First, diethyl 2,5-dihydroxy terephthalate is added to and mixed with a solvent such as dimethyl sulfoxide to prepare a dispersion solution. Next, POSS is added to the dispersion solution and reacted to synthesize terephthalate substituted with POSS. The structural formula of the terephthalate substituted with POSS synthesized through the above process is represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, R ₂ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

POSS used in synthesizing the terephthalate substituted with POSS is preferably represented by the following formula (4).

[Formula 4]

R ₄ in Formula 4 is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms.

In the synthesis of terephthalate substituted with POSS, the hydroxyl group of the diethyl 2,5-dihydroxy group and the chloride group of POSS represented by the formula (4) react with each other, and the reactivity of the hydroxy group and the chloride group is very excellent. Since the reaction temperature is as low as about 120 ℃ has the advantage of easy synthesis.

In addition, the mixing molar ratio of the diethyl 2,5-dihydroxy terephthalate and the POSS represented by the formula (4) is preferably 1: 2 to 1: 3, more preferably 1: 2 to 1: 2.5. When the molar ratio of diethyl 2,5-dihydroxyterephthalate to the POSS is less than 1: 2, both hydroxyl groups of diethyl 2,5-dihydroxyterephthalate cannot be substituted with POSS. It is preferable to add POSS more than molar ratio. However, when the POSS is added in excess of the molar ratio of 1: 3, unreacted POSS remains, which is not preferable in terms of manufacturing cost.

When terephthalate substituted with POSS is synthesized through the above process, it is reacted with ethylene glycol to synthesize modified PET grafted with POSS.

The modified PET is preferably prepared through a transesterification reaction, the terephthalate substituted by POSS and ethylene glycol is mixed in a molar ratio of 1: 2 to 1: 3 and polymerized by an in-situ method. It is preferable.

If the mixing molar ratio is less than 1: 2, the production of PET is difficult. If the mixing molar ratio is greater than 1: 3, the excess ethylene glycol interferes with the polymerization. In addition, even after the reaction is completed, ethylene glycol must be completely removed to obtain PET having high molecular weight, so that the mixing ratio of 1: 3 is preferably not exceeded.

Moreover, it is preferable that reaction temperature is 270 degreeC-280 degreeC. Since PET decomposes at about 300 ° C, care should be taken not to exceed 300 ° C, especially in condensation reactions.

In the case of producing the modified PET, a known catalyst may be used as long as the object of the present invention is not inhibited except in particular cases. As the catalyst used in the transesterification reaction, various metal salts such as manganese, cobalt, zinc and calcium may be used as the catalyst of the transesterification reaction. In addition, as the catalyst used in the condensation reaction, various organic or inorganic antimony compounds such as antimony oxide, antimony acetate, and antimony oxalate may be used.

As described in detail above, the nanocomposite of the present invention is improved compatibility of PET and POSS can be effectively dispersed POSS without agglomeration in the PET. In addition, the nanocomposite of the present invention has excellent physical properties such as heat resistance and modulus due to its excellent compatibility, and can be widely used in various fields such as tire cords, sheets, or packaging containers, which are industrial fibers.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example  One

To 70 ml of dimethyl sulfoxide was added 5.1 g of diethyl 2,5-dihydroxyterephthalate and stirred at room temperature for 1 hour to prepare a dispersion solution. Next, 36 g of chloropropylheptaisobutyl POSS was added and mixed to the dispersion solution. At this time, the mixing molar ratio of diethyl 2,5-dihydroxy terephthalate and chloropropylheptaisobutyl POSS was 1: 2.5. Next, 3 g of potassium hydroxide, 0.1 g of potassium iodide, and 50 ml of dimethyl sulfoxide were added to the dispersion solution, and reacted at 120 ° C. for 24 hours, followed by stirring at 150 ° C. for 4 hours, followed by cooling and filtering to form chloropropylheptaisobutyl. Terephthalate substituted with POSS was synthesized.

Example  2

To the reactor was added 15 g of terephthalate and 2 g of ethylene glycol substituted with chloropropylheptaisobutyl POSS synthesized in Example 1 to make a molar ratio of 1: 2.3. After adding 0.12 g of zinc acetate as a catalyst to the reactor and reacting at 190 ° C. to 210 ° C. for about 3 hours, 0.03 g of antimony oxide as a catalyst was added and reacted at 270 ° C. to 280 ° C. for 2 hours. Modified PET was prepared.

Example  3

2 parts by weight of isooctyl POSS and 0.3 parts by weight of modified PET prepared in Example 2 were added to 100 parts by weight of PET, followed by melt mixing at 260 ° C. for 20 minutes to prepare a nanocomposite.

Example  4

100 parts by weight of PET and 5 parts by weight of isooctyl POSS and 0.3 parts by weight of the modified PET prepared in Example 2 were melt mixed at 260 ° C. for 20 minutes to prepare a nanocomposite.

Example  5

100 parts by weight of PET, 2 parts by weight of 1,2 propanediol isobutyl POSS and 0.3 parts by weight of the modified PET prepared in Example 2 were melt mixed at 260 ° C. for 20 minutes to prepare a nanocomposite.

Example  6

100 parts by weight of PET, trisilanoxooctyl POSS 2 parts by weight, and 0.3 parts by weight of the modified PET prepared in Example 2 were melt mixed at 260 ° C. for 20 minutes to prepare a nanocomposite.

Comparative example  One

100 parts by weight of PET and 2 parts by weight of silica were melt mixed at 260 ° C. for 20 minutes to prepare a nanocomposite including silica.

Comparative example  2

100 parts by weight of PET and 2 parts by weight of isooctyl POSS were melt mixed at 260 ° C. for 20 minutes to prepare a nanocomposite.

<Property Evaluation>

Thermogravimetry (TG) was measured using a thermogravimetric analyzer under an air atmosphere at a rate of temperature increase of 10 ° C./min, and the results are shown in FIG. 1. 1, the heat resistance of the nanocomposites of Examples 3 and 5 prepared using modified PET as a compatibilizer is superior to that of the nanocomposites of Comparative Examples 1 and 2 prepared without using a compatibilizer as the temperature increases. I could confirm that.

The viscoelasticity (tan delta) is a KS M ISO 6721-4: 2003 standard, measured at a heating rate of 5 ° C./min and the results are shown in FIG. 2. 2, it was confirmed that the viscoelasticity of the nanocomposite of Example 3 was superior to that of the PET and the nanocomposite of Comparative Example 2, in particular, the nanocomposite of Example 3 in the vicinity of 100 ℃ to the nanocomposite of PET and Comparative Example 2 It can be seen that the physical properties showed significantly superior.

The modulus (storage modulus) was fabricated at 270 ° C using hot press and measured using Dynamic Mechanical Analysis (DMA) using KS M ISO 6721-4: 2003 method. Shown. It was confirmed from FIG. 3 that the nanocomposite of Example 3 exhibits excellent modulus properties evenly from room temperature to high temperature, compared to the nanocomposites of PET and Comparative Example 2.

1 is a graph showing the thermogravimetric analysis results of the nanocomposites of Example 3, Example 5, Comparative Example 1 and Comparative Example 2.

FIG. 2 is a graph showing the results of measuring the viscoelasticity (Tan Delta) of the nanocomposites of PET and Example 3 and Comparative Example 2. FIG.

Figure 3 is a graph showing the results of measuring the modulus of the nanocomposites of PET and Example 3 and Comparative Example 2.

Claims (19)

PET (Polyethyleneterephthalate); POSS (Polyhedral Oligomeric Silsesquioxanes, polyhedral oligomeric silsesquioxanes) dispersed in the PET; And Includes modified PET grafted with POSS as a compatibilizer, The modified PET is a nanocomposite represented by the following formula (1). [Formula 1]

R ₁ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. delete The method of claim 1, The content of the modified PET nanocomposite is 0.1 parts by weight to 1 part by weight based on 100 parts by weight of the PET. The method of claim 1, The modified PET is a nanocomposite obtained by reacting terephthalate substituted with POSS and ethylene glycol. The method of claim 4, wherein Terephthalate substituted with the POSS is a nanocomposite represented by the following formula (2). [Formula 2]

R ₂ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. The method of claim 5, The terephthalate substituted with POSS is a nanocomposite obtained by reacting diethyl 2,5-dihydroxyterephthalate with POSS represented by the following formula (4). [Formula 4]

R ₄ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. The method of claim 1, POSS dispersed in the PET is a nanocomposite represented by the following formula (5), (6) or (7). [Chemical Formula 5]

R ₅ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. [Formula 6]

R ₆ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. [Formula 7]

Here, R ₇ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. The method of claim 1, The amount of POSS dispersed in the PET is 1 to 10 parts by weight compared to 100 parts by weight of PET nanocomposite. (S1) preparing a modified PET grafted POSS; (S2) adding the modified PET and POSS to the PET and mixing the same, The modified PET is a nanocomposite manufacturing method represented by the following formula (1). [Formula 1]

Wherein R ₁ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. delete 10. The method of claim 9, The modified PET in step (S1) is a nanocomposite manufacturing method obtained by reacting terephthalate substituted with POSS and ethylene glycol. The method of claim 11, Terephthalate substituted with the POSS is a nanocomposite manufacturing method represented by the following formula (2). [Formula 2]

R ₂ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. The method of claim 11, When the reaction of the terephthalate and ethylene glycol substituted with POSS, the mixed molar ratio of terephthalate and ethylene glycol substituted with POSS is 1: 2 to 1: 3 nanocomposite manufacturing method. The method of claim 13, Terephthalate substituted with POSS is a nanocomposite manufacturing method, characterized in that obtained by reacting diethyl 2,5-dihydroxy terephthalate and POSS represented by the following formula (4). [Formula 4]

R ₄ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. The method of claim 14, When reacting the diethyl 2,5-dihydroxy terephthalate and the POSS represented by the formula (4), the mixing molar ratio of diethyl 2,5-dihydroxy terephthalate and the POSS represented by the formula (4) is 1: 2 1: 3 is a nanocomposite manufacturing method. 10. The method of claim 9, POSS added in the step (S2) is a nanocomposite manufacturing method represented by the following formula (5), (6) or (7). [Chemical Formula 5]

R ₅ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. [Formula 6]

R ₆ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. [Formula 7]

R ₇ is hydrogen or a linear or cyclic alkyl group having 1 to 10 carbon atoms. 10. The method of claim 9, The content of the POSS added in the step (S2) is a nanocomposite manufacturing method of 1 part by weight to 10 parts by weight relative to 100 parts by weight of PET. 10. The method of claim 9, The content of the modified PET added in the step (S2) is 0.1 to 1 part by weight with respect to 100 parts by weight of PET nanocomposite manufacturing method. 10. The method of claim 9, Wherein (S2) step is a nanocomposite manufacturing method made by melt mixing PET, modified PET and POSS.

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