KR100842873B1 - Polyolefine nano-composite comprising poss and method for manufacturing the same - Google Patents

Abstract

A polyolefin-based nanocomposite comprising polyhedral oligomeric silsesquioxane(POSS) molecules is provided to optimize dispersion of POSS molecules in a non-polar polyolefin resin, thereby realizing excellent heat resistance and high-temperature modulus. A polyolefin-based nanocomposite comprises: a modified polyolefin resin formed by graft polymerization of a polyolefin resin and a silane compound; and polyhedral oligomeric silsesquioxane(POSS) molecules dispersed in the modified polyolefin resin. The polyolefin resin is selected from the group consisting of polyethylene resin, polypropylene resin, polyacetylene resin and polyisobutylene resin.

Description

Polyolefin-based nanocomposites containing POSS molecules and a method of manufacturing the same {Polyolefine Nano-Composite Comprising POSS And Method for Manufacturing The Same}

The present invention relates to a polymer nanocomposite, and more particularly, to a polyolefin-based nanocomposite containing a POSS molecule that can be used for automobile interior and exterior materials.

The polymer nanocomposite is a composite in which polymer, inorganic or metal particles having a size of 1 to 100 nanometers are dispersed in the polymer resin, and the surface area, that is, the interface area of the nanoparticles is very large, and the distance between the particles is greatly reduced. As a result, it is a new concept of next-generation composite material which has greatly improved strength, stiffness, barrier to gas or liquid, abrasion resistance, and high temperature stability without damaging the impact resistance, toughness and transparency of the polymer.

The technology related to the nanocomposite is able to obtain better physical properties even when using a smaller amount of inorganic filler than conventional inorganic filler reinforced composites, and new features such as maximizing mechanical properties and inhibiting penetration by peeling or dispersing the reinforcement to nanosite. And very advantageous in terms of performance / cost. Based on these characteristics, it is attracting worldwide attention as a new material that is expected to be applied to automobiles, electronic information, and civil engineering.

Polymers, which are the main research subjects for the production of polymer nanocomposites, were mainly used for polymers with strong polarity such as nylon, polyester, and epoxy, and nylon is one of them. On the other hand, nonpolar polymers, such as polypropylene or polyethylene, have many problems in the process of preparing nanocomposites, such as coagulation well when the nanocomposites are applied. Therefore, there is a need for a dispersion state optimization technology for developing polymer nanocomposites having excellent physical properties using nonpolar resins such as polyolefin resins.

It is an object of the present invention to provide a polyolefin-based nanocomposite having excellent heat resistance and high temperature modulus because the POSS molecules are well dispersed in a non-polar polyolefin resin.

In order to achieve the above object, the present invention provides a modified polyolefin resin formed by graft polymerization of a polyolefin resin and a silane compound, and a polyolefin including POSS (Polyhedral Oligomeric Silsesquioxane) molecules dispersed in the modified polyolefin resin. System-based nanocomposites are provided.

The polyolefin resin is preferably selected from the group consisting of polyethylene resin, polypropylene resin, polyacetylene resin and polyisobutylene resin.

As the silane compound used for forming the modified polyolefin resin, it is preferable to use a compound represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ is an alkoxy group, a halogen atom or an aryl group or an alkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms. R <_2> is a C1-C10 functional group containing a vinyl group or an acryl group at the terminal group.

The silane compound is preferably selected from the group consisting of vinyltrimethoxysilane, vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane, vinyltriethylsilane, acrylmethoxysilane and acryltriethoxysilane, It is not limited to this.

The amount of the silane compound is preferably 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the polyolefin resin.

POSS molecules contained in the polyolefin-based nanocomposite are preferably those represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ is an alkyl group having 1 to 10 carbon atoms, an alkene group, an aryl group, an alkoxy group or a cycloalkaine group, and R ₂ is a functional group of an oxide or glycidyl group having 1 to 10 carbon atoms.

The POSS is preferably selected from the group consisting of glycidylcyclohexyl-POSS, glycidylcyclopentyl-POSS, glycidylisobutyl-POSS, glycidylisooctyl-POSS and glycidylphenyl-POSS. However, the present invention is not limited thereto.

The amount of POSS is preferably 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the modified polyolefin resin.

The present invention also provides a polyolefin-based nanocomposite comprising graft polymerizing a polyolefin-based resin and a silane compound (S1) and dispersing POSS in the modified-type polyolefin-based resin (S2). It provides a method of manufacturing.

The step (S1) may be carried out by melt mixing the polyolefin resin and the silane compound.

The step (S2) may be carried out by melt mixing the modified polyolefin-based resin and the POSS.

The polyolefin resin used in the step (S1) is preferably used one selected from the group consisting of polyethylene resin, polypropylene resin, polyacetylene resin and polyisobutylene resin.

As the silane compound used in the step (S1), it is preferable to use one represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ is an alkoxy group, a halogen atom or an aryl group or an alkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms. R <_2> is a C1-C10 functional group containing a vinyl group or an acryl group at the terminal group.

The silane compound used in the step (S1) is a group consisting of vinyltrimethoxysilane, vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane, vinyltriethylsilane, acrylmethoxysilane and acryltriethoxysilane. It is preferably selected from, but is not limited thereto.

The amount of the silane compound used in the step (S1) is preferably 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the polyolefin resin.

POSS used in the step (S2) is preferably used as represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ is an alkyl group having 1 to 10 carbon atoms, an alkene group, an aryl group, an alkoxy group, or a cycloalkaine group, and R ₂ is a functional group of an oxide or glycidyl group having 1 to 10 carbon atoms.

POSS used in the step (S2) is glycidylcyclohexyl-POSS, glycidylcyclopentyl-POSS, glycidylisobutyl-POSS, glycidylisooctyl-POSS and glycidylphenyl-POSS It is preferably selected from the group consisting of, but is not limited thereto.

The amount of POSS used in the step (S2) is preferably 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the modified polyolefin resin.

The graft polymerization of the polyolefin resin and the silane compound in the step (S1) is preferably carried out using an initiator in the range of 0.1 part by weight to 1 part by weight with respect to 100 parts by weight of the polyolefin resin.

Hereinafter, the present invention will be described in detail.

The polyolefin-based nanocomposites of the present invention include modified polyolefin-based resins and POSS molecules dispersed therein. The modified polyolefin resin is prepared by graft polymerization of a polyolefin resin and a silane compound.

As the polyolefin resin, it is preferable to use one selected from the group consisting of polyethylene resin, polypropylene resin, polyacetylene resin and polyisobutylene resin, and most preferably polypropylene or polyethylene.

Since the polyolefin resin is a non-polar resin unlike nylon, polyester, and the like, which is a polar resin, when the nanocomposite is prepared by introducing POSS molecules which are fine nanoparticles, the dispersibility of the POSS molecules is poor, so that the polyolefin resin is effectively dispersed in the polyolefin resin. It failed to cause problems such as aggregation. In the present invention, a modified polyolefin-based resin having improved dispersibility by graft polymerization of a polyolefin-based resin and a silane compound has been solved, and a problem of cohesion occurs due to poor dispersibility when POSS molecules are introduced.

As the silane compound used to form the modified polyolefin-based resin, it is preferable to use a compound represented by the following Chemical Formula 1. Representative examples of such silane compounds include vinyltrimethoxysilane, vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane, vinyltriethylsilane, acryltrimethoxysilane, and acryltriethoxysilane. Most preferred are trimethoxysilane and vinyltriethoxysilane.

[Formula 1]

In Formula 1, R ₁ is an alkoxy group, a halogen atom or an aryl group or an alkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms. R <_2> is a C1-C10 functional group containing a vinyl group or an acryl group at the terminal group.

The amount of the silane compound is preferably 1 part by weight to 10 parts by weight, more preferably 5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the polyolefin resin.

If the silane compound is less than 1 part by weight, dispersibility is not improved. If the silane compound is more than 10 parts by weight, the amount of the silane compound is increased, so that the dispersibility is lowered.

As a method for graft polymerization of the polyolefin resin and the silane compound, a melting method, a solution method, a polymerization method, or the like may be used. Melting is a method in which an organic material such as a silane compound is directly mixed with a polymer resin in a molten state, which is most preferable from a commercial point of view.

On the other hand, the graft polymerization of the polyolefin resin and the silane compound may be carried out using an initiator in the range of 0.1 parts by weight to 1 part by weight, more preferably 0.5 parts by weight to 0.75 parts by weight, relative to 100 parts by weight of the polyolefin resin.

Formula 3 illustrates a mechanism in which a vinyl silane is graft copolymerized to polypropylene, and Formula 4 illustrates an example in which polypropylene and vinyl silane are graft copolymerized to synthesize modified polypropylene.

[Formula 3]

[Formula 4]

POSS molecules are applied to various fields such as biopharmaceuticals and electronics by increasing a variety of substituents, that is, polymers on silicon atoms to increase thermal stability, wear resistance and mechanical strength. In general, the basic structure of the POSS molecule is known that the functional group is connected to the polyhedral Si-O backbone. POSS molecules are a set of nanostructures having the empirical RSiO _1.5 , wherein R is a linear aliphatic or aromatic group that may further contain hydrogen, siloxy or cyclic groups, or reactive functional groups.

In the present invention, it is preferable to use the POSS molecule represented by the following formula (2). Such POSS include glycidylcyclohexyl-POSS, glycidylcyclopentyl-POSS, glycidylethyl-POSS, glycidylisobutyl-POSS, glycidylisooctyl-POSS, glycidylphenyl-POSS. Representative. However, it is not limited to this. Formula 5 below shows glycidylisobutyl-POSS.

[Formula 2]

In Formula 2, R ₁ is an alkyl group having 1 to 10 carbon atoms, an alkene group, an aryl group, an alkoxy group, or a cycloalkaine group, and R ₂ is a functional group of an oxide or glycidyl group having 1 to 10 carbon atoms.

[Formula 5]

Formula 5 is glycidylisobutyl-POSS.

The amount of POSS is preferably 1 part by weight to 10 parts by weight, and most preferably 1 part by weight to 3 parts by weight, based on 100 parts by weight of the modified polyolefin-based resin obtained through the graft copolymerization reaction of the polyolefin resin and the silane compound. do. When the amount of POSS is less than 1 part by weight, the content of POSS is small, so that the effects of thermal stability, abrasion resistance, and the like, which are intended for the production of the nanocomposite of the present invention, are insignificant. Disadvantages such as lowering the mechanical strength and lowering the mechanical strength.

As a method of dispersing POSS in the modified polyolefin resin, a polymerization method, a solution method, a melting method, and the like may be used, but a melting method of synthesizing a new material after melting and melting a material to be blended above a melting temperature is used. Most preferably.

The polyolefin-based nanocomposite containing the POSS of the present invention has little agglomeration and high dispersibility in the non-polar polyolefin-based resin of the POSS particles, and is excellent in physical properties such as heat resistance and high temperature modulus.

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

Polypropylene (MI (melting index): 37-42 g / min (ASTM D1238), Tm (melting point): 100 parts by weight of homo polypropylene), 10 parts by weight of vinyl trimethoxysilane, 0.5 parts by weight of initiator 20 minutes melt mixing at 180 ℃ to prepare a modified polypropylene.

Example  2

Using 100 parts by weight of the modified polypropylene prepared by Example 1 and 1 part by weight of glycidyl isobutyl-POSS by melt mixing at 180 ℃ 10 minutes to prepare a nanocomposite containing glycidyl isobutyl-POSS It was.

Example  3

Using 100 parts by weight of modified polypropylene prepared by Example 1 and 3 parts by weight of glycidyl isobutyl-POSS by melt mixing at 180 ℃ 10 minutes to prepare a nanocomposite containing glycidyl isobutyl-POSS It was.

Example  4

Using 100 parts by weight of the modified polypropylene prepared by Example 1 and 5 parts by weight of glycidyl isobutyl-POSS by melt mixing at 180 ℃ for 10 minutes to prepare a nanocomposite containing glycidyl isobutyl-POSS It was.

Example  5

Using 100 parts by weight of the modified polypropylene prepared by Example 1 and 10 parts by weight of glycidyl isobutyl-POSS by melt mixing at 180 ℃ for 10 minutes to prepare a nanocomposite containing glycidyl isobutyl-POSS It was.

Comparative example  One

100 parts by weight of polypropylene and 1 part by weight of glycidyl isobutyl-POSS were melt mixed at 180 ° C. for 10 minutes to prepare a nanocomposite including glycidyl isobutyl-POSS.

Comparative example  2

100 parts by weight of polypropylene and 5 parts by weight of glycidyl isobutyl-POSS were melt mixed at 180 ° C. for 10 minutes to prepare a nanocomposite including glycidyl isobutyl-POSS.

Property evaluation

The structure of the polypropylene and silane compound was graft-polymerized in the wave number 4000-400Cm ^-1 using IR. 1 is an IR spectrum of the modified polypropylene prepared in Example 1, the peak of the silane at 1080Cm ^-1 was confirmed that the polypropylene and the silane graft polymerization.

In the morphology analysis, the melt-mixed sample was prepared at 180 ° C. using a hot press, immersed in liquid nitrogen, and then fractured, and the fracture surface was confirmed by SEM. Figure 2a is a nanocomposite prepared according to Example 2, Figure 2b is a nanocomposite prepared according to Comparative Example 2 Comparing the SEM pictures of the two, in Example 2 POSS is well dispersed without aggregation You can see that. On the other hand, in Comparative Example 2, it can be seen that the POSS is aggregated. Figure 2b shows that the POSS is a poor dispersibility to the polypropylene can be a factor of poor physical properties of the polypropylene.

The modulus of the melt-mixed sample was prepared at 180 ° C. using a hot press and measured using DMA using the KS M ISO 6721-4: 2003 method. Looking at the modulus graph of Figure 3 it can be seen that the modulus of Example 2 is the highest. This is because, as confirmed by the SEM photographs of FIGS. 2A and 2B, the POSS was evenly dispersed in the polypropylene matrix, thereby showing an excellent blending effect of the polypropylene and the POSS.

Tg was measured under a nitrogen gas purge using a thermogravimetric analyzer up to 600 ° C. at a rate of 10 ° C./min at an initial temperature of 80 ° C. The Tg graph of FIG. 4 shows the heat resistance of the polypropylene and the POSS composite, and it was confirmed that the heat resistance of Example 2 was the best.

1 shows the IR spectrum of the modified polypropylene prepared by Example 1. FIG.

Figure 2a shows a SEM picture of the nanocomposite prepared by Example 2, Figure 2b shows a SEM picture of the nanocomposite prepared by Comparative Example 2.

3 is a graph showing the modulus of the nanocomposite prepared by Example 2, Example 3, Comparative Example 1 and unmodified polypropylene.

Figure 4 shows a Tg graph of the nanocomposites prepared by Example 2, Example 3, Comparative Example 1, Comparative Example 2 and unmodified polypropylene.

Claims (19)

Modified polyolefin resins formed by graft polymerization of polyolefin resins and silane compounds; And POSS dispersed in the modified polyolefin resin; Polyolefin-based nanocomposite comprising a. The method of claim 1, The polyolefin-based resin is a polyolefin-based nanocomposite is selected from the group consisting of polyethylene resin, polypropylene resin, polyacetylene resin and polyisobutylene resin. The method of claim 1, The silane compound used to form the modified polyolefin-based resin is a polyolefin-based nanocomposite represented by the following formula (1). [Formula 1]

Here, R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group, halogen atom or aryl group having 1 to 10 carbon atoms. R <_2> is a C1-C10 functional group containing a vinyl group or an acryl group at the terminal group. The method of claim 1, The silane compound is selected from the group consisting of vinyltrimethoxysilane, vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane, vinyltriethylsilane, acryltrimethoxysilane and acryltriethoxysilane. System nanocomposites. The method of claim 1, The amount of the silane compound is 1 to 10 parts by weight based on 100 parts by weight of the polyolefin resin polyolefin nanocomposites. The method of claim 1, POSS contained in the polyolefin-based nanocomposite is a polyolefin-based nanocomposite represented by the following formula (2). [Formula 2]

Here, R ₁ is an alkyl group having 1 to 10 carbon atoms, an alkene group, an aryl group, an alkoxy group or a cycloalkaine group, and R ₂ is a functional group of an oxide or glycidyl group having 1 to 10 carbon atoms. The method of claim 1, The POSS is selected from the group consisting of glycidylcyclohexyl-POSS, glycidylcyclopentyl-POSS, glycidylisobutyl-POSS, glycidylisooctyl-POSS and glycidylphenyl-POSS Polyolefin-based nanocomposites. The method of claim 1, The amount of the POSS is 1 to 10 parts by weight based on 100 parts by weight of the modified polyolefin resin polyolefin-based nanocomposite. (S1) graft polymerization of the polyolefin resin and the silane compound to prepare a modified polyolefin resin; And (S2) dispersing POSS in the modified polyolefin resin; Method for producing a polyolefin-based nanocomposite comprising a. The method of claim 9, Step (S1) is a method for producing a polyolefin-based nanocomposite, characterized in that the polyolefin resin and the silane compound by melting and mixing. The method of claim 9, The step (S2) is a method for producing a polyolefin-based nanocomposite, characterized in that the modified polyolefin resin and the POSS by melting and mixing. The method of claim 9, The polyolefin-based resin used in the step (S1) is a polyolefin-based nanocomposite manufacturing method selected from the group consisting of polyethylene resin, polypropylene resin, polyacetylene resin and polyisobutylene resin. The method of claim 9, The silane compound used in the step (S1) is a method for producing a polyolefin-based nanocomposite represented by the formula (1). [Formula 1]

Here, R ₁ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group, halogen atom or aryl group having 1 to 10 carbon atoms. R <_2> is a C1-C10 functional group containing a vinyl group or an acryl group at the terminal group. The method of claim 9, The silane compound used in the step (S1) consists of vinyltrimethoxysilane, vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane, vinyltriethylsilane, acryltrimethoxysilane and acryltriethoxysilane. Method for producing a polyolefin-based nanocomposite is selected from the group. The method of claim 9, The amount of the silane compound used in the step (S1) is 1 to 10 parts by weight based on 100 parts by weight of polyolefin resin polyolefin-based nanocomposite manufacturing method. The method of claim 9, POSS used in the step (S2) is a method for producing a polyolefin-based nanocomposite represented by the formula (2). [Formula 2]

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms, an alkene group, an aryl group, an alkoxy group or a cycloalkaine group, and R ₂ is a functional group of an oxide or glycidyl group having 1 to 10 carbon atoms. The method of claim 9, POSS used in the step (S2) is glycidylcyclohexyl-POSS, glycidylcyclopentyl-POSS, glycidylisobutyl-POSS, glycidylisooctyl-POSS and glycidylphenyl-POSS Method for producing a polyolefin-based nanocomposite that is selected from the group consisting of. The method of claim 9, The amount of POSS used in the step (S2) is 1 to 10 parts by weight based on 100 parts by weight of the modified polyolefin-based resin manufacturing method of the polyolefin-based nanocomposite. The method of claim 9, The graft polymerization of the polyolefin-based resin and silane compound in the step (S1) is carried out using an initiator within the range of 0.1 to 1 parts by weight relative to 100 parts by weight of the polyolefin-based resin. .

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