KR101735447B1

KR101735447B1 - method of preparing polyolefin nanocomposite including dispersed carbon support on the polyolefin and nanocomposite prepared thereby

Info

Publication number: KR101735447B1
Application number: KR1020150122571A
Authority: KR
Inventors: 윤근병; 이동호; 이승리
Original assignee: 경북대학교 산학협력단
Priority date: 2015-08-31
Filing date: 2015-08-31
Publication date: 2017-05-15
Also published as: KR20170025716A

Abstract

The present invention relates to a method for producing a polyolefin nanocomposite in which a carbon-based support is dispersed, and a nanocomposite produced thereby, and more particularly, to a method for preparing a nanocomposite comprising the steps of (1) adding an organomagnesium compound to a surface- Forming a carbon-based carrier; (2) preparing a catalyst for olefin polymerization or copolymerization in which a magnesium-4 transition metal is supported on a carbon-based support by adding a Group 4 transition metal compound to the magnesium-supported carbon-based support and reacting; (3) an organoaluminum compound and 1 to 15 Adding olefin at atmospheric pressure and heating the mixture at 20 to 100 캜 to prepare a polyolefin masterbatch in which the carbon-based carrier is dispersed; And (4) preparing a polyolefin nanocomposite in which the carbon-based support is dispersed by mixing the master batch and the polyolefin, wherein the carbon-based support is dispersed in the polyolefin nanocomposite. .

Description

The present invention relates to a method for preparing a polyolefin nanocomposite in which a carbon-based support is dispersed and a nanocomposite prepared by the method,

The present invention relates to a method for producing a polyolefin nanocomposite in which a carbon-based support is dispersed, and a nanocomposite produced thereby, and more particularly, to a method for producing a polyolefin nanocomposite in which a carbon-based support of a carbon nanomaterial is completely dispersed on a polyolefin, And a nanocomposite produced by the method. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a method for producing a polyolefin nanocomposite in which a carbon-based support is dispersed.

Polyolefins are used in a variety of fields such as household goods, food packaging, stationery, packaging for industrial products, tools for farming and fishing, automobile bumpers, automobile interior materials, and home appliances.

The polyolefins are generally made from olefin polymers and copolymers, such as ethylene polymers, propylene polymers and ethylene-alpha olefin copolymers, by heterogeneous catalyst systems consisting of titanium compounds and alkyl aluminum compounds.

The polyolefin is produced by a supported catalyst in which a titanium compound typified by titanium tetrachloride is supported on silica, alumina, zeolite, magnesium chloride or the like.

The magnesium compound in the supported carrier of the supported catalyst is manufactured by the emulsion or precipitation method as the most commonly used support, and the magnesium-supported titanium catalyst prepared by using the magnesium compound as the supported product is prepared by slurry, High density polyethylene, linear low density polyethylene, high stereoregular polypropylene and the like.

When the support is silica, a catalyst mainly used for the production of high-density polyethylene and chromium oxide supported on silica is used.

In addition, a silica - supported magnesium - titanium catalyst supported on silica with magnesium compound and reacted with a titanium compound was developed to produce polyethylene having a high solid density by gas phase polymerization.

On the other hand, in recent years, researches on polymer nanocomposites having various functions and addition of nanostructures to polyolefins and copolymers have been actively carried out in the production of polyolefin polymers and copolymers.

That is, a polymer nanocomposite is prepared by adding carbon nanotubes and graphene having excellent mechanical and thermal properties as nanomaterials. Most of them are used for melt mixing or mixing in which a carbon nanotube or graphene is added to a molten polymer in an extruder Polymer nanocomposites are prepared by a solution mixing method in which a carbon nanotube or graphene dispersed in a solvent is added to a polymer solution.

As a method for producing the above polymer nanocomposite, the dispersion of the carbon nanomaterial is not easy, and thus the mechanical and thermal properties of the nanocomposite are reduced.

Thus, the polymer nanocomposite is prepared by in situ polymerization method in which carbon nanotubes or graphenes are dispersed in a polymerization reactor and polymerization is carried out immediately, thereby solving the above-mentioned problems and allowing the carbon nanomaterials to be easily dispersed.

However, the dispersion of the carbon nanomaterial is improved as compared with the melt mixing method or the solution mixing method, and the aggregation of the carbon nanomaterial is not fully dispersed.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing a polyolefin nanocomposite in which a carbon-based support is dispersed.

Another object of the present invention is to provide a polyolefin nanocomposite in which a carbon-based support is dispersed, which is produced by the above-mentioned method for producing a nanocomposite.

According to an aspect of the present invention,

(1) adding an organomagnesium compound to the surface-modified carbon-based carrier and reacting to form a magnesium-supported carbon-based carrier;

(2) preparing a catalyst for olefin polymerization or copolymerization in which a magnesium-4 transition metal is supported on a carbon-based support by adding a Group 4 transition metal compound to the magnesium-supported carbon-based support and reacting;

(3) an organoaluminum compound and 1 to 15 Adding olefin at atmospheric pressure and heating the mixture at 20 to 100 캜 to prepare a polyolefin masterbatch in which the carbon-based carrier is dispersed; And

(4) A process for producing a polyolefin nanocomposite in which a carbon-based support is dispersed, comprising the steps of: preparing a polyolefin nanocomposite in which the carbon-based support is dispersed by mixing the master batch and the polyolefin; do.

In another aspect of the present invention, there is provided a polyolefin nanocomposite in which a carbon-based support is dispersed, the nanocomposite being produced by the method for producing the nanocomposite.

According to the method for preparing a nanocomposite of the present invention, the olefin can be easily grown in the catalyst for olefin polymerization or copolymer supported on the carbon-based carrier of the carbon nanomaterial, and the carbon and the carbon having excellent mechanical and thermal properties A nanocomposite in which the carbon-based support of the nanomaterial is completely dispersed can be easily prepared by preparing a master batch in which the nanomaterial is easily dispersed in the polymerized or copolymerized polyolefin.

In addition, the nanocomposite produced by the method of the present invention is characterized in that the carbon-based support of the carbon nanomaterial is completely dispersed in the polyolefin, so that excellent physical properties such as heat resistance of the carbon nanomaterial are imparted to the nanocomposite, The nanocomposite of the present invention has heat resistance and excellent strength by improving the decomposition temperature and modulus to 20 to 70 ° C and 20 to 100%, respectively, without changing elongation.

Accordingly, the nanocomposite having heat resistance and excellent strength can be widely used in various fields such as high temperature heat resistant materials, structural materials, automobile parts, special machine parts, and the like.

1 is a photograph showing the degree of dispersion of carbon nanomaterials in a nanocomposite according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

According to an aspect of the present invention,

Specifically, the present invention relates to a method for producing a polyolefin nanocomposite in which a carbon-based support is dispersed, comprising the steps of: (1) adding an organomagnesium compound to a surface-modified carbon- Lt; / RTI >

More specifically, step (1) is a step of covalently bonding an organomagnesium compound to a carbon-based carrier, which is a carbon nano material having excellent mechanical and thermal properties, thereby supporting magnesium on the carbon-based carrier. The carbon-based carrier is preferably a surface-modified carbon-based support having a functional group capable of covalently bonding with an organomagnesium compound so as to easily form a covalent bond, and the functional group is not limited, but may be a hydroxyl group or a carboxyl group, Based carrier is graphene oxide or a carbon nanotube oxide.

The organomagnesium compound is R ₁ MgX, and R ₁ is an alkyl having 1 to 20 carbons and X is a halogen. Preferably, the organomagnesium compound is R ₁ MgX wherein R ₁ is 2 to 6 And X is chlorine. More preferably, the organomagnesium compound is n-butyl magnesium chloride (n-BuMgCl).

Next, in step (2) of the present invention, a transition metal of a Group 4 transition metal compound is added to the magnesium-bearing carbon-based carrier, and the reaction is carried out so that the magnesium-4 group transition metal is supported on the carbon- Catalyst.

Specifically, in the step (2), a Group 4 transition metal compound is added to the magnesium-bearing carbon-based carrier, and the magnesium-group transition metal is supported on the carbon-based carrier, 4 group transition metal supported on the carbon-based support, which enables the catalyst to be easily grown on the transition metal of Group 4 transition metal.

Wherein the Group 4 transition metal compound is M (OR ₂ ) _n X _4-n and M is any one selected from the group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf) and ruthenium , R ₂ is alkyl having 1 to 10 carbon atoms, n is 0 to 4, and X is halogen.

Preferably, the Group 4 transition metal compound is titanium tetrachloride.

Also, the catalyst for olefin polymerization or copolymerization in which the magnesium-4-group transition metal prepared in the step (2) is supported on the carbon-based carrier is characterized in that magnesium and titanium are contained in an amount of 0.025 to 65 mmol, The catalyst is comprised of 2 to 15% by weight of magnesium and 1.5 to 6.0% by weight of titanium in 100% by weight of the catalyst, so that the olefin can be easily used on the magnesium-4-group transition metal Olefin can be homopolymerized on the catalyst or can be copolymerized with ethylene and propylene as main monomers and with alpha-olefins other than ethylene as a comonomer.

Next, in step (3) of the present invention, an organic aluminum compound and 1 to 15 Adding olefin at atmospheric pressure and heating at 20 to 100 캜 to prepare a polyolefin master batch in which the carbon-based carrier is dispersed.

The olefin is not limited as a monomer to be polymerized with polyolefin, and the olefin may be at least one selected from the group consisting of ethylene, propylene, alpha olefins, cycloolefins, dienes, trienes, styrenes or cyclic olefins Lt; / RTI >

Specifically, the olefin monomer is at least one member selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Butene, styrene, p-methylstyrene, allylbenzene, divinylbenzene, vinylcyclohexane, vinyltoluene, vinyltoluene, Which is at least one selected from cycloheptane, cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene and cyclopentadiene .

In addition, the organoaluminum compound is added as a cocatalyst in the step (3). The organoaluminum compound is represented by the following formula (1), and the carbon-based support as a carbon nanomaterial can be easily dispersed in the polyolefin master batch.

[Chemical Formula 1]

Wherein R _a , R _b and R _c are the same or different and each represents a hydrogen atom, a halogen atom, a C _1-20 unsubstituted alkyl, a C _1-20 substituted alkyl, a C _3-20 unsubstituted cycloalkyl, C _{3 ~ 20} substituted cycloalkyl, C _{6 ~ 40} aryl, will in any one selected from an aryl alkyl of C _{6 ~ 40} alkylaryl and C _{6 ~ 40} of the R _a, And at least one of R _b and R _c is alkyl.

Specifically, the organoaluminum compound is selected from the group consisting of trimethyl aluminum, dimethyl aluminum chloride, dimethyl aluminum methoxide, methyl aluminum dichloride, triethyl aluminum, diethyl aluminum chloride, diethyl aluminum methoxide, At least one selected from the group consisting of dinonopropyl aluminum chloride, normal propyl aluminum chloride, trinormal butyl aluminum, tripropyl aluminum, triisopropyl aluminum, triisobutyl aluminum and diisobutyl aluminum hydride.

The addition amount of the organoaluminum compound is preferably such that the molar ratio of the Al / Group 4 transition metal to the catalyst containing the Group 4 transition metal is 10-200.

This is because when the molar ratio of the Al / Group 4 transition metal is less than 10, the catalytic activity is significantly lowered, and when the molar ratio of the Al / Group 4 transition metal exceeds 200, excess aluminum remains in the prepared master batch This is because the problem of removing it occurs.

In the step (3), the organoaluminum compound is added to the catalyst so that the molar ratio of the Al / Group 4 transition metal to the catalyst is 10 to 200, the olefin of 1 to 15 atm is added thereto, Thereby preparing a polyolefin master batch in which the carbon-based support as a carbon nano material is easily dispersed.

At this time, the heating temperature is preferably 20 to 100 ° C. If the temperature is less than 20 ° C, the activation energy is too small to polymerize for masterbatch production, and if the heating temperature exceeds 100 ° C, the catalytic active site is decomposed and the masterbatch can not be easily produced .

Finally, the step (4) of the present invention is a step of preparing the polyolefin nanocomposite in which the carbon-based support is dispersed by mixing the master batch and the polyolefin.

Specifically, the polyolefin nanocomposite in which the carbon-based support is dispersed can be prepared by melt-mixing the master batch and the polyolefin, and the nanocomposite thus produced is characterized in that the carbon-based support as the carbon nanomaterial is completely dispersed do.

The polyolefin may be the same as or different from the polyolefin on the master batch and is not particularly limited, The carbon-based support of the nanocomposite produced in the step (4) is preferably graphene oxide or carbon nanotube oxide, and more preferably the carbon-based support is included in the nanocomposite in an amount of 0.01 to 1.0 wt% And is completely dispersed.

The method of the present invention for producing a polyolefin nanocomposite in which a carbon-based support is dispersed is characterized in that it further comprises an inner electron donor and an outer electron donor.

In the present invention, since the internal electron donor may be added to the step (1), the step (1) may include a step of forming a support on which magnesium is supported, adding an internal electron donor to the support, A magnesium-bearing carbon-based carrier containing an internal electron donor can be formed. More particularly, the present invention relates to a magnesium-containing carrier which further comprises an internal electron donor for enhancing an isotactic index to have high stereoregularity by adding an internal electron donor to the magnesium- Thereby forming a carbon-based carrier.

Wherein the internal electron donor comprises one or more ether groups or one or more ketone groups and is represented by the following formulas (2) to (4).

(2)

Substituted cycloalkyl in the general formula 2 R _'1 is a hydrogen atom, C _{1 ~ 20} unsubstituted alkyl, C _{1 ~ 20} alkyl, C _{3 ~ 20} unsubstituted cycloalkyl, C _{3 ~ 20} of the displacement of the ring in the alkyl , C _{6 to} C ₄₀ aryl, C _{6 to} C ₄₀ alkylaryl and C _{6 to} C ₄₀ arylalkyl.

(3)

In Formula 3 R _'2 and R' ₃ are the same or are each independently of one another, a hydrogen atom, C _{1 ~ 20} of the unsubstituted alkyl, beach of C _{1 ~ 20} alkyl, C _{3 ~ 20} substituted for unsubstituted cycloalkyl Is selected from the group consisting of alkyl, substituted cycloalkyl of C _{3 to} C ₂₀ , aryl of C _{6 to} C ₄₀ , alkylaryl of C _{6 to} C ₄₀ , and arylalkyl of C _{6 to} C ₄₀ .

[Chemical Formula 4]

Wherein R ' ₄ , R' ₅ , R ' ₆ and R' ₇ are the same or different from each other and represent a hydrogen atom, a C _1-20 unsubstituted alkyl, a C _1-20 substituted alkyl, C characterized in that _{three or} any one which is ₂₀ unsubstituted cycloalkyl, C _{3 to 20} selected from substituted cycloalkyl, aryl, alkyl of C _{6 - 40} aryl, C _{6 ~ 40} alkylaryl and C _{6 ~ 40} of the .

The method for producing a polyolefin nanocomposite in which the carbon-based support is dispersed according to the present invention may further comprise an external electron donor and the external electron donor is added to the step (3) to further include an external electron donor Allow the master batch to be manufactured.

Specifically, the master batch further comprising the external electron donor improves the properties of the master batch and improves the manufacturing process as the isotactic index is further improved by the external electron donor.

Wherein the external electron donor is represented by Formula 5 below.

[Chemical Formula 5]

In formula _{5 R 'a, R' b} , R 'c and R' _d are the same or are each independently of one another, alkyl, C _{1 ~ 20} substitution of C _{1 ~ 20} unsubstituted alkyl, C _{1 ~ 20} of the Unsubstituted alkoxy groups of C _{1 to} C ₂₀ , unsubstituted cycloalkyl of C _{3 to} C ₂₀ , substituted cycloalkyl of C _{3 to} C ₂₀ , unsubstituted cycloalkoxy groups of C _{3 to} C ₂₀ , substituted cycloalkyl of C _{3 ~ 20} alkoxy group, which phenyl group, selected from substituted phenyl group, phenoxy group, substituted phenoxy group, an aryl alkyl of C _{6 ~ 40} aryl group, C _{6 ~ 40} alkylaryl and C _{6 ~ 40} of the Or more.

Also, the external donor (ED) has a ratio of the organoaluminum compound to Al / ED of 10 to 1000.

This is because there is a problem that the stereoregularity is low when the ratio of Al / ED exceeds 1000, and there is a problem that the catalytic activity is low when the ratio is less than 10.

According to the method for producing a polyolefin nanocomposite in which the carbon-based support of the present invention is dispersed, the carbon-based support of the carbon nanomaterial can be completely dispersed in the polyolefin, so that the nanocomposite having excellent physical properties of the carbon nanomaterial can be produced .

Accordingly, another aspect of the present invention provides a polyolefin nanocomposite in which a carbon-based support is dispersed, which is produced by the nanocomposite manufacturing method.

At this time, the nanocomposite has a decomposition temperature and a modulus of 20 to 70 ° C and 20 to 100%, respectively, with no change in elongation, as it includes the carbon-based support of the carbon nanomaterial, And is a polyolefin nanocomposite in which a support is dispersed.

As described above, according to the method for producing a nanocomposite of the present invention, the carbon support as the carbon nanomaterial is completely dispersed in the polyolefin, the nanocomposite produced by the above-mentioned production method can be produced by the carbon nanomaterial completely dispersed in the polyolefin, It is possible to impart excellent physical properties such as heat resistance, corrosion resistance, electrical conductivity and precision workability to the polyolefin nanocomposite. Therefore, nanocomposites can be widely used in various fields such as high-temperature heat-resisting materials, structural materials, automobile parts, and special machine parts.

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited by the examples.

<Examples>

Preparation of catalyst for polymerization or copolymerization of olefin supported on magnesium-titanium graphene oxide carrier

Example 1-1 When the internal electron donor is diisobutyl phthalate (DIBP)

0.1 ml of graphene oxide was added to 50 ml of tetrahydrofuran (THF) in a Schlenk tube and dispersed using an ultrasonic device. 10 ml of n-butyl magnesium chloride (n-BuMgCl) (0.05 mol) For 24 hours with stirring.

After the reaction was completed, unreacted n-butyl magnesium chloride was removed, washed with purified tetrahydrofuran, and then washed three times with purified n-hexane to prepare graphene oxide having magnesium chloride bound thereto Respectively.

Next, the magnesium chloride-bound graphene oxide was dispersed in 50 ml of purified n-hexane, and then 5 ml of diisobutylphthalate (DIBP) as an internal electron donor was added thereto. The resulting mixture was reacted at 90 ° C for 12 hours, Hexane, and 15 mmol (4.9 ml) of titanium tetrachloride was added by a dropwise addition method, and the mixture was reacted at 80 ° C for 12 hours.

Thereafter, the reaction product was washed with purified n-hexane, and 10 mmol (3.3 ml) of titanium tetrachloride was added thereto by a dropwise addition method, followed by reaction at 80 ° C for 12 hours.

After completion of the reaction, the catalyst was washed with n-hexane to prepare a catalyst for olefin polymerization or copolymerization supported on magnesium-titanium graphen oxide carrier.

Example 1-2 When the internal electron donor is diethyl succinate (DS)

The catalyst for olefin polymerization or copolymerization supported on the graphene oxide carrier of magnesium-titanium of Example 1-2 was prepared by the same method as in Example 1, except that diethyl succinate (DS) was used as an internal electron donor. 1-1. &Lt; / RTI >

&Lt; Example 1-3 > In the case where an internal electron donor was not used

The catalyst for olefin polymerization or copolymerization supported on the graphene oxide carrier of Example 1-3 of the present invention was the same as the catalyst preparation method of Example 1-1 except that no internal electron donor was used Lt; / RTI >

Table 1 below shows the magnesium and titanium contents of the catalysts for olefin polymerization or copolymerization of Examples 1-1 to 1-3 by inductively coupled plasma atomic emission spectrometry (ICP-AES).

catalyst Magnesium (% by weight) Titanium (wt%) Example 1-1 6.2 2.8 Examples 1-2 6.1 2.8 Example 1-3 5.9 2.9

Preparation of polyolefin masterbatches containing graphenoxide

&Lt; Example 2 > Preparation of PE-GO master batch

Into a 1 L high-pressure reactor, 200 ml of n-hexane and 100 ml of triethylaluminum were charged such that the ratio of Al / Ti was 100 based on 1 mole of titanium of the catalyst for olefin polymerization or copolymer supported on the graphene oxide carrier of magnesium- And then 0.05 g of the catalyst of Example 1-3 was added. Next, ethylene was injected into the reactor, and at this time, polyethylene (PE) master including graphene oxide (GO) was produced by reacting the reactor under the conditions of reaction temperature and pressure at 40 DEG C and 6 atm of ethylene pressure for 1 hour. A batch of PE-GO master batches was prepared.

The catalyst activity and the melt index according to the catalyst of Example 1-3 of the PE-GO master batch (Example 2) were 3100 Kg-PE / mol-Ti-hr and 3.0 g / 10 min, respectively.

The catalyst activity was expressed by the concentration of the center metal of the supported catalyst using the amount of polyethylene in the PE-GO masterbatch prepared above. Melt index (MI) was measured by heating the PE-GO, (Inner diameter: 2.09 mm, length: 8 mm) in a predetermined time (minute unit) while measuring the weight of the resin passed through the orifice (inner diameter: 2.09 mm, length: 8 mm).

&Lt; Example 3 > Preparation of PP-GO master batch

&Lt; Example 3-1 > In the case where the external electron donor is cyclohexyldimethoxymethylsilane

In a 1 L high-pressure reactor, 200 ml of n-hexane was added, and the ratio of Al / Ti was adjusted to 100 based on 1 mol of titanium of the olefin polymerization or copolymerization catalyst supported on the magnesium-titanium graphene oxide carrier of Example 1-1. And cyclohexyldimethoxymethylsilane (CHMDMS) as an external donor (ED) were added so that the ratio of Al / ED was 10. Next, 0.05 g of the catalyst of Example 1-1 was added, and propylene was injected into the reactor. At this time, a PP-GO master batch, which is a polypropylene (PP) master batch containing graphene oxide (GO), was prepared by reacting the reaction temperature and pressure at 40 ° C and a pressure of 6 atm for 1 hour, .

Using the catalysts of Examples 1-2 and 1-3 in place of the catalyst of Example 1-1, the catalysts of Examples 1-2 and 1-3, respectively, A master batch was prepared.

&Lt; Example 3-2 > When the external electron donor is dicyclopentyldimethoxysilane

The PP-GO masterbatch of this Example 3-2 was prepared by the same method as in the above Example 3-1 except that dicyclopentyldimethoxysilane (DCPDMS) was used as an external electron donor .

In Example 3-2, PP-GO master batches according to the respective Examples were prepared using Examples 1-1 to 1-3 as catalysts, respectively.

&Lt; Example 3-3 > When an external electron donor is not used

The PP-GO masterbatch of this Example 3-3 was prepared in the same manner as in the above-mentioned Example 3-1 except that no external electron donor was used.

In Example 3-3, the PP-GO master batch according to each Example was also prepared using Examples 1-1 to 1-3 as catalysts.

Table 2 shows physical properties of the PP-GO masterbatches prepared in Examples 3-1 to 3-3 according to external electron donors and catalysts.

At this time, the isotactic index was measured by determining the weight percentage of the insoluble portion by using a Soxhlet extraction apparatus using a n-heptane as a solvent as the resultant PP-GO master batch. The catalyst activity and the melt index were measured by the same method as in Example 2.

Master batch catalyst Out
Electron donor Active catalyst activity
(Kg-PE / mol-Ti-hr) Melting point
(° C) Isotactic index
(weight%) Melt Index
(g / 10 min) Example
3-1 Example 1-1 CHMDMS 0.9 162.0 92.2 0.5 Examples 1-2 1.3 159.7 98.2 0.3 Example 1-3 1.7 159.9 99.3 0.2 Example
3-2 Example 1-1 DCPDMS 1.0 162.2 91.2 0.6 Examples 1-2 1.4 161.0 99.1 0.2 Example 1-3 1.7 161.0 98.3 0.3 Example
3-3 Example 1-1 - 2.1 157.3 66.1 5.2 Examples 1-2 2.5 158.2 85.8 0.5 Example 1-3 2.2 158.2 86.7 0.4

Manufacture of nanocomposites

Example 4 Production of PE-GO Nanocomposite Using PE-GO Masterbatch

In order to produce a PE-GO nanocomposite containing commercially available polyethylene having 0.02, 0.05, 0.2 and 0.5 wt% of graphene oxide, the PE-GO master batch of the above Example 2 was mixed with commercially available polyethylene And melt-mixed in a melting mixer at 220 캜 for 5 minutes.

Thus, a PE-GO nanocomposite containing 0.02, 0.05, 0.2 and 0.5 wt% of graphene oxide in polyethylene was prepared, and the physical properties of the nanocomposite according to the graphene content are shown in Table 3 below.

Graphene oxide
(weight%) Melting point (℃) Decomposition temperature (℃) Modulus (MPa) Tensile Strength (MPa) Elongation (%) - 134.5 345.6 588 28 1300 0.02 135.2 371.1 602 29 1300 0.05 135.5 374.3 615 29 1310 0.2 135.4 385.8 635 31 1390 0.5 134.9 401.4 658 30 1350

Referring to Table 3, the present Example 4 is a process for producing a PE-GO nanocomposite using the PE-GO masterbatch according to Example 2, whereby graphene oxide is contained in the commercially available polyethylene and commercially available graphene oxide The pyrolysis temperature increased to about 56 ℃ and the tensile strength, mechanical strength, was increased by 30% or more without significant change.

In particular, it was confirmed that the elongation did not decrease and remained almost constant.

It is considered that this is because the graphene oxide is completely dispersed on the nanocomposite by preparing the PE-GO nanocomposite using the PE-GO master batch of the second embodiment.

<Example 5> Production of PP-GO nanocomposite using PP-GO master batch

In order to prepare a PP-GO nanocomposite containing commercially available polypropylene graphene oxide in an amount of 0.02, 0.05, 0.2, and 0.5 wt%, in Example 5, the catalyst prepared in Example The PP-GO masterbatch of 3-1 was melted and mixed in a commercially available polypropylene and melt mixer at 240 DEG C for 5 minutes.

PP-GO nanocomposites each containing 0.02, 0.05, 0.2, and 0.5 wt% of graphene oxide in polypropylene were prepared. Physical properties of the nanocomposite according to graphene content are shown in Table 4 below.

Graphene oxide
(weight%) Melting point (℃) Decomposition temperature (℃) Modulus (MPa) Tensile Strength (MPa) Elongation (%) - 162.4 369 180 32 1000 0.02 163.7 413 230 34 600 0.05 164.4 419 230 33 1000 0.2 165.4 421 230 33 1000 0.5 162.7 423 228 33 1000

Referring to Table 4 above, Example 5 shows that the PP-GO nanocomposite is prepared by using the PP-GO masterbatch of Example 3-1, whereby graphene oxide is contained in commercially available polypropylene, The thermal decomposition temperature was increased up to 54 ℃ and the tensile strength, which is mechanical strength, was increased by 30% or more without significant change compared to polypropylene containing no pin oxide.

In particular, it can be seen that the elongation is kept constant without reduction, except when 0.02 wt% of graphene oxide is included.

It is considered that the PP-GO nanocomposite was prepared using the PP-GO masterbatch of Example 3-1, resulting in complete dispersion of graphene oxide on the nanocomposite.

&Lt; Comparative Example 1 > Production of PP-Graphite Nanocomposite (PP-GO master batch unused)

Commercially available polypropylene and graphite were melted and mixed in a molten mixer at 240 ° C for 5 minutes in order to produce a PP-Graphite nanocomposite containing 0.02, 0.05, 0.2 and 0.5% by weight of graphite in a commercially available polypropylene.

PP-Graphite nanocomposites each containing 0.02, 0.05, 0.2 and 0.5% by weight of graphite in polypropylene were prepared, and physical properties of the nanocomposite according to the graphite content are shown in Table 5 below.

Graphite
(weight%) Melting point (℃) Decomposition temperature (℃) Modulus (MPa) Tensile Strength (MPa) Elongation (%) - 162.4 369 180 32 1000 0.02 163.4 389 195 35 20 0.05 163.8 390 220 34 15 0.2 164.0 392 224 34 12 0.5 163.6 395 247 32 10

As shown in Table 5, in Comparative Example 1, commercially available polypropylene and graphite were melted and mixed to contain graphite on the polypropylene. As compared with commercially available polypropylene containing no graphite, the decomposition temperature was about 26 And the modulus increased by 30% or more without a large change in the tensile strength.

However, in Comparative Example 1, the elongation was drastically decreased as compared with commercially available polypropylene containing no graphite, and it was confirmed that the elongation was 15% or less.

This is because unlike Example 5, the graphite contained in the nanocomposite is not easily dispersed in Comparative Example 1, and a sharp decrease in elongation is observed. In Comparative Example 1, Also, it can be confirmed that it is low.

&Lt; Comparative Example 2 > Production of PP-GO nanocomposite without using PP-GO master batch

In order to prepare PP-GO nanocomposites containing commercially available polypropylene graphene oxide at 0.02, 0.05, 0.2 and 0.5 wt%, commercially available polypropylene and graphene oxide were melted and mixed at 240 ° C for 5 minutes in a melt mixer Respectively.

Thus, PP-GO nanocomposites each containing 0.02, 0.05, 0.2 and 0.5 wt% of graphene oxide in polypropylene were prepared. Physical properties of the nanocomposite according to graphene oxide content are shown in Table 6 below.

Graphene oxide
(weight%) Melting point (℃) Decomposition temperature (℃) Modulus (MPa) Tensile Strength (MPa) Elongation (%) - 162.4 369 180 32 1000 0.02 162.4 379 185 34 45 0.05 162.8 385 192 33 55 0.2 164.0 387 195 34 60 0.5 162.9 391 201 33 45

Referring to Table 6, in Comparative Example 2, commercially available polypropylene and graphene oxide were melt-mixed to contain graphene oxide on the polypropylene, and compared with commercially available polypropylene containing no graphene oxide The decomposition temperature was increased to 19 ° C, and the modulus was increased by 10% or more without a large change in the tensile strength.

However, in Comparative Example 2, the elongation was drastically lowered as compared with commercially available polypropylene containing no graphene oxide, and it was confirmed that the elongation was 60% or less.

This is because unlike Example 5, the graphene oxide contained in the nanocomposite is not easily dispersed, and the decomposition temperature is lower than that of Example 5, as well as a sharp drop in elongation .

&Lt; Comparative Example 3 > Production of PP-GO nanocomposite using master batch prepared by Zeigier-Natta catalyst

A PP-GO master batch made from a commercially available Zeigier-Natta catalyst was used to prepare PP-GO nanocomposites containing 0.02, 0.05, 0.2 and 0.5 wt% of graphene oxide in commercially available polypropylene. Respectively.

In this Comparative Example 3, a PP-GO master batch was prepared by mixing in situ polymerization of polypropylene and graphene oxide in the presence of a Ziegler-Natta catalyst in the production of a PP-GO master batch, The batch was melt-mixed in a commercially available polypropylene and a melt mixer at 240 캜 for 5 minutes to prepare a PP-GO nanocomposite.

The physical properties of the PP-GO nanocomposites prepared according to the graphene oxide content are shown in Table 7 below.

Graphene oxide
(weight%) Melting point (℃) Decomposition temperature (℃) Modulus (MPa) Tensile Strength (MPa) Elongation (%) - 162.4 369 180 32 1000 0.02 162.1 372 185 31 220 0.05 162.5 370 182 33 250 0.2 163.0 367 185 32 110 0.5 162.4 373 178 32 50

Referring to Table 7, in Comparative Example 3, graphene oxide was contained on the polypropylene by melt-mixing a commercially available polypropylene and a PP-GO masterbatch made of a Ziegler-Natta catalyst, and graphene oxide It was confirmed that the tensile strength and the modulus were almost the same as those of the commercially available polypropylene which does not contain graphene oxide even though it was included in the polypropylene, I could.

In contrast, in Comparative Example 3, unlike Example 5, it was judged that the graphene oxide contained in the nanocomposite was not easily dispersed.

The degree of dispersion of carbon nanomaterials on the nanocomposite of Examples and Comparative Examples

In order to confirm that the carbon nanomaterial of the nanocomposite produced by the polyolefin master batch in which the carbon-based support was dispersed was completely dispersed, the nanocomposite prepared by the polyolefin master batch in which the carbon- The degree of dispersion of the carbon nanomaterials on the nanocomposite of Comparative Example 1 in which no batch was used and in Comparative Example 3 in which the master batch prepared by the Ziegler-Natta catalyst was used was measured. In order to determine the degree of dispersion of the carbon nanomaterials more accurately, commercially available polypropylene was also compared with Example 5, Comparative Example 1, and Comparative Example 3, which were prepared by coating on a glass plate.

FIG. 1 is a photograph showing the degree of dispersion of the nanocomposite of Example 5, Comparative Example 1, and Comparative Example 3, and the degree of dispersion of carbon nanomaterials on a commercially available commercial polypropylene coated on an organic substrate.

Referring to FIG. 1, from the left, 0.5 weight% of graphene oxide of Example 5, 0.2 weight% of graphene oxide of Example 5, 0.2 weight% of graphite of Comparative Example 1, 0.2 weight% of Comparative Example 3, Propylene. Commercial polypropylene, which is a case where graphite oxide or graphite, which is a carbon nanomaterial, is not contained, can be confirmed to be transparent.

In contrast, the nanocomposite of Example 5 appears black, indicating that graphene oxide is completely dispersed.

On the other hand, since Comparative Example 1 exhibited a light black color, the degree of graphite dispersion was lower than that of Example 5, and Comparative Example 3 showed transparency close to that of commercially available polypropylene without carbon nanomaterials It can be confirmed that graphene oxide is not easily dispersed.

As described above, according to the method for producing a nanocomposite of the present invention, the carbon support as the carbon nanomaterial is completely dispersed in the polyolefin, the nanocomposite produced by the above-mentioned production method can be produced by the carbon nanomaterial completely dispersed in the polyolefin, It is possible to impart excellent physical properties such as heat resistance, corrosion resistance, electrical conductivity and precision workability to the polyolefin nanocomposite.

Particularly, the polyolefin nanocomposite including the carbon nanomaterial has remarkably improved heat distortion temperature and modulus without changing the elongation and tensile strength. Therefore, the nanocomposite can be used as a high temperature heat resistant material, a structural material, Can be widely used in the field.

While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And various modifications and variations are possible within the scope of the appended claims.

Claims

(1) adding an organomagnesium compound to the surface-modified carbon-based carrier and reacting to form a magnesium-supported carbon-based carrier;
(2) preparing a catalyst for olefin polymerization or copolymerization in which a magnesium-4 transition metal is supported on a carbon-based support by adding a Group 4 transition metal compound to the magnesium-supported carbon-based support and reacting;
(3) an organoaluminum compound and 1 to 15 Adding olefin at atmospheric pressure and heating the mixture at 20 to 100 캜 to prepare a polyolefin masterbatch in which the carbon-based carrier is dispersed; And
(4) preparing a polyolefin nanocomposite in which the carbon-based support is dispersed by mixing the masterbatch and the polyolefin, wherein the decomposition temperature and the modulus of the polyolefin nanocomposite are 20 to 70 ° C and 20 to 100 % Based on the total weight of the polyolefin nanocomposite.

The method according to claim 1,
In the step (1), after the magnesium-bearing carbon-based carrier is formed, an inner electron donor is added to the carrier to cause a reaction to form a magnesium-bearing carbon-based carrier containing an inner electron donor Lt; / RTI >
The method of producing a polyolefin nanocomposite in which the carbon-based carrier is dispersed is characterized in that the step (3) further comprises the step of preparing a master batch containing an external electron donor.

The method according to claim 1,
Wherein the catalyst comprises 0.025 to 65 mmol and 0.01 to 50 mmol of magnesium and titanium, respectively, per 1 g of the carbon-based carrier, and the carbon-based carrier is dispersed therein.

The method according to claim 1,
Wherein the catalyst comprises 2 to 15% by weight of magnesium and 1.5 to 6.0% by weight of titanium in 100% by weight of the catalyst, and the carbon-based support is dispersed in the catalyst.

The method according to claim 1,
Wherein the carbon-based carrier is a graphene oxide or a carbon nanotube oxide. The method of producing a polyolefin nanocomposite according to claim 1, wherein the carbon-based carrier is graphene oxide or carbon nanotube oxide.

The method according to claim 1,
Wherein the organomagnesium compound is R ₁ MgX, R ₁ is alkyl having 1 to 20 carbons, and X is halogen. 2. A process for producing a polyolefin nanocomposite according to claim 1, wherein the organomagnesium compound is R ₁ MgX.

The method according to claim 1,
Wherein the Group 4 transition metal compound is M (OR ₂ ) _n X _4-n and M is any one selected from the group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf) and ruthenium , R ₂ is alkyl having 1 to 10 carbon atoms, n is 0 to 4, and X is a halogen.

The method according to claim 1,
Wherein the content of the organoaluminum compound added to the catalyst is such that the molar ratio of the Al / Group 4 transition metal is in the range of 10 to 200.

The method according to claim 1,
Wherein the nanocomposite is dispersed with 0.01-1.0 wt% of graphene oxide or carbon nanotube oxide as a carbon-based support, and the carbon-based support is dispersed.

A polyolefin nanocomposite in which a carbon-based support is dispersed, which is produced by the production method of any one of claims 1 to 9.

11. The method of claim 10,
Wherein the nanocomposite has a decomposition temperature and a modulus of 20 to 70 DEG C and 20 to 100%, respectively, without change in the elongation rate as the nanocomposite contains a dispersed carbon-based carrier, and has heat resistance and strength. Dispersed polyolefin nanocomposite.