JP2003292589A - Polyolefin/polyolefin block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin/polyolefin block copolymer having a new function, and to provide a method for producing the same. <P>SOLUTION: This polyolefin/polyolefin copolymer represented by the general formula [R<SP>1</SP>and R<SP>2</SP>are each H or methyl; (m) is an integer of 10 to 200; (n) is an integer of 10 to 200; (k) is an integer of 5 to 3,000]. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ultra high molecular weight polyolefin / polyolefin block copolymer and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Polypropylene, which is one of the three major general-purpose polymers, is an excellent polymer material which is inexpensive, has excellent oil resistance and chemical resistance, and has a small environmental load. However, since polypropylene is a non-polar polymer and it is difficult to introduce a functional group, it has poor interaction with other polar substances and can be strengthened by mixing with a polymer having another polar group. Difficult, paintability,
It has a problem of poor adhesion.

In recent years, active research has been conducted on new functionalized polypropylene for solving these problems. One of them is the functionalization and diblock copolymerization of vinylidene polypropylene with one terminal synthesized by a polymerization reaction using a metallocene catalyst. this is,
This is based on the fact that hydrogen is selectively desorbed at the β-position at the growth end due to the selection of polymerization conditions, and a vinylidene-type double bond is generated at one end. The double bond at one end can be easily converted into various functional groups, and thus is very useful for functionalizing polypropylene. However, in this case, since the functional group in the molecular chain exists only at one end, there is a limit to the improvement of physical properties. Therefore, it is the current situation that a satisfactory new functionalized polypropylene has not been obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyolefin / polyolefin block copolymer having a novel function which has never been seen and a method for producing the same.

[0005]

The present invention relates to a polyolefin / polyolefin block copolymer represented by the following general formula.

[Chemical 2] (In the formula, R1 and R2 are each a hydrogen atom or a methyl group, m is an integer of 10 to 200, n is an integer of 10 to 200, and k is an integer of 5 to 3000.)

Further, the present invention provides a compound selected from the group consisting of atactic telechelic polypropylene, isotactic telechelic polypropylene, syndiotactic telechelic polypropylene and isotactic telechelic poly-1-butene with a hydroxyl group and a hydroxyl group. The present invention relates to a method for producing a polyolefin / polyolefin block copolymer, which is obtained by maleic anhydride oxidation and then a sequential copolymerization reaction to obtain a block copolymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have made a chemical modification of telechelic polypropylene and telechelic poly-1-butene obtained by thermal decomposition of polypropylene and poly-1-butene (easy reactivity of vinylidene groups at both ends). As a result of diligent studies on the conversion to a substituent) and the subsequent sequential reaction, a novel polyolefin / polyolefin block copolymer was reached, and the present invention was completed.

The main chain of polypropylene is randomly cleaved by thermal decomposition to reduce the molecular weight. Macromolecules, 2
As disclosed in 8, 7973 (1995), by highly controlling the thermal decomposition of polypropylene, telechelic polypropylene having vinylidene groups at both ends can be selectively synthesized in high yield. Such a telechelic polypropylene has a number average molecular weight Mn of about 1000 to 10,000, a dispersity Mw / Mn of 2 or less, and an average number of vinylidene groups per molecule of about 1.8. It has the characteristic of maintaining regularity. The weight average molecular weight of the raw material polypropylene before decomposition is preferably in the range of 10,000 to 1,000,000, and more preferably in the range of 200,000 to 800,000.

As a thermal decomposition device, Journal of Polymer
Science: Polymer Chemistry Edition, 21, 703 (1983)
The device disclosed in US Pat. Pyrex
^(R) Polypropylene was placed in the reaction vessel of a glass pyrolyzer, and the molten polymer phase was vigorously bubbled with nitrogen gas under reduced pressure to extract the volatile products.
While suppressing the subsequent reaction, a thermal decomposition reaction is performed at a predetermined temperature for a predetermined time. After completion of the thermal decomposition reaction, the residue in the reaction vessel is dissolved in hot xylene, filtered while hot, and reprecipitated with alcohol for purification. The reprecipitate is collected by filtration and vacuum dried to obtain telechelic polypropylene.

The thermal decomposition conditions are adjusted by predicting the molecular weight of the telechelic polypropylene from the molecular weight of the polypropylene before decomposition and the primary structure of the block copolymer of the final object, and taking into consideration the results of the experiments conducted in advance. Pyrolysis temperature is 3
The range of 00 ° C to 450 ° C is preferable. If the temperature is lower than 300 ° C, the thermal decomposition reaction of polypropylene may not proceed sufficiently, and if the temperature is higher than 450 ° C, deterioration of the telechelic polypropylene may proceed.

The polyolefin / polyolefin copolymer of the present invention is the atactic telechelic polypropylene, isotactic telechelic polypropylene, syndiotactic telechelic polypropylene, isotactic telechelic poly-1-obtained by the above-mentioned method. It can be obtained by subjecting a compound selected from the group consisting of butene to hydroxylation and maleic anhydride, respectively, and then subjecting it to successive esterification reaction in the presence of a catalyst such as p-toluenesulfonic acid.

The hydroxylation is accomplished by hydroxylating the vinylidene double bonds at both ends of the telechelic polypropylene obtained by pyrolysis by hydroboration followed by an oxidation reaction. Using tetrahydrofuran as a solvent, a boration reagent is first added to hydroborate. As the boration reagent, 9-borane bicyclononane or borane-tetrahydrofuran complex can be used. Hydroxylated water is added to the reaction solution after hydroboration to cause an oxidation reaction to obtain a hydroxylated telechelic polypropylene.

The above-mentioned maleic anhydride oxidation is a vinylidene 2 at both ends of the telechelic polypropylene obtained by thermal decomposition.
The heavy bond is achieved by maleic anhydride oxidation by the Alder-Ehn reaction. Maleic anhydride telechelic polypropylene is obtained by using decahydronaphthalene as a solvent, adding an antioxidant such as maleic anhydride and dibutylhydroxytoluene, and reacting with stirring in a nitrogen gas stream.

The reaction conditions for the above-mentioned sequential esterification reaction are not particularly limited, but it is preferable that the reaction is carried out under reduced pressure without a solvent. In addition, in order to prevent hydrolysis of the produced copolymer, it is desirable to remove water from the system.

Regarding the number of repeating units in the polyolefin / polyolefin copolymer of the present invention, m is 10
It is an integer of -200, Preferably it is an integer of 20-150. N is an integer of 10 to 200, preferably 20 to 150. Furthermore, k is 5 to 30
00 is an integer, preferably 10 to 2000.

Since the polyolefin / polyolefin copolymer of the present invention has a high molecular weight, the entanglement of molecular chains is sufficient, and as a result, it can be formed into a film or the like.
Applications in various fields can be expected.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples. In this example, the following abbreviations were used. PP-OH: hydroxylated polypropylene PP-MA: maleic anhydride polypropylene aPP: atactic polypropylene iPP: isotactic polypropylene sPP: syndiotactic polypropylene iPB: isotactic polybutylene PP-b-PP: polypropylene / polypropylene block Polymer PB-b-PP: Poly-1-butene / polypropylene block copolymer

The following experimental apparatus was used in this example. GPC: HLC-8121 GPC / HT (Tosoh Corporation)
DSC: TG / DTA6200 (Seiko Electronic Industry Co., Ltd.)
FT-IR: 1600-FT-IR (manufactured by Perkin-Elmer Co., Ltd.) The following results were obtained for the synthesis of a multi-block copolymer by melt sequential esterification.

Example 1 APP-OH was placed in an eggplant flask.
0.22 g, sPP-MA 0.11 g, p as a catalyst
-Toluenesulfonic acid (0.0087 g) was charged, and a two-way cock was attached. Then, the pressure inside the flask was reduced to 1 to 2 mmHg, and the reaction was performed in a molten state at 190 ° C. for 24 hours. After the reaction was completed, the flask was returned to room temperature and the copolymer a
0.31 g of PP-b-sPP was recovered. The GPC curves of the raw material and the copolymer are shown in Fig. 1, and the DSC of the raw material and the copolymer are shown.
The curves are shown in FIG. 2 and the molecular weights, dispersities, melting points and enthalpies of fusion of the raw materials and copolymers are shown in Table 1.

[Table 1]

Example 2 APP-OH was placed in an eggplant flask.
0.31 g, iPP-MA 0.23 g, p as a catalyst
-0.0060 g of toluenesulfonic acid was charged and a two-way cock was attached. Then, the pressure inside the flask was reduced to 1 to 2 mmHg, and the reaction was performed in a molten state at 190 ° C. for 24 hours. After the reaction was completed, the flask was returned to room temperature and the copolymer a
0.52 g of PP-b-iPP was recovered. The GPC curves of the raw material and the copolymer are shown in FIG. 3, and the DSC of the raw material and the copolymer are shown.
The curves are shown in FIG. 4, and the molecular weights, dispersities, melting points and enthalpies of fusion of the raw materials and copolymers are shown in Table 2.

[Table 2]

(Example 3) iPP-OH was placed in an eggplant flask.
0.25 g, sPP-MA 0.26 g, p as a catalyst
-Toluenesulfonic acid was charged at 0.011, and a two-way cock was attached. Then, the inside of the flask was depressurized to 1 to 2 mmHg and reacted at 190 ° C. for 24 hours in a molten state. After the reaction was completed, the flask was returned to room temperature and the copolymer iP was used as it was.
0.48 g of P-b-sPP was recovered. The GPC curve of the raw material and the copolymer are shown in FIG. 5, the DSC curve of the raw material and the copolymer are shown in FIG. 6, and the molecular weight, dispersity, melting point and melting enthalpy of the raw material and the copolymer are shown in Table 3.

[Table 3]

(Example 4) iPP-OH was placed in an eggplant flask.
0.22 g, sPP-MA 0.23 g, p as a catalyst
-Toluenesulfonic acid (0.0093 g) was charged, and a two-way cock was attached. Then, the pressure in the flask was reduced to 30 mmHg, and the reaction was performed in a molten state at 190 ° C. for 24 hours. After the reaction was completed, the flask was returned to room temperature and the copolymer iP was used as it was.
0.44 g of P-b-sPP was recovered. The GPC curve of the obtained copolymer is shown in FIG.

(Example 5) iPP-OH was placed in an eggplant flask.
0.22 g, sPP-MA 0.22 g, p as a catalyst
-0.0088 g of toluenesulfonic acid was charged and a two-way cock was attached. Then, the reaction was performed in a molten state at 190 ° C. for 24 hours under normal pressure. After completion of the reaction, the flask was returned to room temperature, and the copolymer iPP-b-sPP was added as it was.
42 g was recovered. The GPC curve of the obtained copolymer is shown in FIG.
It was shown to.

Example 6 An iPB-MA was placed in an eggplant flask.
0.24 g, iPP-OH 0.23 g, p as a catalyst
-Toluenesulfonic acid (0.0093 g) was charged, and a two-way cock was attached. Then, the pressure inside the flask was reduced to 1 to 2 mmHg, and the reaction was performed in a molten state at 190 ° C. for 24 hours. After the reaction was completed, the flask was returned to room temperature and the copolymer i was used as it was.
0.40 g of PB-b-iPP was recovered. The melting enthalpies and melting points of the raw materials and the copolymers are shown in Table 4, the DSC curves of the raw materials and the copolymers are shown in FIG. 8, and the GPs of the raw materials and the copolymers are shown.
The C curve, molecular weight and dispersity are shown in FIG. 9, and IR data of the raw material and the copolymer are shown in FIG.

[Table 4]

[0025]

The novel polyolefin / polyolefin block copolymer of the present invention has an unprecedented high molecular weight.
In particular, the block copolymer produced under reduced pressure and without solvent has an ultrahigh molecular weight. For this reason, the entanglement of the molecular chains sufficiently occurs, and the film can be molded.

[Brief description of drawings]

FIG. 1 aPP-OH, sPP-MA and aPP-b-
It is a figure which shows the GPC curve of sPP.

FIG. 2 aPP-OH, sPP-MA and aPP-b-
It is a figure which shows the DSC curve of sPP.

FIG. 3 aPP-OH, iPP-MA and aPP-b-
It is a figure which shows the GPC curve of iPP.

FIG. 4 aPP-OH, iPP-MA and aPP-b-
It is a figure which shows the DSC curve of iPP.

FIG. 5: iPP-OH, sPP-MA and iPP-b-
It is a figure which shows the GPC curve of sPP.

FIG. 6 iPP-OH, sPP-MA and iPP-b-
It is a figure which shows the DSC curve of sPP.

FIG. 7 is a diagram showing pressure dependence of a GPC curve of iPP-b-sPP.

FIG. 8: iPB-MA, iPP-OH and iPB-b-
It is a figure which shows the DSC curve of iPP.

FIG. 9: iPB-b-iPP, iPP-OH and iPB
It is a figure which shows the GPC curve of MA, molecular weight, and polydispersity.

FIG. 10 iPP-b-iPP, iPP-OH, iPB
It is a figure which shows FT-IR data of MA.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J029 AA01 AB02 AB04 AC03 AD01                       BA01 CA02 HA01 HB06 JE04                       KE03                 4J100 AA03 BA15 BA16 HA11 HA35                       HA42 HA61 HB63 HC09 HC27                       HE01 JA01 JA03

Claims (3)

[Claims] 1. A polyolefin / polyolefin block copolymer represented by the following general formula. [Chemical 1] (In the formula, R ¹ and R ² are each a hydrogen atom or a methyl group, m is an integer of 10 to 200, n is an integer of 10 to 200, and k is an integer of 5 to 3000.) 2. A compound selected from the group consisting of atactic telechelic polypropylene, isotactic telechelic polypropylene, syndiotactic telechelic polypropylene and isotactic telechelic poly-1-butene is hydroxylated and maleic anhydride is oxidized. And then a sequential esterification reaction to obtain a block copolymer, which is a method for producing a polyolefin / polyolefin block copolymer. 3. The method for producing a polyolefin / polyolefin block copolymer according to claim 2, wherein the sequential esterification reaction is carried out under reduced pressure without a solvent.