JP2923026B2 - Butene-1 copolymer and resin composition containing the same - Google Patents

Description

The present invention relates to a copolymer of butene-1 and propylene and an easy-to-use heat-sealing layer containing this copolymer, which is useful for heat-bonding a polyolefin. The present invention relates to a heat-sealing polypropylene resin composition.

[Prior art] An α-olefin polymer having a syndiotactic structure has been known for a long time, and one of them is a syndiotactic polypropylene. However, syndiotactic polypropylene obtained by a method of polymerizing at a low temperature using a conventional catalyst comprising a vanadium compound and an ether and an organoaluminum compound has poor syndiotacticity, and has characteristics as a syndiotactic polypropylene. It was hard to say.

JAEwen et al. Reported that transition metals with asymmetric ligands (Hf
And Zr) by polymerizing propylene using a polymerization catalyst comprising a compound and methylaluminoxane to obtain ¹³ C-N
It has been found for the first time that a polypropylene having good tacticity can be obtained such that the fraction of syndiotactic pentads by MR exceeds 0.8 (J. Amer. Chem. So
c., 1988, 110, 6255-6).

On the other hand, the present inventors have found that polybutene-1 having high syndiotacticity obtained by polymerizing butene-1 can be obtained by using the above catalyst having a high purity. This catalyst has good activity per transition metal, and the obtained polybutene has high tacticity, but the physical properties of the polybutene are relatively poor in balance, and
The transparency of the polybutene moldings is insufficient.

BACKGROUND ART Polypropylene having substantially stereoregularity—substantially isotactic structure and substantially syndiotactic structure has excellent rigidity, excellent appearance such as transparency and gloss, and is used for various applications. As a film,
Copolymers of propylene and ethylene are used to improve the impact resistance and heat sealability, and propylene-ethylene-butene-1 is used as a material having an excellent balance of rigidity, impact resistance and heat sealability. Original copolymers and the like are known.

These copolymers have an excellent balance of rigidity, impact resistance and heat sealability, but it is desired to further improve the heat sealability in order to improve the efficiency in using the film.

[Problems to be Solved by the Invention] An object of the present invention is to provide a copolymer of butene-1 and propylene having a syndiotactic structure, which has relatively excellent impact resistance and excellent transparency.

Another object of the present invention is to provide an easily heat-sealable polypropylene resin composition having excellent heat sealability and other physical properties.

[Means for Solving the Problems] The butene-1 copolymer having a syndiotactic structure according to the present invention has a side of butene-1 unit in ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution. Of the absorption of methylene groups in the chain, based on tetramethylsilane
The absorption intensity observed at 6.9 ppm is 0.3 or more of the absorption intensity of the total absorption of methylene groups in the side chain observed at 27.8 to 26.0 ppm, and the content of propylene units is 0.1 wt% or more and less than 20 wt%, Intrinsic viscosity measured with 135 ° C tetralin solution
It is characterized by being at least 0.05 dl / g.

The easily heat-sealable polypropylene resin composition of the present invention is a stereoregular crystalline polypropylene, in which the propylene unit in the polymer is 98 to 80 wt% and the α-olefin unit having 4 to 12 carbon atoms is 0 to 0%. 18wt%, ethylene unit is 2
It is characterized by comprising 95 to 50 parts by weight of a polymer having a melt flow index of 0.1 to 100 g / 10 min measured at 230 ° C. at 20% by weight and 5 to 50 parts by weight of the butene-1 copolymer. .

The butene-1 copolymer having a syndiotactic structure according to the present invention can be obtained by copolymerizing butene-1 and propylene in the presence of a catalyst. Examples of the polymerization catalyst include the compounds described in the above-mentioned literature of JAEwen et al., But when a homopolymer of propylene is produced even if it has a different structure, the syndiotactic pentad fraction of the obtained polymer ( A. Zambelli et al .: Macromolecules, 6 , 925
(1973), ibid., 8 , 687 (1975)) can be used as long as the catalyst system gives a polymer having a relatively high tacticity of about 0.5 or more, for example, a transition metal having an asymmetric ligand. A catalyst system comprising a compound and an aluminoxane is effective.

As the transition metal compound suitable for producing the copolymer of the present invention, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride or isopropyl (cyclopentadienyl-1) described in the above-mentioned documents can be used.
-Fluorenyl) zirconium dichloride, and further obtained by substituting one or two of these chlorines with another halogen or an alkyl group having 1 to 5 carbon atoms.

The aluminoxane has the formula (Wherein R is a hydrocarbon residue having 1 to 3 carbon atoms). Examples thereof include methylaluminoxane wherein R is a methyl group and m is 5 or more, preferably 10 or more.

The use ratio of the aluminoxane to the transition metal compound is 10 to 1,000,000 mol times, usually 50 to 5,000 mol times.

The polymerization conditions are not particularly limited, and a known polymerization method in the presence of an inert solvent, a bulk polymerization method in a polymerization system substantially free of an inert solvent, or a gas phase polymerization method is used. Normal,
Polymerization temperature is -100 ° C ~ 200 ° C, polymerization pressure is normal pressure ~ 100kg / cm
^2- G. Polymerization at −100 ° C. to 100 ° C. and normal pressure to 50 kg / cm ² -G is particularly preferred.

In the polymerization, the propylene unit content in the copolymer is
The amount of the monomer introduced into the polymerization system was controlled so as to be 0.1 to 20% by weight, preferably 1 to 20% by weight, and the methylene group in the side chain of butene-1 unit measured by ¹³ C-NMR of the copolymer Of the absorptions of the above, the absorption intensity observed at 26.9 ppm with respect to tetramethylsilane is 0.3 or more, preferably 0.4 or more, of the total absorption intensity of the methylene group in the side chain observed at 27.8 to 26.0 ppm. It is desirable to control the amount ratio of the monomers, the polymerization temperature and the like, and further treat the copolymer by a method such as washing with a solvent such as a hydrocarbon having 3 to 20 carbon atoms.

As the hydrocarbon solvent, propylene itself or propane, butane, pentane, hexane, heptane, octane, other than saturated aliphatic hydrocarbon compounds such as nonane,
Aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, or those obtained by substituting part or all of hydrogen with fluorine, chlorine, bromine, or iodine can also be used. As other solvents, those capable of dissolving or dispersing low molecular weight atactic components such as alcohols having 1 to 20 carbon atoms, ethers and esters having 2 to 20 carbon atoms can be used. The washing method is not particularly limited, and is usually 0 ° C.
It is performed at a temperature of 〜100 ° C.

High purity, usually using a catalyst of 90% or more, relatively low temperature,
Usually, polymerization at 100 ° C. or lower is also effective for obtaining the above copolymer.

In the copolymer of butene-1 and propylene according to the present invention, the chain of butene-1 units substantially has a syndiotactic structure, which is specified by the following. That is, it was measured with a 1,2,4-trichlorobenzene solution.
^{In 13} C-NMR, of the absorption of methylene group in the side chain of butene-1 unit, 26.9 ppm based on tetramethylsilane
Is more than 0.3 of the total absorption intensity of methylene groups observed at 27.8 to 26.0 ppm, the content of propylene unit is 0.1 wt% or more and less than 20 wt%, and is measured with a tetralin solution at 135 ° C. The intrinsic viscosity is 0.05 dl / g or more. Here, the parameter specified in the measurement result of ¹³ C-NMR, which is a measure of syndiotacticity, is 0.
If it is smaller than 3, the physical property balance will be poor. If the intrinsic viscosity is less than 0.05 dl / g, the physical properties of the composition, particularly the blocking when formed into a film, are unfavorable. The upper limit of the intrinsic viscosity is about 5 dl / g. Further, when the content of the propylene unit is less than 0.1% by weight, the effect of improving the transparency of the polymer is small, and when the content is 20% by weight or more, the rigidity is not preferable. The propylene-equivalent number average molecular weight measured by gel permeation chromatography is 1,000 or more,
It is particularly preferably 5,000 or more, and the ratio of the weight average molecular weight to the number average molecular weight (hereinafter, referred to as _Mw / _Mn ) is preferably 1.5 to 10.

The substantially stereoregular crystalline polypropylene used as a component of the polypropylene resin composition of the present invention may have an isotactic structure or a syndiotactic structure. This crystalline polypropylene is 98-80wt% propylene unit, 0-18wt%
And a melt flow index measured at 230 ° C. of 0.1 to 100 g / 10 min.

The polypropylene having the above-mentioned isotactic structure means that the absorption mainly attributed to the methylene group of the propylene unit is observed at about 21.4 ppm in a ¹³ C-NMR spectrum, and the polypropylene having the syndiotactic structure is The above absorption is observed at 20.2 ppm.

Polypropylene having an isotactic structure can be obtained by a well-known method, for example, titanium trichloride or a modified product thereof, titanium tetrachloride supported on a carrier such as magnesium chloride together with an electron-donating compound, and organic aluminum, if necessary. Further, when used together with an electron donating compound, propylene and ethylene can be used, if desired, having 4 carbon atoms.
It can be produced by polymerizing together with α-olefin of ~ 12. Various kinds of such polypropylenes can be obtained as commercial products.

On the other hand, polypropylene having a syndiotactic structure is obtained by polymerizing propylene and ethylene together with an α-olefin having 4 to 12 carbon atoms, if desired, under the same polymerization conditions using the same catalyst as used for the polymerization of butene-1. It can be manufactured by doing.

In the case of substantially stereoregular polypropylene, it is necessary that the propylene unit be 98 to 80 wt%, the α-olefin unit having 4 to 12 carbon atoms be 0 to 18 wt%, and the ethylene unit be 2 to 20 wt%. If it is less than 80 wt%, the rigidity of the molded product is poor, and if it exceeds 98 wt%, the impact resistance is poor. Also, an α-olefin unit having 4 to 12 carbon atoms has 18 units.
If the content exceeds wt%, the rigidity of the molded product is poor. If the ethylene unit is less than 2 wt%, the impact resistance and heat sealability are poor. If the content exceeds 20 wt%, the rigidity of the molded product is poor. It is necessary that the melt flow index measured at 230 ° C. is from 0.1 to 100 g / 10 min from the viewpoint of the molded product. Even if the melt flow index is less than 0.1g / 10min,
Even if it exceeds 0 g / 10 min, it becomes difficult to form a film.

The preferred range of each structural unit in the stereoregular crystalline polypropylene is 97 to 85% by weight of a propylene unit, 0 to 15% by weight of an α-olefin unit having 4 to 12 carbon atoms, and 3 to 15% by weight of an ethylene unit. . The preferred range of the melt flow index is 1 to 50 g / 10 min.

The stereoregular crystalline polypropylene and butene-
The mixing ratio of 1 with the copolymer having substantially a syndiotactic structure needs to be 95 to 50 parts by weight for the former and 5 to 50 parts by weight for the latter. If the content of the former is more than 95% by weight, there is no effect of improving the heat sealing property, and if the content is less than 50% by weight, physical properties such as rigidity and blocking properties are poor. The preferred mixing ratio is 90 to 60 parts by weight of substantially stereoregular crystalline polypropylene, and 10 to 40 parts of a copolymer of butene-1 and propylene having a substantially syndiotactic structure.

Various known methods can be used for mixing the substantially stereoregular crystalline polypropylene and the copolymer of butene-1 having a substantially syndiotactic structure. That is, after mixing with a Henschel mixer or the like, a method of melt-mixing with an extruder, a method of mixing with a roll,
For example, a method of mixing with a Brabender or Banbury mixer is used.

The resin composition of the present invention may contain known additives such as an antioxidant, an ultraviolet absorber, an antiblocking agent, and a slip agent, depending on the application, in addition to the above-mentioned polymer.

The copolymer of butene-1 and propylene according to the present invention can be used as a molded product such as a film. In addition, the polypropylene composition of the present invention is useful as a heat seal layer when bonding a polyolefin by heating.

EXAMPLES Examples of the present invention will be described below, but these examples are merely illustrative of the present invention and should not be construed as limiting.

Example 1 In an autoclave having an internal volume of 2, isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method was lithiated, reacted with zirconium tetrachloride, and further purified to obtain isopropyl (cyclopentadienyl). -1-Fluorenyl) zirconium dichloride 5m
g and 0.67 g of methylaluminoxane having a polymerization degree of about 16 manufactured by Tosoh Akzo Co., Ltd. were dissolved in toluene 1 and charged. Then, 25 g of propylene was charged into the autoclave at 30 ° C., and then 460 g of butene-1 was introduced under pressure and polymerized for 1 hour.
After the polymerization, unreacted monomers were purged, 500 ml of methanol was added and the mixture was filtered off, and dried under reduced pressure at 80 ° C. to obtain 44.4 g of a copolymer.

This copolymer was determined by ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution to be based on tetramethylsilane.
The absorption intensity observed at 6.9 ppm is 0.67 of the total absorption intensity observed at 27.8 to 26.0 ppm.
Contained. The intrinsic viscosity (hereinafter referred to as η) measured at 135 ° C. tetralin solution is 0.65 dl / g, and M _w / measured at 135 ° C. in 1,2,4-trichlorobenzene solution by gel permeation chromatography. M _n was 2.1.

This copolymer was press-molded at 210 ° C. to produce a 1 mm sheet, and the following physical properties were measured by the method described for each item.

・ Tensile yield strength: kg / cm ² ASTM D638 (23 ℃) ・ Elongation:% ASTM D638 (23 ℃) ・ Izod (with notch) impact strength: kg ・ cm / cm ASTM D256 (23 ℃, -10 ℃)・ Haze:% ASTM D1003 Tensile yield strength is 30 kg / cm ² , elongation is 47%, Izod impact strength is 56, 68 (23 ℃, -10 ℃ respectively) kg ・ cm / cm, haze is 30% there were.

Comparative Example 1 Polymerization was conducted without using propylene to obtain a polymer having an η of 0.17, a syndiotactic pentad fraction of 0.89, and an M _w / M _n of 1.5. The physical properties were measured in the same manner as in Example 1 except that the physical properties were measured. Was measured, the tensile yield strength was 108 kg / cm ² , the elongation was 38%, and the Izod impact strength was 48, 2.8 (23 each)
° C, -10 ° C) kg · cm / cm, and the haze was 68%.

From the above results, it is apparent that the butene-1 copolymer of the present invention has higher Izod impact strength and superior transparency than the butene-1 homopolymer.

Hereinafter, methods for evaluating physical properties of a film in Examples and Comparative Examples of the present invention will be described. 20 / 10,000 weight ratio of phenolic stabilizer to resin composition or copolymer powder, 5 / 10,000 weight ratio of calcium stearate, 9 / 10,000 weight ratio of lubricant and 25 / 10,000 fine powder of silicon dioxide which is an anti-blocking agent The mixture was added at a weight ratio, and then 30 to 30% using a Henschel mixer (manufactured by Mitsui Miike Seisakusho Co., Ltd.).
Mix at 40 ° C. for 4 minutes. The mixture is kneaded with a 65 mm diameter single screw granulator (manufactured by Toshiba Machine Co., Ltd.) to form pellets, and then the thickness is adjusted at a resin temperature of 250 ° C. using a 40 mm diameter single screw film forming machine (manufactured by Osaka Seiki Co., Ltd.) 30μ, width 25c
A T-die film of m was prepared, and the physical properties of the film were evaluated. The measuring method of each physical property is as follows.

Haze (%): ASTM 1003-53.

-Blocking (%): Two 200mm x 200mm films are superimposed on each other and placed on a flat iron plate.
Calculate as the ratio of the contact area after placing a 2 kg iron plate of mx 200 mm and keeping it at 50 ° C for 24 hours.

・ Young's modulus (kg / mm ² ): Measured with an Instron universal tensile and compression tester using a film of 20 mm × 220 mm.

-Emboss: Determined visually after holding the film at 50 ° C for 30 days.

・ Heat seal temperature: Measured using a thermal gradient tester manufactured by Toyo Seiki Co., Ltd. (Heat seal pressure is 2 kg / cm ² , time 1
The heat seal strength of the heat-sealed sample was measured in seconds using an Instron universal tensile and compression tester.

-Hot tack property: Use a heat seal tester manufactured by Tester Sangyo Co., Ltd. Pressure is applied for 1 ^second at a heat sealing pressure of 1 kg / cm ² and measured as the minimum temperature at which peeling does not occur at a peeling load of 45 g.

・ Melt flow rate: Measured at a temperature of 230 ° C and a load of 2.16 kg according to ASTM D1238-65T.

Example 2 Preparation of Catalyst A vibration mill equipped with four crushing pots having an inner volume of 4 and containing 9 kg of steel balls having a diameter of 12 mm is prepared. 300 g of magnesium chloride, 115 ml of diisobutyl phthalate, and 60 ml of titanium tetrachloride were added to each pot in a nitrogen atmosphere, and pulverized for 40 hours.

Put 5 g of the above co-ground material in a 200 ml flask and add toluene 100
Then, the mixture was stirred at 114 ° C. for 30 minutes, and then allowed to stand to remove the supernatant. Then, using 100 ml of n-heptane at 20 ° C.
The solid content was washed three times and further dispersed in 100 ml of n-heptane to obtain a transition metal catalyst slurry. The obtained transition metal catalyst contained 1.8% by weight of titanium and 18% by weight of diisobutyl phthalate.

Production of Propylene Copolymer 25 kg of propylene and 3.4 kg of butene were charged into a jacketed autoclave, which had been replaced with a sufficiently dried nitrogen having an internal volume of 100 and further replaced with propylene, to prepare for polymerization.

On the other hand, in one flask, 500 ml of n-heptane, 4.7 ml of triethylaluminum, 2.3 ml of cyclohexylmethyldimethoxysilane and 0.35 g of the transition metal catalyst obtained in the above catalyst preparation were mixed as a solid content to prepare 0.35 g of the above internal volume 1
The mixture was press-fitted into the autoclave No. 00. Then, after charging 30 g of hydrogen and 300 g of ethylene, the inside temperature is 65 ° C. through hot water in the jacket so that the gas phase concentration of each component can be maintained at 2.3 mol% of hydrogen, 1.5 mol% of ethylene and 13.5 mol% of butene-1. Hydrogen, ethylene and butene-1 were continuously charged with propylene at 5 kg / h while being polymerized, and after 3 hours, 3.5 ml of diethylene glycol monoisopropyl ether was injected and further stirred at 60 ° C. for 30 minutes. The polymerization was terminated.

The obtained copolymer slurry has an inner diameter of a narrow portion of 15c.
m, the inner diameter of the upper thick part is 30 cm, and the length of the thin part is 5
m, 50k at the top of a countercurrent washing tower with a 1m thick upper part
g / h, 89 mol% of propylene, 5 mol% of propane, 1 mol% of ethylene, butene-15 mol%
Is introduced at a rate of 100 kg / h, and a washing liquid of 110 kg / h is taken from above the countercurrent washing tower, and a copolymer slurry washed from below is taken out at a rate of 40 kg / h. 1 kg of the removed copolymer slurry is placed in an outer tube with an inner diameter of 20 cm and a length of 60 m.
/ cm ² gauge through a heated double tube through steam into a cyclone maintained at atmospheric pressure, and the resulting powder was further dried at 50 ° C and 60 mmHg for 10 hours to obtain 13.0 kg of copolymer. Obtained.

The ethylene content of this propylene copolymer is 2.1 wt%,
Butene was 1.6 wt%, intrinsic viscosity was 1.63 dl / g, and melt flow index was 5.7. The physical properties measured for the obtained film were 2.0 haze, 10% blocking,
The Young's modulus was 69 kg / mm ² , the heat seal temperature was 132.8 ° C., no embossing occurred, and the hot tack temperature was 142.5 ° C.

Production of Copolymer of Butene-1 and Propylene Isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method in an autoclave having an internal volume of 2 was lithiated, reacted with zirconium tetrachloride, and further purified. Isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride 5m
g and 0.67 g of methylaluminoxane having a degree of polymerization of about 16 manufactured by Tosoh Akzo Co., Ltd. dissolved in toluene 1 and charged.
30 g of propylene at ℃, and then 460 g of butene-1
The mixture was press-fitted and polymerized for 1 hour. After the polymerization, unreacted monomers were purged, a large amount of methanol was added and the mixture was filtered off, and dried at 80 ° C. under reduced pressure to obtain 46.8 g of a copolymer.

This copolymer was determined by ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution to be based on tetramethylsilane.
The absorption intensity observed at 6.9 ppm was 0.67, which was 27.8 to 26.0 ppm, and contained 9.5 wt% of propylene. Further, its η was 0.68 dl / g, and M _w / M _n was 2.1.

Production of Resin Composition 80 wt parts of the above propylene copolymer was mixed with 20 wt parts of the above copolymer of butene-1 and propylene, and the film was formed and the physical properties were measured. The haze was 2.1%, the blocking was 10%, the Young's modulus The temperature was 68 kg / mm ² , the heat seal temperature was 122.6 ° C., no embossing occurred, and the hot tack temperature was 128.0 ° C.

Comparative Example 2 A propylene-butene-1 copolymer having an isotactic structure obtained by polymerization using the catalyst supported on magnesium chloride of Example 2 was used.

This copolymer had almost no absorption at 26.9 ppm, the maximum intensity was observed at 27.8 ppm (about 0.7 of the absorption intensity of all methylene groups), the propylene unit content was 10.5 wt%, and η was 0.7 dl / g. Was. Except using this copolymer, it evaluated similarly to Example 2 and found that haze was 2.2, blocking 10%,
The Young's modulus was 63 kg / mm ² , the heat seal temperature was 128.5 ° C., no embossing was found, and the hot tack temperature was 130.0 ° C. The decrease in Young's modulus is large and the hot tack property is slightly inferior.

Comparative Example 3 Example 2 except that the gas phase concentration of ethylene was changed to 3.6 mol%.
Using a propylene copolymer of 4.5 wt% ethylene unit and 1.5 wt% butene-1 unit obtained in the same manner as in the production of the propylene copolymer, and forming a film without adding the propylene-butene-1 copolymer After measuring the physical properties,
The haze was 1.7, the blocking was 10%, the Young's modulus was 50 kg / mm ² , the heat sealing temperature was 124.6 ° C., the embossing was not performed, and the hot tack temperature was 135.0 ° C. By increasing the ethylene content, the same heat sealability as in Example 2 is exhibited, but the Young's modulus is significantly reduced, and the hot tack property is poor.

Example 3 A copolymer of butene-1-propylene having a propylene content of 17.2 wt% was obtained in the same manner as in Example 1 except that the amount of propylene used was 50 g. η was 0.82 dl / g, and the absorption intensity observed at 26.9 ppm was 0.62, which was 27.8 to 26.0 ppm. Except for using this copolymer, a resin composition obtained in the same manner as in Example 1 was formed into a film, and its physical properties were measured. The haze was 2.0, the blocking was 15%, and the Young's modulus was 67 kg / mm ^2.
The heat seal temperature was 118.5 ° C., the surface was raised, none, and the hot tack temperature was 119.5 ° C.

Example 4 Using the catalyst used in Example 1, the internal volume was 2
100 g of propylene and 15 g of butene in an autoclave of
And 2 g of ethylene were injected and polymerized at 20 ° C. for 1 hour. A coalescence was obtained.

The η of this copolymer is 1.25 dl / g, and the melt flow index is 7.2.In ¹³ C-NMR, the absorption intensity observed at 20.2 ppm based on tetramethylsilane is attributed to the methyl group of the propylene unit. With a total absorption intensity of 0.75 or more, the copolymer had a substantially syndiotactic structure.

A resin composition obtained in the same manner as in Example 2 was formed using this copolymer, and the physical properties of the obtained film were measured. The haze was 1.5%, the blocking was 20%, and the Young's modulus was 48kg / mm ² , heat seal temperature 95 ℃, emboss,
None, hot tack temperature was 98 ° C.

[Effect of the Invention] The copolymer of butene-1 and propylene having a substantially syndiotactic structure according to the present invention has relatively excellent impact resistance and good transparency. Further, the polypropylene resin composition according to the present invention is excellent in heat sealability,
In addition, it also has good other physical properties, and is useful as a heat seal layer for bonding a polyolefin by heating.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08F 210: 06) (72) Inventor Koji Kitabayashi 3-4-1-1, Toriishi, Takaishi-shi, Osaka (56) References JP-A-62-62 119213 (JP, A) JP-A-61-106245 (JP, A) JP-A-61-106648 (JP, A) JP-A-3-70713 (JP, A) Makromol. Chem. (1981), 182 (10), 2881-7 (58) Fields studied (Int. Cl. ⁶ , DB name) C08F 10/06-10/08 C08F 210/06-210/08 C08F 4/60 -4/70 C08L 23/02-23/22 CAS ONLINE

Claims (8)

(57) [Claims] (1) In ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution, 26.9 pp of the absorption of a methylene group in the side chain of butene-1 unit was determined based on tetramethylsilane.
The absorption intensity observed at m is 0.3 or more of the absorption intensity of the total absorption of methylene groups in the side chain observed at 27.8 to 26.0 ppm, the content of propylene units is 0.1 wt% or more and less than 20 wt%, and 135 0.05d intrinsic viscosity measured with tetralin solution
l / g or more butene-1 and propylene copolymer. 2. The content of propylene unit is 1 wt% or more and 20 wt%.
2. The copolymer according to claim 1, which is less than. 3. The copolymer according to claim 1, which has a propylene-equivalent number average molecular weight of 1,000 or more as measured by gel permeation chromatography. 4. The ratio of the weight average molecular weight to the number average molecular weight is 1.
The copolymer according to claim 1, which is 5 to 10. 5. A crystalline polypropylene having stereoregularity, wherein the polymer has 98 to 80% by weight of propylene units, 0 to 18% by weight of α-olefin units having 4 to 12 carbon atoms, and 2 to 2% by weight of ethylene units. 95 to 50 wt% of a polymer having a melt flow index of 0.1 to 100 g / 10 min measured at 230 ° C.
Part and ¹³ C- measured in 1,2,4-trichlorobenzene solution.
In NMR, of the absorption of methylene groups in the side chain of butene-1 unit, the absorption intensity observed at 26.9 ppm based on tetramethylsilane is 0.3 or more of the total absorption intensity of methylene groups observed at 27.8 to 26.0 ppm. And a copolymer of butene-1 and propylene having a propylene unit content of 0.1 to 20% by weight and an intrinsic viscosity of 0.05 dl / g or more measured in a tetralin solution at 135 ° C. of 5 to 50% by weight. Heat sealable polypropylene resin composition. 6. A crystalline polypropylene having a stereoregularity of 90 to 60.
The resin composition according to claim 5, wherein the wt part and the butene-1 copolymer comprise 10 to 40 wt parts. 7. The resin composition according to claim 5, wherein the stereoregular crystalline polypropylene has an isotactic structure. 8. The resin composition according to claim 5, wherein the stereoregular crystalline polypropylene has a syndiotactic structure.