JPH06104699B2 - 1-Butene random copolymer and heat-sealability improving agent for thermoplastic resin comprising the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel 1-butene random copolymer. More specifically, a 1-butene random copolymer having a narrow molecular weight distribution and a narrow composition distribution, excellent transparency, surface non-adhesiveness, tensile properties and other properties, such as excellent transparency and blocking resistance. Improving heat sealability and impact resistance by blending with thermoplastic resins such as 1-butene random copolymers and olefin polymers suitable for forming packaging films, sheet materials, and other melt-formed products The present invention relates to a modifier for a thermoplastic resin which is excellent in effect.

[Prior Art] Conventionally, the use of vinyl chloride resin has been predominant in the application field of molding of soft or semi-rigid resin. However, the generation of corrosive gas during waste incineration, the safety against residual monomer and plasticizer Due to such concerns as above, conversion to olefinic soft or semi-hard resin has been desired. Therefore, the demand for the α-olefin-based soft copolymer is increasing more and more in the field of molding or applications such as various resin modifiers.

As the α-olefin soft copolymer, two or more α
-Olefin copolymers are generally known, and as a method for producing the same, two or more kinds in the presence of a titanium-based catalyst composed of a titanium compound and an organoaluminum compound or a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound are used. There is known a method of copolymerizing the α-olefins. The α-olefin soft copolymer obtained by the titanium catalyst is generally inferior in random copolymerizability, has a broad molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the α-olefin soft copolymer obtained with a vanadium catalyst generally has
With an ethylene content of 50 mol% or more, they have improved randomness compared to copolymers obtained with titanium-based catalysts, narrow molecular weight distribution and composition distribution, and are transparent, surface non-adhesive, and mechanical properties. However, it is still insufficient for applications where these performances are strictly required, and there is a need for an α-olefin-based soft copolymer having improved performance.

Recently, as an olefin resin used in such a soft or semi-rigid resin molding application field,
There are olefin-based copolymers such as ethylene-based copolymers, propylene-based copolymers and 1-butene-based copolymers. Of these olefinic soft or semi-hard resins,
Regarding the soft 1-butene random copolymer composed mainly of 1-butene and 1-butene and propylene,
There are numerous suggestions. Among them U.S. Patent No. 3,278,504
U.S. Pat.No. 3,332,921, U.S. Pat.
No. 4,168,361 and British Patent No. 1,018,341 disclose 1-butene random copolymers produced using titanium trichloride or titanium tetrachloride catalysts. However, what is common to these 1-butene random copolymers is that the boiling methyl acetate-soluble component and acetone.
-Because the content of low molecular weight polymer components such as decane mixed solvent (volume ratio 1/1) soluble content is high, and the composition distribution and molecular weight distribution are wide, it was formed from these 1-butene random copolymers. Molded products, especially films and seeds, have large surface tackiness and marked blocking. Also, most of them have low randomness and poor transparency,
It was not possible to obtain molded products with high commercial value.

U.S. Pat. No. 3,278,504 proposes a propylene / 1-butene copolymer having a 1-butene content of 30 to 70 mol%. It is described that the 1-butene-based copolymer is produced by using titanium tetrachloride or titanium trichloride. However, the copolymer produced by such a catalyst system has a boiling methyl acetate-soluble content. It is a soft resin having a content of more than 2% by weight, a large amount of acetone / n-decane mixed solvent (volume ratio 1/1) soluble content, surface tackiness, and poor transparency.

U.S. Pat.No. 3,332,921 and British Patent No. 1,08
No. 4,953 also proposes various 1-butene copolymers having different 1-butene contents produced by using titanium trichloride catalyst. Among these copolymers, 1-butene-containing copolymers are included. The 1-butene copolymer having an amount of 60 to 99 mol% has the same properties as the 1-butene copolymer proposed in the above-mentioned US Pat. No. 3,278,504.

Further, according to the above-mentioned British Patent No. 1,018,341, a transition metal halide such as titanium trichloride and a derivative of phosphoric acid are used in combination to obtain a copolymer having a 1-butene content of 25 to 90 mol%. There is. Among the copolymers specifically disclosed in this proposal, the 1-butene-based copolymer having a 1-butene content of 50 to 90 mol% has an acetone-soluble content of 1.5% by weight or more. Only one is disclosed.
According to the studies by the present inventors, these copolymers have a higher content of boiling methyl acetate-soluble components exceeding 2% by weight, and a soluble content of acetone / n-decane mixed solvent (volume ratio 1/1). It was found that the content of the above was more than 5 × [η] ^−1.2 % by weight, and that the 1-butene-based copolymer had a large surface tackiness and that only a molded article having poor transparency could be obtained. .

Further, U.S. Pat. No. 4,168,361 discloses a propylene / 1-butene copolymer having a propylene content in the range of 40 to 90 mol%. Among these copolymers, 1-butene As for the copolymer having a butene content of 50 to 60 mol%, similarly to the above, according to the study by the present inventors, the content of the acetone / n-decane mixed solvent-soluble component is high, and the 1-butene system From the copolymer, it is possible to obtain only a molded product having high surface tackiness and poor transparency.

On the other hand, a method of obtaining an amorphous random copolymer by polymerizing at high temperature using a titanium trichloride-based catalyst is disclosed in JP-A-50-38787.
It is proposed in Japanese Patent Publication No.

According to the studies made by the present inventors, the copolymer obtained by this method has a methyl acetate-soluble content of more than 2% by weight, is inferior in tensile properties, and cannot be used for resin applications.

Further, the applicant of the present invention has disclosed that in JP-A No. 54-85293, 1-butene / propylene random copolymer containing 1-butene as a main component, which has a narrow composition distribution, a small amount of boiling methyl acetate-soluble components, and a small surface tackiness. A polymer was proposed. However,
The content of the low molecular weight component of the 1-butene / propylene copolymer provided by this proposal, especially the content of the low molecular weight polymer represented by the boiling methyl acetate-soluble component, and the surface of a molded article made of the copolymer It is clear that the tackiness is considerably improved as compared with the conventional one, but the molecular weight distribution (w / n) of the 1-butene random copolymer is 3.6, which is not sufficiently narrow, and the copolymer To improve impact resistance, the content of low molecular weight polymer components in the polymer, especially low molecular weight polymer components represented by acetone / n-decane mixed solvent (volume ratio 1/1) soluble component, is still high. In addition, a molded article of a resin composition obtained by blending the polypropylene resin with the 1-butene / propylene random copolymer, for example, a film, has drawbacks such that the surface tackiness easily increases with time, and the surface is non-tacky and transparent. Sex Ability has been difficult to say that is still sufficient for applications in the field which is highly required. Further, the 1-butene / propylene random copolymer according to this proposal has low crystallinity and is inferior in mechanical properties such as rigidity, and is unsuitable for use in fields where these mechanical properties are highly required. It was enough.

On the other hand, as a new Ziegler type olefin polymerization catalyst different from conventionally known titanium-based catalysts or vanadium-based catalysts, a catalyst comprising a zirconium compound and aluminoxane is disclosed in JP-A-58-19309 and JP-A-59- 952
925, JP 60-35005, JP 60-35006
JP-A-60-35007 and JP-A-60-35009, respectively. These prior art documents also exemplify copolymers of two or more kinds of α-olefins, for example, Example 7 in JP-A-58-19309 and Example 1 in JP-A-60-35006. -Example 3, JP-A-60-3
In Example 10 and Example 11 of 5007, an ethylene / α-olefin copolymer having an α-olefin content of 3 to 43 mol% is disclosed.
All of the α-olefin copolymers have a wide molecular weight distribution and composition distribution, or have performances such as transparency, surface non-adhesiveness and mechanical properties, and performance as a modifier of a thermoplastic resin, depending on the application of the application field. In many cases, the α-olephane-based soft copolymers having improved performances are satisfactorily demanded.

[Problems to be Solved by the Invention] The present inventors have found that conventional 1-butene random copolymers have a wide molecular weight distribution and composition distribution and a large content of low molecular weight polymers, Recognizing that the molded product obtained from the copolymer is inferior in mechanical properties such as surface non-adhesiveness, transparency, and rigidity, these physical properties of the 1-butene random copolymer are compared to those of the conventional 1-butene random copolymer. Research and development have been carried out with the aim of providing an improved 1-butene random copolymer.

As a result, the present inventors have found that the 1-butene component and the number of carbon atoms are in the range of 3 to 12 and α-other than 1-butene.
A 1-butene random copolymer comprising an olefin component and having a 1-butene component as a main component, and also having the characteristic values defined in the following (A) to (I), which have not been described in the related art. We discovered that a 1-butene random copolymer can exist and succeeded in its synthesis.

Furthermore, this novel 1-butene random copolymer has a narrower molecular weight distribution and composition distribution than the conventionally known 1-butene random copolymer, and is soluble in low molecular weight polymer components, especially in boiling methyl acetate. Content of the low molecular weight polymer component represented by both the component and the soluble component in the acetone / n-decane mixed solvent (volume ratio 1/1) is small, and molding obtained from the 1-butene random copolymer It was discovered that the body is particularly excellent in mechanical properties such as surface non-adhesiveness, transparency and rigidity.

Therefore, an object of the present invention is to provide a novel 1-butene random copolymer which comprises a major amount of 1-butene component and an α-olefin component other than 1-butene and having a carbon atom number of 3 to 12. To do.

Further, another object of the present invention is to provide a modifier for a thermoplastic resin having an excellent effect of improving heat sealability or impact resistance by blending it with a thermoplastic resin such as an olefin polymer. is there.

The above as well as many other objects and advantages of the present invention will become more apparent in the following description.

[Means and Actions for Solving Problems] According to the present invention, a 1-butene random compound comprising a 1-butene component and an α-olefin component other than 1-butene in the range of 3 to 12 carbon atoms. (A) The composition of the copolymer is such that the propylene component exceeds 60 mol%.
98 mol% or less and the α-olefin component is in the range of 2 to less than 40 mol%, and (B) the intrinsic viscosity [η] measured in decalin at 135 ° C.
It is in the range of 0.5 to 6 dl / g, and (C) gel permeation chromatography (GP
The molecular weight distribution (w / n) measured in C) is in the range of 3 or less, and (D) the melting point [T _m ] measured by a differential scanning calorimeter is 40.
To (E) the crystallinity measured by X-ray diffractometry is 5 to 130 ° C.
60%, (F) Soluble content in boiling methyl acetate [W ₁ % by weight] is 1% by weight or less, (G) Acetone / n-decane mixed solvent at 10 ° C (volume ratio) Soluble content [W ₂ % by weight] in 1/1) is 4 x [η] ^-1.2
In the ¹³ C-NMR spectrum of the (H) copolymer, a signal based on two methylene chains between two adjacent tertiary carbon atoms is observed in the copolymer main chain in an amount of less than 1% by weight. And (1) the standard deviation of the composition distribution of the copolymer is in the range of 10 mol% or less, comprising a 1-butene random copolymer and the 1-butene random copolymer Provided is a heat sealability improver for a thermoplastic resin.

In the 1-butene random copolymer of the present invention, the composition (A) of the copolymer is such that the 1-butene component is more than 60 mol% and 98 mol%, preferably 65 to 98 mol%. A carbon atom number of 3 to 12 and an α-olefin component other than 1-butene of 2 to less than 40 mol%,
It is preferably in the range of 2 to 35 mol%. When the content of the 1-butene component in the copolymer is higher than 98 mol% and the content of the α-olefin component is lower than 2 mol%, the type II crystal to the type I crystal of the copolymer Is delayed, the physical properties of the molded product change with time, and the transparency decreases.

The 1-butene random copolymer of the present invention has 3 to 12 carbon atoms, and α-olefin components other than 1-butene include propylene, 1-pentene, 1-hexene, and 4-. Methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-
Α- with 3 and 5 to 12 carbon atoms such as dodecene
An olefin can be illustrated.

In the 1-butene random copolymer of the present invention, 135
The intrinsic viscosity [η] (B) measured in decalin at 0 ° C was 0.
It is in the range of 5 to 6 dl / g, preferably 1 to 5 dl / g. This characteristic value is a measure of the molecular weight of the 1-butene random copolymer of the present invention, and together with other characteristic values, it serves to impart the above-mentioned excellent properties to the random copolymerization. There is.

The molecular weight distribution (w / n) (C) determined by gel permeation chromatography (GPC) of the 1-butene random copolymer of the present invention is 3 or less, preferably 2.8 or less,
It is particularly preferably in the range of 2.5 or less. Since the conventionally proposed 1-butene random copolymer has a w / n value of 3 or more, it cannot be said that the molecular weight distribution is sufficiently narrow, and low molecular weight polymer components are mixed, and therefore the surface is It is inferior in non-adhesiveness and causes blocking. This characteristic value in the 1-butene random copolymer of the present invention, together with other characteristic values, gives the copolymer the above-mentioned excellent properties. The w / n value is measured according to “Gel Permeation Chromatography” published by Maruzen by Takeuchi.

(1) Using a standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda) monodisperse polystyrene), the molecular weight M and its GPC (Gel Permeation Chromatograph) count are measured, and the correlation diagram calibration between the molecular weight M and EV (Elution Volume) is performed. Create a curve. The concentration at this time is 0.02 wt%.

(2) Take a GPC chromatograph of the sample by GPC measurement,
The number average molecular weight n in terms of (1) standard polystyrene,
The weight average molecular weight w is calculated to obtain the w / n value. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation] (a) A sample is dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to be 0.1 wt%.

(B) Anti-aging agent 2,6 in the Erlenmeyer flask containing the sample
-Di-tert-butyl-p-cresol is added at 0.05 wt% with respect to the polymer solution.

(C) The Erlenmeyer flask is heated to 140 ° C and stirred for about 30 minutes to dissolve it.

(D) Pour the liquid on GPC.

[GPC measurement conditions] The measurement was performed under the following conditions.

(B) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample volume 400 μl (d) Temperature 140 ° C (v) Flow rate 1 ml / min 1-butene of the present invention The melting point [hereinafter, sometimes abbreviated as DSC melting point] (D) of a random copolymer of the series determined by a differential scanning calorimeter is 40 to 130 ° C., preferably 50.
To 125 ° C. The presence of the DSC melting point is a measure indicating that the DSC melting point is a copolymer having crystallinity, which is distinguished from the conventional amorphous 1-butene random copolymer, and is included together with other characteristic values. Is useful for giving the above-mentioned excellent properties to the copolymer. Here, the DSC melting point is the temperature of the maximum endothermic peak (Tm obtained by measuring a press sheet having a thickness of 0.1 mm at least 20 hours after molding at 20 to 200 ° C. at a temperature rising rate of 10 ° C./min. ).

The crystallinity (E) of the 1-butene random copolymer of the present invention measured by X-ray diffractometry is in the range of 5 to 60%, preferably 10 to 60%. This characteristic value is a measure showing that the 1-butene random copolymer of the present invention has excellent tensile properties, and together with other characteristic values, gives the above-mentioned excellent properties to the random copolymer. Is useful to. Crystallinity is the thickness after at least 20 hours after molding 1.
It was determined by X-ray diffraction measurement of a 5 mm pressed sheet.

In the 1-butene random copolymer of the present invention, the amount of soluble components in boiling methyl acetate [W ₂ % by weight] (F) is 1% by weight or less, preferably 0.001% by weight based on the weight of the copolymer.
˜0.5 wt%, particularly preferably 0.005 to 0.3 wt%. This characteristic value is a measure showing the content of the low molecular weight polymer component in the 1-butene random copolymer of the present invention and showing the breadth of the composition distribution and the molecular weight distribution of the copolymer, and has been proposed in the past. The 1-butene random copolymer has a large amount of the boiling methyl acetate-soluble component, is inferior in surface non-tackiness, and is a cause of large blocking property. This characteristic value in the 1-butene random copolymer of the present invention, together with other characteristic values, serves to give the above-mentioned excellent properties to the copolymer. In the present invention, the boiling methyl acetate-soluble content was measured by the following method.
That is, a 1 mm x 1 mm x 1 mm strip sample is put in a cylindrical glass filter, the reflux frequency is set to once for 5 minutes, and the sample is extracted with a Soxhlet extractor for 7 hours. It was dried to a constant weight (10 mmHg or less) and its weight was determined, and the boiling methyl acetate soluble content weight was determined from the weight difference from the original sample. Soluble content of boiling methyl acetate [W ₁ ]
Was determined as a percentage of the boiling methyl acetate soluble content relative to the original sample weight.

In the 1-butene random copolymer of the present invention, 10 ℃
Acetone / n-decane mixed solvent (solvent ratio 1/1)
Soluble content [W ₂ % by weight] (G) is 4 × [η] ^−1.2 % by weight or less, preferably 0.1% by weight, based on the weight of the copolymer.
05 × [η] ^{-1.2 to} 3.5 × [η] ^-1.2 wt%, particularly preferably 0.1 × [η] ^{-1.2 to} 3 × [η] ^-1.2 wt% (where [η] is It is the numerical value of the intrinsic viscosity of the copolymer, which is the value excluding the dimensions). This characteristic value is a scale showing the content of the low molecular weight polymer component in the 1-butene random copolymer of the present invention and showing the composition distribution and the range of the molecular weight of the copolymer. The conventionally known 1-butene random copolymer has a large amount of the acetone / n-decane mixed solvent-soluble component, is inferior in surface non-tackiness, and is a cause of large blocking property. This characteristic value in the 1-butene random copolymer of the present invention, together with other characteristic values, serves to give the copolymer the above-mentioned excellent properties. In the present invention, the soluble content of the copolymer in the mixed solvent is measured and determined by the following method. That is, in a 150 ml flask equipped with a stirring blade, 1 g of the copolymer sample, 0.05 g of 2,6-ditert-butyl-4-methylphenol and 50 ml of n-decane were placed, and 12
Dissolve on 0 ° C. oil bath. After dissolution, the mixture is allowed to cool naturally at room temperature for 30 minutes, 50 ml of acetone is added thereto in 30 seconds, and the mixture is cooled on a water bath at 10 ° C for 60 minutes. The solution in which the precipitated copolymer and low molecular weight polymer component are dissolved is separated by a glass filter, and the solution is dried at 10 mmHg at 150 ° C. until a constant weight is obtained,
The weight was measured, and the soluble amount of the copolymer in the mixed solvent was calculated and determined as a percentage with respect to the weight of the sample copolymer. In addition, in the above-mentioned measuring method, stirring was continuously performed from the time of dissolution until immediately before the excess.

In the 1-butene random copolymer of the present invention, 1-
Arrangement state of butene component and the α-olefin component (H)
In the ¹³ C-NMR spectrum of the copolymer, a signal based on two linked methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain is not observed. More specifically explaining this, in the copolymerization of 1-butene and other α-olefin, the following bond, In both cases, a signal of one isolated methylene group is observed between two adjacent tertiary carbon atoms, but a signal based on two continuous methylene chains is not observed. This indicates that in the copolymer, when the 1-butene component and the α-olefin component are copolymerized, all the components have a regular head-to-tail bond arrangement.

On the other hand, in the 1-butene / α-olefin copolymer,
The following combination, , A signal based on two consecutive methylene chains is observed between two adjacent tertiary carbon atoms. This indicates that a head-to-head bond and a tail-to-tail bond exist when the 1-butene component and the α-olefin component are copolymerized in the copolymer.

Therefore, in the 1-butene random copolymer of the present invention, this identification is based on the 1-butene component constituting the copolymer and α
-Indicates the arrangement state of the olefin component and, together with other property values, serves to give the copolymer excellent properties. The measurement of ¹³ C-NMR of the copolymer is usually carried out at a measurement temperature of a solution of about 200 mg of the copolymer dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
The operation was carried out under the conditions of 120 ° C., measurement frequency 25.05 MHZ, spectrum width 1500 HZ, filter width 1500 HZ, pulse repetition time 4.2 seconds, pulse width 7 μs and cumulative number of 2000 to 5000 times.

Spectral analysis is done by LPLindeman, Anal. Chem., 43 1245.
(1971), JCRandall, Macromolecular, 11 , 592 (197
8) Based on the report of et al.

The standard deviation value σ (I) of the 1-butene content of the 1-butene random copolymer of the present invention is 10 mol% or less, preferably 5 mol% or less. The standard deviation value σ is the 1-butene system. It is a measure showing the randomness of a random copolymer, and further includes a characteristic value (I) in addition to the characteristic values (A) to (H).
A copolymer satisfying the above condition shows more excellent physical properties. The standard deviation value σ of the 1-butene random copolymer of the present invention was calculated and determined by the following formula based on the composition distribution of the copolymer. The composition distribution of the copolymer was measured by an extraction-type column fractionation method in which the extraction temperature was changed stepwise from 0 to 130 ° C. in 5 ° C. steps with a p-xylene solvent. Was extracted for 4 hours with 2 l of p-xylene per 10 g of the copolymer sample.

Here, represents the average content (mol%) of 1-butene in the copolymer, and x represents 1-butene content (mol%), f
(X) indicates the differential weight fraction of the component having the 1-butene content x (mol%).

The 1-butene random copolymer of the present invention satisfies the characteristic values specified in (A) to (I) described above. The more preferable 1-butene random copolymer of the present invention further satisfies at least one of the following characteristic values (J) to (N).

In the 1-butene random copolymer of the present invention, JIS
Yield point stress (J) measured by the method of K7113 is 10k
g / cm ² or more, preferably in the range of 20 to 200 kg / cm ² ,
The stress at break (K) measured by the method of JIS K7113 is
200 kg / cm ² or more, preferably 250 to 600 kg / cm ² , particularly preferably in the range of 300 to 550 kg / cm ² , JIS K
Elongation at break (L) measured by the method of 7113 is 250%
Above, preferably in the range of 300 to 1000%. The characteristic values of the yield stress (J), the stress at break (K), and the elongation at break (L) of the 1-butene random copolymer of the present invention were measured according to the JIS K7113 tensile test method.
That is, the sample is 1 mm thick molded by JIS K6758.
JIS K71 punched from the press sheet of 19 hours after molding
Using No. 2 type 13 test piece, pulling speed 50 at 25 ℃
It is measured in mm / min after 20 hours from the above press sheet forming. When the yield point did not appear clearly, the 20% elongation stress was taken as the yield point stress.

The torsional rigidity (M) of the 1-butene random copolymer of the present invention measured by the method of JIS K6745 is 80, for example.
It is in the range of 0 kg / cm ² or more, preferably 1000 to 2000 kg / cm ² . As a method of measuring the torsional rigidity, JIS K6758
Using a strip-shaped test piece with a length of 64 mm and a width of 635 mm punched out from a 1 mm thick pressed sheet after 9 days, 10 days after the pressed sheet was formed, it was loaded with a twist angle of 50 to 60 degrees in an atmosphere of 25 ° C. The value after 5 seconds was measured.

Also, JIS K of the 1-butene random copolymer of the present invention
The Young's modulus (N) measured by the method of 7113 is, for example,
400 kg / cm ² or more, preferably to 1000 not in the range of 3500 kg / cm ^2. The Young's modulus (N) of the 1-butene random copolymer of the present invention is preferably in accordance with the general formula 3500-30b ≧ K ≧ 1000-15b in relation to the content rate b mol% of the α-olefin component. Represented. The Young's modulus can be measured by the above (J),
The tensile test was performed in the same manner as in the measurements of (K) and (L).

The 1-butene random copolymer of the present invention has a crystal type II.
Since it is fixed to the mold, there is a characteristic that the change with time of physical properties is small. On the other hand, for example, a homopolymer of 1-butene has three types of crystal forms (type I, type II and type III), and it is known that mutual crystal transition occurs with changes in temperature and time. Since the transition from the metastable type II crystal form to the stable type I crystal form is slow at room temperature, various changes such as deformation of the molded product and changes in physical properties over time are actually applied to the molded product. There were some drawbacks, such as the difficulties involved.

The 1-butene random copolymer of the present invention may be copolymerized with a trace amount of other α-olefins, such as ethylene and propylene, as long as the physical properties described above are not impaired.

The 1-butene random copolymer of the present invention has a predetermined amount of 1
-Butene and 3 to 12 carbon atoms (excluding 4)
An α-olefin in the range of (A), a zirconium compound having (A) at least two indenyl groups, a substituted indenyl group or a form in which a partial hydride thereof is bonded through ethylene as a ligand, and (B) ) It can be produced by polymerizing in the presence of a catalyst comprising aluminoxane.

The zirconium compound may have two or more indenyl groups, substituted indenyl groups or partial hydrides thereof, but those having two indenyl groups, substituted indenyl groups or partial hydrides thereof are preferable.

Examples of the zirconium compound include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methylene zirconium monochloride, ethylene bis (indenyl) ethyl zirconium monochloride. , Ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4,5,
6,7-Tetrahydro-1-indenyl) methyl zirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1- Indenyl)
Zirconium dibromide, ethylene bis (4-methyl-
1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium Examples thereof include dichloride and ethylenebis (4,7-dimethyloxy-1-indenyl) zirconium dichloride.

Specific examples of the aluminoxane (B) as a catalyst constituent used in the method of the present invention include the general formula [I] or the general formula [II]. (In the formula, R represents a hydrocarbon group, and m is 2 or more, preferably
An organoaluminum compound represented by 20 or more, particularly preferably an integer of 25 or more) can be exemplified. In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group,
It is preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably an integer of 20 or more, particularly preferably an integer of 25 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) Trialkylaluminum is added to a hydrocarbon medium suspension containing a compound containing adsorbed water, a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, and aluminum sulfate hydrate. To react.

(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of organic metal component.

In the present invention, the above catalyst system is used to produce a copolymer of 1-butene and an α-olefin having a carbon number of 3 to 12 (excluding 4) in a specific ratio. It was discovered that a copolymer having properties that have never been proposed can be obtained. 1
The copolymerization with -butene and the α-olefin can be carried out in either a liquid phase or a gas phase, but it is particularly preferably carried out in a liquid phase. When carried out in the liquid phase, it is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; benzene and toluene. Aromatic hydrocarbons such as xylene, petroleum fractions such as gasoline, kerosene, and light oil, and other raw material olefins can also be used as the hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

The use ratio of the zirconium compound when carrying out the method of the present invention by the liquid phase polymerization method is usually 10 ⁻⁷ to 10 ⁻² g atom / as the concentration of zirconium metal atom in the polymerization reaction system.
l, preferably in the range of 10 ⁻⁶ to 10 ⁻³ gram atom / l. The aluminoxane content is usually 10 as the concentration of aluminum atoms in the polymerization reaction system.
^-4 to 10 ^-1 gram atom / l, preferably 10 ^-3 to 5 ×
The amount is in the range of 10 ^-2 gram atom / l, and the ratio of aluminum atom to zirconium metal atom in the polymerization reaction system is usually not 20 ^{6 but} preferably in the range of 50 to 10 ⁵ .

The copolymerization of the present invention can be carried out in the same manner as the polymerization of olefins using a conventional Ziegler type catalyst. The copolymerization temperature is usually selected in the range of -80 to 50, preferably -60 to 30. The polymerization is preferably carried out under pressure, usually atmospheric pressure to 20 kg / cm, preferably 2 to 15 k.
It is preferably carried out under a pressure of about g / cm ² . The raw materials supplied to the polymerization reaction system are 1-butene and 3 to 12 carbon atoms.
It is a mixture consisting of α-olefins in the range (except 4). The 1-butene content in the polymerization raw material olefin is usually 60 to 99.5 mol%, preferably 65 to 99 mol%, the content of the α-olefin is usually 0.5 to 40 mol%, preferably 1 to 35 mol% Is the range. The molecular weight of the copolymer can be controlled by adjusting the hydrogen and / or the polymerization temperature and the proportion of the catalyst component used.

The 1-butene random copolymer of the present invention is different from the conventionally proposed ones in that it is not sticky and has various other properties as described above. By the existing molding method such as this copolymer, extrusion molding, hollow molding, injection molding, press molding, and vacuum molding, it can be molded into films, sheets, hollow containers, and various other products, and can be used for various purposes. In particular, it is suitable as a packaging film because of its excellent transparency, blocking resistance, heat sealability and flexibility. Due to the above-mentioned properties, it is also suitably used as a protective film of metal or the like.

When molding, various stabilizers, antioxidants, UV absorbers,
An antistatic agent, a lubricant, a plasticizer, a pigment inorganic inorganic or organic filler can be blended. Examples of these are 2,6
-Di-tert-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]] methane, 4,4'-butylidenebis (6-tert-butyl -M-cresol), tocopherols, ascorbic acid, dilaurylthiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N, N- (bis-2-hydroxyethyl) alkylamine, 2- (2'-hydroxy) -3 ', 5'-di-tert-
Butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc, clay, gypsum, glass equipment, titania, calcium carbonate, carbon black, petroleum It may be resin, polybutene, wax, synthetic or natural rubber and the like.

The copolymer of the present invention can also be used as a mixture with another thermoplastic resin. Examples of these are high density, medium density or low density polyethylene, polypropylene, poly-
Examples thereof include 1-butene, poly-4-methyl-1-pentene, ethylene, vinyl acetate copolymer, Surlyn A, ethylene, vinyl alcohol copolymer, polystyrene, and maleic anhydride graft products thereof.

The 1-butene random copolymer of the present invention improves impact resistance, low temperature impact resistance, flex resistance, transparency, and low temperature heat sealability by being mixed with various thermoplastic resins as a modifier. can do. Examples of the thermoplastic resin include other ethylene-based polymers containing ethylene as a main component, crystalline olefin-based polymers other than the ethylene-based polymer, and engineering resins.

By blending the 1-butene random copolymer of the present invention with another ethylene polymer containing ethylene as a main component, such as polyethylene, impact resistance of a molded product of the other ethylene polymer, low temperature resistance Impact resistance, bending resistance, transparency, and low temperature heat sealability can be improved. As the ethylene polymer, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-
Penten, 1-octene, 1-decene, 1-dodecene,
Α having 3 to 20 carbon atoms such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
An ethylene-based copolymer or the like which is a copolymer with an olefin and contains ethylene as a main component can be exemplified. Intrinsic viscosity [η] measured in decalin at 135 ℃
Is usually in the range of 0.5 to 20 dl / g.

When the 1-butene random copolymer of the present invention is blended with the ethylene polymer, the blending ratio is usually 1 to 100 parts by weight, preferably 2 to 60 parts by weight, relative to 100 parts by weight of the ethylene polymer. The resulting ethylene-based polymer composition in the range of parts, if necessary, an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weathering stabilizer, an antistatic agent, Various additives such as a nucleating agent, a pigment and a filler can be blended in an appropriate mixing ratio. The ethylene polymer composition can be prepared according to a conventionally known method.

Further, by adding the 1-butene random copolymer of the present invention to a crystalline olefin polymer other than the ethylene polymer, the impact resistance of a molded article made of the crystalline olefin polymer, particularly The low temperature impact resistance can be improved. Furthermore, a film having a well-balanced blocking resistance, transparency, and heat sealability can be obtained. Specific examples of the crystalline olefin polymer other than the ethylene polymer include polypropylene, poly-1-butene, and poly-4.
In addition to -methyl-1-pentene, propylene / ethylene copolymers, 1-butene / ethylene copolymers, and the like, α-olefins such as propylene, 1-butene, 1-hexene (a ₁ ) And ethylene, propylene, 1-
Butene, 1-hexene, 4-methyl-1-pentene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like α-olefins having 2 to 20 carbon atoms, said α-olefin (a ₁ ). And a crystalline α-olefin-based copolymer composed of an α-olefin (a ₂ ) different from the above. The intrinsic viscosity [η] of the crystalline olefin polymer measured in Delin at 135 ° C. is usually in the range of 0.5 to 10 dl / g and the crystallinity is 5%.
Or more, preferably 20% or more.

When the 1-butene random copolymer of the present invention is blended with the crystalline α-olefin polymer, the blending ratio is usually 1 to 100 relative to 100 parts by weight of the crystalline α-olefin polymer. Parts by weight, preferably in the range of 2 to 60 parts by weight. In the crystalline α-olefin polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an agglomeration inhibitor, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, The crystalline α-olefin polymer composition in which various additives such as pigments and fillers can be added can be prepared according to a conventionally known method.

Furthermore, by blending the 1-butene random copolymer of the present invention with various engineering resins, the physical properties of the engineering resin, such as impact resistance and sliding characteristics, can be improved. When the engineering resin is an engineering resin having a polar group, maleic acid and citracone are added to the 1-butene random copolymer of the present invention in order to improve the affinity or dispersibility to the engineering resin. Modified 1-butene random copolymer obtained by graft-copolymerizing unsaturated carboxylic acid such as acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate and dimethyl itaconic acid Preference is given to using polymers. The graft ratio of the unsaturated dicarboxylic acid or its derivative component is usually 0.02 to 50 parts by weight with respect to 100 parts by weight of the 1-butene random copolymer, specifically as an engineering resin, specifically polyethylene terephthalate, Polybutylene terephthalate and other polyesters, hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactam,
Polyamide such as, polyarylene oxide such as polyphenylene oxide, polyacetal, ABS, AES, polycarbonate and the like can be exemplified 1-butene random copolymer or a modified product thereof in a proportion of 100 parts by weight of the engineering resin. Normally 0.2 to 20
If necessary, the engineering resin composition in the range of parts by weight includes an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, The engineering resin composition to which various additives such as pigments and fillers can be added can also be prepared according to a conventionally known method.

By blending the 1-butene random copolymer of the present invention with various rubber-like polymers, physical properties of the rubber-like polymerization, such as chemical resistance and rigidity, can be improved. Specific examples of the rubber-like polymer include ethylene / propylene / non-conjugated diene copolymer, ethylene / 1-butene / non-conjugated diene copolymer, polybutadiene rubber, polyisoprene rubber, styrene / butadiene / styrene block copolymer. A polymer etc. can be illustrated. The compounding ratio of the 1-butene random copolymer is the rubber-like polymer 10
It is usually in the range of 1 to 100 parts by weight with respect to 0 parts by weight. If necessary, various fillers such as a filler, a cross-linking agent, a cross-linking aid, a pigment and a stabilizer can be added to the rubber-like polymer composition. The rubbery polymer composition can be prepared according to a conventionally known method.

[Examples] Next, the method for producing the 1-butene random copolymer of the present invention will be specifically described with reference to Examples.

Example 1 (a) Preparation of ethylenebis (indenyl) zirconium dichloride Tetrahydrofuran 100 ml was inserted into a 400 ml glass flask sufficiently replaced with nitrogen and then cooled to -195 ° C. 8.2 g of zirconium tetrachloride was added thereto, and the temperature was gradually raised to room temperature to form a suspension. Lithium salt of bis (indenyl) ethane (ref.J.Organometal.Chem., 232 , 233 (1982)) 35 subsequently dissolved in 80 ml of tetrahydrofuran 35
Mmol was added, and the mixture was stirred at 20 ° C. for 2 hours. Thereafter, hydrogen chloride gas was blown in for a few seconds, and then tetrahydrofuran and hydrogen chloride gas were immediately removed under reduced pressure to obtain a solid. The solid was washed with 10% hydrochloric acid, water, ethanol and diethyl ether and dried under reduced pressure. 4.9 g of ethylenebis (indenyl) zirconium dichloride was obtained.

(B) Preparation of ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride Ethylenebis (indenyl) zirconium dichloride 4.5 synthesized above in the stainless steel autoclave of 1.
After charging g, platinum (IV) oxide 300 mg and dichloromethane 100 ml, hydrogen was introduced to make 100 kg / cm ² · G. 1 at 20 ° C
The hydrogenation reaction was carried out for an hour. The reaction mixture was transferred into 1 dichloromethane, the platinum (IV) oxide was removed and the dichloromethane was removed to give a solid. The solid was washed with petroleum ether and recrystallized with hot toluene to obtain 2.9 g of ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride.

(C) Preparation of Methylaluminoxane MgCl 2 was added to a 2 L glass flask sufficiently purged with argon.
It was charged with ₂ · 6H ₂ O 70g of toluene 625 ml, trimethylaluminum 1.25 diluted after cooling toluene 625 ml to 0 ℃
Mol was added dropwise. After the dropping, raise the temperature to 60 ° C and
The reaction was carried out for 96 hours. After the reaction, solid-liquid separation was performed by filtration, and the separated liquid was used as an aluminoxane solution for polymerization. Toluene was partially removed from the separated liquid to prepare a sample for molecular weight measurement. The molecular weight determined by freezing point depression in benzene was 1570, and the m value of the aluminoxane was 25.

(D) Polymerization 20 liters of purified toluene and 10 kg (179 mol) of 1-butene were added to a stainless steel autoclave having an internal volume of 100 liters which had been sufficiently replaced with nitrogen.
And 315 g (7.5 mol) of propylene were charged at -20 ° C,
Subsequently, methylaluminoxane equivalent to 400 mg of aluminum atom equivalent, and ethylenebis (4,5, equivalent to 0.4 mg of zirconium atom equivalent)
6,7-Tetrahydro-1-indenyl) zirconium dichloride was charged and polymerization was carried out at -20 ° C for 20 hours. Polymerization was stopped by adding a small amount of methanol and unreacted 1-butene and propylene were purged. Further, the catalyst residue was removed with warm water containing a small amount of hydrochloric acid and methanol, and then the polymer solution was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was further washed with methanol and then dried under reduced pressure at 100 ° C. for 24 hours. Thus, 540 g of the copolymer was obtained. The copolymer had a 1-butene content of 94.1 mol% and a [η] of 1.77 as measured by ¹³ C-NMR.
dl / g, w / n determined by GPC is 2.21, melting point Tm measured by DSC analysis is 120 ° C, crystallinity measured by X-ray diffraction method is 55%, boiling methyl acetate soluble content is 0.05% by weight and Acetone-n-decane mixed solvent soluble content 0.10% by weight
Met. The standard deviation σ of the 1-butene content obtained by the composition fractionation method is 0.9 mol%, the yield stress measured according to JIS K7113 is 165 kg / cm ² , and the stress at break is 490 kg.
/ cm ² , elongation at break was 400%. Furthermore, the torsional rigidity was 1500 kg / cm ² , and the Young's modulus was 3200 kg / cm ² . In the ¹³ C-NMR spectrum of the copolymer, no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain was observed.

Examples 2 to 4 and Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the ratio of 1-butene and propylene supplied in the polymerization of Example 1, the polymerization temperature and the polymerization time were changed. In the ¹³ C-NMR spectrum of the copolymer, a signal based on two continuous methylene chains between two adjacent tertiary carbon atoms in the main chain of the copolymer was observed in each copolymer. Was not done. The polymerization results are shown in Table 1.

Example 5 Ethylenebis (indenyl) zirconium dichloride synthesized in the same manner as in Example 1 was converted into zirconium atom.
Example 1 was repeated except that the polymerization was carried out under the conditions shown in Table 1 using 0.50 mg of atom. In the ¹³ C-NMR spectrum of the obtained copolymer, no signal based on two continuous methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain was observed. The polymerization results are shown in Table 1.

Examples 6 to 7 The same procedure as in Example 1 was repeated except that 1-hexene or 4-methyl-1-pentene was used in place of propylene in the polymerization of Example 1 and the polymerization was carried out under the conditions shown in Table 1. It was In the ¹³ C-NMR spectrum of the copolymer, no signal based on two continuous methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain was observed. The polymerization results are shown in Table 1.

Comparative Example 2 1-Butene 5 was added to a stainless steel autoclave with an internal volume of 20 l.
kg (89 mol) and propylene 200 g (4.8 mol) were charged at room temperature, and hydrogen was further introduced so that the hydrogen partial pressure in the polymerization vessel became 1 kg / cm ² . Continued, in terms of aluminum atoms
Diethyl aluminum chloride corresponding to 20 milligram atoms and titanium trichloride (TAC-141 manufactured by Toho Titanium) corresponding to 10 milligram atoms in terms of titanium atoms were charged and polymerization was started. The polymerization was carried out at 60 ° C for 1 hour. The subsequent operation was performed in the same manner as in Example 1. In this way, 640 g of a copolymer was obtained. The physical properties of the copolymer are shown in Table 1.

Example 8 The same result as in Example 6 except that 1-decene was used as the α-olefin, and as a result, the 1-butene content was 97.3 mol%, the intrinsic viscosity was 2.00 dl / g, and the w / n was 2.40. Tm is 100
℃, crystallinity 40%, boiling methyl acetate solubles 0.23% by weight, acetone-n-decane solubles 0.44% by weight, standard deviation 0.3 mol%, yield stress 60kg / cm ² , fracture Point stress 410
kg / cm ² , elongation at break 680%, torsional rigidity 1200kg / c
570 g of a copolymer having m ² and Young's modulus of 1500 kg / cm ² was obtained.

Application Examples 1 to 7 and Comparative Application Examples 1 and 2 Preparation of Polypropylene Composite Film 1-butene random copolymer and crystalline propylene random copolymer (ethylene content 6.5 mol%) obtained in each Example and Comparative Example. , Intrinsic viscosity 2.3dl / g, DSC melting point 135 ℃,
The crystallinity was 52%) and the mixture was melt-mixed at a ratio of 50/50, and the composition was fed to a two-layer film die at a resin temperature of 240 ° C. On the other hand, crystalline polypropylene (base viscosity 3.2dl / g, DSC melting point 162 ° C, crystallinity 65
%) Is melted, supplied to the die at a resin temperature of 240 ° C., and coextruded to form a base layer (40 μ) of the crystalline polypropylene and a layer (10 μ) of the crystalline propylene random copolymer. The formed polypropylene composite film was created. The blocking property, haze, slip property, scratch property and heat seal property of the composite film were evaluated according to the following methods.

(1) Blocking property It was evaluated according to ASTM D1893. A polypropylene composite film was cut into a piece having a width of 10 cm and a length of 15 cm, and the surfaces on which the crystalline propylene random copolymer composition had been laminated were overlapped with each other, and a glass plate having a load of 10 kg was placed between them.
Leave in an air oven at 50 ° C. Samples were taken out after 1 day and 7 days, the peel strength was measured by a universal testing machine, and the peel strength per 1 cm was taken as a blocking value.

(2) Haze The haze of the film formed according to ASTM D1003 was measured before aging in an air oven at 50 ° C., one day after aging, and 7 days after aging.

(3) Slip property The static friction coefficient and the dynamic friction coefficient of the film formed according to ASTM D1894 were measured before aging in an air oven at 50 ° C, one day after aging, and seven days after aging.

(4) Scratch property The surfaces of the polypropylene composite film on which the crystalline propylene random copolymer composition is laminated are overlapped, and rubbed 15 times with a 5 kg iron block as a load, and then the haze of the sample is (1). And the difference (Δ haze) from the haze of the sample before rubbing was determined.

(5) Heat-sealing property The surfaces of the polypropylene composite film on which the crystalline propylene random copolymer composition is laminated are overlapped and heat-sealed at a pressure of ² kg / cm ² at each temperature for 1 second with a seal bar having a width of 5 mm. After that, it was left to cool. A 15 mm wide test piece was cut from this sample and the crosshead speed was 200 mm / min.
Shows the strength when the heat-sealed portion was peeled off. Also,
The polypropylene composite film was allowed to stand in an air atmosphere at 50 ° C. for 1 week, and the value measured by the above method was taken as the heat seal strength after heat treatment.

The evaluation results are shown in Table 2.

Comparative Application Example 3 The same procedure as in Application Examples 1 to 7 and Comparative Application Examples 1 and 2 was repeated except that the 1-butene random copolymer was not used. The heat seal strength was 250.

[Effects of the Invention] As described above, the 1-butene random copolymer of the present invention has a narrow molecular weight distribution and composition distribution, is excellent in transparency, is non-tacky on the surface, and has low crystallinity.

The above copolymer of the present invention is incorporated into a thermoplastic resin to improve various properties of the resin.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08F 210: 00)

Claims (2)

[Claims] 1. A 1-butene component and 3 to 3 carbon atoms.
A 1-butene random copolymer having an α-olefin component other than 1-butene in the range of 12 and having a composition of (A) in which the 1-butene component exceeds 60 mol%.
98 mol% or less and the α-olefin component is in the range of 2 to less than 40 mol%, and (B) the intrinsic viscosity [η] measured in decalin at 135 ° C.
It is in the range of 0.5 to 6 dl / g. (C) Gel permeation chromitography (GP
The molecular weight distribution (w / n) measured in C) is in the range of 3 or less, and (D) the melting point (Tm) measured by a differential scanning calorimeter is 40.
To (E) the crystallinity measured by X-ray diffractometry is 5 to 130 ° C.
60%, (F) Soluble content in boiling methyl acetate [W ₁ % by weight] is 1% by weight or less, (G) Acetone / n-decane mixed solvent at 10 ° C (volume ratio) Soluble content [W ₂ % by weight] in 1/1) is 4 x [η] ^-1.2
In the ¹³ C-NMR spectrum of the copolymer (H), the signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain is in the range of not more than 10% by weight. Not observed, the standard deviation value of the composition distribution of (I) copolymer is in the range of 10 mol% or less, 1-butene random copolymer. 2. A 1-butene component and 3 to 3 carbon atoms.
A 1-butene random copolymer having an α-olefin component other than 1-butene in the range of 12 and having a composition of (A) in which the 1-butene component exceeds 60 mol%.
98 mol% or less and the α-olefin component is in the range of 2 to less than 40 mol%, and (B) the intrinsic viscosity [η] measured in decalin at 135 ° C.
It is in the range of 0.5 to 6 dl / g. (C) Gel permeation chromitography (GP
The molecular weight distribution (w / n) measured in C) is in the range of 3 or less, and (D) the melting point (Tm) measured by a differential scanning calorimeter is 40.
To (E) the crystallinity measured by X-ray diffractometry is 5 to 130 ° C.
60%, (F) Soluble content in boiling methyl acetate [W ₁ % by weight] is 1% by weight or less, (G) Acetone / n-decane mixed solvent at 10 ° C (volume ratio) Soluble content [W ₂ % by weight] in 1/1) is 4 x [η] ^-1.2
In the ¹³ C-NMR spectrum of the copolymer (H), the signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain is in the range of not more than 10% by weight. Not observed, the standard deviation value of the composition distribution of the (I) copolymer is in the range of 10 mol% or less. Improving heat sealability for a thermoplastic resin comprising a 1-butene random copolymer Agent.