JPS62119214A - 1-butene random copolymer and use thereof - Google Patents

Abstract

PURPOSE:To provide the titled copolymer composed of ethylene and 1-butene, having narrow molecular weight distribution and compositional distribution, specific viscosity, melting point, crystallinity, solubility and NMR spectrum and excellent transparency and blocking resistance and useful as a packaging film. etc. CONSTITUTION:Ethylene and 1-butene are copolymerized in the presence of a catalyst composed of an indenyl group-containing zirconium compound and alumino-oxane to obtain the objective copolymer composed of 1-50mol% ethylene component and 50-99mol% 1-butene component, having an intrinsic viscosity [eta] of 0.5-6dl/g measured in decalin at 135 deg.C, a molecular weight distribution (Mw/Mn) of <=3, a melting point of 30-130 deg.C measured by differential scanning calorimeter and a crystallinity of 1-60% measured by X-ray diffraction, containing <=1wt% component soluble in boiling methyl acetate and <=4X[eta]<-1.2>wt% component soluble in acetone/n-decane mixture (1/1 by volume) at 10 deg.C, free from alphabeta and betagamma signals assigned to methylene chain between two adjacent tert-carbon atoms in the main chain measured by <13>C-NMR spectrum and having the B value defined by formula I (PB is molar fraction of 1- butene; PE is molar fraction of ethylene; PBE is molar fraction of dyad chain) falling in the range of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel 1-butene-based random copolymer. More specifically, the molecular weight distribution and composition distribution are narrow;
A 1-butene-based random copolymer with excellent transparency, surface non-adhesiveness, tensile properties and other properties, such as transparency,
The present invention relates to a 1-butene-based random copolymer suitable for forming packaging films, sheet-shaped articles, other molded articles, and other melt-molded articles with excellent blocking properties.

[Conventional technology]

Conventionally, the use of vinyl chloride resin has been advantageous in the field of molding applications for soft or semi-hard resins, but there are problems such as the generation of corrosive gas when incinerating waste and safety concerns regarding residual monomers and plasticizers. It has become desirable to switch from olefin-based soft or semi-rigid resins. Therefore, the demand for α-olefin-based soft copolymers is increasingly expanding in the field of molding or as modifiers for various resins.

The α-olefin-based soft copolymer includes two or more α-olefin-based soft copolymers.
- Copolymers of olefins are generally known, and the method for producing them is to use two or A method of copolymerizing α-olefins larger than this is known. α-olefin-based soft copolymers obtained with titanium-based catalysts generally have poor random copolymerizability;
It has a wide molecular weight distribution and composition distribution, and is poor in transparency, surface non-adhesion, and mechanical properties. In other words, α-olefin soft copolymers obtained using vanadium catalysts generally have an ethylene content of 50 mol% or more, and they have improved randomness compared to copolymers obtained using titanium catalysts. , molecular weight distribution and composition distribution become narrower and transparency;
Although surface non-adhesiveness and mechanical properties are considerably improved, these properties are still insufficient for applications where these properties are strictly required.
Furthermore, there is a demand for soft α-olefin copolymers with improved properties.

Recently, olefin resins that have been used in the field of molding soft or semi-hard resins include:
There are olefin copolymers such as ethylene copolymers, propylene copolymers, and 1-butene copolymers. Among these olefin-based soft/Jj' or semi-hard resins, there are many proposals regarding soft 1-butene-based random copolymers consisting of 1-butene and propylene, which are mainly composed of 1-butene. . Among them, U.S. Patent No. 3,
278,504, U.S. Pat. No. 3,332,92
1 specification, U.S. Patent No. 4.168.361 specification,
British Patent No. 1.01 & 341 discloses a 1-butene-based random copolymer produced using a titanium trichloride or titanium tetrachloride-based catalyst.

However, what these 1-butene-based random copolymers have in common is that boiling methyl acetate solubles and acetone
Since the content of low molecular weight polymer components such as n-decane mixed solvent (volume ratio 1/1) is high, and the composition distribution and molecular weight distribution are wide, it is possible to form from these 1-butene-based random copolymers. Molded objects, especially films and sheets, have high surface tackiness and are prone to blocking. Furthermore, most of them have low randomness and poor transparency, making it impossible to obtain molded products with high commercial value.

U.S. Pat. No. 3.27a504 discloses propylene 1-butene containing 30 to 70 mol%.
Butene copolymers have been proposed.

It is described that the 1-butene-based copolymer is produced using titanium tetrachloride or titanium trichloride, but the copolymer produced using such a catalyst system has a boiling methyl acetate soluble content. It is a soft resin with a content of more than 2% by weight, a large content of acetone/exo-decane mixed solvent (volume ratio 1/1) soluble content, surface tackiness, and poor transparency.

The above-mentioned US Pat. No. 4,332.921 and British Patent No. 1,084,953 also describe various types of 1-2 with different 1-butene contents produced using titanium trichloride catalysts.
Ten-based copolymers have been proposed, and among these copolymers, 1-butene containing 60 to 99 moles of 1-butene is preferred.
The butene-based copolymer is disclosed in the above-mentioned U.S. Patent No. 3.278.504.
It has the same properties as the 1-butene copolymer proposed in the specification.

Further, according to the specification of British Patent No. 1,018,341, a copolymer having a 1-butene content of 25 to 90 mol% is obtained by using a transition metal halide such as titanium trichloride in combination with a phosphoric acid derivative. There is.

Among the copolymers specifically disclosed in this proposal, a 1-butene copolymer with a 1-butene content of 50 to 90 mol% has an acetone soluble content of 1.5%.
Only those with a weight of 9 or above are disclosed. According to the study results of the present inventors, these copolymers have a soluble content of boiling methyl acetate exceeding 2% by weight, and are soluble in acetone/n-decane mixed solvent (volume ratio 1/1). The content of 1-butene-based copolymers is 5×[η]-12% by weight, which means that only molded products with high surface tackiness and poor transparency can be obtained from the 1-butene-based copolymer. Understood.

Furthermore, the aforementioned U.S. Pat. No. 4,168,361 discloses propylene/1-2 tene copolymers having a propylene content in the range of 40 to 90 moles; Among them, the copolymers with a 1-butene content of 50 to 60 mol% also have a high content of soluble components in acetone/n-decane mixed solvent, according to the study conducted by the present inventors. The 1-butene copolymer has a high surface tackiness and only molded articles with poor transparency can be obtained.

On the other hand, a method for obtaining an amorphous random copolymer by polymerizing at high temperature using a titanium trichloride catalyst was disclosed in JP-A-50-38.
This is proposed in Publication No. 787.

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

In addition, the present applicant has found that in %KOKAI Publication No. 54-85298, the composition distribution is narrow, the boiling methyl acetate soluble content is small,
We have proposed a 1-butene/propylene random copolymer mainly composed of 1-butene, which has low surface tackiness. However, the content of low molecular weight components of the 1-butene/propylene copolymer provided by this proposal, especially the content of low molecular weight polymer expressed as boiling methyl acetate soluble content, and molded products made of the copolymer It is clear that the surface adhesion of 1-
Molecular weight distribution of butene-based random copolymer (M w /
M n ) is 6 and is not sufficiently narrow, and it is difficult to understand the low molecular weight polymer component in the copolymer, especially acetone/n-
Decane mixed solvent (volume ratio 1/1) has a higher content of low molecular weight polymer components represented by soluble content, and the 1-butene/glopylene random is added to 4-lipropylene resin to improve impact resistance. Molded products made of resin compositions containing polymers, such as films, have drawbacks such as the tendency for surface tackiness to increase over time. It was still difficult to say that it was sufficient for the purpose. Furthermore, the 1-butene/glosellene random copolymer proposed by this proposal has low crystallinity and poor mechanical properties such as rigidity, making it suitable for applications in fields where these mechanical properties are highly required. However, it was still insufficient.

On the other hand, as a new Ziegler-type olefin polymerization catalyst different from the conventionally known titanium-based catalysts or vanasium-based catalysts, catalysts made of a zirconium compound and aluminoxane are disclosed in JP-A-58-19309 and JP-A-59-1999. 952925, JP 60-35005, JP 60-35006, JP 60-3
This method has been proposed in Japanese Patent Application Laid-open No. 5007 and Japanese Patent Application Laid-Open No. 60-35009, respectively. These prior art documents also exemplify copolymers of two or more α-olefins, such as Example 7 of JP-A-58-19309 and Example 7 of JP-A-60-55006. Ethylene/α-olefin copolymers having an α-olefin content of 5 to 45 mol% are disclosed in Examples 1 to 3, and Examples 10 and 11 of JP-A-60-35007, respectively. but,
All of these ethylene/α-olefin copolymers have wide molecular weight distributions and composition distributions, or are used in fields such as transparency, surface non-adhesion, mechanical properties, and performance as modifiers for thermoplastic resins. are often insufficient depending on the application, and there is a strong demand for soft α-olefin copolymers with improved performance.

[Problem that the invention seeks to solve]

The present inventors discovered that conventional 1-butene-based random copolymers have a wide molecular weight distribution and composition distribution, and a high content of low-molecular-weight polymers. Recognizing that it is inferior in mechanical properties such as non-adhesiveness, transparency, and rigidity, we developed a 1-butene-based random copolymer with improved physical properties compared to conventional 1-butene-based random copolymers. We have been conducting development research with the aim of providing a combination.

As a result, the present inventors have developed a 1-2 ten based random copolymer consisting of a 1-butene component and an ethylene component, and having the 1-butene component as a main component, and which is described below (A) or 1). We have discovered that a 1-butene-based random copolymer, which has not been described in any known literature, can exist and has succeeded in its synthesis.

Furthermore, this new 1-butene-based random copolymer has a narrower molecular weight distribution and composition distribution than conventional 1-butene-based random copolymers, and has a narrower molecular weight distribution and composition distribution than conventional 1-butene-based random copolymers. and a molded article obtained from the 1-butene-based random copolymer, which has a low content of low molecular weight polymer components expressed both in soluble content in acetone/n-decane mixed solvent (volume ratio 1/1). discovered that it has particularly excellent mechanical properties such as surface non-adhesion, transparency, and rigidity.

Therefore, an object of the present invention is to provide a new 1-butene-based random copolymer consisting of 1-butene component and ethylene component as main components, and uses thereof.

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

[Wherein, P represents the molar fraction of the 1-butene component contained in the copolymer, P8 represents the molar fraction of the ethylene component, P is E from 1-butene of all dvad chains Shows the mole fraction of tyrene chains]

This is achieved by a 1-2 ten-based random copolymer characterized in that the B value expressed by % is in the range of the following formula %.

In the 1-butene-based random copolymer of the present invention, the composition CA) of the copolymer has an ethylene component in the range of 1 to 50 mol%, preferably 1 to 40 mol%;
- The content of the butene component is in the range from 50 to 99 mol%, preferably from 60 to 99 mol%. If the content of the 1-butene component in the copolymer is small (50 mol%) and the content of the ethylene component is greater than 50 mol%, the content of low molecular weight components in the copolymer will increase. , transparency, blocking properties, and slitting properties are reduced. Furthermore, when the content of the 1-butene component is greater than 99 mol% and the content of the ethylene component is less than 1 mol%, the transition from type I crystals to type I crystals of the copolymer is slow. As the physical properties of the product change over time, their transparency also deteriorates.

In the 1-butene-based random copolymer of the present invention, 13
The intrinsic viscosity [η] (B) measured in decalin at 5°C is
0.5 to 6 dL/g, preferably 1 to sdl,
It is in the range of Q. This characteristic value is a measure of the molecular weight of the 1-butene-based random copolymer of the present invention, and when combined with other characteristic values, it is useful for providing the above-mentioned random copolymer with excellent properties. There is.

The molecular weight distribution (Mw/un) (C) of the 1-butene-based random copolymer of the present invention determined by permeation chromatography (GPC) is 3 or less, preferably 2.8.
Below, it is particularly preferably in the range of 2.5 or less. The 1-butene-based random copolymer that has been proposed so far is M'
Since the w/J/B value is 3 or more, the molecular weight distribution cannot be said to be sufficiently narrow, and low molecular weight polymer components are mixed9, resulting in poor surface non-adhesion and causing blocking. There is. This characteristic value of the 1-butene-based random copolymer of the present invention, together with other characteristic values, gives the copolymer the above-mentioned excellent properties. Furthermore, Mw/
The Mn value can be measured using the "r Rubermeation Chromatography Jl'lL:" written by Takeuchi and published by Maruzen.

This was done according to the following method.

(1) Standard polystyrene with known molecular weight (Toyo Soda (#
) using monodisperse polystyrene), the molecular weight M and its G
P C (Gel permeation Chrom
ato-grap) count and molecular weight M and E.
A correlation diagram calibration curve of V (Elution Vottbmg) is created. The concentration at this time was 0-0:2 wt%.

(Take a GPC chromatograph of the sample by 210PC measurement, calculate the number average molecular weight Kn and weight average molecular weight Mw in polystere/conversion according to (1) above, and calculate Mw / M' n
Find the value. The sample preparation conditions and GpC measurement conditions at that time are as follows.

[Sample preparation method]

(a) Separate the sample into an Erlenmeyer flask together with O-sochlorobenzene solvent to a concentration of 0.1 wt%.

(b) Add anti-aging agent 2 to the Erlenmeyer flask containing the sample.
0.05 wt% of 6-not-tart-butyl-P-cresol is added to the polymer solution.

(c) Heat the Erlenmeyer flask to 140°C and stir for about 30 minutes to dissolve.

(c) Apply the solution to GpC.

[GPC measurement conditions]

0) Device W (manufactured by LterS (150(:'
-A'LC/GpC) (B) Column Toyo Soda p (OAiH Thai f
) (C) Sampling amount 400μ) Temperature 140℃ (E) Flow rate 1ml/mi? + The melting point (hereinafter sometimes abbreviated as DSC melting point) (D) of the 1-butene-based random copolymer of the present invention measured by a differential scanning calorimeter is 60 to 130°C, preferably 40 to 120°C. within the range of The presence of the DSC melting point is a measure indicating that the copolymer has crystallinity that is distinguishable from conventional amorphous 1-butene-based random copolymers, and together with other characteristic values, This helps to provide the copolymer with the above-mentioned excellent properties. Here, the DSC melting point is 10°C/mi? It is the temperature (Tm) of the maximum endothermic peak obtained by measuring from 20 to 200°C at a heating rate of L.

The crystallinity (E) of the 1-butene-based random copolymer of the present invention as measured by X-ray diffraction is in the range of 1 to 60%, preferably 1 to 55%. This characteristic value is
This is a measure showing that the 1-butene-based random copolymer of the present invention has excellent tensile properties, and together with other property values, it serves to provide the above-mentioned excellent properties to the random copolymer. The crystallinity is determined by the thickness of 1.20 hours after molding.
It was determined by X-ray diffraction measurement of 5 press sheets.

In the 1-butene-based random copolymer of the present invention, the amount of soluble content in boiling methyl acetate [W1 weight (F)] is 1% by weight or less, preferably 0.0% based on the weight of the copolymer.
01 to 0.3% by weight, particularly preferably 0.005 to 0
．． It is in the range of 1% by weight.

This characteristic value indicates the content of the low molecular weight polymer component in the 1-butene-based random copolymer of the present invention, and is a measure indicating the width and narrowness of the composition distribution and molecular weight distribution of the copolymer,
The 1-butene-based random copolymers that have been proposed so far have a large amount of boiling methyl acetate that can be decomposed, resulting in poor surface non-stick properties and high blocking properties. This property value in the 1-butene-based random copolymer of the present invention, together with other property values, serves to provide the copolymer with the above-mentioned excellent properties. In the present invention, the boiling methyl acetate soluble content was measured by the following method. That is,
Put a sample sample of about 1 m x 1 si + x 1 - into a cylindrical glass filter, extract with a Soxhlet extractor for 7 hours with a reflux frequency of about 15 degrees, and make the extracted residue constant in a vacuum dryer (vacuum level 10w5HQ or less). The weight of the sample was determined, and the weight of the boiling methyl acetate soluble content was determined from the weight difference with the original sample. Boiling methyl acetate soluble content [
W1] was determined as the percentage of the weight of the boiling methyl acetate soluble content to the weight of the original sample.

In the 1-butene-based random copolymer of the present invention, 10
Acetone/n-decane mixed solvent (volume ratio 1/
The amount C' of the soluble component in 1) (G) is 4 x -1,2 [η] weight% or less, preferably 0.05 and -1, based on the weight of the copolymer.
2-1,2 [η] to 55×[η] weight%, particularly preferably 0. I X (:η) ~3×[η]-1
-2-1.2% by weight (here, [η] is the value of the intrinsic viscosity of the copolymer, excluding the dimension). This characteristic value is a measure that indicates the content of the low molecular weight polymer component in the 1-butene-based random copolymer of the present invention and indicates the width of the composition distribution and molecular weight distribution of the copolymer. Conventionally known 1-butene-based random copolymers have a large amount of soluble content in the acetone/n-decane mixed solvent, which causes poor surface non-adhesion and high blocking properties. This property value in the 1-butene-based random copolymer of the present invention, together with other property values, serves to provide the copolymer with the above-mentioned excellent properties. In the present invention, the amount of the copolymer soluble in the mixed solvent is determined by the following method. That is, a 1F copolymer sample, 0.0
Add 5P of 2,6-sotart-butyl-4-methylphenol and 50- of n-decane and dissolve on a 120°C oil bath. After dissolution, the mixture is allowed to cool naturally at room temperature for 30 minutes, then 50 g of acetone is added over 50 seconds, and the mixture is cooled on a 10° C. water bath for 60 minutes. The solution containing the precipitated copolymer and the low molecular weight polymer component was filtered and separated using a glass filter, the solution was dried at 10wHQ at 150°C until it reached a constant weight, the weight was measured, and the copolymer was added to the mixed solvent. The soluble content of the polymer was calculated and determined as a percentage of the weight of the sample copolymer. In the above measurement method, stirring was performed continuously from the time of dissolution until just before week F.

In the 1-2 ten-based random copolymer of the present invention, when looking at the arrangement state (H) of the ethylene component and 1-butene component, the "C-NMR spectrum of the copolymer shows that the copolymer main chain αβ and βγ signals based on the methylene chain between two adjacent 5th-class carbon atoms in ethylene are not observed.To explain this more specifically, ethylene and
In a copolymer with butene, the following bond: When viewed from the tertiary carbon on the left derived from 1-butene, the five methylene groups in the center are α and β from the left.

On the other hand, when viewed from the tertiary carbon on the cloth side, they are located at positions α, β, and γ from the right side. Therefore, in the above bonding unit, there are methylene groups that give αγ and ββ signals, but there are no methylene groups that give αβ and βr signals.

Similarly, in the following bond α in which 1-butenes are bonded head-to-tail, there is only a methylene group that gives the αα signal, and there is no methylene group that gives the αβ and βr signals.

On the other hand, the bonds below each have a methylene group giving a βr signal and an αβ signal.

As is clear from the above explanation, it is clear that in the 1-butene-based random copolymer of the present invention, the bonding direction of ethylene and 1-butene is regular. This specification in the 1-butene-based random copolymer of the present invention indicates the arrangement state of the ethylene component and 1-butene component constituting the copolymer, and together with other characteristic values, the above-mentioned It helps give the copolymer excellent properties.

The 1-butene copolymer of the present invention has the following formula (I) 2P
-P P [wherein, P8 represents the molar fraction of the ethylene component in the copolymer, P represents the molar fraction of the 1-butene component, and P represents the 1-butene-ethylene of all dvadE chains. The B value (H) represented by the following formula (2), which represents the mole fraction of the chain, is in a range that satisfies the following formula (2). Furthermore, the B value of the 1-2 ten-based random copolymer of the present invention is determined by the molar fraction of the ethylene component in the copolymer (in relation to pH, preferably the general formula %), more preferably General formula 1, Q + 0.4 X P ≦B≦1/(1-P
F, ), particularly preferably within a range that satisfies the general formula (%).

In the 1-butene-based random copolymer of the present invention, the characteristic value consisting of the B value is an index representing the distribution state of each monomer component in the copolymer chain, and the larger the B value, the fewer block-like chains. This indicates that the copolymer has a uniform distribution of ethylene and 1-butene components, excellent randomness, and a narrow composition distribution. It helps impart properties to the copolymer.

The B value is L, p, Lindgman, Anal,
Chem.

43.1245 (1971) and J, C, Ra%-
dall, Maoromolaculga, i 5
, 353 (1982), each component content pH11 was calculated from PB and PBE.9. P1! ! ,
PB and PBK are IaC-NJiR of the copolymer sample.
Determined from spectrum measurements. That is, the "C-NMR" of a sample in which approximately 200 μ of the copolymer was uniformly dissolved in 1 wLt of hexachlorogetatsuene in a sample tube of 10 IIIφ.
Normally, the measurement temperature is 120°C, the measurement frequency is 25.05MHz, and the spectrum width is 1sooHz.

Filter width 1500Hz, pulse repetition time 4.2
sec, A, n, width 7 p 5ttc, total number of times 2
Measured under the measurement conditions of 000 to 5000 times, and from this spectrum, P1! , PB, PBK were determined.

The 1-butene-based random copolymer of the present invention satisfies the characteristic values specified in (A) to 1) above. A more preferred 1-butene-based random copolymer of the present invention also satisfies at least one of the following characteristic values <1> to 0).

In the 1-butene-based random copolymer of the present invention, JI
Yield point stress measured by the method of S K7113 (
J) is 1 to 200kl? /cri, preferably in the range of 2 to 180kII/d, JISK7113
The stress at break (K) measured by the method of
000 Yu/ffl, preferably in the range of 5 to 800 Yu/d, and the elongation at break (L) measured by the method of JIS K7115 is 50,096 or more, preferably 350
It ranges from 1000% to 1000%.

In the present invention, the characteristic values of the stress at yield point (J), stress at break (K) and elongation at break (L) are determined according to JIS f
It was measured according to the tensile test method of f7113. That is, the sample was molded according to JIS K675B and had a thickness of 111I! A JIS K711302 type test piece punched out from a press sheet after 19 hours of molding was m-, 25
Measurement was performed 20 hours after the press sheet was formed at a tensile speed of 50 m/min in an atmosphere of .degree. When the yield point did not clearly appear, 20% elongation stress was taken as the yield point stress.

JISK67 of the 1-butene-based random copolymer of the present invention
The torsional rigidity (&) measured by the method of No. 45 is for example in the range from 5 to 300 am/cds, preferably from 10 to 2000 to 9/cIl.

JIS K675 is used to measure torsion and rigidity.
Using a rectangular test piece with a length of 64 ys and a width of 635 ys punched 9 days after molding from a press sheet with a thickness of 11I formed in accordance with 8. The value was measured 5 seconds after the load was applied.

In addition, the JIS of the 1-2 ten-based random copolymer of the present invention
Young's modulus (N) measured by the method of K7113
is, for example, 10 to 50001 V/d1, preferably 2
0 to 4000kg/c! It is in the range of l. Furthermore, the Young's modulus (N) of the 1-butene-based random copolymer of the present invention
is preferably expressed by the general formula in relation to the ethylene component content of 6 moles. The Young's modulus was measured by the same tensile test method as in the measurements of (J), (K), and (L) above.

The standard deviation value σ(0) of the 1-butene content of the 1-butene-based random copolymer is 9, for example, 0.4 d mol % or less, preferably α 2 d mol % or less (where d is the 1 - Indicates the mol% content of the ethylene component in the butene-based random copolymer). The standard deviation value σ is a measure showing the randomness of the 1-butene-based random copolymer, and is a measure of the randomness of the 1-butene-based random copolymer. Coalescence shows excellent physical properties. 1- of the present invention
The standard deviation value σ of the butene-based random copolymer was calculated and determined by the following formula based on the composition distribution of the copolymer. The composition distribution of the copolymer was measured using an extraction column fractionation method in which the extraction temperature was changed in steps of 5°C from 0 to 130°C using p-xylene solvent. extracted copolymer sample 102 using p-xylene 21 for 4 hours.

σ= (fo”O(z −z )”/ (z) dr;
]"Here, i indicates the average content (mol%) of 1-butene in the copolymer, 2 indicates the 1-1 content (mol%),
/(Z) indicates the differential weight fraction of the component having the 1-f ten content (mol %).

The 1-butene-based random copolymer of the present invention is characterized in that its physical properties change less over time because crystal transition progresses more rapidly than in a 1-butene homopolymer. On the other hand, for example, 1-butene homopolymer has ss crystal types (I type, ■ type, and ■ type), and it is known that mutual crystal transitions occur as temperature and time change. However, especially at room temperature, the transition from the metastable ■-type crystal form to the stable I-type crystal form is slow, so when applying it to actual molded products, there are concerns such as deformation of the molded product and changes in physical properties over time. It had many drawbacks, including various difficulties.

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

The 1-butene-based random copolymer of the present invention has a lower molecular weight polymer component content than conventionally known ethylene/1-butene-based random copolymers in the entire range of 1-butene component content. It has the characteristics of low viscosity, excellent transparency, excellent surface non-adhesiveness, and excellent rigidity and other mechanical properties.

The 1-butene-based random copolymer of the present invention combines a predetermined amount of ethylene and 1-butene in a form in which (A) at least two indenyl, substituted indenyl groups, or partially hydrogenated products thereof are bonded via ethylene. It can be produced by polymerization in the presence of a catalyst consisting of a turconium compound having a group as a ligand and (73) aluminoxane.

Examples of the above-mentioned zirconium compounds include ethylenebis(indenyl)dimethylturconium, ethylenebis(indenyl)dimethylturconium, and ethylenebis(indenyl)dimethylturconium.
indenyl)noethyl sorbonium, ethylenebis(indenyl)sobuenylsolconium, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)ethylzirconium monochloride,
Ethylenebis(indenyl)methylturconium monopromide, ethylenebis(indenyl)zirconium chloride, ethylenebis(indenyl)zirconium sopromide, ethylenebis(4,5,6゜7-tetrahydro-1-indenyl)tumethyl Zirconium, ethylenebis(a*5t6r7-tetrahydro-1-indenyl)
Methylzirconium monochloride, ethylene bis(4,
5,6,7-ftrahydro-1-indenyl)zolconium chloride, ethylenebis(415t6t7--F
-trahydro-1-indenyl) zirconium sopromide, ethylenebis(4-methyl-1-indenyl)turconium chloride, ethylenebis(5-methyl-1-indenyl)zirconium sopromide,
indenyl) zirconium chloride, ethylenebis(
6-methyl-1-indenyl) zirconium chloride, ethylenebis(7-methyl-1-indenyl)zorconium chloride, ethylenebis(5-methoxy-1-
indenyl) zirconium chloride, ethylenebis(
2,3-methyl-1-indenyl)zolconium chloride, ethylenebis(4,7-somethyl-1-indenyl)zolconiumchloride, ethylenebis(1,7
-somesoxy-1-indenyl) zirconium dichloride and the like.

Specifically, the aluminum/oxane (B) as a catalyst component used in the method of the present invention has the general formula [I] or the general formula [11] R2^1i0^1←O-^IR2[111B (in the formula , R represents a hydrocarbon group, and l represents a number of 2 or more, preferably 20 or more, particularly preferably 25 or more). In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, 1 is an integer of 2 or more, It is preferably a number 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) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate,
A method in which trialkyl aluminum is added to a suspension in a hydrocarbon medium such as aluminum sulfate hydrate and reacted.

(2) A method in which water is allowed to act directly on trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydro7ran.

Among these methods, method (1) is preferably employed. Note that the aluminoxane may contain a small amount of organometallic component.

In the present invention, we have discovered that by producing a copolymer of 1-butene and ethylene in a specific ratio using the catalyst system described above, a copolymer with properties never proposed before can be obtained. It is something that

The copolymerization of 1-butene and ethylene can be carried out in either the liquid phase or the gas phase, but it is particularly preferable to carry out the copolymerization in the 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, methylcyclobencune, cyclohexane, and cyclooctane; benzene; Aromatic hydrocarbons such as toluene and xylene; petroleum distillates such as gasoline, kerosene, and light oil; and olefins as raw materials can also be used as hydrocarbon media. Among these hydrocarbon media, aromatic hydrocarbons are preferred.

The proportion of the zirconium compound used when carrying out the method of the present invention in the 1-butene liquid phase polymerization method is usually 10-7 to 1 in terms of the concentration of zirconium metal atoms in the polymerization reaction system.
0-2 gram atom/l, preferably in the range of 10''G to 10-3 gram atom/l. Also,
The proportion of aluminoxane used is usually 10''4 to 10% as the concentration of aluminum atoms in the polymerization reaction system.
−'Durham atom/! , preferably 10-3 to 5X1
The amount is in the range of 0-2 gram atoms/l, and the ratio of aluminum atoms to turconium metal atoms in the polymerization reaction system is usually in the range of 20 to 106, preferably 50 to 105.

The copolymerization of the present invention can be carried out in the same manner as the polymerization of olefins using a conventional Nagler type catalyst.

The copolymerization temperature is usually selected within the range of -80 to 50, preferably -60 to 3().

Further, the polymerization is preferably carried out under pressure, usually normal pressure to 30 kg/0 m2, preferably 2 to 15 kg/0 m2.
The raw material supplied to the polymerization reaction system, which is preferably carried out under a pressure of about kg/cm2, is a mixture of 1-butene and ethylene. The content of 1-butene in the combined raw material olefin is usually 60 to 99.9 mol%, preferably 70 to 99.8 mol%, and the ethylene content is usually 0.1 to 40 mol%, preferably 0.2 to 2
It is in the range of 0 mol%. The molecular weight of the copolymer can be adjusted by adjusting the hydrogen and/or 2fi temperature, and further by changing the proportion of catalyst components used.

The 1-butene-based random copolymer of the present invention is different from conventionally proposed copolymers in that it is non-sticky and has various other properties as described above. This 1-butene-based random copolymer can be molded into pipes, films, sheets, hollow containers, and various other products by any molding method such as extrusion molding, injection molding, press molding, and vacuum forming.
It can be used for various purposes. It is suitable as a packaging film because it has particularly good blocking resistance and heat sealability. Due to the above properties, it can also be suitably used as a protective film for metals and the like.

Furthermore, since the yield point stress is large, it is also suitable for use as a hot water pipe.

During molding, various stabilizers, antioxidants, ultraviolet absorbers,
Antistatic agents, lubricants, plasticizers, pigments, inorganic or organic fillers can be incorporated, examples of which include 2.6
-NoLert-butyl-p-cresol, tetrakis[methylene-3-(3,5-:/-terL 7'thyl-4-hydroxyphenyl)frobionate J methane, 4,4'-butylidenebis(6Lert-butyl- -cresol), tocopherols, ascorbic acid,
Norauryl thiodibrobionate, phosphate stabilizer, I
II? Fatty acid moaglyceride, 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, lath M&fiber, titania, calcium carbonate, carbon black, petroleum resin, polybutene, wax, synthetic or natural rubber, etc. may be used.

In addition, the 1-butene-based random copolymer of the present invention improves impact resistance, low-temperature impact resistance, -1 flexibility, and low-temperature heat sealability by blending it into various thermoplastic resins as a modifier. can do. Examples of the thermoplastic resin include other ethylene polymers containing ethylene as a main component, crystalline olefin polymers other than the ethylene polymers, and engineering resins.

By blending the 1-butene-based random copolymer of the present invention with other ethylene-based polymers containing ethylene as a main component, such as polyethylene, the impact resistance and low-temperature resistance of molded products of the ethylene-based polymer can be improved. It becomes possible to improve impact resistance, bending resistance, and low-temperature heat sealability. Other ethylene 1 polymers mentioned above include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and propylene, i-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, -Dodecene, 1
- Carbons such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. 1f5JK number of molecules is 3 to 2
Examples include ethylene-based copolymers containing ethylene as a main component, which are copolymers with α-olefin of 0. Its intrinsic viscosity [η], measured in decalin at 135° C., is usually in the range of 5 to 20 dIl/g.

When the 1-butene-based random copolymer of the present invention is blended with the ethylene-based polymer of the original material, the blending ratio is usually 1 to 100 parts by weight, preferably 2 parts by weight, per 100 weight ITtlflS of the ethylene-based polymer of the pond. and 60 parts by weight. The obtained ethylene polymer composition contains an antioxidant, a hydrochloric acid absorber, an anti-aggregation agent, a heat stabilizer, an ultraviolet M absorber, a lubricant, a weather stabilizer, an antistatic agent, a nucleating agent, and a pigment, as necessary. It is also possible to mix various additives such as , Hikari, and so on.

The mixing ratio is appropriate. The ethylene polymer composition can be prepared according to conventionally known methods.

In addition, by blending the 1-butene-based random copolymer of the present invention with a crystalline olefin-based polymer other than the other ethylene-based polymer, it is possible to improve the impact resistance of a molded product made of the crystalline olefin-based polymer. In particular, it is possible to improve the low-temperature RRTR impact resistance, and furthermore, a film with well-balanced blocking resistance, transparency, and slip property can be obtained. Examples of the crystalline olefin M polymer other than the ethylene polymer include polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and propylene/ethylene copolymer. , 1-butene copolymer with propylene, 1-butene-propylene copolymer, etc., α-olefins (IT) such as propylene, 1-butene, 1-hexene, etc. and ethylene, propylene, 1-butene,
1-hexene, 4-methyl-1-pentene, ]-octene, 1-decene, 1-tothiene, 1-tetradecene,
A crystalline a-olefin consisting of an α-olefin (a2) having 2 to 20 carbon atoms such as 1-hexadecene, 1-octadecene, and 1-eicosene, which is different from the α-olefin (al). Examples include olefin copolymers. The intrinsic viscosity of the crystalline olefin polymer measured in decalin at 135°C [ηJ
is usually in the range of 0.5 to 10 dIl/g, and the crystallinity is 5% or more, preferably 2()% 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°O overlapped portion of the crystalline α-olefin polymer. It ranges from 1 to 100 parts by weight, preferably from 2 to 60 parts by weight. The crystalline α-olefin PS polymer composition may optionally contain an antioxidant, a hydrochloric acid absorber, an anti-aggregation agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer,
Various additives such as antistatic agents, nucleating agents, pigments, and light absorbers can also be blended. The crystalline α-olefin polymer composition can be prepared according to conventionally known methods.

Furthermore, the 1-butene-based random copolymer of the present invention can be blended with various engineering resins to achieve the engineering + Ai IJk? The physical properties of the material, such as impact resistance and sliding properties, can be improved.

When the engineering resin is an engineering resin having a polar group, in order to improve the affinity or dispersibility for the engineering resin, 1-
Butene-based random copolymer contains maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride,
It is preferable to use a modified ethylene-based random copolymer obtained by copolymerizing an unsaturated carboxylic acid such as itaconic anhydride, dimethyl maleate, dimethyl citraconate, or dimethyl itaconate, or a derivative component of Hososhi.

The proportion of the unsaturated nocarboxylic acid or its derivative component is usually in the range of 0.02 to 50 parts by weight based on 100 parts by weight of the 1-1-butene type copolymer.

Specific examples of engineering resins include polyesters such as polyethylene terephthalate and polybutylene tere-7grate, hexamenalene anopamide, octamenalene anopamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactam, etc. polyamide, polyarylene oxide such as polyphenylene oxide, polyacetal, ABS, AES.

Examples include polycarbonate.

The blending ratio of the 1-butene-based random copolymer* or its modified product is usually in the range of 0.2 to 20 parts by weight per 100 parts by weight of the engineering resin. The engineering resin composition may optionally contain an antioxidant, a hydrochloric acid absorber, an anti-aggregation agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, a nucleating agent, a pigment, a photonic agent, etc. Various additives can be blended. The engineering T14 fat composition can also be prepared according to conventionally known methods.

The 1-butene-based random copolymer of the present invention can be blended with various rubber-like polymers to improve the physical properties of the rubber-like polymers, such as chemical resistance and rigidity.

Specifically, the rubbery polymer includes, for example, ethylene.
Examples include propylene/non-conjugated diene copolymer, ethylene/1-butene/non-conjugated diene copolymer, polybutanoene rubber, polyisoprene rubber, and styrene/butadiene styrene block copolymer. Wear. Part 1-
The blending ratio of the butene-based random copolymer is usually in the range of 1 to 10 parts by weight per 100 parts by weight of the rubbery polymer. Various fillers such as a filler, a crosslinking agent, a crosslinking aid, a pigment, and a stabilizer can be added to the rubbery polymer composition as required. The rubbery polymer composition can be prepared according to conventionally known methods.

[Example] Example 1 (,) Ethylenebis(indenyl)norconium dichloride was poured into a 400 ml fluoride tank sufficiently purged with nitrogen! ! After inserting 100 ml of tetrahydrofuran into Fusco 7, it was 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. Subsequently, the lithium salt of bis(indenyl)ethane (ref, J
, Organometal, Chew, , 232.2
33 (1982)) and stirred for 2 hours at 20"C. After that, hydrogen chloride gas was blown into the mixture for a few seconds, and the tetrahydro7rane and hydrogen chloride gas were immediately removed under reduced pressure to obtain a solid. The residue was washed with 10% hydrochloric acid, water, ethanol and diethyl ether, and dried under reduced pressure.4.9 g of ethylene bis(inchenyl)zirconium dichloride was obtained.

(11) Preparation of ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium chloride Ethylene bis(indenyl) zirconium chloride 4 synthesized above in the stainless steel autoclave of 11
*After charging 300 mg of 5 g s platinum (IV) oxide and 100 ml of dichloromethane, hydrogen was introduced and the temperature was 1,000 ml.
kH/cm2G. After the hydrogenation reaction was carried out at 20° C. for 1 hour, the reaction mixture was transferred into dichloromethane (11), and the platinum (IV) oxide was separated from the furnace, and the dichloromethane was removed to obtain a solid.

After washing this solid with petroleum ether, it was recrystallized with hot toluene to obtain ethylene bis(415°6 + 7
7.9 g of trahi-r-lo-1-indenyl)norconium chloride 2 was obtained.

(e) MgC1z61 was placed in a flask made of stainless steel, with the pores of methylaluminoxane sufficiently replaced with argon.
After cooling to 0° C., 1.25 mol of trimethylaluminum diluted with 625 IIll of toluene was added dropwise.

After the addition was completed, the temperature was raised to 60° C. and the reaction was continued at that temperature for 96 hours. After the reaction, solid-liquid separation was performed by filtration, and the separated liquid was used for polymerization as an aluminoxane solution. Molecule excluding toluene from some separated liquid! i (used as a sample for measurement. Molecular weight determined by coagulation in benzene and gel precipitation was 15
70, and the m value of the aluminum 7 oxane was 25.

(d) Purified toluene 201,1-butene 10kg was placed in a stainless steel autoclave with an internal volume of 1001, which was sufficiently purged with nitrogen.
(179 moles) and 560 g (20 moles) of ethylene were charged at -20°C, followed by methylaluminoxane, which is equivalent to 400 milligram atoms in terms of aluminum raw r-, and 0.4 milligram atoms in terms of zirconium X+a atoms. Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)norconium chloride was charged and polymerization was carried out at -20°C for 15 hours. It's T. Polymerization was stopped by adding a small amount of methanol to remove unreacted 1-butene and ethylene. Further, the catalyst residue was removed with warm water containing a small amount of hydrochloric acid and methanol, and then the polymerization solution was poured into a large amount of methanol to precipitate a polymer. After further washing the precipitated polymer with methanol, 1 (
61 was dried under reduced pressure overnight at O'C.
0 g of copolymer was obtained. "1-Butene content of the copolymer measured by C-NMI (81.8 mol%, G
tl”iu/Mn1i2 obtained from PC, 31, DS
(The melting temperature measured by four folds, -χ'rl11, is 91℃,
Crystallinity measured by line diffraction method is 14%, B value is 1
．． 16, [ri] is 2.32 dl/, boiling #acid methyl soluble content is 0.03% by weight and acetone/n/decane mixed solvent soluble content is 0.40% by weight "II" 7) Ivy Mata, JIS K7113i: Yield point stress measured according to 30 kg/am2, breaking point stress 140 kg/cm
”, the elongation at break was 710%.Furthermore, the torsional rigidity was 210kH/cm2, and the Young's modulus was 500k@/
Cm', the C1 deviation value σ of the 1-butene content is 1.
It was 5%. *The resulting polymer (l”C-N
αβ for MR spectrum.

No signal based on βγ was observed.

Examples 2 to 4, Comparative Examples 1 to 2 Polymerization was carried out in the same manner as in Example 1, except that the FN polymerization of 1-butene and ethylene supplied in the polymerization of Example], the polymerization temperature, and the polymerization time were changed. of the obtained copolymer
No signals based on αβ or βγ were observed in the C-NMR spectrum.

The polymerization results are shown in Table 1.

Example 5 Same as Example 1 except that ethylenebis(indenyl)zirconium chloride synthesized in the same manner as in Example 1 was used with 0.45 μIJ gram atom in terms of zirconium atom, and the polymerization time was set to 0 hours. Polymerization was carried out in the same manner. The 13cm NMR spectrum of the obtained copolymer shows αβ, βγ.
No signal was observed. Table 1 shows the polymerization results.
Shown below.

Comparative Example 3 1-butene 5 kg (s9 moles) and ethylene 40 g (1°4 moles) were placed in a stainless steel autoclave with an internal volume of 201 cm.
and hydrogen2. :(g (1,2 mol) was charged at room temperature,
Subsequently, noethylaluminum chloride corresponding to 20 milligram atoms in terms of aluminum atoms and titanium trichloride (TAC-131, manufactured by Toho Titanium Co., Ltd.) corresponding to 10 milligram atoms in terms of titanium atoms were charged to initiate polymerization. Polymerization was carried out at 70°C for 1 hour. The subsequent operations were carried out in the same manner as in Example 1. Strain this and 750g
A copolymer was obtained. Table 1 shows the physical properties of the copolymer.

Application Examples 1 to 5, Comparative Application Examples 1 to 3 The 1-butene-based random copolymer obtained in each Example and Comparative Example and polypropylene ([riJ=2.1di/g,
(ethylene content: 1.9 mol%) were melt-mixed in a ratio of 25/75, and then a 30 μm thick 'r-Gui film with a molding temperature of 200-250°c't' was prepared using a 30+ueφ extruder.

(1) Evaluation of blocking properties The above films were evaluated according to ASTM D1893.9 Films of 10 cm width and 15 clI length were stacked on top of each other, and a load of 10 kg was placed on them using two sheets of glue with scissors.
Place in an air oven at 50°C.

The sample was taken out after 1 day and after 7 days, and the peeling strength was measured using a universal testing wk machine, and the peeling strength per 3 cm was taken as the blocking value.

(2) Transparency The above film was exposed to 50'C air open for 21 minutes, and the film was evaluated as As'r M D before aging, after 1 day of aging, and after 1 day of aging.
1003 611: Haze was measured according to the same method.

(3) Slip property ΔS 1"M l) The static friction coefficient and dynamic friction coefficient of the film were measured before knee-song, 1 day after knee-song, and 70 days after knee-song, according to 18', 34. Above (1)
The results of ~(3) are shown in 1 & 2.

1. Effects of the Invention J As described above, the 1-butene-based Hungum copolymer of the present invention has a narrow molecular weight distribution and composition distribution, excellent transparency, surface non-adhesion, and low crystallinity.

The above-mentioned copolymer of the present invention is characterized by various properties of the thermoplastic resin by blending it with the resin. Patent Applicant: Mitsui Petrochemical Industries, Ltd. 1.7 - Two Idiots

Claims (1)

[Scope of Claims] 1. A 1-butene-based random copolymer consisting of an ethylene component and a 1-butene component, wherein (A) the composition is such that the ethylene component is 1 to 50 mol%;
and 1-butene component is in the range of 50 to 99 mol%, (B) intrinsic viscosity [η] measured at 135°C in decalin
is in the range of 0.5 to 6 dl/g, and (C) gel permeation chromatography (GP
The molecular weight distribution (@M@w/@M@n) measured in C) is 3
(D) The melting point [Tm] measured by differential scanning calorimeter is in the range of 30 to 130°C; (E) The degree of crystallinity is 1 to 1 as measured by X-ray diffraction. 60%, (F) the amount of soluble matter in boiling methyl acetate [W_1% by weight] is in the range of 1% by weight or less, (G) the acetone/n-decane mixed solvent at 10°C (
The amount of soluble matter [W_2 weight%] to volume ratio 1/1) is 4× [
η〕＾−＾1＾. (H) αβ and βγ based on methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain in the ^1^3C-NMR spectrum of the copolymer. (I) General formula B≡P_B_E/(2P_B・P_E)
[In the formula, P_B represents the molar fraction of the 1-butene component contained in the copolymer, P_E represents the molar fraction of the ethylene component, and P_B_E is the total dyad
A 1-butene-based random copolymer characterized in that a B value represented by the following formula, 1.00≦B≦2, is in the range of 1.00≦B≦2. 2. (A) Its composition is in the range of 1 to 50 mol% of ethylene component and 50 to 99 mol% of 1-butene component, (B) Intrinsic viscosity [η] measured at 135 ° C. in decalin
is in the range of 0.5 to 6 dl/g, and (C) gel permeation chromatography (GP
The molecular weight distribution (@M@w/@M@n) measured in C) is 3
(D) Melting point [Tm] measured by differential scanning calorimeter is in the range of 30 to 130°C; (E) Crystallinity measured by X-ray diffraction is 1 to 60% (F) The amount soluble in boiling methyl acetate [W_1% by weight] is within the range of 1% by weight or less, (G) The acetone/n-decane mixed solvent at 10°C (
The amount of soluble matter [W_2 weight%] to volume ratio 1/1) is 4× [
η〕＾−＾1＾. (H) αβ and βγ based on methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain in the ^1^3C-NMR spectrum of the copolymer. (I) General formula B≡P_B_E/(2P_BP_E)
In the formula, P_B represents the molar fraction of the 1-butene component in the copolymer, P_E represents the molar fraction of the ethylene component, and P_B_E is the molar fraction of the 1-butene-ethylene chain in all dyad chains. A compounding agent for a thermoplastic resin comprising a 1-butene-based random copolymer comprising an ethylene component and a 1-butene component and having a B value expressed by the following formula: 1.00≦B≦2.