JPH02145611A - Propylene random copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer comprising propylene and a specific diene as essential components, containing an unsaturated carbon bond, having high reactively, having low raw material cost and catalyst cost, by using a Ziegler type high stereoregular polymerization catalyst. CONSTITUTION:Raw materials are copolymerized in the presence of a Ziegler type high stereoregular polymerization catalyst comprising 84-99.5mol% unit shown by formula I, 0-15mol% unit shown by formula II and 0.5-15mol% unit shown by formula III (one of R<a> and R<b> is H and the other is methyl) to give the aimed copolymer having 0.01-200g/10 minutes melt flow rate and >=10% crystallinity by X-ray diffraction method. The copolymer is preferably obtained by copolymerizing propylene with 7-methyl-1,6-octadiene and, if necessary, ethylene at 50-80 deg.C polymerization temperature under 1-50kg/cm<2>G polymerization pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Field of Application The present invention relates to new random I-polymers based on propylene. More specifically, the present invention aims to eliminate unsaturated carbon bonds containing propylene and a specific diene as essential components.
This invention relates to a random copolymer.

It is well known that propylene homopolymers and copolymers (hereinafter collectively referred to as propylene polymers) are being developed for use in a wide range of fields due to their excellent properties. It is as follows.

On the other hand, since these polymers are essentially saturated hydrocarbons, they have poor chemical reactivity and are limited in graft reactions and crosslinking reactions, and they also have poor stone contact and paintability mainly due to their polar groups. It is also known that there is a problem that printability is significantly inferior.

Various inventions have been proposed with the aim of solving these problems, but among them, one that is considered to be particularly closely related to the present invention is Japanese Patent Application Laid-Open No. 55-1659.
No. 07, JP-A-56-30414, JP-A-56-36
No. 508, JP-A-62-115007, JP-A-62-
115008 and other publications. These inventions relate to copolymerization of propylene and 1,4-diene, and this copolymer has attracted attention as a reactive polypropylene because it has an unsaturated double bond in its side chain.

However, as far as the present inventors know, these inventions require the use of large amounts of expensive 1,4-diene compounds because the copolymerizability of 1,4-dienes is not necessarily high. In addition, since it is necessary to charge a large amount of a 1,4-diene compound with low reactivity into the polymerization system, the amount of copolymer produced (i.e., catalyst activity) relative to the amount of catalyst used is
However, there is a problem that the catalyst cost tends to be high.

[Summary of the invention]

Summary The present invention aims to provide a solution to these problems, and attempts to achieve this objective by providing a copolymer of propylene and a specific branched diene. .

Therefore, the propylene random copolymer according to the present invention is
It is characterized by being defined by the following (1) to (4).

(1) It must be obtained by copolymerization in the presence of a Ziegler type highly stereoregular polymerization catalyst.

(2) Melt flow rate is 0.01 to 200g/10
be minute.

(3) Crystallinity as determined by X-ray diffraction method is 20% or more.

(4) Consists of the following repeating units (1) to (III), each with a content of (1) 84 to 99.5 mol%, (■
)0 to 15 mol%, and (I[r) 0. 5-15
mole%.

(III) Effect The resin obtained by the present invention can be widely applied by taking advantage of its reactivity. For example, it can be printed on paintable exterior or interior parts of automobiles and home appliances, their skin materials, and surfaces. It is applied to containers such as bottles, films, and sheets, packaging materials, crosslinked foams, heat-resistant wire coatings, and reinforcing materials for rubber products, as well as to the introduction of various functional groups and polymer grafting.

[Detailed description of the invention]

1. Polymerization Catalyst The propylene random copolymer according to the present invention is obtained by copolymerization in the presence of a Ziegler type highly stereoregular polymerization catalyst. In the present invention, for example, the Ziegler type highly stereoregular polymerization catalyst may be one formed from a reduced highly active titanium trichloride composition and a dialkyl aluminum halide, or one formed from a reduced highly active titanium trichloride composition and a dialkyl aluminum halide, or a catalyst containing titanium, magnesium, halogen, and an electron donor as essential components. A catalyst formed from a solid titanium catalyst component and an organoaluminum compound can be used. A preferred example of a highly active titanium trichloride composition used as a component of the former Ziegler-type highly stereoregular polymerization catalyst is, for example, one in which titanium tetrachloride is reduced with an H-organic aluminum compound and then treated with a complexing agent. Furthermore, it is precipitated from titanium trichloride liquefied with a complexing agent, which is activated by heat treatment, pulverization treatment, or chemical treatment with a Lewis acid such as titanium tetrachloride. Examples include those activated by processing.

Regarding such reduced type highly active titanium trichloride compositions, JP-A-47-34478, JP-A-48-64170, JP-A-51-151787, JP-A-52-40348, JP-A-52-138083, JP-A-52 -499% issue, same 52-
140922 and 52-14092 can be used as they are or with appropriate modification.

Examples of dialkyl aluminum halides include diethyl aluminum chloride, diisobutyl aluminum chloride, di-n-propylaluminum chloride, di-n-hexyl aluminum chloride, and the like.

In addition to these two components, various compounds can be added to this catalyst as a third component for various purposes, for example, to improve stereoregularity. Examples of such compounds include ethers, amines, ketones, carboxylic acid esters, carboxylic acid amides, trialkylphosphines, triarylphosphines, triarylphosphites, phosphoric acid amides, and silicic acid. Electron donors such as esters are preferred.

On the other hand, the solid titanium catalyst component comprising titanium, magnesium, halogen, and an electron donor as essential components constituting the latter catalyst is disclosed in JP-A-59-80406;
145206, 61197607, 61-2042
02, 61211312, 61-213207, 61-213210, 61-213211, 61-
254610, 61-266413, 612713
04, 62-72702, 62], 87706,
62-187707, 62236805, 62-
236806, 62-246906, 62-257
906, 62297303, 63-39901, 63-83105, 63-89513, 63-92
615, 63-97605, 63-156806,
The catalyst components described in each publication of No. 63 156807 are preferred.

Hydrocarbon residue or hydrogen having about 1 to 20 carbon atoms, R5 is the same as R4 or a hydrocarbon residue having about 1 to 20 carbon atoms that may be different, X is a halogen, and n and m are each 0≦n≦2.0≦m≦1
is the number of ). Specific examples include:
(a) Trialkylaluminum, such as triethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc.; (b) Alkylaluminum halide, such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethyl Aluminum sesquichloride, ethylaluminum dichloride, etc., (c) dialkylaluminum hydride, such as diethylaluminum hydride, diisobutylaluminum hydride, etc., (d) alkylaluminum alkoxide, such as diethylaluminum ethoxide, diethylaluminum butoxide, diethylaluminum phenoxide, etc. It will be done.

These organoaluminum compounds (a) to (c) and other organometallic compounds, for example R8, are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different. ) can also be used in combination with an alkyl aluminum alkoxide. for example,
A combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum jetoxide, a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride Can be used in combination. The amount of these organometallic compounds to be used is not particularly limited, but the weight ratio to the solid catalyst component is 0. It is preferably within the range of 5 to 1000. To improve the stereoregularity of the polymer, ether, ester,
An electron donating compound such as an amine can also be added and coexisting.

2. Production of random copolymer Propylene and 6-methyl-
The random copolymer of the present invention can be obtained by mixing and contacting 1,6-octadiene or 7-methyl-1,6-octadiene (hereinafter abbreviated as branched 1,6-diene) and, if necessary, ethylene. . The amount ratio of each monomer in the system does not need to be constant over time; it is convenient to supply each monomer at a constant mixing ratio, or it is also possible to change the mixing ratio of monomers to be supplied over time. It is possible. Further, in consideration of the copolymerization reaction ratio, any monomer, especially branched 1,6-dienes, can be added in portions.

The branched 1,6-dienes can be used by being supplied into the system as one kind or a mixture of two kinds of 6-methyl-1.6-octadiene and 7-methyl-16-octadiene. Especially when controlling reactivity, If! Branch 1 of class I
,6-diene is preferably used, 7-methyl-
1,6-octadiene is particularly preferred.

Any polymerization mode may be used as long as the catalyst component and each monomer are brought into efficient contact with each other. Specifically, the slurry method uses an inert solvent, the slurry method uses propylene and branched 1,6-dienes as solvents without substantially using an inert solvent, or the slurry method uses substantially no liquid solvent and uses each monomer. A gas phase method that maintains the substance in a substantially gaseous state can be adopted.

The polymerization conditions are not necessarily the same depending on the process employed, but generally the polymerization temperature is 30 to 150°C, preferably 40 to 100°C, particularly preferably 50 to 80°C,
The polymerization pressure is 0 to 90 kg/cdG, preferably 0 to 60 kg/cdG, particularly preferably 1 to 60 kg/cdG.
50kg/c♂61 is appropriate.

It is also preferable to use a catalyst in which propylene has been polymerized with 111 in advance before copolymerization for the purpose of improving activity, reducing solvent-soluble by-product polymers, or preventing a drop in melting point. At this time, the proportion of propylene 1114 homopolymerized parts in the total copolymer is usually 10 or less, preferably 5% by weight or less, and the product polymer is based on the propylene homopolymer (DSC). It is preferable that the peak is not observed.

In this case, the polymerization temperature during propylene homopolymerization is generally equal to or lower than the temperature of the subsequent copolymerization. Therefore, the temperature during propylene homopolymerization is 0 to 70°C, preferably 5 to 50°C. The pressure is usually normal pressure to 20 kg/c4G, preferably normal pressure to 5 kg/cJG.

However, it is not necessarily limited to this as long as the ratio of the propylene homopolymerized portion to the target copolymer is within the above-mentioned predetermined range.

The molecular weight of the copolymer can be controlled by adding hydrogen into the polymerization system.

3. Copolymer (1) Composition The copolymer obtained by the present invention is a random copolymer, and (1) the propylene-derived recycled H3 content is 84 to 99.5 mol%, preferably 87 to 99.5 mol%. 5 mol%, (■) ethylene-derived repeating unit, i.e. -
←CH2-CH2→- is 0 to 15 mol 5'6, preferably 0 to 8 mol%, and (III) repeating units derived from branched 1,6-diene, that is, CH3 is 0. 5-15 mol%, preferably 0.5-8 mol%
, and. Here, "consisting of" means
This indicates that purposeful other components or other components that inevitably coexist with each other other than the above three components may be included. Also,
Since the copolymer according to the present invention is a random copolymer,
The repeat +B positions (1) to (III) are randomly (that is, randomly) arranged.

If the proportion of propylene units is less than 84 mol %, the crystallinity will be too low, resulting in a rubbery substance, which is not preferable. On the other hand, if this (11-position) exceeds 99.5 mol%, the content of branched 1,6-diene units becomes too low, and the reactivity based on the side chain unsaturated bond intended by the present invention cannot be sufficiently exhibited. .

When the branched 1,6-diene unit contains both 6-methyl-1,6-octadiene and 7-methyl-1,6-octadiene units, it appears as the sum of both units. Branch 1,
If the 6-diene unit content is less than 0.5 mol %, sufficient reactivity cannot be obtained for the same reason as above. On the other hand, 15 mol%
Exceeding this is not preferable because the crystallinity decreases too much.

In the present invention, ethylene units are optionally introduced as necessary for the purpose of adjusting or improving the physical properties required of the copolymer, such as transparency, flexibility, and melting point, depending on the use of the copolymer. be.

Therefore, the ethylene unit aljA is used for the copolymer,
Decisions will be made as appropriate depending on other circumstances. However, if the ethylene unit content exceeds 15 mol %, a copolymer with satisfactory crystallinity cannot usually be obtained.

Therefore, the preferred composition is 87 to 99 propylene units.
．． 5 mol%, ethylene units 0-8 mol%, branched 1,6
- 065 to 8 mol % of diene units, particularly preferably 90 to 99 mol % of propylene units, 0.5 to 6 mol % of ethylene units, and 1 to 6 mol % of branched 1,6-diene units.
It is mole%. (2) Molecular weight The molecular weight of the copolymer of the present invention is determined by a melt flow rate (M F R) of 0.01 to 200 g measured at 230°C and a load of 2.16 kg in accordance with JIS K6758.
/10 minutes, preferably 0.02-100g/10 minutes,
Particularly preferred is a molecular weight corresponding to 0.05 to 50 g/10 min. If it is less than this range, molding will be difficult, and if it exceeds this range, the mechanical properties will deteriorate significantly, and both are not preferred.

(3) Melting point The melting point of the copolymer of the present invention is 100 to 160°C, preferably 110 to 15°C, as determined by DSC at the peak melting temperature.
The temperature range is 5°C, particularly preferably 120°C to 150°C. If it is less than this range, the heat resistance of the propylene resin cannot be exhibited, and furthermore, it becomes a rubbery substance, which is not preferable.

(4) Crystallinity The crystallinity of the copolymer of the present invention as determined by X-ray diffraction is 20
It is in the range of at least 30% by weight, preferably from 30 to 55% by weight. Below this range, the heat resistance of the propylene resin cannot be exhibited.

[Experiment example]

The present invention will be explained in more detail below using experimental examples. Although these experimental examples were polymerized by a slurry polymerization method, the embodiments of the present invention are not limited to this method.

The experimental methods used in the Examples and Comparative Examples below are as follows.

(1) MFR (230℃, 2.16kg) JIS K
-6758 [: g/10 min] (2) Crystallinity X-ray diffraction method (3) Three-point bending modulus J I S K-7203 Ckg/c♂] (4) Tensile stress at break, elongation J I S K -6758 (kg/cJ) C%] (
5) Tensile yield point stress J Is K-6758Ckg/c4"J (6) Izod impact strength J Is K-7110 [kg-cm/cn+) (
7) Melting point DSC peak value (℃) (8) Comonomer composition 1H-NMR [mol %] Example 1 [Preparation of supported catalyst] 12 m + 1 φ stainless steel was placed in a 0.41 luntore ball mill that was thoroughly dried and purged with nitrogen. Filled with 40 balls, 20 g of MgCl2 and 15.5 ml of dihebutyl phthalate were introduced into the balls, and the mixture was heated in a rotary ball mill for 4 hours.
Grind for 8 hours. After the pulverization was completed, the mixed pulverized composition was taken out from the mill in a dry box. Subsequently, 8.8 grams of the pulverized composition was introduced into a flask that had been sufficiently purged with nitrogen, and 25 milliliters of n-hebutane and TiC14 were added.
25 ml was introduced and the reaction was carried out at 100°C for 3 hours. After the reaction was completed, it was thoroughly washed with n-hebutane.

When a part of the obtained solid component [component (i)] was taken out and analyzed for composition, it was found that the Ti-containing melon was 3.01 times evercent.

Next, the sufficiently purified n
50 milliliters of -hebutane was introduced, and 5 grams of component (i) obtained above was introduced thereinto, followed by 1.1 milliliters of synthetic H3CH3, and the mixture was kept in contact at 30 DEG C. for 2 hours. After contacting, thoroughly wash with n-hebutane and remove the components (
A).

[Production of copolymer]

In a 1 liter autoclave, add 7-methyl-1,
70 ml of 6-octadiene and 350 ml of n-heptane
0.9 g of triethylaluminum and 0.18 g of the supported catalyst prepared by the above method were added in this order. Next, after adding 10,100 N of hydrogen, the temperature was raised without pressurizing propylene, and polymerization was carried out at 65° C. and 3 kg/c (gauge pressure) for 2 hours. After copolymerization, n
After deactivating the catalyst with -butanol, the catalyst residue was extracted with water and the solid copolymer was recovered by centrifugation and dried. The obtained copolymer weighs 250 g and has a bulk density of 0.
．． It was 49z/cc.

The MFR of this copolymer is 11 g/10 min, the melting peak by DSC is 151°C, and the crystallinity by X-ray diffraction is 3.
It was 7.5% by weight. In addition, 7- by 'H-NMR
The content of methyl-1,6-octadiene is 2.3 mol%
It was confirmed that there was no chain of 7-methyl-1,6-octadiene monomer units and that it was a random copolymer.

After molding this copolymer, we measured its mechanical properties and found that the three-point bending modulus was 8,600 kg/cJ, the tensile stress at yield was 260 kg/cd, and the stress at tensile break was 350 kg/c.
d. The tensile elongation at break was 500%, and the Izot impact strength was 4.6 kg-cm/am.

On the other hand, the solution obtained by centrifuging the copolymer slurry was concentrated to recover 3.1 g of an amorphous polymer. As a result,
The catalytic activity was 1406 g/g.catalyst, and the by-product rate of soluble polymer was 1.2% by weight.

Example 2 In Example 1, the amount of 7-methyl-1,6-octadiene charged was 100 ml, and the amount of n-hebutane charged was 3.
Copolymerization was carried out in the same manner as in Example 1 except for the volume of 20 ml and a solid copolymer was recovered. The obtained copolymer weighed 220 g.

On the other hand, the amount of soluble polymer was 13.2 g.

The MFR of this crystalline copolymer is 16 g/10 min, DSC
The melting peak was 149°C, the crystallinity was 34.0%, and the content of 7-methyl-1,6-octadiene was 3.
．． It was 5 mol%, and there was no chain of diene units.

The mechanical properties of a molded product of this copolymer include a three-point bending modulus of 7100 kg/cJ and a tensile stress at yield point of 220 kg.
/ci, tensile stress at break is 440 kg/ci, tensile elongation at break is 750%, Izod impact strength is 9, 8
kg-cm/cm.

Example 3 In a 1 liter autoclave, 7-methyl-1,
400 ml of 6-octadiene was charged, and 0.9 g of diethylaluminum chloride and 0.28 g of titanium trichloride manufactured by Marubeni Tsurubei were added in this order. Then hydrogen 30
After adding ON-ml, increase the total pressure to 3 kg/c with propylene.
d (gauge pressure), and this state was maintained at 25° C. for 20 minutes. Thereafter, the temperature was started to increase without pressurizing propylene, and copolymerization was carried out at 55° C. and 9.5 kg/cd (gauge pressure) for 4 hours. The obtained solid copolymer is 1
79 g, and the soluble polymer was 57 g.

The MFR of this crystalline copolymer is 4.1 g/10 min.
The melting peak by DSC was 148°C, and the crystallinity was 32.
The content of 7-methyl-1,6-octadiene was 4.6 mol%, and there was no chain of diene units.

The mechanical properties of a molded product of this copolymer include a three-point bending modulus of 5570 kg/c♂ and a tensile yield point stress of 190 kg/c♂.
cJ, tensile stress at break is 440 kg/cj.

Tensile elongation at break is 780%, Izot impact strength is 14
kg-c+Tl/cm.

Example 4 In Example 1, the amount of supported catalyst was changed to 0.10 g, and when the temperature reached 65°C and 3 kg/cm (gauge pressure), ethylene charging was started, and ethylene was added during copolymerization. Copolymerization was carried out in exactly the same manner as in Example 1, except that s and og were charged. The obtained solid copolymer weighed 253 g, and the soluble polymer weighed 19 g.

The MFR of this crystalline copolymer is 4.2 g/10 min, DS
The melting peak due to C was 132°C, the crystallinity was 2865% by weight, and the ethylene content was 4.9% by mole. 7-methyl-
The content of 1,6-octadiene is 2.2 mol%,
There was no chain of diene units.

The mechanical properties of a molded product of this copolymer include a three-point bending modulus of 3500 kg/c+T and a tensile stress at yield point of 170 k.
g/c+#, tensile stress at break was 430 kg/cJ, tensile elongation at break was 8509 ci, and Izod impact strength could not be measured because the sample did not break.

Comparative Example 1 In Example 2, 8=2 (molar ratio) mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene was used instead of 7-methyl-1,6-octadiene. Copolymerization was carried out in exactly the same manner as in Example 2, except that . The obtained solid copolymer weighed 61 g, and the iJ-soluble polymer weighed 1.1 g.

The M F R of this crystalline copolymer is 6.7 g/10 min.
The melting peak by DSC was 154°C, and the crystallinity was 47.
The content of 7-methyl-1,6 octadiene was 1.7 mol%, and there was no chain of diene units.

The mechanical properties of a molded product of this copolymer include a three-point bending modulus of 9700 kg/cJ and a tensile stress at yield point of 354 kg.
/ci, tensile stress at break is 405 kg/cl.

Tensile elongation at break is 650%, and Izot impact strength is 2.
It was 8 kg-cm/cm.

These results show that the method of the present invention has excellent copolymerizability, extremely high catalytic activity, and the same or higher mechanical properties.

N person agent Sa Wisteria male

Claims (1)

[Scope of Claims] A propylene random copolymer characterized by being defined by the following (1) to (4). (1) It must be obtained by copolymerization in the presence of a Ziegler type highly stereoregular polymerization catalyst. (2) Melt flow rate is 0.01-200g/10
be minute. (3) Crystallinity as determined by X-ray diffraction method is 20% or more. (4) Consisting of the following repeating units (I) to (III),
The respective contents are (I) 84 to 99.5 mol%, (II
)0 to 15 mol%, and (III) 0.5 to 15 mol%
, to be. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (R^a and R^b, one indicates a hydrogen atom and the other indicates a methyl group)