JPS62115007A - Unsaturated copolymer - Google Patents

Abstract

PURPOSE:To obtain a low-melting, lowly crystalline, thermoplastic, resinous, unsaturated copolymer, by random-copolymerizing propylene with a 2-12C alpha-olefin other than propylene and a specified branched 1,4-diene. CONSTITUTION:60-99mol% propylene is copolymerized with 0.5-20mol% 2-12C alpha-olefin other than propylene (e.g., ethylene) and 0.01-30mol% branched 1,4-diene of the formula (wherein R<1> is an 8C or lower alkyl and R<2-3> are each H or an 8C or lower alkyl provided that both of R<2> and R<3> can not be H atoms at the same time (e.g., a mixture of 4-methyl-1,4-hexadiene with 5-methyl-1,4- hexadiene at a mixing ratio of 95:5-5:95) to obtain a thermoplastic resinous unsaturated copolymer of a MI of 0.01-200g/10min.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention is directed to propylene, α-olefins having 2 to 12 carbon atoms (excluding propylene), and specific 1,4-
This invention relates to an unsaturated copolymer obtained by random copolymerization of dienes.

Olefin polymer resins such as polyethylene, polypropylene, and polybutene-1 are easy to manufacture, low cost, and have excellent moldability, transparency, packaging properties, insulation, water and land resistance, chemical resistance, mechanical strength, etc. is used in a very wide range of fields.

For example, these olefin polymer resins are used in almost all fields such as various packaging films, wire covering materials, pipes, containers, foams, automobile parts, home RT parts, and sheets.

On the other hand, since these olefin polymer resins are saturated hydrocarbons, they are significantly superior in surface properties that primarily require polar groups, such as contact bending, paintability, printability, anti-banding properties, and antifogging properties. It has been pointed out that it is inferior and has a major drawback, but to this day, there is still no fundamental solution to this problem.

Furthermore, in propylene resins, the main chain scission reaction by radicals takes precedence over the crosslinking reaction, so a radical crosslinking method using peroxide or high-energy electron beams does not yield a crosslinked product. As a countermeasure to this problem, there is a method of blending various crosslinking aids made of polyfunctional compounds, but there are problems such as bleeding of low molecular weight residues, deterioration of weather resistance, and deterioration of various physical properties.

(2) Prior art and problems There are many inventions related to the copolymerization of α-olefins and non-conjugated dienes, but among them, one that is particularly closely related to the present invention is British Percentage No. 1,268,149. No. 3,933,769 and US Pat. No. 3,991,262.

The invention of British Patent No. 1,268.149 uses a special titanium trichloride composition that has been highly refined and colloidal as the transition metal component of the polymerization catalyst, and the average amount of copolymer produced is It is characterized by being colloidal with a particle size of 0.02 to 0.5 microns. Since the purpose of this invention is to produce a fine Yfi-containing copolymer for thin layer coating, titanium tetrachloride is reduced with an organoaluminum compound as a condition for preparing the titanium trichloride catalyst component. α with a small number of carbon atoms of 6 or more
-Olefins are present. However, when such a finely divided titanium trichloride catalyst component is used, the resulting unsaturated copolymer particles are also significantly finely formed. This causes major obstacles to production on an industrial scale, such as increased viscosity in the polymerization tank, difficulty in removing polymerization heat, and difficulty in recovering unsaturated co-electrolyte composites.

The inventions according to U.S. Pat. The polymer is characterized by being rubber-like, and a resin-like copolymer cannot be obtained.

The present inventors have already developed a random copolymer of ethylene and a specific 1,4-diene (1? Publication No. 30413/1983) with the aim of solving the problems of the conventional technology.
, a random copolymer of propylene and a specific 1,4-diene (JP-A-56-30414), and a block copolymer of propylene, ethylene, and a specific 1,4-diene (JP-A-59-1989) -155416). However, all of these known techniques lack transparency and flexibility.

The present invention is to develop a low melting point and low crystal resin containing propylene as the main component, and to improve transparency, flexibility, and moldability, and to further expand the field of application.
Chiru.

The present invention can be applied to a wide range of applications by taking advantage of this feature, such as preventing shear heat generation when forming raw sheets for cross-linking and foaming, and containers such as transparent bottles and bags that can be printed on the surface.
Applications include packaging materials, paintable exterior or interior parts of automobiles and home appliances, their skin materials, and flexible and heat-resistant core wire coating materials.

(3) Detailed Description of the Invention and -" (1) Composition The copolymer of the present invention has a propylene content of 60 to 99 mol% and an α-olefin having 2 to 12 carbon atoms (however, propylene is p and formula (I
) (hereinafter referred to as branch 1.4)
- It is a random copolymer having a content of 0.01 to 30 mol% (abbreviated as diene).

When the branched 1,4-diene content is less than 0.01 mol%,
For the side chain non-t@-FD bond intended by the present invention! If the amount exceeds 30 mol %, the polymerization rate will drop significantly, making it unsuitable for industrial production.

When the content of α-olefins having 2 to 12 carbon atoms (excluding propylene) is less than 0.5 mol%, the melting point becomes high;
If it exceeds 20 mol %, the elastic modulus decreases too much, which defeats the purpose of the present invention.

If the propylene content is less than 60 mol %, it is not preferable because the elastic modulus decreases too much, the coalescence rate decreases, and the by-product acid of the polymer soluble in the d-medium increases.

On the other hand, if it exceeds 99 mol %, both the branched 1,4-diene content and the C2-C12 α-olefin content become low, making it impossible to achieve the object of the present invention.

A preferred composition of the copolymer has a propylene content of 70 to 70%.
98 mol%, the content of α-olefins having 2 to 12 carbon atoms is 0.7 to 17 mol%, and the content of branched 1,4-dienes is 0.05 to 25 mol%, particularly preferably the propylene content is 75-98 mol%, α of I&A2-12
-Olefin content 1-15 mol% and branching 1.4-
The diene content is 0.5 to 20 mol%.

(2) Molecular weight The molecular weight of the copolymer of the present invention is determined by a melt flow rate (MFR) of 0.01 to 2001/10 minutes, measured at 230°C and a load of 2.16# in accordance with JIS K-6758.
Preferably 0.05~toor,'t.

minute, particularly preferably from 0.1 to so t/xo minute. Outside this range, molding becomes difficult.

(3) Melting point The melting point of the copolymer of the present invention is an important index that defines its properties such as transparency, flexibility, and low-temperature moldability. This melting point is the temperature at the peak position of melting by DSC, and is 10
The temperature is selected within the range of 0°C to 153°C, preferably 115°C to 153°C, particularly preferably 125°C to 150°C. Above the melting point shown here, the copolymer cannot exhibit its properties such as transparency, flexibility, and low-temperature moldability. On the other hand, if the melting point is too low, the heat-resistant properties of the propylene resin cannot be exhibited, and furthermore, it becomes a rubber-like copolymer, which does not meet the purpose of the present invention.

2 1.4-Diene In the present invention, "random copolymer" refers to propylene units,
α-olefin unit and branched 1,4-diene unit (1)
In addition to the completely disordered distribution of branched 1°4-diene units (I
) also means that the distribution is tapered, for example.

The branched 1,4-diene to form a copolymer with propylene and an α-olefin is represented by formula (I).

Here, R1 represents an alkyl group having 8 or less carbon atoms, preferably 5 or less, R2 and R3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms, preferably 5 or less, and R2 and R3 are both hydrogen atoms. Certain cases shall be excluded.

Specific examples of these branched 1,4-dienes include 4
-Methyl-1,4-hexadiene, 5-methyl-1,4
-hexadiene, 4-ethyl-1,4-hexadiene,
4,5-dimethyl-1,4-hequinadiene, 4-methyl-1,4-hebutadiene, 4-':r-f-1,4-
Hebutadiene, 5-methyl-1,4-hebutadiene, 4
-ethyl-1,4-octadiene, 5-methyl-1,4
-octadiene, 4-n-propyl-1,4-decadiene, and the like. Among these, especially 4-methyl-1,
4-hexadiene and 5-methyl-1,4-hexadiene are preferred.

These branched 1,4-dienes may be a mixture of two or more of them, especially a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (mixing ratio: 95: 5 to about 5:95) is suitable.

λ α-olefin having 2 to 12 carbon atoms α-olefin having 2 to 12 carbon atoms used in the present invention (
(excluding propylene) specifically ethylene, phthene-1,3-methylbutene-1, pentene-1,3-methylpentene-1,4-methylpentene-1, hexene-1
, octene-1, decene-1, dodecene-1, and styrene. Among them, ethylene, butene-11
Hexene-1,4-methylpentene-1 and octene-1 are preferred, especially ethylene, and butene-1, especially ethylene, of practical importance.

4. Production (1) Polymerization catalyst The copolymer of the present invention can be produced using a Ziegler-Natsuta catalyst, which basically consists of a halogen compound whose transition metal component is titanium or a composition thereof, and an organometallic compound. Preferred is a stereoregular polymerization catalyst for α-olefin polymerization.

The titanium halogen compound or its composition is preferably a titanium chloride-containing solid catalyst component supported on a carrier such as titanium trichloride or magnesium chloride obtained by various manufacturing methods. As titanium trichloride, in particular, titanium tetrachloride is reduced with an organoaluminum compound, treated with a complexing agent, and then treated with a Lewis acid such as titanium tetrachloride. Examples include compositions obtained by precipitating titanium trichloride and preferably treating it with a Lewis acid such as titanium tetrachloride. Examples of the chloride-containing solid catalyst component of supported titanium include supported titanium components whose essential components are magnesium, chlorine, titanium, and an electron donor. -8210
3, 54-94591, 55-59069, 58
-19307, ]] Tsukasa 58-32604 Tsukasa 58-3
2605, 58-117205, 58-18370
8, No. 59-149905, No. 60-130607, Patent Application No. 60-45662, No. 60-53849, No. 60-
The solid catalyst components described in each No. 54838 can be exemplified.

The organometallic compound is preferably an organometallic compound of metals of groups I to II of the periodic table, and organoaluminum compounds are particularly preferred. Examples of organoaluminum compounds include compounds represented by the following formulas.

RnMX3-n where R4 represents a hydrocarbon residue having approximately 1 to 10 carbon atoms, X represents a hydrogen atom, a halogen atom, an alkoxy group having approximately 1 to 15 carbon atoms, an aryl oxide, or a siloxy group; This is a number expressed by n≦3.

Specific examples of these organoaluminum compounds are as follows. (a) Trimethylaluminum, triethylaluminum, triinobutylaluminum,
Trialkylaluminum such as triimprenylaluminum and tri-n-hexylaluminum; (b) dialkylaluminum halides such as diethylaluminum chloride, diisobutylaluminum chloride, and di-n-propylaluminum chloride; (c) diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum hydrides such as) alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, n-propylaluminum sesquichloride, (v) methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminium chloride Alkylaluminum cibaride, (to)diethylaluminum ethoxide, diethylaluminum (2,6
- dialkyl aluminum siloxides or aryl oxides such as (tert-butyl) phenoxyto;
(g) Dialkyl aluminum siloxides such as diethyl aluminum trimethyl siloxide. These organic aluminum compounds may be reacted with water or amines. Further, these organoaluminum compounds may be used alone or in a mixture of two or more.

In addition to the transition metal component and the four organic metal components, it is also possible to add various compounds as the third component of the catalyst for various purposes, for example, to improve the regularity of standing trees. As this third component, ``1'' hydroxide, iodine, etc. are preferably used. Examples of electron donors include carboxylic acid esters, sulfites, ethers, phosphines, phosphine oquinides, phosphoric acid amides, amines, organic antimony compounds, phosphoric acid esters, phosphites, and amine oxides. , silicic acid esters, etc. can be expressed in ml.

(2) Polymerization conditions using a Ziegler-Natsuta catalyst in which the copolymerized transition metal component is a halogen-containing titanium compound or a composition thereof can generally be used. That is, the polymerization temperature is 0
-200°C, preferably 20-150°C, particularly preferably 30-100°C, polymerization pressure normal pressure -1 sokg/i,
Preferably normal pressure to 90ky/cl, particularly preferably normal pressure to 50 kg/i, d! Appropriate.

There is no particular restriction on the polymerization method, either a slurry method or a solution method using an inert solvent, in which a solvent is essentially added, and one or more of propylene, α-olefin and branched 1,4-diene is used as the solvent. A slurry method or a solution method, which has a different function, or a gas phase method, which does not use a substantially liquid solvent and keeps each hexamer in a substantially gaseous state, can all be applied to the present invention.

In order to obtain a random copolymer, it is necessary that each monomer is present during polymerization, but the ratio of their amounts does not need to be constant over time. That is, it is convenient to supply each monomer at a fixed mixing ratio, and it is also possible to change the mixing ratio over time. Further, any of the monomers can be added in portions taking into account the copolymerization reaction ratio.

Surprisingly, molecular purification by hydrogen is easily achieved when ethylidene norbornene or 1,4-hexadiene is used as the comonomer.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples. Although these actual Itm examples were polymerized by the slurry method, the implementation of the present invention izQ j4 is not limited to this method.

The test methods used in the following examples and ratio/bite examples are as follows (11MFR (230°C, 2.16#) JIS K-
6758 (r/lo min) (2) Density 1 JIS K-7112 (r/ctI) (3) Three-point bending modulus JIS K-7203 (#, /cn) (4) Tensile stress at break, elongation JIS K -6758 (#/m) (%) (5) Tensile yield point stress JIS K-67s8 (Ay/cj) (6)
Haze JIS K-6714C%] (7) Melting point DSC peak value [℃] (8)
Comonomer composition 'H-NMR (mol%) Implementation: Evening 11-1 Into an autoclave with a capacity of 100 liters, 4-methyl-
Charge 40 liters of an 8:2 mixture (molar ratio) of 1,4-hequinadiene and 5-methyl-1,4-hexadiene (hereinafter this mixture will be abbreviated as methyl-1,4-hexadiene), and add diethylaluminum. Chloride 18f and titanium trichloride 4.12 manufactured by Marubeni Nlupay were added in this order.

Next, hydrogen and propylene were added to bring the total pressure to 1.5Ay.
/c+J (gauge pressure) and maintained at 25° C. for 15 minutes so that the hydrogen concentration was 2.0%. By further pressurizing pyrene, the total pressure is 6 #/cnl (gauge FE) and the hydrogen ei degree is 6
．． Polymerization was carried out at 55° C. for 6 hours so that the polymerization yield was 8%.

During this polymerization, ethylene was fed at a constant rate of 0.48 ml.

After the polymerization, 0.8 liters of n-butanol was added to inactivate the catalyst. The remaining catalyst was extracted with water, and the solid copolymer was recovered by centrifugation and dried.

The obtained copolymer has a weight of 7.5k”/’#J1!!
The degree was 0.46t/CC. Table 1 shows the properties of this co-1k coalescence.

On the other hand, F7'X of the polymerization slurry was subjected to α4, and a drifting polymer 1.1A9 was recovered. -Example-2 In Example-1, except that the total pressure was 4 filtration/- (gauge pressure) at 55°C, and the hydrogen concentration was 3.1%, Example-
I regretted the polymerization and disposal of Gokura bonds under the same conditions as 1. A copolymer 5.2# with a bulk density of 0.43''/i and an amorphous polymer 1.3# were obtained.The various properties of these copolymers are shown in Table 1.
Shown below.

Example-3 Hexane 2 was added to an 8h200 liter autoclave.
Prepare 0 liters and add 5 liters of diethyl aluminum chloride.
1f and Marubeni Tsurupei Sanshio 1 Hitetan 10? were added in this order. Next, hydrogen and propylene were added until the total pressure was 1.0 dirt/cyi (gauge pressure) and the hydrogen a degree was 2.
It was kept at 40° C. for 10 minutes so that the volume was 0%. Here,
Fifty liters of quinadiene was injected into the methyl. Furthermore, propylene was press-fitted and the total pressure was 5kLJ/i (gauge pressure).
Polymerization was carried out at 55° C. for 5 hours while controlling the hydrogen concentration to 3.2% by volume. During this polymerization, 0.55# of ethylene was completely fed.

After the polymerization, 2.5 liters of methanol was added to inactivate the catalyst, the catalyst residue was extracted with water, and the solid copolymer was recovered by centrifugation and dried. Bulk density 0.46 r/i
18.54 kv of a copolymer and 1.7 kv of an amorphous polymer were obtained. Table 1 shows the properties of this copolymer.

Example 4 [Preparation of 1-sized carrier catalyst] Dehydrated and deoxygenated n was placed in a flask that was sufficiently purged with nitrogen.
- Introducing 100 ml of hebutane, devoid of Mg
0.1 mol of C12, 0.195 mol of Ti(0-n-C4Hs)4, then 0.0 mol of n-04H90H.
07 mol was introduced, and the reaction was carried out at 90°C for 2 hours. After the reaction was completed, 15 milliliters of methylhydroborinoxane (20 centistokes) was introduced at 40°C and reacted for 3 hours. The solid component produced was washed with n-hebutane.

Add this solid component to a flask that has been sufficiently purged with nitrogen.
0.03 mol (Mg content = 4.3 weight percent) in terms of fL molecules was introduced, and 50 milliliters of dehydrated and deoxygenated n-hebutane was introduced. A mixture of 25 ml of n-hebutane, 0.0025 mol of ethyl benzoate, and 0.05 mol of silicon tetrachloride was introduced at 30°C for 30 minutes, heated to 50°C, and reacted for 1 hour. After the reaction was completed, it was washed twice with 1 liter of n-hebutane. Next, 12 ml of titanium tetrachloride and 0.0 ml of ethyl benzoate were added.
0007 mol was introduced over 30 minutes at 30°C, and 90°C
The reaction was carried out for 1 hour. After the reaction was completed, the supernatant liquid was extracted, and then the same amount of titanium tetrachloride and ethyl benzoate were introduced.
The reaction was carried out at 05°C for 1 hour. After the reaction was completed, it was thoroughly washed with n-hebutane and used as a catalyst component.

'ri　containing charge was 2.53 soft X-cents.

[Production of copolymer]

Methyl-
Prepared 60 liters of 1,4-hexadiene, 182 liters of triethylaluminum, 7 liters of diphenyldimethoxy.
．． 5? J? and supported catalyst 4.5 prepared by the method described above.
f/ was added in this order. Next, hydrogen and propylene were added to make the hydrogen concentration 1.0% by volume and the total pressure 1.5H/cd.
(gauge pressure) was kept at 40° C. for 15 minutes. At the same time as the temperature was raised, feed of propylene and ethylene was started, and the total pressure was 8 people 1/- (gauge pressure) and hydrogen 1.0 once.
Polymerization was carried out at 60° C. for 4 hours while controlling the volume to %. Incidentally, during this polymerization, ethylene 0.95A9 was fed at a constant rate.

The resulting combined slurry is centrifuged to reduce the bulk density to 0.
．． 42? /- solid copolymers 16.2 to 9 and an amorphous polymer 1.4A9 were obtained. The properties of this copolymer are shown in Figure 1.

Reference Example Example-1 was divided into 552 parts of diethylaluminium chloride, 129 parts of 1' Hititanium manufactured by Marubeni Tsurubei Co., Ltd., a total pressure of 4 kf1/i (gauge pressure), a hydrogen concentration of 4.2 volume %, and ethylene. Except that I didn't feed it.
Polymerization and post-polymerization treatment were carried out under the same conditions as in Example-1. Copolymer 12.2A9 with bulk density o, 46y/cj
And, amorphous polymers 1, 2~ were obtained. The various properties of this copolymer are shown in &11/C.

(Margin below)

Claims (1)

[Claims] Propylene, α-olefins having 2 to 12 carbon atoms (excluding propylene), and branched 1,4-dienes represented by the following formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ ( I ) (Here, R^1 is an alkyl group having 8 or less carbon atoms, R^2
and R^3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms. However, R^2 and R^3 are not both hydrogen. ) with a propylene content of 60
~99 mol%, content of branched 1,4-diene is ~0.01
a thermoplastic, substantially Resin-like unsaturated copolymer.