JPS6219444B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a rubbery random copolymer based on propylene/1-butene or propylene/1-butene/polyene. The present inventors previously proposed a low-crystalline propylene/1-butene random copolymer with good transparency and no surface tackiness in Japanese Patent Application No. 54-155068 and Japanese Patent Application No.
It was proposed in No. 52-153003. The copolymer is
It has a wide range of uses as a soft or semi-hard resin, but it is also used in hoses, tubes, toys, bottles,
There has also been a demand for softer polyolefin materials for miscellaneous goods and many other fields. Traditionally, such polyolefin materials include ethylene/propylene copolymer rubber (EPR) or ethylene/propylene/polyene copolymer rubber (EPT), which have good transparency and gloss.
were known, but their generally low tensile strength limited their range of application in cases where vulcanization was not performed. For example, ethylene-propylene copolymer rubbers such as those mentioned above cannot be used alone due to lack of strength because they cannot be vulcanized when used as thermoplastic elastomers, which have been in increasing demand in recent years, and polyethylene, polypropylene, etc. It was necessary to use a mixture of resins. The present inventors have searched for a polyolefin rubber that has practical tensile strength even without vulcanization and is superior in terms of transparency, gloss, etc., and has found that even in the unvulcanized state, it is superior to the above-mentioned ethylene rubber. It also has a significantly high tensile strength, has sufficient practical strength, and can be used as a thermoplastic elastomer with excellent scratch resistance. It has been discovered that sulfurable rubbery random copolymers can be produced. Furthermore, in comparison with the most similar copolymers described in conventional literature and the similar copolymers related to the earlier application of the present inventors, the rubbery random copolymer has It is a substantially amorphous rubber-like random copolymer that is structurally distinct and has not been described in any prior literature, particularly in that it has the properties of (D) and (F) under the binding property conditions of (F). I discovered that. Furthermore, the rubbery random copolymer exhibits excellent tensile properties even when vulcanized, and
Because it is a soft rubber due to its molecular structure, EPR,
It has been found that it is also useful in uses different from the aforementioned ethylene-propylene-based cured rubbers such as EPT, such as use as a blend for improving the physical properties of cured rubbers. Therefore, an object of the present invention is to provide a rubbery random copolymer having the above-mentioned unique properties, a vulcanizate thereof, and a method for producing the same. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. According to the present invention, (A) consists of propylene and 1-butene, or propylene and 1-butene and polyene, and (B) propylene/1-butene (molar ratio) is 35/65.
~59/41, and (C) has an iodine number of 30 or less, and (D) has no observed melting point based on differential scanning calorimetry (DSC) thermal analysis, or has a melting point below 40°C, preferably below about 20°C. , (E) a rubber having an intrinsic viscosity [η] of 0.5 to 6.0 dl/g as measured in decalin at 135°C, and (F) a boiling diethyl ether soluble content of 50% by weight or less random copolymers can be provided. Conventionally, copolymer rubbers mainly composed of propylene and 1-butene have been known. However, (A) above
Rubbers made of propylene/1-butene or propylene/1-butene/polyene copolymers having the properties listed in (F) have not been described in any literature. As a conventionally known propylene/1-butene copolymer rubber, a propylene/1-butene copolymer rubber manufactured using a vanadium catalyst component and an organoaluminum compound catalyst component is known. However, this type of rubber contains a significantly large amount of boiling diethyl ether soluble matter and does not satisfy the requirement (F) specified for the copolymer of the present invention. This type of rubber has the disadvantage that its tensile strength is unsatisfactory. On the other hand, propylene and 1-
It is well known that it is difficult to obtain a substantially amorphous copolymer when copolymerized with butene. , propylene/1
The prior art for polymerizing -butene mixtures is presented and is described as producing large amounts of hexane-insoluble crystalline propylene/1-butene copolymers. In JP-A No. 50-38787, which is extremely surprising and unexpected in view of the above facts, it is stated that copolymerization at a high temperature of at least 140°C or higher is an essential requirement. An amorphous propylene/1-butene copolymer was obtained from a hexane-soluble propylene/1-butene copolymer in the presence of a catalyst consisting of a trialkyl aluminum or an organic polylithium aluminum compound and titanium trichloride. is reported. Furthermore, as a certain characteristic of the copolymer thus obtained, the content insoluble in boiling diethyl ether is 40% by weight or less, that is, the content soluble in boiling diethyl ether is 40% by weight or less.
It is specifically noted that the content is 60% by weight or more. As specified in (F) above, the rubbery random copolymer of the present invention has a boiling diethyl ether soluble content of 50% when measured under the conditions described below that can increase the soluble content even more than in the above proposal. % by weight or less, has low surface tackiness, high tensile strength, and is excellent in transparency, scratch resistance, and gloss. On the other hand, the above-mentioned proposed copolymer has a large boiling diethyl ether soluble content of 60% by weight or more, has high surface tackiness, and has poor transparency, scratch resistance, and gloss. It is also stated that in order to produce the above proposed copolymer, setting the polymerization temperature in the presence of the above catalyst is critical, and it is essential to adopt a high temperature of at least 140°C or higher. However, the copolymer of the present invention is copolymerized under specific bonding conditions described below, and the polymerization temperature is usually less than 140°C, preferably about
It is carried out at a temperature below 120℃. Furthermore, the above-mentioned patent application proposed by the present inventors
155068 and Japanese Patent Application No. 153003, the melting point (Tm) based on the DSC thermal analysis of the above requirement (D) is 40.
℃ or more, whereas in the rubbery random copolymer of the present invention, Tm is not observed, or even if it is observed, it is less than 40℃, preferably about 20℃ or less, which is substantially amorphous. It has structural characteristics. The rubbery random copolymer of the present invention has the property of satisfying the above requirement (D) under the conditions of having the property of satisfying the bonding requirements of the above requirements (A) to (F). It is distinguished from the two previously proposed copolymers mentioned above. As a result, unlike the above-mentioned two proposed copolymers, this copolymer can be used for rubber-like purposes in that it has low permanent deformation and has rubber-like properties. The (B) molar ratio of propylene and 1-butene in the copolymer rubber of the present invention is preferably from 35/65 to 59/41.
40/60 to 55/45. When the copolymer of the present invention is used after being vulcanized, it is preferable that polyene is further copolymerized. Examples of the polyene include conjugated dienes such as butadiene, isoprene, and piperylene; 1,4-hexadiene;
1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-ethylidene -2-norbornene, 5-methylene-2-norbornene, 5
- non-conjugated dienes such as isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-
3-isopropylidene-5-norbornene, 2-
propenyl-2.2-norbornadiene, 1.
Typical examples include trienes such as 3,7-octatriene and 1,4,9-decatriene. The amount of polyene copolymerized is limited to an amount such that the (C) iodine value of the copolymer is 30 or less,
Preferably, the number ranges from about 5 to about 25. (D) No melting point observed based on differential scanning calorimeter (DSC) thermal analysis of the copolymer of the present invention40
C, preferably not observed or less than 20 C, more preferably no melting point observed under the measurement conditions. Note that when measuring the melting point by DSC, the sample is heated to 200℃.
After leaving for 5 minutes at 20°C/min, cool to -40°C at a rate of 10°C/min, leave at -40°C for 5 minutes, then cool to 20°C/min.
Measurements are made from -40°C to 200°C at a heating rate of min. (E) Intrinsic viscosity [η] measured in decalin at 135°C is a measure of molecular weight, and is defined as the range that shows physical properties that are actually useful as a rubber.
In the present invention, the amount selected is usually 0.5 to 6.0 dl/g, preferably about 1.0 to about 5.0 dl/g. The copolymers of this invention are substantially soluble in boiling hexane. However, (F) boiling ether (diethyl ether) soluble content is 50% by weight or less, more preferably about 40% by weight or less, more preferably about 30% by weight or less, particularly about 20% by weight or less. The boiling diethyl ether soluble content was measured as follows. That is, a strip sample of approximately 1 mm x 1 mm x 1 mm and glass beads of equal weight (100 to 200 mesh) are mixed well, placed in a cylindrical glass filter (G3), and extracted using a Soxhlet extractor for 6 hours. In this case, the reflux frequency is approximately once/5 minutes. The weight percent of insoluble content is determined by weighing the dissolved or insoluble part. It is a copolymer rubber mainly composed of propylene and 1-butene, and is different from similar copolymer rubbers proposed in the past in that it contains very little boiling ether soluble content. The copolymer rubber of the present invention usually has an elongation at break of about
400% or more, and the stress at break is 50Kg/cm ² or more. Note that such tensile properties were measured by a method according to JIS K6301. In other words, the sample has an inner diameter of 18 mm and an outer diameter of 22 mm, punched out from a 1 mm thick press sheet formed according to JIS K6758.
Using a ring-shaped test piece, the measurement is performed at a tensile speed of 500 mm/min in an atmosphere of 25°C. The copolymer of the present invention that satisfies the above conditions has low surface tackiness and is excellent in transparency, gloss, heat aging resistance, strength properties, etc. Furthermore, when the rubbery random copolymer of the present invention is vulcanized, it exhibits excellent physical properties similar to those of vulcanized ethylene-propylene copolymer rubber (e.g., EPR, EPT), but unlike EPR and EDT, it is soft. Because it is a type of rubber, it can be used in fields different from known ethylene-propylene copolymer rubbers. To produce the copolymer rubber, (a) it contains at least magnesium, titanium, halogen, and an electron donor, and has a specific surface area of 100
m ² /g or more, halogen/titanium (molar ratio) is 4
, and the electron donor/titanium (molar ratio)
0.2 or more, (b) an organoaluminum compound, and (c) ethers, alcohols, phenols,
At least one electron donor selected from ketones, aldehydes, acid anhydrides, carboxylic acids, and organic acid esters, and in the case of ethers per one aluminum atom of the organoaluminum compound (b), Approximately 0.001 to approximately 10 mol, alcohols, phenols, ketones,
Approximately 0.001 for aldehydes or acid anhydrides
~Less than 1 mole, approximately 0.001 for carboxylic acids
~0.5 mol, approximately 0.5 mol for organic acid esters
It can be produced by random copolymerization of propylene and 1-butene or propylene and 1-butene and a polyene in the presence of a catalyst formed from 0.001 to about 0.1 mole. The above-mentioned complex (a) has a composition that does not substantially change when washed with hexane at room temperature,
The specific surface area is 100 m ² /g or more, preferably about 150 to about 800 m ² /g, and the halogen/titanium (molar ratio) is 4.
magnesium/titanium (mole ratio) is usually greater than about 3, preferably about 5 to about 50, electron donor/titanium (molar ratio) ) is in the range of 0.2 or more, usually about 6 or less, preferably about 0.4 to about 3, more preferably about 0.8 to about 2. It is desirable that the X-ray spectrum of the composite exhibits amorphous properties or is in a highly amorphous state compared to that of ordinary commercially available magnesium dihalides.
The halogen in the complex (a) is chlorine, bromine, iodine, or fluorine, with chlorine being particularly preferred. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid esters, ethers, acid amides,
Oxygen-containing electron donors such as acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and the like can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol; 6 to 15 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, naphthol, etc. Phenols; acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
3 carbon atoms such as acetophenone and benzophenone
Ketones having 2 to 15 carbon atoms; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate,
Ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, γ-
Organic acid esters with 2 to 18 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acid halides with 1 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, etc. , methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, and other ethers having 2 to 20 carbon atoms; Carboxylic acids, acid anhydrides with 2 to 30 carbon atoms such as formic anhydride, acetic anhydride, benzoic anhydride, toluyl anhydride, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, methylamine, ethylamine, diethylamine, Amines such as tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile; and aluminum, silicon, tin, etc. that have these functional groups in their molecules. The following compounds can be mentioned. Two or more types of these electron donors can be used. Complex (a) may contain other metals, elements, and functional groups, and may be mixed with a solid inert diluent before use. Methods for producing the composite (a) are known, for example, as disclosed in JP-A-50-108385 and JP-A-50-126590.
No. 51-20297, No. 51-28189, No. 51-
No. 64586, No. 51-92885, No. 51-127185, No. 51
−136625, No. 52-87489, No. 52-100596,
No. 52-104593, No. 52-147688, No. 52-151691
No., Patent Application No. 51-76085, No. 51-114630, No. 51
-114631, No. 52-14068, No. 52-22754, etc. A few examples of these methods will be briefly described. (1) Magnesium compound, preferably Mg(OR) _o
X _2-o (R is a hydrocarbon group, preferably, e.g.
_C1 to _C10 alkyl group, _C6 to _C12 aryl group, _C3 to _C8 cycloalkyl group, 0≦n≦
2. A magnesium compound of the formula (X is halogen), more preferably magnesium chloride, and an organic acid ester are mechanically mixed in the presence or absence of a small amount of hydrocarbon, silicon compound, aluminum compound, alcohol, phenol, etc. The pulverized product is strongly pulverized, and the pulverized product is, for example,
No. 14068, Japanese Patent Application No. 52-22754, a titanium halide, preferably titanium tetrachloride, is reacted with or without treatment with a silicon compound, an organoaluminum compound, etc., or these with an alcohol. . (2) A magnesium halide, preferably magnesium chloride, is reacted with an alcohol (or phenol) as exemplified above and an organic acid ester as exemplified above, and then an organoaluminum compound as exemplified above or an organoaluminum compound as exemplified above, 92885
A silicon halide as exemplified in No. 1 is reacted, and a titanium compound, preferably titanium tetrachloride, is further reacted. (3) The product obtained in (1) or (2) above is further reacted with an organic acid ester such as those exemplified above and a titanium compound, preferably titanium tetrachloride. (4) The product obtained in (1) or (2) above is reacted with an organic acid ester as exemplified above, a titanium compound, preferably titanium tetrachloride, and an organoaluminum compound as above. The titanium of the composite (a) produced using titanium tetrachloride by the methods (1), (2), and (3) above is often tetravalent. In addition, when titanium tetrachloride is used in the method (4) above, the titanium in the composite (a) is often mixed with tetravalent titanium and trivalent titanium, although it varies depending on the amount of organic aluminum compound used for the reaction. is a mixture of titanium. In addition to the above method, countless variations are possible by changing the order of addition of the reaction reagents, performing the reaction multiple times, or adding other additional reaction reagents. However, whichever method is adopted, the halogen, titanium,
Magnesium, mutual ratio of electron donors, surface area,
It is desirable that the X-ray spectrum be in the range or state described above. Electron donors preferably contained in the complex (a) include organic acid esters,
Those that do not have active hydrogen such as ethers, ketones, tertiary amines, acid halides, and acid anhydrides, and organic acid esters or ethers are particularly preferred, and among them, aromatic carboxylic acid esters and alkyl group-containing Ether is also preferred.
Representative examples of suitable aromatic carboxylic acid esters include lower alkyl esters such as benzoic acid, lower alkylbenzoic acid, and lower alkoxybenzoic acid. The lower word here has a carbon number of 1
It means those having 1 to 4 carbon atoms, and those having 1 or 2 carbon atoms are particularly preferred. Preferred alkyl group-containing ethers are ethers having 4 to 20 carbon atoms such as diisoamyl ether and dibutyl ether. As the organoaluminum compound (b), a compound having at least one Al-carbon bond in the molecule can be used, for example, (i) a compound having the general formula R ¹ _n Al
(OR ² ) _o HpXq (where R ¹ and R ² are carbon atoms,
It usually contains 1 to 15 hydrocarbon groups, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other.
X is halogen, m is 0<m≦3, n is 0≦p<
3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3), (ii) general formula M ¹ AlR ¹ ₄
(Here, M ¹ is Li, Na, or K, and R ¹ is the same as above) Complex alkylated products of Group 1 metals and aluminum can be mentioned. Examples of the organoaluminum compounds that belong to (i) above include the following. General formula R ¹ mAl
(OR ² ) _3-n (where R ¹ and R ² are the same as above. m
is preferably a number of 1.5≦m≦3), the general formula
R ¹ mAlX _3-n (where R ¹ is the same as above, X is halogen, m is preferably 0<m<3), general formula R ¹ mAlH _3-n (where R ¹ is the same as above) m is preferably 2≦m<3), general formula R ¹ mAl
(OR ² )nXq (where R ¹ and R ² are the same as above.
X is halogen 0<m≦3, 0≦n<3, 0≦q<
3 and m+n+q=3). Among the aluminum compounds belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum,
In addition to trialkenylaluminums such as triisoprenylaluminum, dialkylaluminum alkoxides _{such as diethylaluminium ethoxide and dibutylaluminum butoxide, and alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, R 12} ^. ₅ Al( ^OR2 _{) 0.5}
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquichloride, etc., with an average composition of Partially halogenated alkyl aluminum, diethylaluminium hydride, such as alkyl aluminum sesquihalogenides such as bromide, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc.
Dialkyl aluminum hydrides such as dibutyl aluminum hydride, partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide partially alkoxylated and halogenated alkyl aluminums such as Also
A compound similar to (i) may be an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , Examples include: Examples of compounds belonging to (ii) above include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use tolylalkyl aluminum and alkyl aluminum halide. Representative examples of the catalyst component (C) include ethers, alcohols, phenols, ketones, aldehydes, acid anhydrides, carboxylic acids among the electron donors contained in the catalyst component (a), Examples include those similar to organic acid esters. In the present invention, the copolymerization of propylene and 1-butene or propylene and 1-butene and polyene is preferably carried out in a liquid phase. Further, in liquid phase copolymerization, it is preferable to adopt conditions such that the copolymer is dissolved. In liquid phase copolymerization, inert solvents such as propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; methylene chloride, ethyl chloride, ethylene chloride, and chlorobenzene. Halogenated hydrocarbons such as can be used as reaction media. Alternatively, the copolymerization component itself can be used as the reaction medium. In the case of liquid phase polymerization, the concentration of the composite (a) component in the polymerization system is approximately 1% per liquid phase on a titanium atom basis.
The concentration of the organoaluminum compound (b) is preferably from about 0.1 to about 50 mmol based on aluminum atoms per liquid phase. The amount of the organoaluminum compound to be used is such that the ratio of aluminum atoms to titanium atoms in component (a) is preferably about 1/1 to about 1000/
1, more preferably about 1/1 to about 200/1. On the other hand, in the case of ethers, the amount of catalyst component (c) used is about 0.001 to about 10 mol, preferably about 10 moles per aluminum atom of organoaluminum compound (b).
0.001 to about 8 moles, more preferably about 0.1 to about 5 moles, in the case of alcohols, phenols, ketones, aldehydes or acid anhydrides, about
0.001 to less than 1 mole, preferably about 0.001 to about 0.99 mole, more preferably about 0.1 to about 0.9 mole
Mol, for carboxylic acids, about 0.001 to about 0.5
moles, preferably about 0.001 to about 0.4 moles, more preferably about 0.01 to about 0.35 moles, and in the case of organic acid esters, about 0.001 to about 0.1 moles, preferably about 0.001 to about 0.05 moles, even more preferably about
0.01 to about 0.03 mole. However, it goes without saying that when two or more of these components are used as a mixture, the optimum molar ratio with the organoaluminum compound (b) will be slightly different from when only one component is used. The copolymerization of the present invention can be carried out in the same manner as the polymerization reaction of olefin using a typical Ziegler type catalyst. The copolymerization temperature is generally selected to be in the range of 10 to less than 140°C, preferably in the range of about 50 to about 120°C. The polymerization is preferably carried out under pressure, usually normal pressure to 50 kg/cm ² , especially 2 to 50 kg/cm 2 .
It is preferable to carry out under pressure of about 20° C./cm ² . The molar ratio of propylene and 1-butene is 35/65 to 59/
41. To produce a copolymer with an iodination of 30 or less, the supply ratio of propylene/1-butene ( molar ratio)
It is preferable that the ratio is about 10/90 to 70/30, and the concentration of polyene in the polymerization vessel is about 1 mol/or less. During copolymerization, hydrogen, dialkylzinc, organomagnesium compounds, etc. may be present in the polymerization system for the purpose of controlling the molecular weight or for other purposes. The copolymer rubber of the present invention can be used alone or mixed with other synthetic rubbers or natural rubbers as a material for tubes, hoses, etc. The copolymer rubber of the present invention can also be used as it is or by vulcanizing the mixture with other synthetic rubbers or natural rubbers in fields where hot-flow rubbers have conventionally been used. Vulcanizing agents used in vulcanized rubber formulations include sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and sulfur compounds such as selenium dimethyldithiocarbamate. , magnesium oxide, zinc white, red lead, and other metal compounds. Among these, sulfur is preferred. Sulfur is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the rubber component.
Used in parts by weight. Further, a vulcanization accelerator can be used if necessary. As a vulcanization accelerator, N-
Cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N.N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-
Thiazoles such as (2,4-dinitrophenyl), mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, and benzothiazyl-disulfide; diphenylguanidine, triphenylguanidine, di-ortho-tolyl Guanidine series such as guanidine, orthotolyl biguanide, and diphenylguanidine phthalate; acetaldehyde-aniline reaction product; butyraldehyde-aniline condensate; aldehyde amine or aldehyde-ammonia series such as hexamethylenetetramine and acetaldehyde ammonia; 2-mercaptoimidazoline Imidazoline series such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, di-ortho-tolylthiourea; thiourea series such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide Thiuram series such as hydride, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate,
Examples include dithioate salts such as zinc ethyl phenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, selenium dimethyl dithiocarbamate, and tellurium diethyldithiocarbamate; xanthate systems such as zinc dibutyl xanthate; . These vulcanization accelerators are usually 0.1 to 20 parts by weight, preferably 0.2 parts by weight, per 100 parts by weight of the rubber component.
It is used in a proportion of 1 to 10 parts by weight. In addition, vulcanization accelerators, activators, dispersants, fillers,
Softeners, plasticizers, tackifiers, colorants, foaming agents,
Foaming aids, lubricants, anti-aging agents, and other additives may also be used. Examples of fillers include inorganic fillers such as carbon black, white carbon (silicic acid compounds), calcium carbonate, talc, and clay; high styrene resins, coumaron indene resins, phenolic resins, lignin, modified melamine resins, petroleum resins, etc. Mention may be made of organic fillers. Among these, inorganic fillers are particularly preferably used. Softeners include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Resin oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinole, palmitic acid, barium stearate, calcium stearate, and zinc laurate; petroleum Examples include synthetic polymeric substances such as resins. Plasticizers include phthalate esters, adipate esters, sebacate esters, phosphoric acid esters, etc. Tackifiers include coumaroindene resin, terpene/phenol resin, xylene/formalin resin, etc. Colorants include inorganic and organic pigments.Blowing agents include sodium bicarbonate, ammonium carbonate, N・N'-dinitrosopentamethylenetetramine, azocarbonamide, azobisisobutyronitrile, benzenesulfonyl hydrazide, toluenesulfonite hydrazide, calcium azide. , paratoluenesulfonyl azide, etc. As the foaming aid, salicylic acid, phthalic acid, urea, etc. can be used. Further, the compound can be manufactured by a known method using an open roll mill, a Banbury mixer, a kneader, or the like. Vulcanization method is usually 100℃~250℃, preferably 120℃
Vulcanization can be carried out at a temperature of .degree. C. to 200.degree. C. for a period of usually 10 minutes to 60 minutes, preferably 20 minutes to 40 minutes. The copolymer rubber of the present invention can also be mixed with a thermoplastic resin to modify the resin, for example to improve impact resistance or soften the resin. For example, high density, medium density or low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-
Pentene, ethylene/vinyl acetate copolymer, Surlyn A, ethylene/vinyl alcohol copolymer,
It can be used by mixing with polystyrene, maleic anhydride grafted products thereof, and the like. When using a copolymer rubber, various stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, pigments, inorganic or organic fillers, etc. can be added. Examples of these include 2,6-di-tert-butyl-p-cresol, tetrakis[methylene-3-(3,5-di-tert-butyl-4
-Hydroxyphenyl)propionate] methane, 4,4'-butylidenebis(6-tert-butyl-m-cresol), tropherols, dilaurylthiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N/N -(bis-2-hydroxyethyl)alkylamine, 2-(2'-hydroxy-3', 5'-di-tert-butylphenyl)-5
-Chlorbenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc, clay, gypsum, glass fiber, titania, calcium carbonate, carbon black, petroleum resin, polybutene, wax etc. can be mentioned. Example 1 [Catalyst Preparation] 20 g of anhydrous magnesium chloride, 4.6 ml (32.16 m
mol) of ethyl benzoate and 3.0 ml of ethylpolysiloxane (viscosity 20C.S. (25℃)) in a stainless steel (SUS-32) bowl with a diameter of 15 mm in a nitrogen atmosphere.
The product was placed in a stainless steel (SUS-32) ball mill cylinder with an internal volume of 800 ml and an internal diameter of 100 mm, containing 2.8 kg, and left in contact for 100 hours with an impact acceleration of 7.8 G. 10 g of the obtained solid treated product was suspended in 100 ml of titanium tetrachloride, and after contact at 80°C for 2 hours with stirring, the solid component was collected by filtration, and free titanium tetrachloride was no longer detected in the washing solution. After washing with purified hexane until drying, a titanium-containing solid catalyst component (a) is obtained.
The catalyst component contained 2.0% by weight of titanium, 66.0% by weight of chlorine, and 6.5% by weight of ethyl benzoate, and had a surface area of 200 m ² /g. [Polymerization] A copolymerization reaction of propylene and 1-butene was continuously carried out using two glass polymerization vessels equipped with stirring blades. That is, toluene is continuously supplied as a polymerization solvent from the top of the polymerization vessel at a rate of 4/hour.
On the other hand, the polymerization liquid in the polymerization vessel is always at 1 level from the bottom of the polymerization vessel.
The polymerization liquid is continuously extracted so that The composite (a) was used as a catalyst, and the titanium concentration in the polymerization vessel was 0.02 mmol/triethylaluminum (b), and the concentration in the polymerization vessel was 1.0 mmol/.
Ethyl ether as an electron donor (c) was continuously fed into the polymerization vessel from the top of the vessel so that the concentration in the vessel was 1.0 mmol/. Also, a mixed gas of propylene and 1-butene (propylene 30 mol%, 1-butene 70
mol %) at a rate of 400 per hour. The copolymerization reaction was carried out at 70°C by circulating hot water through a jacket attached to the outside of the polymerization vessel. When the copolymerization reaction is carried out under the conditions described above, a propylene/1-butene copolymer can be obtained in a uniform solution state. A small amount of methanol was added to the polymerization liquid taken out from the bottom of the polymerization vessel to stop the polymerization reaction, and after removing the catalyst residue with warm water to which a small amount of hydrochloric acid and methanol had been added, the polymerization liquid was poured into a large amount of methanol. to precipitate the polymer. The precipitated polymer was further washed with methanol and
It was dried under reduced pressure at ℃ overnight. Through the above operations, propylene/1-butene copolymer was obtained at a rate of 120 g/hour. The propylene content measured by nuclear magnetic resonance spectroscopy was 45.1 mol%, no melting point was observed by DSC analysis, the intrinsic viscosity was 1.35 dl/g measured in decalin at 135°C, and the boiling point was n.
- Hexane insoluble content was 0%, boiling diethyl ether soluble content was 19.6% by weight. In addition, the stress at break measured according to JIS K630193
Kg/cm ² and elongation at break was 830%. Furthermore, this copolymer had no tackiness on the surface of the press sheet. Examples 2 and 3 The same operation as in Example 1 was repeated by changing the mixing ratio of the propylene/1-butene mixed gas supplied. The polymerization results are shown in Table 1.

[Table] Examples 4 to 18 The same operations as in Example 1 were repeated using various compounds instead of diethyl ether as the electron donor (c), which is a component of the polymerization catalyst. The polymerization results are shown in Table 2.

[Table] Examples 19 and 20 The same operation as in Example 1 was repeated using triisobutylaluminum and diethylaluminium chloride instead of triethylaluminum as the organoaluminum compound (b) which is a component of the polymerization catalyst. The polymerization results are shown in Table 3.

[Table] Reference Examples 21-23 In Example 1, the concentration of complex (a) in the polymerization vessel was
Synthesize a propylene/1-butene/polyene copolymer by carrying out the same procedure except that polyene is continuously supplied to the polymerization vessel in addition to propylene and 1-butene as monomers so that the amount is 0.05 mmol/monomer. did. The obtained copolymer was vulcanized at 160℃ for 30 minutes using the following compounding method, and then vulcanized according to JIS K6301.
Physical properties were measured according to the following. The results are shown in Table 4.

【table】

【table】

【table】

[Table] Example 24 Here, an example is shown in which a polymerization reaction was carried out continuously under pressure in a hexane solvent using hydrogen as a molecular weight regulator. In 15 stainless steel polymerization vessels equipped with stirring blades, propylene was added as a monomer at 118 Nl/hr and 1-butene was added as a liquid at 2/hr (propylene/1-butene =
20/80 (mol/mol)), hydrogen was supplied as a molecular weight regulator at a rate of 1 Nl/hr, and hexane was supplied at a rate of 10/hr. On the other hand, the polymerization liquid was continuously drawn out from the lower part of the polymerization vessel so that the polymerization liquid in the polymerization vessel was always 5%. In addition, the composite (a) of Example 1 was used as a catalyst so that the titanium concentration in the polymerization vessel was 0.08 mmol/
Triisobutylaluminum (b) was adjusted to a concentration of 1.6 mmol/in the polymerization vessel, and an electron donor was
As (c), the concentration of n-butyl ether in the polymerization vessel is
Each was fed into the polymerization vessel from the top of the vessel at a concentration of 4.8 mmol/mole. The polymerization temperature was maintained at 60°C by circulating hot water through a jacket attached to the outside of the polymerization vessel. Polymerization solution is Example 1
A copolymer was obtained at a rate of 282 g/hour. The propylene content of the copolymer was 44.4 mol%, no melting point was observed, and the intrinsic viscosity was 3.51 dl/g.
n-hexane insoluble content 0, ethyl ether soluble content
18.7% by weight, stress at break 116Kg/cm ² , elongation at break
It was 730%. Example 25 Polymerization was carried out at 30°C instead of 70°C in Example 1.
The same operation was repeated except that The results are shown in Table 5. Examples 26 and 27 The same operation as in Example 24 was repeated except that the polymerization temperature was 100°C and 120°C. Table 5 shows the results.
Shown below.

[Table] Example 28 [Catalyst Preparation] Titanium-containing solid component (a) was obtained by carrying out the same operation as in Example 1 except that 4.5 ml of di-n-propyl ether was used instead of 4.6 ml of ethyl benzoate. Ta. The catalyst component contained 1.8% by weight of titanium, 64.0% by weight of chlorine and 5.1% by weight of n-propyl ether, and had a surface area of 220 m ² /g. [Polymerization] Using the composite (a), the same operation as in Example 1 was repeated to obtain a copolymer at a rate of 100 g/hour. Copolymer propylene content 49.9 mol%,
No melting point was observed by DSC, and the intrinsic viscosity was 1.58 dl/
g, the content insoluble in boiling n-hexane was 0%, and the content soluble in boiling diethyl ether was 20.4% by weight. Moreover, the stress at break before copolymerization was 101 Kg/cm ² and the elongation at break was 820%, and the surface of the press sheet had no tackiness. Example 29 [Catalyst Preparation] 0.1 mol of anhydrous magnesium chloride was suspended in 300 ml of kerosene, and 0.4 mol of ethyl alcohol and 0.1 mol of ethyl benzoate were added thereto at room temperature.
I stirred it for an hour. Next, 0.3 mol of diethylaluminium monochloride was added dropwise at room temperature, and the mixture was stirred for 1 hour. The solid portion of the product was taken and thoroughly washed with kerosene, then suspended in 300 ml of kerosene solution containing 30 ml of titanium tetrachloride, and reacted at 80° C. for 2 hours. After the reaction was completed, the supernatant was removed by decanting, and the solid was thoroughly washed with fresh kerosene. This catalyst component (a) contained 2.5% by weight of titanium, 58.0% by weight of chlorine, and 9.5% by weight of ethyl benzoate, and had a surface area of 180 m ² /g. [Polymerization] Using the composite (a), the same operation as in Example 1 was repeated to obtain a copolymer at a rate of 113 g/hour. The propylene content of the copolymer is 46.9 mol%,
No melting point was observed by DSC, and the intrinsic viscosity was 1.39 dl/
g, the content insoluble in boiling n-hexane was 0%, and the content soluble in boiling diethyl ether was 20.8% by weight. Further, this copolymer had a stress at break of 90 Kg/cm ² and an elongation at break of 850°C, and had no adhesive force on the surface of the press sheet. Comparative Example 1 Here, for comparison with the present invention, an example will be shown in which a propylene/1-butene copolymer with low crystallinity is obtained based on a conventional method (Japanese Patent Laid-Open No. 50-38787). After replacing the stainless steel autoclave 2 equipped with a stirring blade with nitrogen in advance, 450 ml of hexane,
1 mol of propylene, 4 mol of 1-butene, and 14.2 mmol of triethylaluminum as a catalyst are charged. After heating the autoclave to 140°C, 28.4 mmol of titanium trichloride-A was added into the autoclave to initiate polymerization. After carrying out the reaction at a polymerization temperature of 140° C. for 1 hour, a small amount of methanol was added into the autoclave to stop the polymerization. Unreacted monomers were expelled and the polymerization solution was treated in the same manner as in Example 1 to obtain 85 g of a copolymer. The propylene content of the copolymer is 49.8 mol%, the melting point is 73℃, the limit is 2.18
dl/g, boiling n-hexane insoluble content was 0%, and boiling diethyl ether soluble content was 91% by weight. Moreover, this copolymer had a stress at break of 52 Kg/cm ² and an elongation at break of 930%, and tackiness was observed on the surface of the press sheet. Comparative Example 2 Here, an example will be shown in which an amorphous propylene/1-butene copolymer synthesized using a vanadium catalyst has a higher ether-soluble content and poorer strength and physical properties than the copolymer of the present invention. A copolymerization reaction of propylene and 1-butene was carried out using vanadium oxytrichloride and diethylaluminum monochloride as polymerization catalysts. That is, 55 ml of hexane as a solvent was placed in a glass polymerization vessel 1 which had been previously purged with nitrogen, and then 50 mmol of dimethylaluminum monochloride was added. Atmosphere: propylene/1-butene mixed gas (propylene 35 mol%, 1-butene 65 mol%)
After the mixed gas was dissolved and saturated at 20°C, 6 mmol of vanadium oxytrichloride was added to initiate polymerization. After carrying out a copolymerization reaction at 20° C. for 10 minutes while blowing mixed gas, a small amount of methanol was added to the polymerization solution to stop the rubber formation. The polymerization solution was treated in the same manner as in Example 1 to obtain 23 g of a copolymer. The propylene content of the copolymer was 51.0 mol%, and no melting point was observed by DSC.
Intrinsic viscosity 1.08 dl/g, boiling n-heptane insoluble content 0
%, boiling diethyl ether soluble content was 93% by weight. Moreover, this copolymer had a stress at break of 10 Kg/cm ² and an elongation at break of 1100%, and its strength and physical properties were extremely inferior to those of the copolymer of the present invention.

Claims (1)

[Scope of Claims] 1 (A) consisting of propylene and 1-butene, or propylene and 1-butene and polyene, (B) propylene/1-butene (molar ratio) 35/65
~59/41, (C) has an iodine number of 30 or less, (D) has no observed melting point based on differential scanning calorimetry (DSC) thermal analysis or is less than 40°C, (E) 135°C, A rubbery random copolymer characterized by having an intrinsic viscosity [η] measured in decalin of 0.5 to 6.0 dl/g, and (F) a boiling diethyl ether soluble content of 50% by weight or less. 2. The rubbery random copolymer of claim 1, wherein the (D) melting point based on differential scanning calorimetry (DSC) thermal analysis is not observed or is less than about 20°C. 3. The rubbery random copolymer according to claim 1 or 2, which is substantially soluble in boiling n-hexane.