JPH0550537B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a stabilizer-containing high molecular weight 3-methylbutene-1 polymer having excellent stretchability and impact resistance. [Prior Art] In recent years, resins with excellent heat resistance, mechanical strength, electrical properties, chemical resistance, moisture absorption resistance, etc. have become increasingly important as various molding materials or stretched film materials. For example, in terms of stretched film materials, polyethylene terephthalate film and polyimide film are currently typically used for magnetic recording base films and flexible printed wiring boards, but these are not necessarily satisfactory in terms of physical properties. isn't it. That is, polyethylene terephthalate film has insufficient heat resistance, and polyimide film has a large hygroscopic expansion coefficient and is expensive. Furthermore, poly(4-methylpentene-1), which is a heat-resistant polyolefin having characteristics such as electrical properties, chemical resistance, and moisture absorption resistance, does not necessarily have satisfactory physical properties in terms of heat resistance and mechanical strength. On the other hand, 3-methylbutene-1 polymer has been known as a crystalline heat-resistant polyolefin with a high melting point, but it generally has poor elongation properties and impact resistance, and is not necessarily used as a variety of molding materials or stretched film materials. It is difficult to say that it is a satisfactory resin, and it is thought that it has not been commercially produced until now. For example, if we consider the case of making a stretched film from 3-methylbutene-1 polymer, generally speaking, plastic film is stretched at a temperature below the melting point of the plastic and above the second-order transition point to achieve planar orientation. However, 3-methylbutene-1 polymer is stretched at a temperature of about 50°C to 310°C. However, since the elongation at break of this polymer is relatively small, stretching tends to be uneven, and when stretched at a high magnification, the film breaks, making it difficult to obtain a stretched film. The reason for the physical properties of such 3-methylbutene-1 polymer is the 3-
One example of this is that the methylbutene-1 polymer has a low molecular weight. [Object of the Invention] In order to improve the drawbacks of conventional 3-methylbutene-1 polymers, the present inventors conducted intensive studies on increasing the molecular weight of 3-methylbutene-1 polymers, and developed 3-methylbutene-1 polymers. The present inventors have discovered that the stretchability and impact resistance of 3-methylbutene-1 polymer can be greatly improved by increasing the molecular weight, that is, the melt viscosity of the polymer, to a certain value or higher and containing a stabilizer. . To explain in more detail how to increase the molecular weight of the 3-methylbutene-1 polymer, the 3-methylbutene-1 polymer has a high melting point, and the processing temperature must necessarily be high. Since the 3-methylbutene-1 polymer is a type of polyolefin, the decrease in molecular weight due to deterioration during processing at such high temperatures cannot be ignored. Therefore, in order for a high molecular weight 3-methylbutene-1 polymer to maintain the above-mentioned improved stretchability and impact resistance during stretching or molded products, it is necessary to include an appropriate stabilizer during processing. It is necessary that the initial high molecular weight can be maintained even after the treatment. In other words, the gist of the present invention is to
Melt viscosity at 0.11/sec is 1×10 ⁴ poise or more,
and 3-methylbutene-1 containing certain stabilizers
or a copolymer composition of 3-methylbutene-1 and butene-1. [Structure of the Invention] The present invention will be described in detail below. The 3-methylbutene-1 polymer of the present invention is a homopolymer of 3-methylbutene-1 or a copolymer of 3-methylbutene-1 and butene-1, and has a melt viscosity that exceeds that of a conical disk type rotational rheometer. Use 330℃,
The polymer has a shear rate of 1×10 ⁴ poise or more as measured at a shear rate of 0.11/sec or an angular velocity of 0.1 radian/sec.
More preferably, it needs to be 5×10 ⁴ poise or more; if it is less than this, the stretchability and impact resistance will be poor. Further, in consideration of moldability, the upper limit is 1×10 ⁹ poise or less, preferably 1×10 ⁸ poise or less. Butene-1 is preferably present in the polymer in an amount of 40% by weight or less, more preferably 20% by weight or less. If the copolymerization component exceeds this level, 3-methylbutene-1
The heat resistance, rigidity, and strength of the polymer are poor, making it undesirable. 3-Methylbutene- having such a melt viscosity
Although the method for producing the 3-methylbutene-1 polymer is not necessarily limited, for example, a high molecular weight 3-methylbutene-1 polymer can be easily obtained by the following method invented by the present inventors. can. That is, in an aliphatic, alicyclic or aromatic hydrocarbon such as hexane, hebutane, cyclohexane or benzene, in a liquid olefin, or in the absence of a solvent, the aluminum content is 0.15 or less in terms of the atomic ratio of aluminum to titanium, and in the presence of a catalyst system consisting of a solid titanium trichloride catalyst complex containing a complexing agent and aluminum diisobutyl monochloride or further as a third component an electron donating compound such as an ether, ester, amine or amide, the polymerization temperature is 0. Polymerize 3-methylbutene-1 alone or 3-methylbutene-1 and butene-1 at ~150°C.
This is a method of copolymerizing. Such a solid titanium trichloride catalyst complex was developed by
55-8451, 55-8452, 55-8003, 54-
No. 27871, No. 55-39165, and Japanese Unexamined Patent Publication No. 47-34478. Alternatively, 3-methylbutene-1 may be polymerized alone in the presence of the above catalyst or a commonly known Ziegler catalyst, or 3-methylbutene-1 and butene-1 may be polymerized.
It is also possible to partially crosslink a polymer obtained by copolymerizing with. In the present invention, a stabilizer is added to the 3-methylbutene-1 polymer obtained by the method described above, so that it can maintain a high molecular weight without deteriorating even after processing as referred to in the present invention.
"High molecular weight 3 methylbutene-1 containing stabilizer
Polymer” is obtained. The stabilizer to be used is tetrakis(2,4 ditertiarybutylphenyl) 4, which has a particularly high boiling point or decomposition initiation temperature among phosphorus types.
A combination of 4'biphenylene phosphonite and a hindered phenolic antioxidant, pentaerythritol tetrakis [3-(3,5 ditertiarybutyl-4 hydroxyfer) propionate], is used. In addition to the above combination, long-term heat and oxidation resistance,
It is also possible to add other types of stabilizers, such as metal inhibitors, to impart weatherability. The amount of stabilizer added is based on the total amount of stabilizer added per 100 parts of 3-methylbutene-1 polymer.
It is 0.001 part to 2 parts. Using a stabilizer in an amount greater than the above range is not only ineffective, but also causes bleeding of the stabilizer or deterioration of physical properties, which is undesirable. If the amount of stabilizer is less than the above range, the effect will be insufficient. There are no particular restrictions on the method of adding the stabilizer, and 3
It is used depending on how the methylbutene-1 polymer is used. Examples of the addition method include a method in which a solution of the stabilizer dissolved in a solvent is sprinkled onto the 3-methylbutene-1 polymer powder, uniformly dispersed, and then dried; A method in which the stabilizer is mixed in a mixer such as a ribbon blender or a silo blender, or a method in which a solution of the stabilizer dissolved in a solvent is sprinkled onto the 3-methylbutene-1 polymer powder to uniformly disperse it, and then the mixture is melt-kneaded uniformly in an extruder. Examples include. There are no particular limitations on the method of processing the 3-methylbutene-1 polymer according to the present invention, but it is important to avoid raising the processing temperature too high or prolonging the processing time.
This is contrary to the intention of the present invention, which is to obtain a molded product of a high molecular weight 3-methylbutene-1 polymer.
A suitable molding temperature is 280°C to 360°C, depending on the melting point of the 3-methylbutene-1 polymer used. Further, it is desirable that the molding time be 20 minutes or less. Examples of the molding method include injection molding, extrusion molding, compression molding, and powder coating methods. Furthermore, since the elongation properties are greatly improved by increasing the molecular weight, a stretched high-strength film can also be obtained by stretching a film obtained by compression molding, T-die extrusion, or inflation molding. [Example] Examples will be shown below, but the present invention is not limited to the examples. The mechanical properties of the 3-methylbutene-1 polymer molded products in the examples are values measured according to ASTM-D638. To measure the melt viscosity, first, 3-methylbutene-1 polymer was heated to 330°C for 6 minutes, and the diameter was 50 mm.
The sample is compression molded into a disk-shaped sheet with a thickness of 1 mm. In particular, when a 3-methylbutene-1 polymer without a stabilizer is used as a sample, thermal deterioration during compression molding is severe, so it is necessary to accurately control the temperature and time during molding. Next, the melt viscosity of this sample was measured in a nitrogen stream at 330° C. and an angular velocity of 0.1 rad/sec using a conical disk type rotational rheometer. A conical disk (cone type plate) with a diameter of 50 mm and a cone angle of 0.04 radian was used. In the measurement, a sample piece was sandwiched between a cone type plate and a sample stage set at 330℃, and as the sample was gradually heated and melted, the cone type plate was lowered until the sample thickness was 50μ.
Measurement begins at the point where . The higher the melt viscosity of each sample, the longer it takes for the thickness to reach 50 μm, and the melt viscosity cannot be measured until then. On the other hand, the 3-methylbutene-1 polymer was thermally degraded not only during sample molding as described above but also during melt viscosity measurement.
The melt viscosity decreases over time. What we want to obtain in this measurement is the melt viscosity of the sample obtained by compression molding at a time when it has not deteriorated. Therefore, in this application, the melt viscosity is defined as the time when the sample is set in a conical disk type rotating rheometer.
From this point, the melt viscosity was measured over time, and the obtained data was extrapolated to time 0, and the value obtained was adopted. Production example 1 (A) Production of a homogeneous titanium trichloride solution 150 ml of purified toluene and titanium tetrachloride were placed in a 500 ml four-necked flask purged with dry argon.
Add 90 mmol and add di-n-butyl ether.
90 mmol was added. Titanium tetrachloride and di-n-butyl ether reacted with some heat and were uniformly dissolved in toluene to obtain an orange-yellow homogeneous solution.
A solution prepared by dissolving 45 mmol of diethylaluminum monochloride in 20 ml of toluene was gradually added to the solution while stirring and maintaining the solution at 25° C., thereby obtaining a dark orange homogeneous solution of titanium trichloride. (B) Formation of precipitate of titanium trichloride and production of catalyst When the homogeneous solution of titanium trichloride obtained in step (A) above was heated to 95°C, a precipitate of purple titanium trichloride was formed during the heating process. Admitted. After stirring at 95° C. for 60 minutes, the precipitate was separated and washed five times with 100 ml of n-heptane to obtain a fine particulate purple titanium trichloride catalyst complex.
Elemental analysis showed that the catalyst complex had a composition of the formula TiCl ₃ (AlCl ₃ ) 0.004 [(nC ₄ H ₉ ) ₂ O] 0.05. Example 1 Using the solid titanium trichloride catalyst complex obtained in Production Example-1 in an induction stirring autoclave with a capacity of 2,
Polymerization of methylbutene-1 was carried out as follows. 1.1 g of the solid titanium trichloride catalyst complex obtained in Production Example-1 and 15 mmol of diisobutylaluminum monochloride were placed in an autoclave that had been sufficiently vacuum-dried and purged with nitrogen. Then, 820g of 3-methylbutene-1 was charged, and polymerization was carried out at 80°C for 3 hours. Then isobutyl alcohol 25
ml was injected under pressure to stop the polymerization and expel the excess unreacted monomer. Next, 1000 ml of n-hexane was introduced, and after stirring at 50°C for 30 minutes, the supernatant liquid was taken out and the catalyst component in the polymer was washed away. After repeating this operation five times, it was dried to obtain 350 g of white powdered poly-3-methylbutene-1. Irganox 1010* ¹ , Irgafos P-
0.2 parts each of EPQ* ² (all manufactured by Ciba Geigy, Japan; Irganox and Irgafos are trademarks) was added to homogenize. The melting point of this copolymer is 307℃, and the melt viscosity is 4.5×
It was 10 ₅ poise. The mechanical properties and melt viscosity of the molded product obtained by injection molding this powder at a cylinder temperature of 340°C are shown below.
Shown in 1. In addition, 200 μm was obtained by compression molding using the above powder.
After forming a thick film, it was uniaxially stretched at 200°C. The mechanical properties of the obtained stretched film are shown in Table 2. *1 Irganox 1010: Pentaerythritol Tetrakis [3-(3,5 ditertiarybutyl 4-hydroxyphenyl) propionate] *2 Irgafos P-EPQ: Tetrakis (2,
4,4' Vinyphenylene Phosphonite Example 2 In Example-1, a small amount of butene-1 was introduced every 5 minutes at the same time as the polymerization started, and Polymerization was carried out in exactly the same manner as in Example 1, except that 15% by weight of butene-1 was copolymerized, and the same stabilizer was added. This copolymer had a melting point of 260° C. and a melt viscosity of 8×10 ⁵ poise. 300% of this powder
Table 1 shows the mechanical properties and melt viscosity of the molded product obtained by injection molding at °C. Table 2 shows the mechanical properties of the film obtained by extruding a 200 .mu. thick sheet using a T-die at a temperature of 300.degree. C. and then uniaxially stretching the film at a stretching temperature of 100.degree. Comparative Example 1 Example-1 except that the polymerization temperature was 20°C and the co-catalyst was triethylaluminum.
Polymerization was carried out in exactly the same manner. The melting point was 303°C. The melt viscosity of the polymerized powder to which 0.2 part of DLTP* ⁴ was added as a stabilizer was 2.4×10 ³ poise, which was a very low viscosity. Table 1 shows the mechanical properties of a sheet obtained by press-molding the above polymerized powder at 330°C. Further, the film was extruded using a T-die and uniaxially stretched in the same manner as in Example 1, but the film broke during stretching. As described above, when the obtained 3-methylbutene-1 polymer has a low melt viscosity, that is, a low molecular weight, it has a low elongation at break, and therefore lacks stretchability. *4 DLTP (manufactured by Ciba Geigy)
IRGANOXPS800) Dilaurylthiopropionate Comparative Example 2 Polymerization was carried out in exactly the same manner as in Example-1 except that diethylaluminum chloride was used as the co-catalyst. The melting point was 307°C. When 0.2 parts of DLTP was added to this polymer powder, the melt viscosity was as low as 9.9×10 ³ poise. Table 1 shows the mechanical properties and melt viscosity of a sheet obtained by compression molding this polymer powder. Further, a film was formed by compression molding and uniaxially stretched in the same manner as in Example 1, but high-magnification stretching was not possible. Table 2 shows the physical properties of the 1.5 times stretched product. Comparative Example 3 In Example 3, pelletizing and injection molding were carried out in the same manner as in Example 1 except that no stabilizer was added. The melt viscosity of the pellets was 1.2×10 ³ poise, which was much lower than that of the pellets of Example 1 in which a stabilizer was added. Table 1 shows the mechanical properties of the molded product obtained by injection molding at a cylinder temperature of 320°C. Example 3 In Example-1, an autoclave with a capacity of 5 was used, the polymerization temperature was set to 80°C, and the other conditions were as in Example-1.
1. Copolymerize butene-1 and methylbutene-1 in a similar manner to Example-2 to obtain 850 g of 3-methylbutene-1-butene-1 copolymer powder with a melting point of 285°C.
I got it. To this polymerized powder, 0.2 parts each of Irganox 1010 and Irgaphos P-EPQ were added and pelletized at a cylinder temperature of 320°C. The melt viscosity of this pellet was 1.8×10 ⁵ poise. Table 1 shows the physical properties and melt viscosity of a test piece obtained by injection molding this pellet at 320°C.

【table】

〔Effect of the invention〕

As described above, 3-methylbutene-1 according to the present invention
Polymer molded products not only have excellent rigidity, strength, heat resistance, chemical resistance, solvent resistance, and electrical properties, but also have improved impact resistance and elongation properties, which were disadvantageous in the past. It can be a useful material in the field of

Claims (1)

[Claims] 1 Melt viscosity at 300℃ and shear rate of 0.1/sec is 1
× ¹⁰ Add 100 parts by weight of a homopolymer of 3-methylbutene-1 or a copolymer of 3-methylbutene-1 and butene-1 with a size of 4 poise or more to Renphosphonite and pentaerythritol tetrakis [3-(3,5 ditertiarybutyl-4 hydroxyphenyl) propionate] from 0.001 to
A 3-methylbutene-1 (co)polymer composition characterized in that it contains 2 parts by weight.