JPH0554481B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a high molecular weight graft-modified 3-methylbutene-1 polymer which has excellent stretchability and impact resistance and is also effective as a powder coating material. 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 films and polyimide films are currently typically used for magnetic recording base films and flexible printed wiring boards, but these films do not always have satisfactory physical properties. It's not a thing. In other words, polyethylene terephthalate film has insufficient heat resistance,
Polyimide film has a high 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. Regarding powder and granules, conventionally known polyolefin powders are not necessarily good in terms of particle size and shape, and furthermore, the coating films made of these powders have the disadvantage of being poor in oil resistance and heat resistance. For example, in the case of polyethylene, polypropylene, etc., the film itself softens at temperatures above 100°C, and
Melting occurs at 160℃. In addition, the oil resistance was poor, and it had the disadvantage that it could not withstand use at all, especially at high temperatures. 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 this is thought to be the reason why 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 to achieve planar orientation. , 3-methylbutene-1 polymer will be stretched at a temperature of about 50°C to 310°C. However, since the elongation at break of the polymer is relatively small, stretching tends to be uneven, and when stretched at a high ratio, the film breaks, making it difficult to obtain a stretched film. One of the reasons for the physical properties of the 3-methylbutene-1 polymer is that the 3-methylbutene-1 polymers described in conventional literature have a low molecular weight. In order to improve the drawbacks of 3-methylbutene-1 polymer, the present inventors have made extensive studies to obtain a high molecular weight graft-modified 3-methylbutene-1 polymer. The graft-modified 3-methylbutene-1 polymer has excellent stretchability, impact resistance, and other properties such as heat resistance, and also has excellent powder properties and is effective as a powder coating material. We have discovered that this is the case, and have arrived at the present invention. That is, the gist of the present invention is a homopolymer of 3-methylbutene-1, or a homopolymer of 3-methylbutene-1 and α-1 having 2 to 12 carbon atoms.
0.001 to 5% by weight of unsaturated carbon atoms capable of graft reaction based on the weight of a 3-methylbutene-1 copolymer obtained by polymerizing olefin and/or polyene in an amount of 40% by weight or less based on the weight of 3-butylbutene-1. Monomers based on acids and their derivatives,
A graft-modified 3-methyl-butene-1 polymer having a melt viscosity of 1×10 ³ poise or more at 330°C and a shear rate of 0.1 ¹ /sec, in which part or all of the 3-methyl-butene-1 polymer has been graft-reacted. , the present invention will be explained in detail. More specifically, the graft-modified 3-methylbutene-1 polymer of the present invention relates to a graft-modified 3-methylbutene-1 polymer having a uniform particle shape and particle size distribution. The melt viscosity of the polymer was determined using a cone-disc rotating rheometer at 330°C and a shear rate of 0.1 ¹ /sec.
That is, it needs to be 1×10 ³ poise or more, more preferably 1×10 ⁵ poise or more when measured at an angular velocity of 0.1 radian/sec. Below this range, the stretchability and impact resistance are poor. Also, considering moldability, the upper limit is 1×10 ⁹ poise or less, preferably 1×
10 ⁸ poise or less is selected. Furthermore, among the above-mentioned polymers, if it is desired to obtain a polymer having particularly high stretchability and impact strength, it is possible to combine 3-methylbutene-1 and other α-olefins as a polymer before graft modification. It is desirable to use copolymers. 3-methylbutene-1
Examples of α-olefins having 2 to 12 carbon atoms to be copolymerized with ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1
1, styrene, vinylcyclohexane, etc. Examples of the polyene include butadiene, hexadiene, methylhexadiene, ethylidene norbornene, and the like. The copolymerization method may be so-called random copolymerization or block copolymerization. Among these, preferably 3-
Homopolymers of methylbutene-1, random copolymers of 3-methylbutene-1 and ethylene, propylene, butene, etc., block copolymers, 3-methylbutene-1
It is a copolymer of methylbutene-1 and a small amount of diene. The content of these copolymerized components in the polymer is preferably 40% by weight or less, more preferably 20% by weight or less. If the copolymerization component exceeds this range, the heat resistance, rigidity, and strength of the 3-methylbutene-1 copolymer will deteriorate, which is not preferable. In this application, when 3-methyl-butene-1 is used as a powder coating by modifying 3-methyl-butene-1 with a monomer made of an unsaturated carboxylic acid or its derivative, especially when coating metal or polar resin surfaces, etc. The adhesion properties with adherends are improved. Monomers used for such modification are usually well-known monomers. Examples include monocarboxylic acids and derivatives thereof such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as dicarboxylic acids and derivatives thereof such as maleic acid and citraconic acid, and vinyl monomer esters such as vinyl acetate. As the grafting method, all known methods can be used except for methods such as solution grafting and melt grafting that cause large changes in particle shape, but vapor phase grafting using ionizing radiation,
Slurry grafting using a radical initiator catalyst in a suitable medium as well as gas phase grafting can be mentioned. The type, amount, etc. of the graft monomer can be determined as appropriate depending on the actual purpose of use.
The amount is selected from 0.001 to 5% by weight, preferably 0.001 to 2% by weight, based on the weight of the 3-methylbutene-1 polymer. The method for producing the 3-methylbutene-1 polymer used in the present invention is not necessarily limited, but for example, high molecular weight 3-methylbutene can be easily produced by the following method invented by the present inventors. -1 polymer can be obtained. i.e. hexane,
In aliphatic, cycloaliphatic or aromatic hydrocarbons such as heptane, cyclohexane and benzene, in liquid olefins, or in the absence of solvent, the aluminum content is determined by the atomic ratio of aluminum to titanium.
0.15 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
This method involves polymerizing 3-methylbutene-1 alone at ~150°C, or copolymerizing 3-methylbutene-1 and an α-olefin and/or polyene having 2 to 12 carbon atoms. That is, it can be produced by polymerization in a slurry state in a suitable dispersion medium, monomers and copolymerized monomers, or by a gas phase method in a diluent gas. 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. The 3-methylbutene-1 polymer powder thus obtained has a particle shape that is spherical, elliptical, or similar, and is essentially free of clear edges, edges, and thread-like or whisker-like materials. It has the characteristics of being uniform and having a narrow particle size distribution. Particle size distribution is important in determining fluidity, and the Rosin-Ramler (Rosin-Ramler) ratio shown in the formula below is important.
It is preferable that the n value according to the Rammler distribution is 2 or more. R=100exp(-D _p /D _pp ) ⁿ [%] (In the formula, R is the cumulative distribution on the sieve, and D _pp is R=
Showing a particle size of 36.8%. ) Also, the obtained 3-methyl-butene-1 polymer,
The weight average particle diameter of the graft-modified polymer is 500 μm or less, more preferably 100 to 300 μm.
It is m. This is determined by classifying by sieve and integrating weight diameter at 50%. Because of these characteristics, the graft-modified 3-methylbutene-1 polymer powder can be used for various processing applications. The first thing to mention is powder coating materials, which have good flow properties and can form a uniform coating. For example, as will be clear from the examples below, it is useful as a powder coating material for steel plates. With particles obtained by ordinary mechanical pulverization, it is difficult to achieve close contact between the particles due to their irregular particle shapes, but with the graft-modified 3-methylbutene-1 particles of the present invention, good film formation can be achieved. Further, the film obtained from the methylbutene-1 powder according to the present invention does not soften even at a high temperature of 200°C, is resistant to hydrocarbon solvents such as hot toluene, and has sufficient resistance to acidic and alkaline aqueous solutions. Furthermore, as a result of improved impact resistance, the high molecular weight 3-methylbutene-1 polymer has excellent physical properties such as heat resistance, mechanical strength, and electrical properties as well as chemical resistance, solvent resistance, and transparency as a variety of molding materials. It is promising for various uses. Furthermore, various additives such as pigments, filler powders, surface treatment agents, stabilizers, etc. can be added as appropriate to the polymer of the present invention. Especially when used as a paint,
It can also be used in combination with powder coatings made of different polymers such as epoxy resins, and in particular can be used to improve the impact resistance of thermosetting powder coatings. Examples will be shown below, but the present invention is not limited to the examples. The mechanical properties of the 3-methylbutene-1 polymer in the examples are values measured according to ASTM-D638. To measure the melt viscosity, first, 3-methylbutene-1 polymer was heated at 330°C for 6 minutes with a diameter of 50 mm.
A sample was compression molded into a disk-shaped sheet with a thickness of 1 mm. Next, measurements were made using a conical disk type rotary rheometer at 330°C and an angular velocity of 0.1 radian/sec in a nitrogen stream. A cone type plate with a diameter of 50 mm and a cone angle of 0.04 radian was used for this measurement. Before starting the measurement, place the sample on a cone-type plate at 330°C, compress it until the sample thickness is 50μ, and then perform the measurement. The compression time is proportional to the melt viscosity of each sample and requires a certain amount of time. On the other hand, 3
-The melt viscosity of the methylbutene-1 polymer decreases over time due to thermal deterioration during this measurement. Therefore, the melt viscosity defined in the present invention was determined to be the melt viscosity when the thermal history of the sample was 0 hours by extrapolation. 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., to obtain 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 reveals that this catalyst complex has the formula _TiCl3
It had a composition of (AlCl _{3 ) 0.004 [} (nC ₄ H ₉ ) ₂ O] _0.05 . Example 1 Using the solid titanium trichloride catalyst complex obtained in Preparation Example 1 in an induction stirring autoclave with a capacity of 2,
Polymerization of methylbutene-1 was carried out as follows. 0.724 mmol of the solid titanium trichloride catalyst complex obtained in Production Example 1 and 6.16 mmol of di-iso-butylaluminum monochloride were charged into an autoclave which had been sufficiently vacuum-dried and purged with nitrogen. Then, after charging 630g of liquefied 3-methylbutene-1,
Polymerization was carried out at ℃ for 3.5 hours. Then, 25 ml of isobutyl alcohol was charged to stop the polymerization, and excess unreacted monomer was expelled. 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 286.4 g of white powdery poly-3-methylbutene-1. The obtained polymer particles were white powder, and when classified by sieve, the average particle size (50% weight diameter) was 210μ.
The particles had a well-uniform particle size, with an n value of 3.5 based on the Rosin-Rammler plot. According to the microscopic observation of the particles, as shown in Figure 1, they are almost spherical particles and their composite appearance, and there are no edges, sides, or ridges on the whole.
Moreover, it did not contain thread-like or whisker-like substances. The melt viscosity of this product at 330°C was 7×10 ⁵ poise. 0.2 parts by weight of Irganox 1010 and 0.2 parts by weight of Irgafos P-EPQ as additives to 100 parts by weight of the obtained poly-3-methylbutene-1 (both are stabilizers manufactured by Nippon Ciba-Geigy). 320 after adding trademark)
Pelletization was carried out using an extruder at .degree. The melting point of this product was 304°C. The mechanical properties of the obtained polymer are shown in Table 1. 1 g of maleic anhydride and 0.2 g of dicumyl peroxide were added to 50 g of the obtained polymer powder per 100 g of polymer powder.
It was dissolved in cc of acetone and impregnated. Acetone was distilled off while gradually increasing the temperature using a rotary evaporator, and the temperature was further increased and stirring was performed at 150° C. for 2 hours. The obtained powder was washed repeatedly with acetone and then dried to obtain a graft modified 3 containing 0.2% by weight of maleic anhydride with a melt viscosity of 1×10 ⁴ poise and an average particle size (50% weight diameter) of 210 μm.
Methylbutene-1 powder was obtained. A fluidized bed for coating was prepared in which this modified polymer powder was fluidized with a nitrogen stream preheated to 100°C, and a steel plate preheated to 400°C was immersed for about 2 seconds to perform surface coating. A coating film with a thickness of about 0.8 mm was obtained. In order to measure the adhesion of the paint film, cross cuts were made on the paint film at 2 mm intervals and an attempt was made to remove the cellophane tape, but no peeling occurred.

【table】

[Table] Comparative Example 1 In the example, powder coating was performed in the same manner as in Example 1 using polymerized powder before graft modification with maleic anhydride. As a result of trying to remove the Sellotape in the same manner as in Example 1, the painted board was removed. Reference Example 1 The polymerized powder of Example 1 was molded into a rod with a diameter of 2 mm using a screw extruder at 340° C., and then ground in a Wiley type grinder to prepare a powder. The pulverized product had a wide particle size distribution, including whisker-like particles, and many irregularly shaped particles with many corners. (Figure 2) This crushed particle is sieved and 74 μm ~
An attempt was made to form a fluidized bed using a 500 μm section, but fluidization was not performed smoothly and partial blow-through occurred. The formed coating film had large thickness unevenness, some protruding parts, and was not beautiful.

[Brief explanation of the drawing]

Figure 1 shows the 3-methylbutene obtained in Example 1.
As shown in Reference Example 1, the particles of No. 1, FIG.
These are microscopic photographs of particles obtained by mechanical pulverization.

Claims (1)

[Scope of Claims] 1 Homopolymer of 3 methyl butene-1, or 3 methyl butene-1 and α-olefin and/or polyene having 2 to 12 carbon atoms
3 formed by polymerization of 40% by weight or less based on the weight of 1
With respect to the weight of the copolymer of methylbutene-1,
Part or all of the 3-methylbutene-1 polymer was grafted with 0.001 to 5% by weight of monomers of graft-reactable unsaturated carboxylic acids and their derivatives, melted at 330°C and a shear rate of 0.1 ¹ /sec. A graft-modified 3-methylbutene-1 polymer having a viscosity of 1×10 ³ poise or more. 2. Graft modification 3 according to claim 1, which is in the form of a powder with a weight average particle diameter of 500 μm or less
Methylbutene-1 polymer.