JP3603420B2 - Crystalline chlorinated polyolefin and method for producing the same - Google Patents

Description

【００１９】
実施例１
１００リットルのオートクレーブに水８０リットル、アルキルジフェニルエーテルジスルホン酸ナトリウム８０ｇ、ポリスチレンスルホン酸ナトリウム８０ｇおよび粉末状のＰＯ−１ １０ｋｇを投入し、温度１０５℃で１５重量％まで塩素化した後、塩素ガス供給を中断し温度１３０℃まで加熱し、その後温度１００℃まで冷却し、その温度で３０重量％まで塩素化した。常法で水洗、乾燥後、得られた塩素化物 １００重量部に、フタル酸ジオクチル ２０重量部、ジオクチル錫マレートポリマー ２重量部およびステアリン酸カルシウム １重量部を加えラボプラストミルを用いて温度１４０℃で５分間混練りした後、プレス成形機を用いて温度１７０℃、圧力１５０ｋｇ／ｃｍ^２ の条件で各試験片を作製した。試験片について各物性を測定した。その結果を表２に示す。
【００２０】
実施例２、３、比較例１〜５
表２に示した原料ポリオレフィンを用いた以外は実施例１と同様にして行った。得られた結果を表２に示す。
なお、比較例５においては、混練りできなかった。
【００２１】
【表２】

【００２２】
【発明の効果】
本発明の結晶性塩素化ポリオレフィンは、ゴム弾性および圧縮永久歪に優れ、かつ耐溶剤性も良好であるので熱可塑性エラストマーとして有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a crystalline chlorinated polyolefin which is excellent in rubber elasticity and compression set and has good solvent resistance and is suitable as a thermoplastic elastomer.
[0002]
[Prior art]
The chlorinated polyolefin is a chlorinated product obtained by chlorinating a polyolefin such as polyethylene in an aqueous suspension system. Among the chlorinated products, crystalline ones are being developed for use as thermoplastic elastomers in addition to uses such as ABS resin modifiers or electric wire sheaths.
Thermoplastic elastomers are substances having rubber elasticity, but do not have a crosslinked structure unlike ordinary rubbers, so they can be recycled and are expected to be used in the future.
[0003]
[Problems to be solved by the invention]
However, conventional crystalline chlorinated polyolefins have problems that not only rubber elasticity and compression set are inferior but also solvent resistance is insufficient.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a crystalline chlorinated polyolefin having excellent rubber elasticity and compression set and excellent solvent resistance.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above object can be achieved by using a specific polyolefin as a raw material, and have completed the present invention based on this finding. That is, the present invention is a polyolefin having a metallocene compound of a transition metal selected from IV B periodic table, the properties of the following which is obtained by polymerization using a catalyst consisting of an organic aluminum oxy compound (a) ~ (d) And a chlorinated polyolefin having a chlorine content of 20 to 50% by weight and a heat of crystal fusion measured by a differential scanning calorimeter of 2.0 to 100 mJ / mg. .
(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 1.5 to 3.0.
(B) a melt flow rate of 0.01 to 100 g / 10 min; (c) a heat of crystal fusion measured by a differential scanning calorimeter of 80 mJ / mg or more; and (d) a crystal melting peak temperature of 70 ° C. measured by a differential scanning calorimeter. [0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The raw material polyolefin used in the present invention is a homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1, a copolymer of ethylene and α-olefin, or It is a polymer having crystals of two or more copolymers of these α-olefins. Here, the copolymer includes a random or block copolymer. Further, two or more of these polyolefins can be used in combination.
[0006]
Further, the raw material polyolefin needs to have the following properties (a) to (d).
First, (a) the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 1.5 to 3.0. Mw / Mn is preferably from 1.6 to 2.8, more preferably from 1.8 to 2.5. If Mw / Mn is less than 1.5, the workability is reduced. On the other hand, if it exceeds 3.0, the mechanical strength decreases, which is not preferable.
Further, (b) the melt flow rate (measured under the conditions 4 in Table 1 in accordance with JIS K7210, hereinafter referred to as “MFR”) is 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min. In particular, 0.1 to 30 g / 10 minutes is suitable. If the MFR is less than 0.001 g / 10 minutes, the processability is poor. On the other hand, if it exceeds 100 g / 10 minutes, problems such as agglomeration in the chlorination reaction may occur, which is not preferable.
(C) The heat of crystal fusion measured with a differential scanning calorimeter (DSC) is 80 mJ / mg or more, preferably 100 mJ / mg or more, and particularly preferably 120 to 200 mJ / mg. When the heat of crystal fusion is less than 80 mJ / mg, it is difficult to obtain a chlorinated polyolefin having a desired amount of crystal.
Further, (d) the crystal melting peak temperature measured by a differential scanning calorimeter is 70 ° C. or higher, preferably 80 ° C. or higher, and particularly preferably 100 ° C. or higher. If the crystal melting peak temperature is lower than 70 ° C., not only does the chlorination reaction fail, but also the mechanical strength is poor, which is not preferable.
[0007]
Examples of the polyolefin satisfying the above-mentioned conditions include, for example, those obtained by polymerization using a so-called metallocene catalyst comprising a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organic aluminum oxy compound. No. Examples of the transition metal selected from Group IVB of the periodic table include zirconium, titanium, hafnium, and the like. Examples of the organic aluminum oxy compound include, for example, a compound containing adsorbed water or a salt containing water of crystallization, for example, an aromatic hydrocarbon solvent in which aluminum sulfate hydrate, magnesium chloride hydrate, or the like is suspended. Conventionally known aluminoxanes obtained by adding and reacting an organoaluminum compound such as an alkylaluminum are exemplified. The metallocene catalyst is described in detail in JP-A-62-121709, JP-A-62-121711, JP-A-62-129303, and the like.
[0008]
As a method for chlorinating the polyethylene under aqueous suspension, a conventionally known method can be used. For example, anionic or nonionic surfactants such as sodium alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, and polyoxyethylene alkyl allyl ether as dispersants and anions such as sodium polystyrene sulfonate and formalin condensate of sodium alkyl allyl sulfonate. A method of chlorinating by introducing a chlorine gas at a temperature in the range of 80 to 140 ° C. in combination with a polymer surfactant. The chlorination method is described in detail in, for example, JP-A-51-138791 and JP-A-6-248015.
[0009]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
The measuring method used is shown below.
(1) Weight average molecular weight, number average molecular weight Measured using a gel permeation chromatograph (manufactured by Waters, ALC-150C).
(2) MFR
The measurement was performed under Table 4 and Condition 4 in accordance with JIS K7210.
(3) Heat of crystal fusion Measured using a differential scanning calorimeter according to JIS K7121 and K7122.
(4) Crystal melting peak temperature This is the peak temperature when the heat of crystal melting is measured using a differential scanning calorimeter.
(5) Chlorine content A precisely weighed sample was burned in a test tube, and the generated hydrogen chloride was collected in pure water and neutralized and titrated with an aqueous sodium hydroxide solution.
(6) Hardness test A spring-type hardness test (A type) was performed according to JIS K6301.
(7) Compression set In accordance with JIS K6301, the compression set was measured under conditions of 25% compression, a temperature of 70 ° C., and a compression time of 22 hours.
(8) Solvent Resistance 15 g of a sample was placed in 300 ml of tetrahydrofuran and stirred at room temperature for 2 hours. The remaining sample was dried and weighed, and the decrement was expressed in% by weight.
[0010]
The production example of the raw material polyolefin is shown below.
<Adjustment of aluminoxane>
50 ml of dry toluene was added to a 200 ml flask sufficiently purged with nitrogen, and 2.5 g of Al ₂ (SO ₄ ) ₃ .14H ₂ O was suspended therein. After cooling to −20 ° C., 30 mmol of trimethylaluminum (27 ml of a 1.11 mol / l toluene solution) was added over 15 minutes, and the mixture was heated to 80 ° C. and stirred for 7 hours. Thereafter, the aluminum sulfate compound was removed under a nitrogen atmosphere, and 70 ml of a 0.35 mol / l aluminoxane toluene suspension was recovered.
<Loading of aluminoxane on carrier>
25 ml of toluene and 1.5 g of silica (Davison 952 calcined at 300 ° C. for 4 hours) were added to a 100 ml flask sufficiently purged with nitrogen, and the above-mentioned methylaluminoxane (0.35 mol (in terms of Al atom) toluene) was added to the suspension. (Solution, methyl group / aluminum atom = 1.32) 37 ml was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure. Heptane (50 ml) was added, and the mixture was stirred at 80 ° C. for 4 hours. Thereafter, washing was performed twice at 80 ° C. with heptane to obtain a solid component.
<polymerization>
533 ml of a hexane solution of trinormal butyl aluminum (0.5 mol / l), 15 g of the solid catalyst component prepared above, and bis (n-butylcyclopentadienyl) were placed in a 500-liter stainless steel autoclave sufficiently purged with nitrogen. After introducing a solution of 83.3 mg of zirconium dichloride in 333 ml of toluene and 267 liters of isobutane, the temperature was raised to 70 ° C. Polymerization is started by introducing a mixed gas of ethylene and hydrogen (hydrogen / ethylene (molar ratio) = 3 × 10 ⁻⁵ ), and polymerization is performed at an ethylene pressure of 10 kg / cm ² at 70 ° C. for 30 minutes to obtain a polymer (hereinafter referred to as “polymer”). 34 kg).
[0011]
At the time of polymerization, two kinds of polymers (hereinafter, referred to as “PO-2” and “PO-3”, respectively) were used in the same manner as described above except that 16.7 kg and 30 kg of 1-hexene were introduced in addition to a mixed gas of ethylene and hydrogen. 42 kg and 43.5 kg were obtained.
[0012]
For comparison, polyethylene produced by the following method was used.
<Catalyst preparation>
To a 500-liter reactor purged with nitrogen, 4.7 kg of magnesium ethylate and 100 liters of hexane were added to form a slurry. 7.8 kg of tetrabutoxytitanium and 8.7 kg of tetrabutoxyzirconium were added, and the mixture was stirred at 90 ° C. for 2 hours. After lowering the internal temperature to 40 ° C., 55.0 kg of ethyl aluminum dichloride was added dropwise over 100 minutes while maintaining the temperature at 40 ° C. The temperature was raised to 65 ° C., and the mixture was stirred for 1 hour, and then washed with hexane until chloride ions could not be confirmed in the washing liquid to obtain a catalyst slurry.
<polymerization>
The dehydrated and purified isobutane and triisobutylaluminum were continuously fed into a polymerization vessel having an internal volume of 200 liters at a rate of 117 liters / hr and triisobutylaluminum at a rate of 175 mmol / hr and a rate of 50 g / hr, respectively. While discharging at a speed, at 80 ° C., the ethylene concentration was 1.0% by weight, the ratio of hydrogen to ethylene was 1.05 ⁻³ (w / w), and the ratio of 1-butene to ethylene was 12.0 (w). / W), and was continuously polymerized under the conditions of a total pressure of 41.0 kg / cm ² and an average residence time of 0.8 hr to obtain a polymer (hereinafter referred to as “PO-A”).
[0013]
<Catalyst preparation>
To a 500-liter reactor purged with nitrogen, 4.7 kg of magnesium ethylate and 100 liter of toluene were added to form a slurry. 7.8 kg of tetrabutoxytitanium was added, and the mixture was stirred at 90 ° C. for 2 hours. After the internal temperature was lowered to 40 ° C., 30.0 kg of ethyl aluminum dichloride was added dropwise over 100 minutes while maintaining the temperature at 40 ° C. After the temperature was raised to 60 ° C. and the mixture was stirred for 1.5 hours, it was washed with hexane until chloride ions could not be confirmed in the washing liquid to obtain a catalyst slurry.
<polymerization>
The dehydrated and purified isobutane and triisobutylaluminum were continuously supplied to a 200 liter polymerization vessel at a rate of 117 liter / hr and 175 mmol / hr and the above catalyst at a rate of 25 g / hr, respectively. While discharging at a constant rate, the ethylene concentration was kept constant at 1.0 ° C. at 80 ° C. and the hydrogen to ethylene concentration ratio was kept at 1.05 ⁻³ (w / w), and the total pressure was 41.0 kg / cm. ^2. Continuous polymerization was performed under the conditions of an average residence time of 0.8 hr to obtain a polymer (hereinafter, referred to as “PO-B”).
[0014]
<Catalyst preparation>
Under a nitrogen atmosphere, 20 kg of magnesium ethylate, 1.66 kg of granular aluminum trichloride, and 2.72 kg of diphenyldiethoxysilane were placed in a grinding container having a capacity of 160 liters containing about 260 kg of porcelain balls having a diameter of 15.4 mm. Next, co-milling was performed for 4 hours using a vibrating ball mill under the conditions of an amplitude of 8 mm and a frequency of 1200 rpm. After co-milling, the contents were separated from the porcelain balls under a nitrogen atmosphere. 20 kg of the co-ground product and 80 liters of heptane were added to a 500 liter nitrogen purged reactor. After stirring, 41.6 liters of titanium tetrachloride were added dropwise at 25 ° C. with stirring, followed by stirring at 90 ° C. for 90 minutes. Next, the resultant was washed with hexane until chloride ions could not be confirmed in the washing liquid to obtain a catalyst slurry.
<polymerization>
The dehydrated and purified isobutane and triisobutylaluminum were continuously supplied to a polymerization vessel having an inner volume of 200 liters at a rate of 117 liters / hr and triisobutylaluminum at a rate of 175 mmol / hr and a rate of 5.0 g / hr, respectively. At 80 ° C., the ethylene concentration was 1.0% by weight, the hydrogen to ethylene concentration ratio was 0.75 × 10 ⁻³ (w / w), and the 1-butene to ethylene concentration ratio was 6 at 80 ° C. 0.0 (w / w), and continuously polymerized under the conditions of a total pressure of 41.0 kg / cm ² and an average residence time of 0.8 hr to obtain a polymer (hereinafter referred to as “PO-C”). Obtained.
[0015]
A polymer (hereinafter referred to as “PO-D”) was obtained in the same manner as in PO-C except that the concentration ratio of hydrogen to ethylene was 1.02 × 10 ⁻³ (w / w) and 1-butene was not supplied. Was.
[0016]
<Catalyst preparation>
Under a nitrogen atmosphere, 15 kg of anhydrous magnesium chloride and 6.5 kg of AA-type titanium trichloride were placed in a grinding container having a capacity of 160 liters containing about 260 kg of stainless steel balls having a diameter of 15.4 mm. Next, co-milling was performed for 44 hours using a vibrating ball mill under the conditions of an amplitude of 8 mm and a frequency of 1200 rpm. After co-milling, the contents were separated from the balls under a nitrogen atmosphere. 15 kg of the co-ground product and 200 liters of toluene were added to a 500 liter nitrogen purged reactor. After stirring, 55 liters of tetrahydrofuran was added dropwise at 40 ° C. over 20 minutes while stirring, followed by stirring at 40 ° C. for 3 hours. Next, the catalyst was washed with hexane until tetrahydrofuran could not be confirmed in the washing liquid to obtain a catalyst slurry.
<polymerization>
The dehydrated and purified isobutane and triisobutylaluminum were continuously supplied to a polymerization vessel having an inner volume of 200 liters at a rate of 117 liters / hr and triisobutylaluminum at a rate of 175 mmol / hr and a rate of 5.0 g / hr, respectively. At 80 ° C., the ethylene concentration was 1.0% by weight, the hydrogen to ethylene concentration ratio was 4.0 × 10 ⁻³ (w / w), and the 1-butene to ethylene concentration ratio was 12 at 80 ° C. 0.0 (w / w), and continuously polymerized under the conditions of a total pressure of 41.0 kg / cm ² and an average residence time of 0.8 hr to obtain a polymer (hereinafter referred to as “PO-E”). Obtained.
[0017]
The Mw / Mn ratio, MFR, crystal fusion heat and crystal fusion peak temperature of each of the above polyolefins were measured. Table 1 shows the results.
[0018]
[Table 1]

[0019]
Example 1
80 liters of water, 80 g of sodium alkyldiphenyletherdisulfonate, 80 g of sodium polystyrenesulfonate and 10 kg of powdered PO-1 were charged into a 100 liter autoclave, chlorinated to a weight of 15% at a temperature of 105 ° C., and then supplied with chlorine gas. It was interrupted and heated to a temperature of 130 ° C., then cooled to a temperature of 100 ° C. and chlorinated at that temperature to 30% by weight. After washing with water and drying in a conventional manner, 100 parts by weight of the obtained chlorinated product, 20 parts by weight of dioctyl phthalate, 2 parts by weight of dioctyltin malate polymer and 1 part by weight of calcium stearate were added, and the temperature was 140 ° C. using a Labo Plastomill. After kneading for 5 minutes, each test piece was prepared using a press molding machine at a temperature of 170 ° C. and a pressure of 150 kg / cm ² . Each physical property of the test piece was measured. Table 2 shows the results.
[0020]
Examples 2 and 3, Comparative Examples 1 to 5
The procedure was performed in the same manner as in Example 1 except that the raw material polyolefin shown in Table 2 was used. Table 2 shows the obtained results.
In Comparative Example 5, kneading was not possible.
[0021]
[Table 2]

[0022]
【The invention's effect】
The crystalline chlorinated polyolefin of the present invention is useful as a thermoplastic elastomer because it is excellent in rubber elasticity and compression set and has good solvent resistance.

Claims (2)

A metallocene compound of a transition metal selected from IV B periodic table, the polyolefin having the properties below obtained polymerized by using a catalyst consisting of an organic aluminum oxy compound (a) ~ (d) chlorinating give A chlorinated polyolefin having a chlorine content of 20 to 50% by weight and a heat of crystal fusion measured by a differential scanning calorimeter of 2.0 to 100 mJ / mg.
(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 1.5 to 3.0.
(B) a melt flow rate of 0.01 to 100 g / 10 min; (c) a heat of crystal fusion measured by a differential scanning calorimeter of 80 mJ / mg or more; and (d) a crystal melting peak temperature of 70 ° C measured by a differential scanning calorimeter. that's all A metallocene compound of a transition metal selected from IV B periodic table, the aqueous suspension under the polyolefin having the properties described below obtained by polymerization using a catalyst consisting of an organic aluminum oxy compound (a) ~ (d) A method for producing a crystalline chlorinated polyolefin having a heat of crystal fusion of 2.0 to 100 mJ / mg, characterized in that it is chlorinated.
(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 1.5 to 3.0.
(B) a melt flow rate of 0.01 to 100 g / 10 min; (c) a heat of crystal fusion measured by a differential scanning calorimeter of 80 mJ / mg or more; and (d) a crystal melting peak temperature of 70 ° C measured by a differential scanning calorimeter. that's all