JP3800797B2 - Chlorinated polyolefin - Google Patents

Description

【００５１】
【表２】

【００５２】
【発明の効果】
本発明の塩素化ポリオレフィンは、柔軟性でありかつ優れたゴム弾性を有しながら、透明性と加工性に優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a chlorinated polyolefin which is flexible and has excellent rubber elasticity and excellent transparency and processability.
[0002]
[Prior art]
Chlorinated polyethylene is an elastic body that has excellent heat resistance, oil resistance, chemical resistance, and weather resistance, flexibility, and excellent rubber elasticity. It is used.
In the non-crosslinking field, it is applied as an impact resistance improver for PVC and for blending with ABS, PE, PP, etc. to impart flame retardancy. In addition, chlorinated polyethylene has excellent heat resistance, oil resistance, chemical resistance, weather resistance, flexibility, and excellent rubber elasticity. Used as vulcanized rubber for automobiles.
[0003]
Further, various studies have been made on use as a non-vulcanized rubber having excellent heat resistance, oil resistance, chemical resistance and weather resistance, flexibility and excellent rubber elasticity. However, the known chlorinated polyethylene is excellent in rubber elasticity but has a drawback of being inferior in transparency, and its use for non-vulcanized rubber applications requiring transparency, such as films and sheets, has been limited. In addition, the transparency as used in the field of this invention means that a film and a sheet do not have turbidity, and it is represented by the small haze (haze value) prescribed | regulated to JISK7105.
[0004]
Japanese Patent Application Laid-Open No. 7-90018 discloses that an ethylene / α-olefin copolymer rubber before chlorination has a vinylidene bond at the molecular end, and this is present at 0.05 to 1.00 per 1000 carbon atoms. A characteristic chlorinated ethylene / α-olefin copolymer rubber has been proposed, and a prechlorinated ethylene / α-olefin copolymer rubber having a vinylidene bond at the same molecular terminal is produced by a metallocene catalyst. It has been shown that the 100% modulus after vulcanization can be slightly higher. Accordingly, it is known to chlorinate copolymers of ethylene and 1-olefin polymerized with a metallocene catalyst. However, JP-A-7-90018 does not select a specific molecular weight distribution and does not mention the processability of the resulting chlorinated polyolefin. Moreover, a specific chlorination method is not illustrated, and therefore, it has not succeeded in producing a chlorinated olefin polymer excellent in transparency of the present invention.
[0005]
Further, as an example of the starting raw material polyolefin that satisfies the specific conditions of JP-A-9-110927 and JP-A-9-110929, the molecular weight distribution (Mw / Mn) polymerized by a metallocene catalyst is 1.5 to 3.0. Polyolefins are mentioned, but such a chlorinated product having a narrow molecular weight distribution has poor processability and has a definite defect that the smoothness of the film and sheet cannot be maintained.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to obtain a chlorinated polyolefin excellent in transparency and processability for use in non-vulcanized rubber applications requiring transparency, such as films and sheets.
[0007]
[Means for Solving the Problems]
In the present invention, an olefin polymer selected from an ethylene homopolymer or a copolymer of ethylene and 1-olefin has the following characteristics (1) to (4), and the olefin polymer is subjected to aqueous suspension chlorination: A chlorinated polyolefin having a chlorine content of 20 wt% to 50 wt%:
(1) The olefin polymer is a polymer polymerized with a metallocene catalyst,
(2) The density of the olefin polymer is 0.90 g / cm ³ or more,
(3) The melt flow index of the olefin polymer is 0.01 to 100 (g / 10 min), and (4) the molecular weight distribution (Mw / Mn) of the olefin polymer is 4.0 to 50. ;
I will provide a.
[0008]
When obtaining a chlorinated polyolefin, it is preferable that the chlorine introduction rate is 0.2 kg / hr or less, especially 0.1 kg / hr or less, per 1 kg of the olefin polymer, up to a chlorine content of less than 5% by weight.
[0009]
The olefin polymer used in the present invention is an ethylene homopolymer or a copolymer of ethylene and 1-olefin.
[0010]
The 1-olefin in the copolymer of ethylene and 1-olefin used in the present invention is a 1-olefin essentially copolymerizable with ethylene. The 1-olefin is preferably a 1-olefin having 3 to 8 carbon atoms. Specific examples of 1-olefin are propylene, 1-butene, 1-hexene, 4-methylpentene-1, and the like. The amount of 1-olefin is not more than 50% by weight of the copolymer, for example 25 to 5% by weight. A copolymer of ethylene and 1-olefin used in the present invention can be obtained by copolymerizing ethylene and one or more of these 1-olefins.
The olefin polymer is generally a resin.
[0011]
The olefin polymer used in the present invention needs to be an olefin polymer polymerized with a metallocene catalyst. Olefin polymers polymerized with the metallocene catalyst are commercially available.
[0012]
The metallocene catalyst is described in detail in JP-A-60-35008, JP-A-62-1121709, JP-A-62-121711, JP-A-62-129303, and the like. JP-A-60-35008 discloses a copolymer of ethylene and 1-olefin having a molecular weight distribution (Mw / Mn) of 2 to 50. Examples of metallocene catalysts include mono-, di-, and tricyclopentadienyl derivatives of transition metals, and zirconium hydride compounds having a group having a conjugated π electron as a ligand.
[0013]
As a polymerization method for obtaining the olefin polymer, there are a solution polymerization method, a slurry polymerization method, a gas phase polymerization method, and a high pressure polymerization method, and any polymerization method can be adopted.
The olefin copolymer used in the present invention uses, for example, an alumoxane solution, bis (pentamethylcyclopentadienyl) zirconium methyl, and bis (cyclopentadienyl) titanium diphenyl as a polymerization catalyst, and ethylene and 1-hexene. And polymerized at a polymerization temperature of 50 ° C. to 80 ° C., and the amount of hydrogenation was changed by a conventional method. I. And the density can be controlled by changing the amount ratio of ethylene and 1-hexene.
[0014]
The olefin polymer used in the present invention needs to have a density of 0.90 g / cm ³ or more. If the density is less than 0.90 g / cm ³ , the adhesiveness of the polymer is increased, and the polymer is fused during aqueous suspension chlorination, which is not preferable.
[0015]
The melt flow index (M.I.) of the olefin polymer used in the present invention needs to be 0.01 to 100 (g / 10 min). If it is less than 0.01, workability is inferior. On the other hand, if the melt flow index exceeds 100, there is an inconvenience that the agglomeration tends to occur during the chlorination reaction by the aqueous suspension method, and it is not preferable because it adheres when processed into a film or sheet. A preferred melt flow index is 0.05 to 20, especially 0.1 to 10 (g / 10 min).
[0016]
The olefin polymer used in the present invention needs to have a molecular weight distribution (Mw / Mn) of 4.0 to 50. When the molecular weight distribution (Mw / Mn) is less than 4.0, the processability is inferior, and when processing into a film or a sheet, there is a drawback that the smoothness of the sheet cannot be maintained. When the molecular weight distribution (Mw / Mn) exceeds 50, it is not preferable because the problem of being easily agglomerated during the chlorination reaction by the aqueous suspension method occurs, and it is not preferable because it adheres when processed into a film or sheet. Mw (weight average molecular weight) and Mn (number average molecular weight) are determined by GPC (gel permeation chromatography).
[0017]
The molecular weight distribution (Mw / Mn) of the olefin polymer used in the present invention is preferably 10-30. When the molecular weight distribution (Mw / Mn) is 10 to 30 which is a preferable range, the film and the sheet have better processability when processed into a film and sheet, and a smooth sheet can be obtained, and the film and sheet have high strength. It becomes possible to do.
[0018]
Aqueous suspension chlorination can be performed by introducing chlorine into a reaction vessel (gas phase region or liquid phase region of the reaction vessel) while suspending the olefin polymer powder in water. Chlorine is introduced in liquid or gaseous form, but is preferably introduced in gaseous form. The average particle diameter of the olefin polymer powder is usually 10 to 500 micrometers. The concentration of the olefin polymer in the suspension is generally 5 to 30% by weight. Generally, in the aqueous suspension chlorination, the chlorine introduction rate is 0.01 kg / hr or more, for example, 0.02 to 2.0 kg / hr per kg of the olefin polymer. The reaction temperature for chlorination is 50 to 140 ° C. The reaction time for chlorination is generally 10 minutes to 10 hours. In the chlorination reaction, the pressure in the gas phase region in the reaction vessel is generally 0.5 to 5.0 kg / cm ² .
[0019]
The chlorinated ethylene polymer (chlorinated polyolefin) of the present invention has a chlorine content of 20 to 50% by weight, preferably 25 to 45% by weight. The chlorine content means the weight percentage of chlorine atoms based on the chlorinated ethylene polymer. When the chlorine content is less than 20% by weight, transparency and workability are poor. On the other hand, when the chlorine content exceeds 50% by weight, the thermal stability is deteriorated, and a colored film and sheet can be obtained.
[0020]
Up to a chlorine content of 5% by weight, when the chlorine introduction rate is 0.2 kg / hr or less per 1 kg of the olefin polymer, it is flexible and has excellent rubber elasticity but excellent transparency and workability. A chlorinated ethylene polymer, particularly a polymer excellent in transparency can be produced. The chlorine introduction rate up to a chlorine content of 5% by weight is preferably 0.2 kg / hr or less, particularly 0.1 kg / hr or less, per 1 kg of the olefin polymer.
The chlorine introduction rate after the chlorine content exceeds 5% by weight may be 0.3 kg / hr or more, for example, 0.5 to 1.5 kg / hr, per kg of the olefin polymer.
[0021]
Since the chlorinated ethylene polymer of the present invention is flexible and has excellent rubber elasticity, it is excellent in transparency and processability, so that it can be used as a film or sheet for non-vulcanizing applications. As a method of processing the chlorinated ethylene polymer of the present invention into a film or a sheet or the like, a method of making a film or a sheet using various calendar rolls, or a film or a sheet using an extruder equipped with a T-die Methods and the like. When processing into a film or sheet, it is possible to add a small amount of additives within a range not impairing the transparency of the chlorinated ethylene polymer of the present invention.
[0022]
Furthermore, since the chlorinated ethylene polymer of the present invention is easily dissolved in an organic solvent such as benzene, toluene and xylene, it can also be used as a coating material for paints and canvases.
Furthermore, the chlorinated ethylene polymer of the present invention can be applied as an impact modifier for PVC in the non-crosslinking field, or for blending with ABS, PE, PP, etc. to impart flame retardancy. is there.
[0023]
Furthermore, the chlorinated ethylene polymer of the present invention can be used after vulcanization.
[0024]
As the vulcanizing agent, mercaptotriazines and organic peroxides can be used. Specific examples of mercaptotriazines include 1,3,5-trithiocyanuric acid, methoxy-3,5-dimercaptotriazine, 1-hexylamino-3,5-dimercaptotriazine, 1-diethylamino-3,5- Examples thereof include dimercaptotriazine, 1-dibutylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,5-dimercaptotriazine, 1-phenylamino-3,5-dimercaptotriazine and the like. Specific examples of the organic peroxide include dialkyl peroxides such as di-t-butyl-peroxide and di-t-butylcumyl-peroxide, 1,1-bis (t-butylperoyl) 3, Examples thereof include peroxyketals such as 3,5-trimethylcyclohexene.
[0025]
Mercaptotriazines as vulcanization aid components are amines, specifically n-hexylamine, octylamine, dibutylamine, tributylamine, trioctylamine, di (2-ethylhexyl) amine, dicyclohexylamine, hexamethylenediamine Etc. can be illustrated.
[0026]
The metal compound serving as the acid acceptor mixed with the vulcanizing agent provides the stability of the crosslinked product and an appropriate crosslinking rate. Specifically, the metal compound is an oxide, hydroxide, or group II metal of the periodic table. Carboxylates, silicates, carbonates, phosphites, borates, Group IVA metal oxides, basic phosphites, basic carbonates, basic carboxylates, basic sulfites Salt, tribasic sulfate and the like. Specific examples include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, slaked lime, quicklime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, magnesium phosphite, calcium phosphite. , Zinc white, tin oxide, risurge, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, three Examples thereof include basic lead sulfate.
[0027]
The amount of the above-mentioned vulcanization component is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the chlorinated ethylene polymer. Further, at the time of vulcanization of mercaptotriazines, 0.5 to 3 mol of the above vulcanization auxiliary component is blended with respect to 1 mol of the vulcanizing agent component. The acid acceptor component is suitably in the range of 0.5 to 20 parts by weight per 100 parts by weight of the polymer.
[0028]
The vulcanized rubber compound includes various kinds of compounding agents commonly used in the art, such as fillers, reinforcing agents, plasticizers, stabilizers, anti-aging agents, lubricants, viscosity-imparting agents, pigments, It is free to add flame retardants. Further, a small amount of thermoplastic resin and rubber can be freely added for improving wear and moldability, and short fibers and the like can be freely added for improving strength and rigidity.
[0029]
The above vulcanized rubber compound can be mixed with a rubber kneader such as a normal roll, kneader or intermixer, and molding and crosslinking can be carried out with a press or an injection molding machine to obtain a rubber molded product. The crosslinking conditions can be suitably performed at 100 to 200 ° C. for several minutes to 2 hours.
[0030]
【Example】
In the following, the embodiment will be described in more detail.
In addition, each physical property shown in an Example was calculated | required based on the following.
Melt flow index (MI) (g / 10 min)
It was measured based on A method test condition 4 of JIS K7210.
Density was measured based on JIS K7112.
Molecular weight distribution (M w / M n )
Measurement was performed based on the GPC method at a measurement temperature of 135 ° C. using o-dichlorobenzene as a solvent.
Chlorine content (wt%)
The chlorine content in the polymer was measured by a flask combustion method.
Haze value The obtained chlorinated ethylene polymer was kneaded for 3 minutes with two 140-inch 8 inch rolls, and then a roll sheet having a thickness of about 2 mm was taken out and pressed at a temperature of 140 ° C. Then, a press sheet having a thickness of about 2 mm is obtained, and haze (haze value) is measured according to the method of JIS K-7105. The haze is an indicator of transparency.
[0031]
The workability <br/> workability is measured as follows. That is, the obtained chlorinated ethylene polymer was kneaded for 3 minutes with two rolls of 140 inches at 8 inches, adjusted to a gap between rolls of 0.2 mm, and a thin roll sheet was taken out to visually check the smoothness of the surface. The following five types were determined.
A: Very smooth.
A: Smooth.
○: Pretty smooth.
Δ: Slightly not smooth
X: Not smooth at all.
[0032]
Tensile strength It measured based on JISK6301 using the press sheet of thickness 2mm similar to what was used for the haze value measurement.
[0033]
Example 1
Ethylene / 1-hexene copolymer powder (M.I. = 0.2, density = 0.930, molecular weight distribution Mw / Mn = polymerized with a metallocene catalyst (M catalyst) in a 100 L glass lining reaction vessel 15) (Average particle size: 100 micrometers) (hereinafter referred to as raw material polyolefin No. 1) 5 kg of 70 L of water, 2 g of wetting agent and 200 ml of dispersing agent were charged, and the copolymer was maintained while maintaining a temperature of 115 ° C. Until the chlorine content of 5 wt%, the chlorine introduction rate was adjusted to 0.08 kg / hr per 1 kg of ethylene / 1-hexene copolymer. Chlorine gas was introduced into the gas phase portion of the reaction vessel for chlorination. After the chlorine content reaches 5% by weight, the chlorine introduction rate is adjusted to 0.4 kg / hr per 1 kg of ethylene / 1-hexene copolymer. Chlorination was performed. Next, the temperature was raised to 134 ° C., which is the crystalline melting point of the ethylene / 1-hexene copolymer, and maintained for 10 minutes, and then chlorinated at a temperature of 120 ° C. to the final chlorine content of 35 wt% at the same chlorine introduction rate. And washed with water and dried by a conventional method. The properties of the chlorinated ethylene copolymer (chlorinated polyolefin) thus obtained are shown in Table 1.
[0034]
Example 2
The same procedure as in Example 1 was repeated except that the final chlorine content was 22% by weight. The results are shown in Table 1.
Example 3
The same procedure as in Example 1 was repeated except that the final chlorine content was 40% by weight. The results are shown in Table 1.
[0035]
Example 4
An ethylene / 1-hexene copolymer raw material (raw polyolefin No. 1) I. = 0.06, density = 0.945, and molecular weight distribution Mw / Mn = 25 except that the ethylene / 1-hexene copolymer (raw material polyolefin No. 2) polymerized with a metallocene catalyst (M catalyst) is used. Repeated the same procedure as in Example 1. The results are shown in Table 1.
[0036]
Example 5
An ethylene / 1-hexene copolymer raw material (raw polyolefin No. 1) I. = 20, density = 0.920, molecular weight distribution Mw / Mn = 12, except that the ethylene / 1-hexene copolymer (raw polyolefin No. 3) polymerized with a metallocene catalyst was used. The procedure of was repeated. The results are shown in Table 1.
[0037]
Example 6
An ethylene / 1-hexene copolymer raw material (raw polyolefin No. 1) I. = Ethylene, 1-hexene copolymer (raw material polyolefin No. 4) polymerized with a metallocene catalyst with density = 0.930 and molecular weight distribution Mw / Mn = 6.5 The same procedure as in Example 1 was repeated. The results are shown in Table 1.
[0038]
Example 7
Ethylene / 1-hexene copolymer (raw polyolefin No. 1) I. Example 1 except that it was changed to an ethylene / 1-hexene copolymer (raw material polyolefin No. 5) polymerized with a metallocene catalyst having = 0.2, density = 0.930, and molecular weight distribution Mw / Mn = 34. The same procedure was repeated. The results are shown in Table 1.
[0039]
Example 8
Until the chlorine content reached 5%, the same procedure as in Example 1 was repeated except that the chlorine introduction rate was adjusted to 0.05 kg / hr per 1 kg of ethylene / 1-hexene copolymer. It was. The results are shown in Table 1.
[0040]
Example 9
Until the chlorine content reached 5%, the same procedure as in Example 1 was repeated except that the chlorine introduction rate was adjusted to 0.20 kg / hr per 1 kg of ethylene / 1-hexene copolymer. It was. The results are shown in Table 1.
[0041]
Example 10
Until the chlorine content reached 5%, the same procedure as in Example 1 was repeated except that the chlorine introduction rate was adjusted to 0.50 kg / hr per kg of ethylene / 1-hexene copolymer. It was. The results are shown in Table 1.
[0042]
Comparative Example 1
An ethylene / 1-hexene copolymer raw material (raw material polyolefin No. 1) was polymerized with a Ti catalyst to an ethylene / 1-hexene copolymer (M.I. = 0.4, density = 0.930, The same procedure as in Example 1 was repeated except that the molecular weight distribution Mw / Mn = 12) (raw polyolefin No. 6) was used. The results are shown in Table 2.
[0043]
Comparative Example 2
An ethylene / 1-hexene copolymer raw material (raw polyolefin No. 1) I. Example 1 except that ethylene / 1-hexene copolymer (raw material polyolefin No. 7) polymerized with a metallocene catalyst with = 0.4, density = 0.880 and molecular weight distribution Mw / Mn = 10 was used. Chlorination was performed in the same manner as above. Since the agglomeration of the ethylene / 1-hexene copolymer powder occurred at a chlorine content of about 20% by weight, the subsequent operation was stopped.
[0044]
Comparative Example 3
An ethylene / 1-hexene copolymer raw material (raw polyolefin No. 1) I. Example 1 except that it was replaced with an ethylene / 1-hexene copolymer (raw material polyolefin No. 8) polymerized with a metallocene catalyst having a molecular weight distribution Mw / Mn = 12, which is = 0.005, a density = 0.930. The same procedure was repeated. The results are shown in Table 2.
[0045]
Comparative Example 4
An ethylene / 1-hexene copolymer raw material (raw polyolefin No. 1) I. Example 1 except that it was replaced with an ethylene / 1-hexene copolymer (raw material polyolefin No. 9) polymerized with a metallocene catalyst with = 120, density = 0.930, and molecular weight distribution Mw / Mn = 4.5. Chlorination was carried out in the same manner as in Example 1, but the agglomeration of the ethylene / 1-hexene copolymer powder occurred at a chlorine content of about 20% by weight, so the subsequent operation was stopped.
[0046]
Comparative Example 5
Ethylene / 1-hexene copolymer No. 1 to M.M. I. = Ethylene, 1-hexene copolymer (raw polyolefin No. 10) polymerized with a metallocene catalyst having a density = 0.930 and a molecular weight distribution Mw / Mn = 3.5. The same procedure as in Example 1 was repeated. The results are shown in Table 2.
[0047]
Comparative Example 6
Ethylene / 1-hexene copolymer No. 1 to M.M. I. = 0.2, density = 0.930, implemented except that the ethylene / 1-hexene copolymer (raw polyolefin No. 11) polymerized with a metallocene catalyst having a molecular weight distribution Mw / Mn = 1.5 was used. The same procedure as in Example 1 was repeated. The results are shown in Table 2.
[0048]
Comparative Example 7
Ethylene / 1-hexene copolymer No. 1 to M.M. I. Example 1 except that it was changed to an ethylene / 1-hexene copolymer (raw material polyolefin No. 12) polymerized with a metallocene catalyst with 0.1 = 0.1, density = 0.930, and molecular weight distribution Mw / Mn = 60. The same procedure was repeated. The results are shown in Table 2.
[0049]
Comparative Example 8
The same procedure as in Example 1 was repeated except that the final chlorine content was 18% by weight. The results are shown in Table 2.
Comparative Example 9
The same procedure as in Example 1 was repeated except that the final chlorine content was 52%. The results are shown in Table 2.
[0050]
[Table 1]

[0051]
[Table 2]

[0052]
【The invention's effect】
The chlorinated polyolefin of the present invention is excellent in transparency and processability while being flexible and having excellent rubber elasticity.

Claims (2)

An olefin polymer selected from an ethylene homopolymer or a copolymer of ethylene and 1-olefin has the following characteristics (1) to (4), and is an aqueous suspension chlorinated olefin polymer. Chlorinated polyolefins in an amount of 20% to 50% by weight:
(1) The olefin polymer is a polymer polymerized with a metallocene catalyst,
(2) The density of the olefin polymer is 0.90 g / cm ³ or more,
(3) The melt flow index of the olefin polymer is 0.01 to 100 (g / 10 min), and (4) the molecular weight distribution (Mw / Mn) of the olefin polymer is 4.0 to 50. . 2. The chlorinated polyolefin according to claim 1, wherein when the chlorinated polyolefin is obtained, the chlorine introduction rate is 0.2 kg / hr or less per 1 kg of the olefin polymer up to a chlorine content of 5 wt%.