KR20230073130A - Polyethylene and vulcanizable chlorinated polyethylene compositions using the same - Google Patents

Abstract

Polyethylene according to the present invention lowers the ratio of polymer regions in a molecular structure and ensures optimized viscosity and melt index as well as narrow molecular weight distribution, so that premature crosslinking of chlorinated polyethylene obtained by reacting the polyethylene with chlorine is prevented, thereby minimizing a decrease in viscosity even after long-term storage and improving extrusion processability. The present invention provides the polyethylene and a vulcanizable chlorinated polyethylene composition comprising the same. According to the polyethylene, in a GPC curve graph where the x-axis is log MW and the y-axis is dw/dlogMw, the integral value of the area where the log MW value is 5.5 or more is 14 % or less of the total integral value, the molecular weight distribution (Mw/Mn) is 5.8 or less, the complex viscosity (η*(ω500)) measured at a frequency (ω) of 500 rad/s is 650 Pa·s to 850 Pa·s, and MI_5 (melt index measured at 190℃ and 5 kg load) is 1.2 g/10 min to 3.0 g/10 min.

Description

Polyethylene and vulcanizable chlorinated polyethylene composition using the same {POLYETHYLENE AND VULCANIZABLE CHLORINATED POLYETHYLENE COMPOSITIONS USING THE SAME}

The present invention relates to polyethylene and a vulcanizable chlorinated polyethylene composition using the same.

Chlorinated polyethylene, which is produced by reacting polyethylene and chlorine, is known to have better physical and mechanical properties than polyethylene, and since it can withstand particularly harsh external environments, it is used as a packing material and a heat transfer material such as various containers, fibers, and pipes. used

Such chlorinated polyethylene is widely used as a material for rubber products and resin products, or as a raw material for adhesives and paints due to its excellent heat resistance, oil resistance, weather resistance, ozone resistance and abrasion resistance. In particular, chlorinated polyethylene is attracting attention as a rubber material that makes use of its excellent heat resistance, oil resistance, weather resistance and ozone resistance.

Various proposals have already been made regarding the vulcanization of chlorinated polyethylene. For example, various sulfur-containing compounds including organic peroxides and mercaptotriazines have been proposed as vulcanizing agents for chlorinated polyethylene, and since they promote vulcanization of chlorinated polyethylene, various organic vulcanization accelerators including amine compounds are used in combination with the vulcanizing agent It is known to do In addition, it is common knowledge of those skilled in the art that it is necessary to incorporate an acid sorbent slightly generated during vulcanization of chlorinated polyethylene into the vulcanization composition, and for example, Japanese Patent Laid-Open No. 1980-039250 discloses Metal compounds selected from the group consisting of oxides, hydroxides, carboxylates, silicates, carbonates, phosphites, borates, basic sulfites and tribasic sulfates of Group IVA metals have been proposed.

In addition, as a vulcanizing agent for chlorinated polyethylene, a composition for vulcanization containing a thiadiazole-based compound is described in Japanese Patent Laid-open Publication No. 1978-003439 and the like, and basic metal oxides, basic metal salts, basic metal hydroxides, etc. are used as compounding agents. .

However, the above-mentioned vulcanizing agent and its blending agent can be used to increase the strength of the vulcanizate or to maintain the color of the vulcanized product, but when chlorinated polyethylene is mixed with the vulcanizing agent and then stored, the MV (Mooney viscosity) increases As a result, there is a disadvantage in that the extrusion processability is lowered.

Accordingly, in order to improve processability during extrusion along with excellent strength of the vulcanizate, development of a technology capable of maintaining high crosslinking efficiency while minimizing the rate of change in the pattern viscosity (MV) over time even during long-term storage of the chlorinated polyethylene composition is continuously required. there is.

The present invention has a narrow molecular weight distribution and a narrow molecular weight distribution by lowering the polymer region ratio in the molecular structure, which can minimize the rate of change in the pattern viscosity (MV) over time even during long-term storage of the chlorinated polyethylene composition so as to improve processability during extrusion with excellent strength of the vulcanizate. Together, we intend to provide polyethylene with optimized viscosity and melt index.

In addition, the present invention is to provide a vulcanizable chlorinated polyethylene composition containing chlorinated polyethylene using the above-mentioned polyethylene and a chlorinated polyethylene vulcanizate obtained by vulcanizing the same.

According to one embodiment of the present invention, in a GPC curve graph in which the x-axis is log MW and the y-axis is dw/dlogMw, the integral value of the region where the log MW value is 5.5 or more is 14% or less of the total integral value,

The molecular weight distribution (Mw/Mn) is 5.8 or less,

The complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s is 650 Pa·s to 850 Pa·s,

MI ₅ (melt index measured at 190 ^° C, 5 kg load) from 1.2 g / 10 min to 3.0 g / 10 min,

Polyethylene is provided.

In addition, the present invention provides a vulcanizable chlorinated polyethylene composition comprising chlorinated polyethylene using the polyethylene.

In addition, the present invention provides a chlorinated polyethylene vulcanizate obtained by vulcanizing the vulcanizable chlorinated polyethylene composition.

According to the present invention, by lowering the polymer domain ratio in the molecular structure of polyethylene and optimizing the viscosity and melt index with a narrow molecular weight distribution, even during long-term storage of the chlorinated polyethylene composition to improve processability during extrusion with excellent strength of the vulcanizate There is an excellent effect of minimizing the rate of change of the pattern viscosity (MV) over time.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

In addition, terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise", "comprise" or "having" are intended to indicate that there is an embodied feature, number, step, component, or combination thereof, but one or more other features or It should be understood that the presence or addition of numbers, steps, components, or combinations thereof is not precluded.

Also, as used throughout this specification, the terms "about", "substantially" and the like are used at or approximating that value when manufacturing and material tolerances inherent in the stated meaning are given, and Exact or absolute figures are used as an aid to understanding and to prevent exploitation by unscrupulous infringers of the disclosed disclosure.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in more detail.

polyethylene

According to one embodiment of the present invention, it is a chlorinated polyethylene composition to realize a molecular structure with an optimized polymer region, optimize viscosity and melt index along with a narrow molecular weight distribution, and improve processability during extrusion with excellent strength of the vulcanizate. Polyethylene capable of minimizing the change in pattern viscosity (MV) over time even during long-term storage by processing is provided.

In the polyethylene, in a GPC curve graph in which the x-axis is log MW and the y-axis is dw/dlogMw, the integral value of the region in which the Log MW value is 5.5 or more is 14% or less of the total integral value, and the molecular weight distribution (Mw/Mn) is 5.8 or less, the complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s is 650 Pa·s to 850 Pa·s, and MI ₅ (at 190 ^o C, 5 kg load It is characterized in that the measured melt index) is 1.2 g / 10 min to 3.0 g / 10 min.

The polyethylene according to the present invention optimizes the polymer structure, realizes a narrow molecular weight distribution, and is made of chlorinated polyethylene, and after compounding, the early crosslinking effect is suppressed, and the compound MV when stored before extrusion processing It is possible to obtain the effect of improving the change over time.

In particular, if the content of the high molecular weight region in the high molecular structure of high density polyethylene (HDPE), which is a material of chlorinated polyethylene (CPE), is adjusted, the high molecular weight region is reduced in the chlorination reaction product, CPE, as the HDPE polymer structure is maintained almost similarly. The crosslinking reactivity is controlled so that the change rate of the compound MV over time can be minimized.

Meanwhile, the polyethylene according to the present invention may be an ethylene homopolymer that does not include a separate copolymer.

In the polyethylene, in the GPC curve graph in which the x-axis is log MW and the y-axis is dw/dlogMw, the integral value of the region where the Log MW value is 5.5 or more is 14% or less of the total integral value. At the same time, Complex viscosity and melt index MI ₅ (measured at 190 ^o C, 5 kg load) in the high-frequency region along with a narrow molecular weight distribution (Mw/Mn) remain in the optimum range.

Specifically, the polyethylene has a ratio of about 14% or less, or about 0.5% to about 14%, or about 13% or less, or about 13% or less, About 0.8% to about 13%, or about 12% or less, or about 1% to about 12%, or about 11% or less, or about 3% to about 11%, or about 10.5% or less, or about 5% to about 10.5% can In the polyethylene, by optimizing the polymer region in the molecular structure at the ratio described above in the GPC graph, a uniform chlorination reaction occurs to secure high chlorination productivity and processability, and at the same time improve mechanical properties such as tensile strength.

As described above, the polyethylene of the present invention is characterized by optimizing the molecular weight distribution (Mw/Mn) while exhibiting the ratio of polymer regions in the molecular structure to the optimum range.

The molecular weight distribution of the polyethylene is about 5.8 or less or about 2.0 to about 5.8. This means that the molecular weight distribution of polyethylene is narrow. If the molecular weight distribution is wide, since the molecular weight difference between polyethylenes is large, the chlorine content between polyethylenes may vary after the chlorination reaction, making it difficult to uniformly distribute chlorine. In addition, when the low molecular weight component is melted, since the fluidity is high, the pores of the polyethylene particles may be blocked and the chlorination productivity may be reduced. However, since the present invention has the above molecular weight distribution, the difference in molecular weight between polyethylenes after the chlorination reaction is not large, so that chlorine can be uniformly substituted.

For example, the ratio and molecular weight distribution (Mw/Mn, polydispersity index) of regions having a Log MW value of 5.5 or more in the GPC curve graph are measured using gel permeation chromatography (GPC, manufactured by Water).

Here, the molecular weight distribution (Mw/Mn, PDI, polydispersity index) can be calculated by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene, and dividing the weight average molecular weight by the number average molecular weight.

Specifically, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyethylene can be measured using a polystyrene calibration curve. For example, a Waters PL-GPC220 instrument may be used as a gel permeation chromatography (GPC) apparatus, and a Polymer Laboratories PLgel MIX-B 300 mm long column may be used. At this time, the measurement temperature is 160 ^° C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, and the flow rate can be applied at 1 mL / min. The polyethylene samples were pretreated by melting in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ^° C for 10 hours using a GPC analyzer (PL-GP220), respectively, and 10 mg/10mL After preparing to a concentration, it can be supplied in an amount of 200 microliters (μL). The values of Mw and Mn can be derived using a calibration curve formed using polystyrene standard specimens. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g 9 types of /mol can be used.

The polyethylene may have a weight average molecular weight of about 100000 to about 158000 g/mol. Preferably, the weight average molecular weight of the polyethylene can be at least about 11000 g/mol, or at least about 120000 g/mol, or at least about 125000 g/mol, or at least about 130000 g/mol, or at least about 135000 g/mol. there is. In addition, the weight average molecular weight of the polyethylene is about 155000 g / mol or less, or about 152000 g / mol or less, or about 150000 g / mol or less, or about 148000 g / mol or less, or about 146000 g / mol or less, or about 145000 g/mol or less, or about 143000 g/mol or less.

Meanwhile, the polyethylene exhibits an optimal range of about 650 Pa·s to about 850 Pa·s in complex viscosity (η*(ω500)) measured at a frequency (ω) of 500 rad/s. Specifically, the complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s is about 670 Pa s or more, or about 680 Pa s or more, or about 700 Pa s or greater than about 720 Pa·s, or greater than about 740 Pa·s, or greater than about 750 Pa·s, or greater than about 760 Pa·s, or greater than about 770 Pa·s, or greater than about 780 Pa·s , about 840 Pa s or less, or about 830 Pa s or less, or about 820 Pa s or less, or about 815 Pa s or less, or about 810 Pa s or less, or about 805 Pa s or less, or about 800 Pa·s or less, or about 795 Pa·s or less. The polyethylene of the present invention has a complex viscosity (η*( ω500), complex viscosity) may be maintained within the above-described range.

Specifically, the complex viscosity may be measured using a rotational rheometer, for example, a rotational rheometer ARES (Advanced Rheometric Expansion System, ARES G2) of TA Instruments. Polyethylene samples were prepared with a gap of 2.0 mm using parallel plates with a diameter of 25.0 mm at 190 ^° C. Measurement is dynamic strain frequency sweep mode, strain is 5%, frequency is from 0.05 rad/s to 500 rad/s, and a total of 41 points can be measured, 10 points for each decade.

In general, a fully elastic material deforms in proportion to elastic shear stress, which is referred to as Hooke's law. In addition, in the case of a pure viscous liquid, deformation occurs in proportion to viscous shear stress, which is called Newton's law. In a perfectly elastic material, deformation can be recovered again when elastic energy is accumulated and the elastic shear stress is removed. In a perfectly viscous material, since all energy is dissipated through deformation, the deformation is not recovered even if the viscous shear stress is removed. Also, the viscosity of the material itself does not change.

However, in a molten state, polymers have properties intermediate between those of perfectly elastic materials and viscous liquids, which is called viscoelasticity. That is, when polymers are subjected to shear stress in a molten state, the deformation is not proportional to the shear stress, and the viscosity changes according to the shear stress, which is also referred to as a non-Newtonian fluid. This characteristic is due to the complexity of deformation according to shear stress because the polymer has a large molecular size and a complex intermolecular structure.

In particular, in the case of manufacturing a molded article using a polymer, shear thinning is considered important among the properties of non-Newtonian fluids. The shear fluidization phenomenon refers to a phenomenon in which the viscosity of a polymer decreases as the shear rate increases, and the molding method of the polymer is determined according to the shear fluidization characteristics. In particular, when manufacturing large molded articles such as large-diameter pipes or composite pipes or molded articles requiring high-speed polymer extrusion, as in the present invention, considerable pressure must be applied to the molten polymer. Fluidization properties are considered important.

Accordingly, in the present invention, the shear fluidization characteristics are measured through the complex viscosity (η*[Pa.s]) according to the frequency (ω[rad/s]). In particular, by optimizing the complex viscosity at a frequency (ω) of 500 rad/s, excellent chloride productivity and excellent physical properties of the compound can be implemented. In particular, it is possible to predict the range of physical properties such as the pattern viscosity (MV) of chlorinated polyethylene through the complex viscosity at a frequency (ω) of 500 rad/s.

On the other hand, the polyethylene, as described above, exhibits the polymer domain ratio in the molecular structure in the optimal range, and at the same time has a narrow molecular weight distribution (Mw / Mn) and a melt index MI ₅ (190 ^° C, 5 kg) with complex viscosity in the high frequency region It is characterized by maintaining the optimal range of measurement under load).

Specifically, the polyethylene has a melt index MI ₅ of about 1.2 g/10 min to about 3.0 g/10 min, as measured under conditions of a temperature of 190 ^° C and a load of 5 kg according to ASTM D 1238. Preferably, the melt index MI ₅ is at least about 1.3 g/10 min, or at least about 1.4 g/10 min, or at least about 1.5 g/10 min, or at least about 1.8 g/10 min, or at least about 2.0 g/10 min, or greater than or equal to about 2.2 g/10 min, but less than or equal to about 2.95 g/10 min, or less than or equal to about 2.9 g/10 min, or less than or equal to about 2.85 g/10 min, or less than or equal to about 2.8 g/10 min, or less than or equal to about 2.75 g/10 min, or less than or equal to about 2.7 g/10 min g/10 min or less, or about 2.6 g/10 min or less, or about 2.5 g/10 min or less.

In addition, together with the melt index MI ₅ measured under the condition of 5 kg, the high load melt index MI _21.6 measured under the condition of 21.6 kg may be from about 3 g/10 min to about 33.6 g/10 min.

If any one of these melt indices MI ₅ and MI _21.6 is too high, the low molecular content increases, and during the chlorination process, the low molecular melts at high temperature to form lumps, etc., and the shape change of the particles increases, resulting in poor thermal stability. Accordingly, the melt indices MI ₅ and MI _21.6 should be about 2.8 g/10 min or less and about 33.6 g/10 min or less, respectively, in terms of implementing excellent thermal stability. However, as the melt indices MI ₅ and MI _21.6 are lower, the viscosity increases, and physical properties such as pattern viscosity are out of the optimal range when producing chlorinated polyethylene, and in this case, a problem of poor dispersion of inorganic substances may occur. Accordingly, the melt indices MI ₅ and MI _21.6 may be about 1.5 g/10 min or more and about 33.6 g/10 min or more, respectively, in terms of reducing the extrusion processing load and securing excellent physical properties during product processing.

In addition, the polyethylene of the present invention, as described above, while optimizing the melt index MI ₅ , the melt flow index (MFRR _21.6/5 , melt index measured at 190 ^° C and a load of 21.6 kg by the method of ASTM D 1238 divided by the melt index measured at 190 ^° C and 5 kg load). At this time, the melt flow index of the polyethylene (MFRR _21.6/5 , melt index measured at 190 ^o C, 21.6 kg load by the method of ASTM D 1238 divided by melt index measured at 190 ^o C, 5 kg load) can be from about 2 to about 12. Specifically, the melt flow index may be about 2 or more in terms of processability during extrusion, and may be about 12 or less in terms of securing excellent mechanical properties by increasing the Mooney viscosity (MV) of CPE.

Meanwhile, the polyethylene has a density of about 0.945 g/cm ³ to about 0.960 g/cm ³ , or about 0.948 g/cm ³ to about 0.958 g/cm ³ , or about 0.950 g/cm ³ to about 0.957 g/cm ³ , or from about 0.951 g/cm ³ to about 0.956 g/cm ³ , or from about 0.952 g/cm ³ to about 0.955 g/cm ³ . In particular, the density of the polyethylene is about 0.945 g / cm ³ or more, which means that the content of the crystal structure of polyethylene is high and dense, and thus, it has a characteristic that the change of the crystal structure is difficult to occur during the chlorination process. However, when the density of the above-mentioned polyethylene exceeds about 0.960 g/cm ³ , the content of the crystal structure of the polyethylene becomes too large, so that the TREF crystallinity distribution is too wide and the molecular weight distribution is wide, and the CPE processing Heat of fusion increases and processability may deteriorate. Accordingly, the polyethylene of the present invention secures excellent extrusion processability and size stability even in a high-speed extrusion process when applied to wires and cables, and at the same time, in terms of ensuring excellent mechanical properties such as tensile strength, It is desirable to have a density in the range.

On the other hand, polyethylene according to one embodiment of the present invention, as described above, exhibits the polymer region ratio in the molecular structure in the optimal range, and at the same time has a narrow molecular weight distribution (Mw / Mn) and a melt index MI ₅ (with complex viscosity in the high frequency region) 190 ^° C, measured under a load of 5 kg) may be prepared by polymerizing ethylene in the presence of a Ziegler-Natta catalyst in order to maintain the optimum range.

Vulcanizable Chlorinated Polyethylene Composition

According to another embodiment of the present invention, a vulcanizable chlorinated polyethylene composition including chlorinated polyethylene using the polyethylene as described above is provided.

Specifically, the vulcanizable chlorinated polyethylene composition includes chlorinated polyethylene prepared by reacting polyethylene and chlorine as described above, a sulfide-based crosslinking agent or a derivative thereof, and an amine compound or a derivative thereof.

Hereinafter, each component constituting the vulcanizable chlorinated polyethylene composition of one embodiment will be described in detail.

(a) chlorinated polyethylene

In the vulcanizable chlorinated polyethylene composition according to the present invention, the chlorinated polyethylene, as described above, can be prepared by reacting polyethylene with a narrow molecular weight distribution, viscosity and melt index optimized by lowering the polymer region ratio in the molecular structure and reacting with chlorine. .

The reaction with chlorine may be performed by dispersing the prepared polyethylene with water, an emulsifier and a dispersant, and then adding a catalyst and chlorine.

As the emulsifier, polyether or polyalkylene oxide may be used. A polymer salt or organic acid polymer salt may be used as the dispersant, and methacrylic acid or acrylic acid may be used as the organic acid.

As the catalyst, a chlorination catalyst used in the art may be used, and benzoyl peroxide may be used as an example. The chlorine may be used alone or in combination with an inert gas.

The chlorination reaction is preferably carried out at about 60 ^o C to about 150 ^o C, or about 70 ^o C to about 145 ^o C, or about 80 ^o C to about 140 ^o C, and the reaction time is about 10 minutes to about 10 hours, or about 1 hour to about 9 hours, or about 2 hours to about 8 hours is preferred.

Chlorinated polyethylene produced by the above reaction may be further subjected to a neutralization process, a washing process, and/or a drying process, and thus may be obtained in a powdery form.

In the chlorinated polyethylene, when the high-density polyethylene (HDPE) controls the content of the high molecular weight region in the polymer structure, the HDPE polymer structure is maintained almost similar even in CPE, which is a result of the chlorination reaction, and the high molecular weight region is reduced, thereby controlling the early crosslinking reactivity As a result, the change rate of the compound MV over time can be minimized.

Meanwhile, the chlorinated polyethylene may have a chlorine content of, for example, about 20 wt% to about 50 wt%, about 31 wt% to about 45 wt%, or about 35 wt% to about 40 wt%. Here, the chlorine content of the chlorinated polyethylene can be measured using a combustion ion chromatography (Combustion IC, Ion Chromatography) analysis method. As an example, the combustion ion chromatography analysis method uses a combustion IC (ICS-5000/AQF-2100H) device equipped with an IonPac AS18 (4 x 250 mm) column, internal device temperature (Inlet temperature) 900 ^o C, external It can be measured under the conditions of a flow rate of 1 mL/min using KOH (30.5 mM) as an eluent at a combustion temperature of 1000 ^° C as an outlet temperature. In addition, conventional methods in the art may be applied to the device conditions and measurement conditions for measuring the chlorine content.

The chlorinated polyethylene may be, for example, random chlorinated polyethylene.

In addition, the chlorinated polyethylene may be a mixture of polymers having different chlorine content ratios, for example, a blend of a large proportion of chlorine-containing polyethylene with a small proportion of other rubbers and/or resins. For example, chlorinated polyethylene may be a blend of nitrile rubber, acrylic rubber, and the like. Such blending is performed for the purpose of improving oil resistance, heat resistance and the like.

The above-described chlorinated polyethylene is a major component in the vulcanizable chlorinated polyethylene composition of the present invention.

(b) sulfide-based crosslinking agent or a derivative thereof

Meanwhile, the vulcanizable chlorinated polyethylene composition of the present invention includes chlorinated polyethylene prepared by reacting polyethylene and chlorine as described above, and a sulfide-based crosslinking agent or a derivative thereof capable of vulcanizing the above-described chlorinated polyethylene for a vulcanization process.

Specifically, the sulfide-based crosslinking agent may be a thiadiazole-based compound or a disulfide-based compound.

Preferably, the sulfide-based crosslinking agent is 2,5-dimercapto-1,3,4-thiadiazole and 5,5'-dithiodi-1,3,4-thiadiazole-2 (3H) - Thione (5,5'-dithiodi-1,3,4-thiadiazole-2(3H)-thione, manufacturer: Vanderbilt Chemicals, LLC, product name: Vanax-829) may be one or more selected from the group consisting of.

In particular, it is more advantageous to use a disulfide thiadiazole-based crosslinking agent in terms of controlling the vulcanization reaction with chlorinated polyethylene to have a lower MV change rate with time.

The sulfide-based crosslinking agent or a derivative thereof may be included in an amount of 0.1 part by weight to 4 parts by weight based on 100 parts by weight of the chlorinated polyethylene. When the amount of the disulfide-based crosslinking agent or a derivative thereof is less than 0.1 parts by weight based on 100 parts by weight of the chlorinated polyethylene, vulcanization performance may decrease, resulting in deterioration in physical properties of the final product. In addition, when the disulfide-based crosslinking agent or a derivative thereof is used in an amount exceeding 4 parts by weight based on 100 parts by weight of the chlorinated polyethylene, the MV change rate increases due to the increase in the vulcanization reaction or the crosslinking rate decreases, resulting in decreased productivity. The disulfide-based crosslinking agent or its derivative is preferably 0.5 parts by weight or more, or 1 part by weight or more, or 1.5 parts by weight or more, or 1.8 parts by weight or more, and 3.5 parts by weight or less, or 3 parts by weight or less, or 2.5 parts by weight or less. part or less, or 2.45 parts by weight or less.

For reference, in the present specification, "part by weight" means a relative concept expressed as a ratio of the weight of the remaining material based on the weight of a certain material. For example, in a mixture in which the weight of substance A is 50 g, the weight of substance B is 20 g, and the weight of substance C is 30 g, the amounts of substance B and substance C based on 100 parts by weight of substance A are 40, respectively. parts by weight and 60 parts by weight.

On the other hand, "% by weight" means an absolute concept expressed as a percentage of the weight of the weight of a certain material out of the total weight. In the above example mixture, the contents of substance A, substance B, and substance C are 50% by weight, 20% by weight, and 30% by weight, respectively, based on 100% of the total weight of the mixture. At this time, the total content of each component does not exceed 100% by weight.

(c) amine compounds or derivatives thereof

Meanwhile, the vulcanizable chlorinated polyethylene composition according to the present invention blends a sulfide-based crosslinking agent or a crosslinking agent of a derivative thereof with chlorinated polyethylene, and includes an amine compound or a derivative thereof as an organic vulcanization accelerator.

In particular, when only a sulfide-based crosslinking agent is used or a compound other than an amine compound is used in combination, the vulcanization reaction may not be expressed. When an amine compound or a derivative thereof is added to the crosslinking agent, a vulcanization reaction is expressed, so that the physical properties of the final product can be secured.

Specifically, the amine compound is characterized in that it is a secondary amine compound or a tertiary amine compound. For example, the amine compound may include at least two or more C _4-20 alkyl, preferably C _5-15 alkyl, Alternatively, it may contain two or more C _6-12 alkyl or C _7-10 alkyl.

For example, the amine compound is a high molecular-weight fatty amine and may be a secondary amine or a tertiary amine containing at least two or more alkyl groups having 5 or more carbon atoms. For example, the amine compound may be at least one selected from the group consisting of dihexadecylamine, trihexadecylamine, and mixtures thereof.

These amine compounds may be used alone or in combination of two or more.

The amine compound or a derivative thereof is included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the chlorinated polyethylene. The amine compound or derivative thereof is preferably 0.2 parts by weight or more, or 0.3 parts by weight or more, or 0.5 parts by weight or more, or 0.8 parts by weight or more, and 1.9 parts by weight or less, or 1.8 parts by weight or less, or 1.7 parts by weight or less or less, or 1.5 parts by weight or less.

Specifically, the vulcanizable chlorinated polyethylene composition of the present invention contains 0.1 to 4 parts by weight of the sulfide-based crosslinking agent or a derivative thereof, and 0.1 part to 2 parts by weight of the amine compound or a derivative thereof, based on 100 parts by weight of the chlorinated polyethylene described above. It may include wealth.

(d) other additives

On the other hand, as described above, the vulcanizable chlorinated polyethylene composition of the present invention is formulated with chlorinated polyethylene, a sulfide-based crosslinking agent or a derivative thereof, and an amine compound or a derivative thereof, and at least one additive such as an inorganic vulcanization accelerator such as a calcium-based inorganic base may additionally be included.

In particular, when one or more additives such as an inorganic vulcanization accelerator such as a calcium-based inorganic base including calcium (Ca ²⁺ ) are additionally included, the vulcanizable chlorinated polyethylene composition has a Mooney viscosity (MV) when stored for a long time Extrusion processability can be improved by minimizing the rate of change.

Specifically, the vulcanizable chlorinated polyethylene composition includes calcium stearate ([CH ₃ (CH ₂ ) ₁₆ COO] ₂ Ca), calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca(OH) ₂ ), and at least one additive selected from the group consisting of calcium oxide (CaO) may be further included.

The above additives may be used alone or in combination of two or more.

Meanwhile, the calcium-based inorganic base may have a pH (20 °C, H ₂ O) of 7 to 12, 7.5 to 11, or 8 to 10.

The pH can be measured by a pH titration method or a potentiometric pH meter commonly used in the art to which the present invention belongs. Specifically, it can be measured using a pH meter with a glass electrode, for example, a Metter Toleo SevenExellence pH meter. can be measured afterwards.

The calcium-based inorganic base is included in an amount of 0.1 to 4.5 parts by weight based on 100 parts by weight of the chlorinated polyethylene. When the amount of the calcium-based inorganic base is 0.1 parts by weight or less with respect to 100 parts by weight of the chlorinated polyethylene, agglomeration between CPEs may occur, which may cause problems in subsequent processing, or increase the vulcanization reaction to increase the MV change rate It can be. In addition, when the calcium-based inorganic base is used in an amount exceeding 4.5 parts by weight based on 100 parts by weight of the chlorinated polyethylene, vulcanization performance may decrease, resulting in a decrease in physical properties of the final product or affecting the MV change rate or processability. The disulfide-based crosslinking agent or its derivative is preferably 0.3 parts by weight or more, or 0.4 parts by weight or more, or 0.45 parts by weight or more, or 0.48 parts by weight or more, or 0.5 parts by weight or more, and 4.0 parts by weight or less, or 3.8 parts by weight or less. part by weight or less, or 3.5 parts by weight or less, or 3.05 parts by weight or less, or 2.8 parts by weight or less, or 2.5 parts by weight or less, or 2 parts by weight or less.

Specifically, the vulcanizable chlorinated polyethylene composition of the present invention contains 0.1 to 4 parts by weight of the sulfide-based crosslinking agent or a derivative thereof, and 0.1 part to 2 parts by weight of the amine compound or a derivative thereof, based on 100 parts by weight of the chlorinated polyethylene described above. wealth; and 0.1 to 4.5 parts by weight of one or more additives selected from the group consisting of calcium stearate, calcium carbonate, calcium hydroxide, and calcium oxide.

On the other hand, the vulcanizable chlorinated polyethylene composition according to the present invention can minimize the rate of change in the pattern viscosity (MV) over time even during long-term storage of the chlorinated polyethylene composition in order to improve processability during extrusion with excellent strength of the vulcanizate.

Specifically, the vulcanizable chlorinated polyethylene composition may have a pattern viscosity change rate (%) over time of 20% or less and 0 to 20% according to Formula 1 below.

[Equation 1]

Pattern viscosity change over time (%) = [(MV2-MV1) / MV1] X 100

In Equation 1 above,

MV1 is the initial pattern viscosity (MV1) measured under the condition of ML1 + 4 (125 ° C.) by a method based on ASTM D 1646 immediately after preparing the vulcanizable chlorinated polyethylene composition,

MV2 is the pattern viscosity (MV2) measured under ML1+4 (125°C) conditions according to ASTM D 1646 after storing the vulcanizable chlorinated polyethylene composition in an oven at 40°C for 2 weeks.

The vulcanizable chlorinated polyethylene composition has a rate of change (%) of pattern viscosity over time according to Formula 1 of preferably 18% or less, or 17% or less, or 16.8% or less, or 16.5% or less, or 16.0% or less, or 15.8% or less. % or less, or 15.5% or less. However, considering that the pattern viscosity substantially increases during long-term storage, the change rate (%) of the pattern viscosity over time according to Equation 1 may be 0.1% or more, 0.2% or more, or 0.3% or more.

At this time, the vulcanizable chlorinated polyethylene composition, as described above, immediately after blending the chlorinated polyethylene with a specific disulfide-based crosslinking agent or a derivative thereof, an amine compound or a derivative thereof, and a calcium-based inorganic base, a method according to ASTM D 1646 The initial pattern viscosity (MV1) measured under the conditions of ML1 + 4 (125 ° C.) is 40 MU to 90 MU, preferably 43 MU to 80 MU, or preferably 45 MU to 75 MU, or 48 MU to 72 MU, or 50 MU to 70 MU.

In addition, the vulcanizable chlorinated polyethylene composition has a pattern viscosity (MV2) of 45 MU to 100 after storage in an oven at 40 ° C. for 2 weeks and then measured under conditions of ML1 + 4 (125 ° C.) by a method based on ASTM D 1646 MU, preferably 48 MU to 90 MU, or preferably 50 MU to 88 MU, or 52 MU to 85 MU, or 53 MU to 82 MU.

For reference, the unit of the moony viscosity is expressed as MU (mooney unit), and the value of ML1 + 4 is obtained at 125 ° C., M is moony, L is the size of the plate, and 1 means preheating for 1 minute and 4 means reading the value after 4 minutes of rotor operation in the mooney viscometer. The specific measurement method and conditions of the fringe viscosity are as shown in the test examples to be described later, and detailed descriptions are omitted.

As described above, the vulcanizable chlorinated polyethylene composition according to the present invention has the characteristics of maintaining high crosslinking efficiency while minimizing the rate of change in pattern viscosity (MV) over time even during long-term storage.

Specifically, the vulcanizable chlorinated polyethylene composition has an initial crosslinking efficiency (MH-ML, dNm) of 6.5 dNm or more or 6.5 dNm measured under conditions of a vibration angle of 0.5 degrees, a temperature of 180 ° C., and 1 hour by a method based on ASTM D 5289. dNm to 15 dNm, preferably 6.8 dNm or more, or 7.0 dNm or more, or 7.5 dNm or more, or 7.8 dNm or more, or 13.5 dNm or less, or 11 dNm or less, or 10 dNm or less, or 9.0 dNm or less or less, or 8.8 dNm or less.

On the other hand, the vulcanizable chlorinated polyethylene composition of the present invention includes various compounding agents commonly used in the art, such as fillers, reinforcing agents, plasticizers, stabilizers, anti-aging agents, lubricants, viscosity imparting agents, pigments, flame retardants, ultraviolet absorbers, and foaming agents. , a vulcanization regulator, etc. may be appropriately added. In addition, short fibers and the like may be added to improve strength and rigidity.

In order to obtain the vulcanizable chlorinated polyethylene composition according to the present invention, kneading the above compounding materials using a conventional mixing roll, a Van Barry mixer, a twin-screw kneading extruder, various kneaders, etc. do it in shape Molding or vulcanization can be performed using a press, extruder, injection molding machine or the like to obtain a rubber product of a desired shape. Curing conditions are appropriately selected from the range of several minutes to 2 hours at 100 to 200 ° C.

vulcanizate

According to another embodiment of the present invention, a vulcanizate having good vulcanization properties can be obtained by vulcanizing the above-described vulcanizable chlorinated polyethylene composition.

In particular, as described above, the polymer domain ratio in the molecular structure is shown in the optimal range, and the melt index MI ₅ (measured at 190 ^° C, 5 kg load) with a narrow molecular weight distribution (Mw / Mn) and complex viscosity in the high frequency region By vulcanizing a vulcanizable chlorinated polyethylene composition including chlorinated polyethylene prepared using polyethylene maintaining the optimum range, the vulcanized product having excellent strength and improved processability during extrusion is provided.

In order to obtain a laminate or a laminate hose having a layer composed of the vulcanizable chlorinated polyethylene composition, a well-known conventional laminate method or extrusion molding technique can be applied. For example, by directly laminating a layer composed of the vulcanizable chlorinated polyethylene composition on a layer composed of epichlorohydrin rubber, nitrile rubber, nitrile rubber blended with polyvinyl chloride, or acrylic rubber, and vulcanizing the composition, the laminate can be obtained. In addition, a hose composed of an inner layer composed of epichlorohydrin rubber, nitrile rubber, and polyvinyl chloride blended nitrile rubber or acrylic rubber and an outer layer composed of the composition for vulcanization is formed and the composition is vulcanized to obtain a laminated hose. You can get it.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are only for exemplifying the present invention, and do not limit the present invention only to these.

[Example]

<Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-9>

Ethylene was polymerized in the presence of a Ziegler-Tana catalyst to prepare high-density polyethylene (HDPE) having properties shown in Table 1 below in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-9.

The physical properties of the high-density polyethylene (HDPE) were measured in the following manner, and the results are shown in Table 1 below.

1) Melt index (MI, g/10 min):

The melt index (MI ₅ ) was measured under the condition of a load of 5 kg at a temperature of 190 ^° C by the method of ASTM D 1238, and was expressed as the weight (g) of the polymer melted for 10 minutes.

2) density:

Density (g/cm ³ ) of polyethylene was measured according to ASTM D 1505.

3) Polyethylene complex viscosity (Pa s, 500 rad/s):

Complex viscosity for polyethylene according to Examples 1 to 2 and Comparative Examples 1 to 5 under conditions of a frequency (ω) of .05 rad/s to 500 rad/s at 190 ^° C using an ARES Rheometer (complex viscosity) was measured.

Specifically, the complex viscosity of polyethylene was calculated as the complex viscosity η*(ω0. 05) and η*(ω500) were measured. A certain amount of polyethylene was put into the ARES-G2 equipment and a 25 mm parallel plate and ring, and the gap was 2.0 mm by using parallel plates with a diameter of 25.0 mm by pressing them with upper and lower fixtures at 190 ^° C. The measurement was performed in dynamic strain frequency sweep mode, with a strain of 5% and a frequency (angular frequency) ranging from 0.05 rad/s to 500 rad/s, for a total of 41 points, 10 points for each decade. Among them, complex viscosities measured at a frequency (ω) of 500 rad/s are shown in Table 1 below.

4) Molecular weight distribution (Mw/Mn, polydispersity index) and Log MW (more than 5.5) ratio:

The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene are measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water), and the weight average molecular weight is divided by the number average molecular weight to determine the molecular weight distribution (PDI). , Mw/Mn) was calculated.

Specifically, a Waters PL-GPC220 instrument was used as a gel permeation chromatography (GPC) apparatus, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160 ^° C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. Polyethylene samples according to Examples and Comparative Examples were pretreated by melting at 160 ^o C for 10 hours in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT using a GPC analysis device (PL-GP220), respectively. , prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using polystyrene standard specimens. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g / mol of 9 species were used.

In addition, in the log (log) graph of the weight average molecular weight (Mw) of polyethylene measured in this way, that is, in the GPC curve graph in which the x-axis is log MW and the y-axis is dw / dlogMw, the log MW value is 5.5 or more. The ratio (%) for this total integral value was calculated and shown in Table 1 below.

MI ₅
(g/10min) density
(g/mL) complex viscosity
(Pa s) Mw
(kg/mol) PDI
(Mw/Mn) logMw≥5.5
(%) Example 1-1 2.5 0.9544 794 139 5.8 10.5 Example 1-2 1.7 0.9548 815 134 5.4 10.1 Example 1-3 2.8 0.9543 730 143 5.6 9.5 Comparative Example 1-1 1.3 0.9581 740 182 11.6 15.4 Comparative Example 1-2 1.2 0.9517 850 164 6.7 13.9 Comparative Example 1-3 1.1 0.9518 850 167 7.1 14.6 Comparative Example 1-4 0.45 0.9508 1370 213 5.3 19.0 Comparative Example 1-5 1.5 0.9520 800 153 5.7 15.3 Comparative Example 1-6 2.9 0.9531 645 122 5.8 13.7 Comparative Example 1-7 1.2 0.9580 875 157 5.8 14.0 Comparative Example 1-8 1.0 0.9576 848 150 5.7 14.0 Comparative Example 1-9 3.2 0.9574 656 174 5.8 13.8

As shown in Table 1, in contrast to the comparative example, the example shows the polymer domain ratio in the molecular structure in the optimal range, and at the same time, the melt index MI ₅ ( 190 ^o C, measured at 5 kg load) were all implemented within the optimization range.

<Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-9>

Using the high-density polyethylene (HDPE) according to Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-9, after preparing chlorinated polyethylene (CPE) powder as follows, a crosslinking agent and a crosslinking aid/additive were added. By adding and mixing, the vulcanizable chlorinated polyethylene compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-9 were prepared.

I) Preparation of chlorinated polyethylene

5000 L of water and 550 kg of the high-density polyethylene (HDPE) of Example 1-1 were introduced into the reactor, sodium polymethacrylate as a dispersant, oxypropylene and oxyethylene copolyether as an emulsifier, and benzoyl peroxide as a catalyst After raising the temperature from 80 ^o C to 132 ^o C at a rate of 17.3 ^o C/hr, the mixture was chlorinated with gaseous chlorine at a final temperature of 132 ^o C for 3 hours. At this time, in the chlorination reaction, gaseous chlorine was injected at a pressure of 0.3 MPa in the reactor at the same time as the temperature was raised, and the total input amount of the chlorine was 700 kg. The chlorinated reactant was added to NaOH to neutralize it for 4 hours, washed again with running water for 4 hours, and finally dried at 120 ^° C to prepare chlorinated polyethylene in powder form.

Also, the high-density polyethylene (HDPE) of Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-9 was also prepared as chlorinated polyethylene in powder form in the same manner as described above.

II) Preparation of chlorinated polyethylene composition

As described above, in 100 parts by weight of each of the chlorinated polyethylene powders prepared using the high density polyethylene (HDPE) of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-9, 5,5 parts by weight of a crosslinking agent '-Dithiodi-1,3,4-thiadiazole-2(3H)-thione (5,5'-dithiodi-1,3,4-thiadiazole-2(3H)-thione, manufacturer: Vanderbilt Chemicals, LLC , Product name: Vanax-829) 2.25 parts by weight, high molecular-weight fatty amine, dihexadecyl amine, NH((CH2)15CH3)2 as a crosslinking aid, manufacturer: Vanderbilt Chemicals, LLC, product name: Vanax-882B 0.9 parts by weight were mixed to prepare vulcanizable chlorinated polyethylene compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-9, respectively.

Using the vulcanizable chlorinated polyethylene compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-9 prepared as described above, roll-mill at room temperature to prepare sheet specimens, For the sheet prepared in this way, each physical property was measured as follows.

1) Initial fringe viscosity (MV1) and fringe viscosity after aging (MV2)

The initial texture viscosity (MV1) and the texture viscosity after aging (MV2) were measured under the conditions of ML1+4 (125 ° C.) by a method based on ASTM D 1646.

Specifically, the initial pattern viscosity (MV1) was measured immediately after preparing sheet specimens as described above using the chlorinated polyethylene compositions of Examples and Comparative Examples. In addition, after storing the sheet prepared in this way in an oven at 40 ° C. for 2 weeks, MV was measured after aging for 2 weeks, and the pattern viscosity (MV2) after aging was expressed. From the initial fringe viscosity (MV1) and the fringe viscosity after aging (MV2) measured as described above, the change rate (%) of the fringe viscosity over time was calculated according to Equation 1 below.

[Equation 1]

Pattern viscosity change over time (%) = [(MV2-MV1) / MV1] X 100

In Equation 1 above,

MV1 is the initial pattern viscosity (MV1) measured under the condition of ML1 + 4 (125 ° C.) by a method based on ASTM D 1646 immediately after preparing the vulcanizable chlorinated polyethylene composition,

MV2 is the pattern viscosity (MV2) measured under ML1+4 (125°C) conditions according to ASTM D 1646 after storing the vulcanizable chlorinated polyethylene composition in an oven at 40°C for 2 weeks.

For reference, the unit of the moony viscosity is expressed as MU (mooney unit), and the value of ML1 + 4 is obtained at 125 ° C., M is moony, L is the size of the plate, and 1 means preheating for 1 minute and 4 means reading the value after 4 minutes of rotor operation in the mooney viscometer.

The initial pattern viscosity (MV1) and the pattern viscosity after aging (MV2) of the vulcanizable chlorinated polyethylene compositions of Examples and Comparative Examples measured as described above, and the percentage change (%) of the pattern viscosity calculated therefrom are shown in Table 2 below. same as bar

Early MV
(MV1, MU) MV after tracing
(MV2, MU) MV rate of change
(%) Example 2-1 69.7 80.5 15.5 Example 2-2 62.3 71.2 14.3 Example 2-3 65.7 73.4 11.7 Comparative Example 2-1 60.8 79.7 31.1 Comparative Example 2-2 69.6 107.0 53.7 Comparative Example 2-3 79.3 119.8 51.1 Comparative Example 2-4 123.4 170.2 37.9 Comparative Example 2-5 81.1 107.1 32.1 Comparative Example 2-6 62.7 76.7 22.3 Comparative Example 2-7 68.9 86.3 25.3 Comparative Example 2-8 70.1 88.8 26.7 Comparative Example 2-9 115.6 143.6 24.2

As shown in Table 2, chlorinated polyethylene prepared using the polyethylene of Examples 1-1 to 1-3 in which the viscosity and melt index were optimized with a narrow molecular weight distribution by lowering the polymer domain ratio in the molecular structure according to the present invention. It can be seen that the vulcanizable chlorinated polyethylene compositions of Examples 2-1 to 2-3, including Comparative Examples, can significantly improve the rate of change in pattern viscosity over time (2 weeks) to 11.7% to 15.5% compared to Comparative Examples.

Claims (18)

In a GPC curve graph in which the x-axis is log MW and the y-axis is dw/dlogMw, the integral value of the region where the log MW value is 5.5 or more is 14% or less of the total integral value,
The molecular weight distribution (Mw/Mn) is 5.8 or less,
The complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s is 650 Pa·s to 850 Pa·s,
MI ₅ (melt index measured at 190 ^° C, 5 kg load) from 1.2 g / 10 min to 3.0 g / 10 min,
polyethylene.
According to claim 1,
The polyethylene is an ethylene homopolymer,
polyethylene.
According to claim 1,
In the polyethylene, in a GPC curve graph in which the x-axis is log MW and the y-axis is dw/dlogMw, the integral value of the region where the Log MW value is 5.5 or more is 0.5% to 14% of the total integral value,
polyethylene.
According to claim 1,
The polyethylene has a molecular weight distribution (Mw / Mn) of 2.0 to 5.8,
polyethylene.
According to claim 1,
The polyethylene has a complex viscosity (η*(ω500), complex viscosity) measured at a frequency (ω) of 500 rad/s of 700 Pa·s to 820 Pa·s,
polyethylene.
According to claim 1,
The polyethylene has an MI ₅ (melt index measured at 190 ^° C, 5 kg load) of 1.5 g / 10 min to 2.8 g / 10 min,
polyethylene.
According to claim 1,
The polyethylene has a melt index MI _21.6 (measured at 190 ^° C, 21.6 kg load) of 3 g / 10 min to 33.6 g / 10 min,
polyethylene.
According to claim 1,
The polyethylene, the melt flow index (MFRR _21.6/5 , melt index measured at 190 ^o C, 21.6 kg load by the method of ASTM D 1238 divided by melt index measured at 190 ^o C, 5 kg load) is 2 to 12 people,
polyethylene.
According to claim 1,
The polyethylene has a density of 0.945 g/cm ³ to 0.960 g/cm ³ ,
polyethylene.
Containing chlorinated polyethylene prepared by reacting the polyethylene of any one of claims 1 to 9 with chlorine, a sulfide-based crosslinking agent or a derivative thereof, and an amine compound or a derivative thereof,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
The sulfide-based crosslinking agent is a thiadiazole-based compound or a disulfide-based compound,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
The sulfide-based crosslinking agent is composed of 2,5-dimercapto-1,3,4-thiadiazole and 5,5'-dithiodi-1,3,4-thiadiazole-2(3H)-thione. At least one selected from the group,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
Based on 100 parts by weight of the chlorinated polyethylene, including 0.1 part by weight to 4 parts by weight of the sulfide-based crosslinking agent or a derivative thereof,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
The amine compound includes at least two or more C _4-20 alkyls,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
The amine compound is at least one selected from the group consisting of dihexadecylamine and trihexadecylamine,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
Based on 100 parts by weight of the chlorinated polyethylene, including 0.1 part by weight to 2 parts by weight of the amine compound or a derivative thereof,
A vulcanizable chlorinated polyethylene composition.
According to claim 10,
The vulcanizable chlorinated polyethylene composition has a rate of change (%) over time of pattern viscosity according to the following formula 1 of 20% or less,
Vulcanizable Chlorinated Polyethylene Composition:
[Equation 1]
Pattern viscosity change over time (%) = [(MV2-MV1) / MV1] X 100
In Equation 1 above,
MV1 is the initial pattern viscosity (MV1) measured under the condition of ML1 + 4 (125 ° C.) by a method based on ASTM D 1646 immediately after preparing the vulcanizable chlorinated polyethylene composition,
MV2 is the pattern viscosity (MV2) measured under ML1+4 (125°C) conditions according to ASTM D 1646 after storing the vulcanizable chlorinated polyethylene composition in an oven at 40°C for 2 weeks.
A chlorinated polyethylene vulcanizate obtained by vulcanizing the composition according to claim 10.