KR100985294B1 - Blend Product of NBR and PVC in Pellet Form and Method for Preparing the Same - Google Patents

Abstract

Polymer blend of NBR 60 to 90% by weight and PVC 10 to 40% by weight, at least one selected from Ba-Zn-based heat stabilizer and Ca-Zn-based heat stabilizer with respect to 100 parts by weight of the polymer blend 0.5- A blend product of NBR and PVC is disclosed comprising 2 parts by weight, 0.5-3 parts by weight of tin (Sn) thermal stabilizer, and 2-8 parts by weight of epoxy-based heat stabilizer. Pellet-like blends of NBR and PVC produced in accordance with the present invention can be easily achieved in the subsequent process uniform mixing with other rubber products and other additives contribute to the productivity of the final product. In addition, the manufacturing method according to the present invention contributes to cost reduction of the product because the operation can be performed even if a small number of people in the manufacturing process.

NBR, PVC, Tin heat stabilizer, Epoxy heat stabilizer, Pellets shape, Rubber product, Blend product

Description

Blend Product of NBR and PVC in Pellet Form and Method for Preparing the Same

The present invention relates to a blended product of NBR and PVC in a pellet shape and a method for producing the same, and more particularly, to NBR and PVC that can be produced in a pellet shape by extrusion method by including a specific heat stabilizer and by a specific treatment. It relates to a blended product of the present invention and a method for producing the same.

Synthetic rubber NBR products are used for oil hoses, oil seals, etc. among automotive rubber parts based on excellent oil resistance characteristics, and are also used as industrial rubber products such as hydraulic hoses and flooring materials that require oil resistance and safety soles. However, NBR has a disadvantage of weak ozone resistance and weatherability due to double bonds. In order to remedy these shortcomings of NBR, PVC which is compatible with NBR and excellent in use is currently used.

Synthetic rubber NBR products are generally made in a bale shape (700 mm x 500 mm x 200 mm) as shown in FIG. On the other hand, blend products of NBR and PVC are conventionally manufactured in a sheet shape (500 mm x 300 mm x 10 mm) as shown in FIG. These blends of NBR and PVC are then used to produce the required type of vulcanized rubber product through the process of mixing with additives such as carbon black, softener, vulcanizing agent. At this time, the blend product of NBR and PVC may be blended with other rubber products as needed.

However, sheet-like blends of NBR and PVC are difficult to blend uniformly with other rubber products and other additives in subsequent processes, resulting in poor productivity of the final product and also a great deal of work for the manufacture of blended products of NBR and PVC. There was a problem that personnel should be put in.

The present invention has been made to solve the above problems of the prior art. Accordingly, it is an object of the present invention to provide a blended product of NBR and PVC in pellet form and a method of making the same.

Blend product of NBR and PVC according to the present invention is a polymer blend of NBR 60 ~ 90% by weight and PVC 10 ~ 40% by weight, Ba-Zn-based heat stabilizer and Ca-Zn-based heat based on 100 parts by weight of the polymer blend 0.5 to 2 parts by weight of a metal based heat stabilizer selected from at least one stabilizer, 0.5 to 3 parts by weight of a tin (Sn) based heat stabilizer, and 2 to 8 parts by weight of an epoxy based heat stabilizer. This blend product is preferably in a pellet shape, which pellet shape is formed by extrusion of an extruder.

The blend product of NBR and PVC according to the present invention is also a polymer blend of NBR 60 to 90% by weight and PVC 10 to 40% by weight, with respect to 100 parts by weight of the polymer blend, 1 to 5 weight of tin (Sn) thermal stabilizer Part, may be configured to include 2 to 8 parts by weight of an epoxy-based heat stabilizer.

Method for producing a blend product of NBR and PVC according to the present invention is a polymer blend of NBR 60 ~ 90% by weight and PVC 10 ~ 40% by weight, based on 100 parts by weight of the polymer blend, Ba-Zn-based heat stabilizer and Ca- Injecting a raw material comprising 0.5 to 2 parts by weight of a metal-based heat stabilizer, 0.5 to 3 parts by weight of tin (Sn) -based heat stabilizer, and 2 to 8 parts by weight of epoxy-based heat stabilizer selected from the Zn-based heat stabilizer into the extruder And kneading the raw materials in the extruder and extruding through the die of the extruder, and cutting the extrudate extruded through the die into pellets. In this manufacturing method, during the extrusion process, the screw of the extruder is preferably cooled by the cooling water, and the extrudate discharged from the die of the extruder is preferably cooled by the injection of cooling water immediately after being discharged from the die. .

Pellet-like blends of NBR and PVC produced in accordance with the present invention can be easily achieved in the subsequent process uniform mixing with other rubber products and other additives contribute to the productivity of the final product. In addition, the manufacturing method according to the present invention contributes to cost reduction of the product because the operation can be performed even if a small number of people in the manufacturing process.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Figure 3 is a photograph showing a blended product of pellet-shaped NBR and PVC prepared according to the method of the present invention.

Figure 4 is a schematic manufacturing process diagram of the prior art (current method) to manufacture in a sheet shape and the technology according to the present invention (improved method) to produce a pellet shape in the blend product of NBR and PVC according to the manpower input state Schematic diagram showing.

As shown in Figure 3, the blended product of NBR and PVC according to the present invention has a pellet shape. One method for producing a blend of NBR and PVC into such pellet shape is to extrude the blend of NBR and PVC by an extruder.

Conventionally, raw materials including NBR and PVC were manufactured in a sheet shape using an open mill, and Ba-Zn-based heat stabilizers and / or Ca-Zn-based heat stabilizers were used as heat stabilizers. However, these heat stabilizers alone could not be applied to the extrusion method. This is because PVC is carbonized by the heat generated during extrusion. Therefore, conventionally, the blended product of NBR and PVC could not be manufactured by the extrusion method.

Accordingly, the present invention is to produce a blended product of NBR and PVC in a pellet shape by the extrusion method. To this end, the present invention primarily improves the raw materials. That is, the blend product of NBR and PVC according to the present invention is a polymer blend of NBR 60 to 90% by weight and PVC 10 to 40% by weight, based on 100 parts by weight of the polymer blend, Ba-Zn-based heat stabilizer and Ca-Zn 0.5 to 2 parts by weight of a metal based heat stabilizer selected from at least one of the thermal stabilizers, 0.5 to 3 parts by weight of a tin (Sn) based heat stabilizer, and 2 to 8 parts by weight of an epoxy based heat stabilizer.

The present invention increases the thermal stability of the raw material by applying a specific heat stabilizer to the blend of NBR and PVC so that the carbonization of PVC does not occur even if the extrusion method is applied. Specifically, the heat stabilizer used in the present invention essentially includes a tin heat stabilizer and an epoxy heat stabilizer.

Tin-based thermal stabilizers in the blend of NBR and PVC of the present invention provides a high thermal stability. Such tin-based heat stabilizers are more excellent in thermal stability than other metal-based heat stabilizers, such as Ba-Zn-based heat stabilizers or Ca-Zn-based heat stabilizers conventionally used. Therefore, in the present invention, if the tin-based heat stabilizer is not included, it is impossible to obtain excellent thermal stability enough to apply the extrusion method. The amount of tin-based heat stabilizer used in the present invention is preferably 0.5 to 3 parts by weight based on 100 parts by weight of the polymer blend of NBR and PVC. When too little tin-based heat stabilizer is included, the thermal stability of the raw material cannot be sufficiently increased, and carbonization of PVC cannot be prevented, and in too many cases, the economic efficiency of the input amount is not good compared to the effect of improving the thermal stability. Examples of such tin-based heat stabilizers include mercaptide-based, maleate-based, and laurate-based compounds. Examples of laurate-based heat stabilizers include butyltin laurate complex, octyltin laurate complex, methyltin laurate complex, and the like. In the examples herein, butyltin laurate composite was used as a tin-based heat stabilizer.

In the blended product of NBR and PVC of the present invention, the epoxy-based heat stabilizer has a synergistic effect together with the tin-based heat stabilizer to further improve thermal stability, and also gives plasticity to the raw material to prevent PVC carbonization, kneading and extrusion. It is assumed to contribute. In the present invention, the thermal stability is not improved enough to sufficiently prevent the PVC carbonization with the tin-based heat stabilizer, and the synergistic effect on improving the thermal stability may be obtained only when the tin-based heat stabilizer and the epoxy-based heat stabilizer are combined. In addition, since the epoxy thermal stabilizer is plastic as an organic compound, plasticity can be imparted to the raw material. The amount of the epoxy thermal stabilizer is preferably 2 to 8 parts by weight based on 100 parts by weight of the polymer blend of NBR and PVC. If the amount of epoxy thermal stabilizer is too small, the improvement of thermal stability is insufficient, and it is difficult to manufacture into pellet shape, and if the amount is too large, there is a possibility that a bleeding phenomenon that occurs to the surface may occur. Not desirable Epoxy-based heat stabilizers used in the present invention may be epoxidized vegetable oil, in particular ESO (Epoxidized Soybean Oil).

On the other hand, in order to supplement the plasticity of the epoxy-based heat stabilizer or to exert a synergistic effect with the blend product of the present invention may further comprise a plasticizer. Such plasticizers may be included in an amount of 2 to 6 parts by weight, based on 100 parts by weight of the polymer blend of NBR and PVC. The plasticizer that can be used in the present invention is not particularly limited, and particularly suitable plasticizers include phthalate plasticizers such as dioctylphthalate, adipate-based and ester plasticizers, and the like.

In the present invention, it may further include a metal-based heat stabilizer used for the thermal stabilization of the raw material in the conventional method. In the present specification, the metal-based heat stabilizer refers to a metal-based heat stabilizer except for a tin-based heat stabilizer, which is commonly used for thermal stabilization of raw materials in a conventional method. Examples of such metal-based heat stabilizers include Ba-Zn-based heat stabilizers and Ca-Zn-based heat stabilizers, and the amount of these metal-based heat stabilizers is 0.5 to 2 parts by weight based on 100 parts by weight of the polymer blend made of NBR and PVC. . The use of these metal-based thermal stabilizers is meaningful in that the amount of tin-based thermal stabilizer can be used less. Generally, tin-based heat stabilizers are among the most expensive, while Ba-Zn-based heat stabilizers and Ca-Zn-based heat stabilizers are cheaper than tin-based heat stabilizers. Therefore, in the case of including only the tin-based heat stabilizer as the metal-based heat stabilizer may be better in terms of the effect on the same amount, the effect on the input raw material by replacing some of the amount of the tin-based heat stabilizer with another metal-based heat stabilizer It is possible to secure more economical. Accordingly, the blend product of the present invention may include other metal thermal stabilizers in the amounts mentioned above, and the total weight of the metal thermal stabilizer and the tin thermal stabilizer is 1 to 5 parts by weight based on 100 parts by weight of the polymer blend. It is desirable to disclaim.

The polymer blend of NBR and PVC used in the present invention is preferably composed of 60 to 90% by weight of NBR and 10 to 40% by weight of PVC. If the amount of NBR is too large, it is insufficient to achieve the purpose of obtaining through blending with PVC, that is, achieving the improvement of ozone resistance and weather resistance, and if the amount of NBR is too small, the characteristics of rubber do not reach the desired degree. You can't. NBR used in the present invention is generally understood to be a copolymer of 2-propenenitrile and butadiene, but 2-propenenitrile derivatives such as 3-methyl-2-propenenitrile = 2-butene Nitrile) and butadiene and copolymers of acrylonitrile and butadiene.

The NBR used in the present invention preferably has a weight average molecular weight in the range of 300,000 to 600,000, and its glass transition temperature is preferably in the range of -25 to -35 ° C. PVC used in the present invention is to impart properties such as ozone resistance, weather resistance and wear resistance, it is preferable that the weight average molecular weight is in the range of 100,000 to 300,000.

In this way, when the thermal stability of the raw material of the blended product is increased, the extrusion temperature in the extruder can be increased, and as a result, the head pressure of the extruder can be lowered, thereby facilitating extrusion.

In addition, the blend product of NBR and PVC according to the present invention is a polymer blend of NBR 60 ~ 90% by weight and PVC 10 ~ 40% by weight, based on 100 parts by weight of the polymer blend, 1 ~ 5 weight of tin (Sn) -based heat stabilizer It can comprise, including 2-8 weight part of epoxy-type heat stabilizers. As mentioned above, some of the tin-based heat stabilizers used for the process of making the blend products of the present invention and subsequent thermal stability may or may not be replaced with other metal-based heat stabilizers. It may also include other possible heat stabilizers.

Next, the present invention is to produce a blended product of NBR and PVC in the form of pellets by the extrusion method. That is, the production method of the present invention is a polymer blend of NBR 60 to 90% by weight and PVC 10 to 40% by weight, at least among Ba-Zn-based heat stabilizer and Ca-Zn-based heat stabilizer based on 100 parts by weight of the polymer blend. Injecting a raw material containing 0.5 to 2 parts by weight of a metal-based heat stabilizer, 0.5 to 3 parts by weight of a tin (Sn) -based heat stabilizer, and 2 to 8 parts by weight of an epoxy-based heat stabilizer into the extruder, the raw material in the extruder After kneading and extruding through a die of the extruder, and cutting the extrudate extruded through the die into a pellet shape.

In addition, the production method of the present invention is a polymer blend of NBR 60 ~ 90% by weight and PVC 10 ~ 40% by weight, 1 to 5 parts by weight of tin (Sn) -based heat stabilizer, epoxy based on 100 parts by weight of the polymer blend Injecting a raw material containing 2 to 8 parts by weight of the heat stabilizer into the extruder, kneading the raw material in the extruder and extruding through the die of the extruder, and cutting the extrudate extruded through the die into a pellet shape It may be configured to include.

The present invention further improves on the manufacturing method in the above-described manufacturing method. That is, the present invention allows the screw of the extruder to be cooled by the coolant during the extrusion process. Cooling the screw of the extruder with cooling water is a method that can be applied when extruding resins such as PVC and PP, but there is no example applied to NBR products or blended products of NBR and PVC. By such a cooling method, the carbonization of the PVC by the heat of the screw can be prevented.

In addition, in the production method of the present invention, the extrudate discharged from the die of the extruder is preferably cooled by the injection of cooling water immediately after discharged from the die. In the case of extruding the rubber composition by an extruder, it is not easy to cool and cut the extrudate to make pellets since the extrudate expands as it passes through the die and also contracts after expansion. In other words, not only the cutting is easy, but the uniformity of the pellets is greatly reduced, and the state of the product is not uniform. In order to solve this problem, in the present invention, as soon as the extrudate is discharged from the die, the coolant is sprayed on the extrudate to cool the extrudate. In addition, in the manufacturing method of the present invention, when the extrudate passes through the die, expansion and contraction occur, but the workability problem due to expansion and contraction is caused by spraying cooling water to cool the extrudate and immediately cutting the extrudate to make pellets. none. In the present invention, an extruder for producing a blend product of NBR and PVC can be used that is commonly used, it is preferable that the barrel temperature is set in the range of approximately 70 to 120 ℃. In addition, the temperature of the extrudate discharged from the die of the extruder before cooling by the cooling water in such an extruder is preferably 90 ~ 140 ℃, it can be set to approximately 120 ℃. In the extruder set as described above, the temperature of the cooling water is preferably 80 to 90 ° C. If the temperature of the cooling water is too low, the extrudate is rapidly cooled and there is a risk of the extrudate blocking the nozzle inlet.

When the blended product of NBR and PVC is manufactured in a pellet shape according to the manufacturing method of the present invention as described above, in addition to the advantages due to the pellet shape of the product, as shown in FIG. The advantage is that the attraction can be much less than in the conventional way.

Hereinafter, the present invention will be described through specific examples. However, the following examples are merely embodiments of the present invention and should not be understood as limiting the scope of the present invention.

[Example]

Examples 1-2 and Comparative Examples 1-2

The raw material of the composition shown in Table 1 below was put into an extruder, and then extruded to produce a blended product of NBR and PVC into pellets. The screw of the extruder was cooled by cooling water and as soon as it exited the die the extrudate was cooled by cooling water and then cut and made into pellets. At this time, the barrel temperature of the extruder was 90 to 100 ° C, the temperature of the extrudate before being cooled by the cooling water in the die was approximately 120 ° C, and the temperature of the cooling water was 80 to 90 ° C.

TABLE 1

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Remarks NBR 70 70 70 70 PVC 30 30 30 30 Plasticizer (DOP) 3 5 3 3 Thermal Stabilizer (Ca-Zn) One 0.5 0.5 0.5 Thermal Stabilizer (Ba-Zn) One 0.5 0.5 0.5 Thermal Stabilizer (Tin Type) One One One Heat stabilizer (epoxy clock) 3 6 * ESO Appearance Appearance × △ ○ ◎ Note 1)

Note 1) Appearance of Pellet: It is judged whether or not Pellet's PVC is carbonized, and it is a criterion for determining whether the product is defective or not.

* In the above table, CZ-200 (Songwon Industry) was used as Ca-Zn-based heat stabilizer, BZ-210 (Songwon Industry) was used as Ba-Cd-based heat stabilizer, and TL- was used as tin-based heat stabilizer. 600 (Songwon Industrial) was used, and ESO (Epoxidized Soybean Oil) was used as an epoxy thermal stabilizer.

As can be seen from the results in Table 1, conventional metal-based heats used when manufacturing sheet-shaped products using conventional open mills without using epoxy-based heat stabilizers as tin-based heat stabilizers and auxiliaries. In Comparative Example 1 using only a stabilizer, a substantially pellet-shaped product was not produced. In the case of Comparative Example 2 in which a metal-based heat stabilizer and a tin-based heat stabilizer were used together, a pellet shape was made to some extent, but not enough to be commercialized.

On the other hand, Examples 1 and 2 according to the present invention was formed satisfactorily pellets and there was no shortage even to commercialize.

1 is a photograph showing a synthetic rubber NBR product having a lump shape (700 mm x 500 mm x 200 mm).

2 is a photograph showing a blend product of NBR and PVC in a sheet shape (500 mm x 300 mm x 10 mm) manufactured according to a conventional method.

Figure 3 is a photograph showing a blended product of pellet-shaped NBR and PVC prepared according to the method of the present invention.

Figure 4 is a schematic manufacturing process diagram of the prior art (current method) to manufacture in a sheet shape and the technology according to the present invention (improved method) to produce a pellet shape in the blend product of NBR and PVC according to the manpower input state Schematic diagram showing.

Claims (17)

Polymer blend of NBR 60 to 90% by weight and PVC 10 to 40% by weight, at least one selected from Ba-Zn-based heat stabilizer and Ca-Zn-based heat stabilizer with respect to 100 parts by weight of the polymer blend 0.5- 2 parts by weight, tin (Sn) -based heat stabilizer, 0.5 to 3 parts by weight, and epoxy-based heat stabilizer 2 to 8 parts by weight, characterized in that formed into a pellet shape by extrusion of the extruder Blended product of NBR and PVC. delete The method of claim 1, The tin-based heat stabilizer is selected from the group consisting of mercaptide-based, maleate-based, and laurate-based compounds Blended product of NBR and PVC. The method of claim 1, The total weight of the metal-based heat stabilizer and the tin-based heat stabilizer is 1 to 5 parts by weight based on 100 parts by weight of the polymer blend. Blended product of NBR and PVC. The method of claim 1, The epoxy-based heat stabilizer is characterized in that the epoxidized Soybean Oil (Epoxidized Soybean Oil) Blended product of NBR and PVC. delete Polymer blend of NBR 60-90 wt% and PVC 10-40 wt%, 1 to 5 parts by weight of tin (Sn) -based heat stabilizer and 2 to 8 parts by weight of epoxy-based heat stabilizer, based on 100 parts by weight of the polymer blend. Pellet-like blend of NBR and PVC. Polymer blend of NBR 60 to 90% by weight and PVC 10 to 40% by weight, at least one selected from Ba-Zn-based heat stabilizer and Ca-Zn-based heat stabilizer with respect to 100 parts by weight of the polymer blend 0.5- Injecting a raw material comprising 2 parts by weight, 0.5 to 3 parts by weight of tin (Sn) thermal stabilizer, and 2 to 8 parts by weight of epoxy-based heat stabilizer to the extruder, Kneading the raw material in the extruder and extruding it through a die of the extruder, and Cutting the extrudate extruded through the die into pellets; Process for producing blended products of NBR and PVC in pellet form. The method of claim 8, During the extrusion process, the screw of the extruder is cooled by cooling water, characterized in that Process for producing blended products of NBR and PVC in pellet form. The method of claim 8, The extrudate discharged from the die of the extruder is cooled by the injection of cooling water immediately after discharged from the die Process for producing blended products of NBR and PVC in pellet form. The method of claim 9, The extrudate discharged from the die of the extruder is cooled by the injection of cooling water immediately after discharged from the die Process for producing blended products of NBR and PVC in pellet form. The method of claim 10, The temperature of the cooling water is characterized in that 80 ~ 90 ℃ Process for producing blended products of NBR and PVC in pellet form. 13. The method of claim 12, The temperature of the extrudate discharged from the die of the extruder before being cooled by the cooling water is characterized in that 100 ~ 140 ℃ Process for producing blended products of NBR and PVC in pellet form. The method of claim 8, The tin-based heat stabilizer is selected from the group consisting of mercaptide-based, maleate-based, and laurate-based compounds Process for producing blended products of NBR and PVC. The method of claim 8, The total weight of the metal-based heat stabilizer and the tin-based heat stabilizer is 1 to 5 parts by weight based on 100 parts by weight of the polymer blend. Process for producing blended products of NBR and PVC. The method of claim 8, The epoxy-based heat stabilizer is characterized in that the epoxidized Soybean Oil (Epoxidized Soybean Oil) Process for producing blended products of NBR and PVC. Polymer blend of 60 to 90% by weight of NBR and 10 to 40% by weight of PVC, 1 to 5 parts by weight of tin (Sn) -based heat stabilizer, and 2 to 8 parts by weight of epoxy-based heat stabilizer, based on 100 parts by weight of the polymer blend Feeding the raw material to the extruder, Kneading the raw material in the extruder and extruding it through a die of the extruder, and Cutting the extrudate extruded through the die into pellets; During the extrusion process, the screw of the extruder is cooled by the cooling water, and the extrudate discharged from the die of the extruder is cooled by the injection of cooling water immediately after being discharged from the die Process for producing blended products of NBR and PVC in pellet form.

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