KR101677495B1 - Environmental flexible Polyamide compound - Google Patents

Abstract

The present invention relates to a polyamide resin composition comprising 1 to 10 parts by weight of a maleic anhydride-grafted polyolefin elastomer, 0.1 to 5 parts by weight of a nucleating agent, 0.1 to 5 parts by weight of a release agent, 0.1 to 5 parts by weight of a primary antioxidant, And 0.1 to 5 parts by weight of an antifogging agent.
According to the present invention, caprolactam, which is a harmful substance added to the conventional flexible polyamide, is not added and the flexibility of the polyamide resin is effectively added using a maleic anhydride-graft-polyolefin elastomer, and the nucleating agent, , The process efficiency of the flexible polyamide resin can be increased.

Description

[0001] Environmental flexible polyamide compound [0002]

The present invention relates to an eco-friendly flexible polyamide compound, and more particularly to a flexible polyamide to which a maleic anhydride-graft-polyolefin elastomer is added to impart flexibility of polyamide.

The polyamide was first synthesized in 1928 by Wallace Carothers of Du Pont. Polyamide refers to a synthetic polymer in which structural units constituting its main chain are linked by amide groups, and polyamide in which structural units linked by amide groups are mainly composed of aliphatic monomers is referred to as nylon.

At present, many kinds of nylon are commercialized according to their synthesized monomers and production methods, and the most commercially available products are nylon 6 and nylon 6,6. Among these, nylon 6 is lightweight, has high strength, has excellent abrasion resistance and elasticity, and is widely used in industry. The mechanism for the production of nylon 6 is as follows. Caprolactam, which is a monomer, is ring-opened by water under high temperature and pressure, and the ring-opened reactive caprolactam reacts with the caprolactam or the terminal of the polymer And the molecular chain is grown through the chain polymerization reaction.

Nylon 6 may have a process for producing caprolactam-nylon 6 by additionally adding caprolactam, which is a monomer, as a softener in order to increase flexibility according to its industrial use. However, the addition amount of caprolactam is limited and it lacks the ability to add flexibility. In addition, most of the above process is a process in which caprolactam is added by artificially compounding, and the caprolactam addition process proceeds according to a high temperature compounding (extrusion) process. At this time, the vent of the extruder causes pollution There is a serious problem in the environment in which caprolactam as a substance flows out into the atmosphere.

Korean Patent Laid-Open No. 10-2007-0115133 discloses a process for producing a resin by adding a maleic anhydride-polypropylene to a nylon 6 resin by using a twin-screw extruder for the purpose of automobile interior and exterior materials, industrial materials and architectural materials Impact resistance and flame retardancy are known, there is a disadvantage in that flexibility is poor.

Korean Patent Registration No. 10-0295071 discloses a technique of polymerizing a polyamide resin and a specific graft-modified ethylene / 1-butene random copolymer to improve flexibility, low-temperature impact resistance and flame resistance, but it is also possible to add a caprolactam monomer There is a disadvantage that it can cause environmental problems.

In addition, the country still depends on imports of flexible polyamides, and precise guidelines are needed to manufacture polyamides with excellent flexibility.

The present invention relates to a process for producing a high-pressure rubber hose by using a maleic anhydride-graft-polyolefin elastomer, in which the flexibility of nylon is remarkably increased and, in particular, It is an object of the present invention to provide an environmentally friendly flexible polyamide compound which does not contain monomers.

In order to achieve the above-mentioned object, the present invention provides a polyamide resin composition comprising 1 to 10 parts by weight of a maleic anhydride-graft-polyolefin elastomer, 0.1 to 5 parts by weight of a nucleating agent, 0.1 to 5 parts by weight of a release agent, 0.1 to 5 parts by weight of a primary antioxidant and a secondary antioxidant,

Preferably, the maleic anhydride-grafted-polyolefin elastomer is prepared by grafting a metallocene linear low density polyethylene, maleic anhydride and an initiator peroxydicumyl peroxide, wherein the grafting ratio of maleic anhydride is from 1 to 10 %. ≪ / RTI >

Preferably, the maleic anhydride may include 0.5 to 10 parts by weight based on 100 parts by weight of the metallocene linear low density polyethylene, and the peroxide diluent may include 0.1 to 5 parts by weight.

Also, preferably, the weight average molecular weight of the maleic anhydride-graft-polyolefin elastomer may be 20,000 to 500,000.

Preferably, the nucleating agent is selected from adipic acid, 1,2,3,4-dibenzylidene sorbitol, 1,2,3,4-bis (p-methylbenzylidene) sorbitol, 1,2,3,4- At least one selected from 4-bis (p-ethylene sorbitol), bis (4-t-butylphenyl) sodium phosphate, NaH ₂ PO ₄ , Ph ₃ Pb ₃ (PO ₄ ) ₂ , Talc and kaolin .

Preferably, the releasing agent is selected from the group consisting of paraffin wax, paraffin wax, low molecular weight ethyl vinyl acetate (EVA), stearic acid, cetyl alcohol, stearyl alcohol, butyl stearate, glycol monostearate, glycerin monooleate, It is possible to use at least one selected from the group consisting of stearic acid, arginic acid, arginic acid, arginic acid, arginic acid, aryestearate, calcium stearate, barium stearate, magnesium stearate, stearamide, oleamide, erucamide and pentaerythrityl tetrastearate.

Preferably, the primary antioxidant is 3,3'-Bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide, Tetrakis- [3- di-tert-butyl-4-hydroxyphenyl) propionate may be used.

Preferably, the secondary antioxidant is Tris (2,4-di-tert-butylphenyl) phosphite.

Preferably, the step of condensing the caprolactam monomer to produce a polyamide resin, the step of extracting a monomer to remove unreacted materials and side reactants, the step of extracting a monomer mixture comprising the polyamide resin and the maleic anhydride-graft-polyolefin elastomer, Adding a releasing agent, a primary antioxidant, and a secondary antioxidant, followed by reactive extrusion.

Preferably, the extrusion pressure of the reaction extrusion step is 100 to 1000 psig, the rotation speed is 50 to 300 RPM, and the extrusion temperature is 150 to 300 ° C.

The present invention does not add a caprolactam monomer, which is a conventional softening additive added to produce a flexible polyamide, and therefore does not have a fatal effect on a worker and does not cause serious environmental problems.

Further, the flexibility of the polyamide resin can be added by using the maleic anhydride-graft-polyolefin elastomer.

And, by providing appropriate proportions of additives such as nucleating agents, releasing agents and antioxidants, the process efficiency of the flowable polyamide resin can be increased.

1 is a view showing a process for producing an environmentally friendly fluid polyamide compound of the present invention.
2 is a view showing an extrusion process of the environmentally friendly fluid polyamide compound of the present invention.
3 is a graph showing the graft ratio according to the maleic anhydride content ratio in the process of producing the maleic anhydride-graft-polyolefin elastomer of the present invention.
FIG. 4 is a graph showing the grafting ratio of the maleic anhydride-graft-polyolefin elastomer according to the content of the initiator in the process of the present invention.

The present invention relates to an eco-friendly flexible polyamide compound prepared from a polyamide resin, a maleic anhydride-graft-polyolefin elastomer, a nucleating agent, a releasing agent and an antioxidant, wherein 100 parts by weight of the polyamide resin is mixed with maleic anhydride- 0.1 to 5 parts by weight of a polyolefin elastomer, 0.1 to 5 parts by weight of a nucleating agent, 0.1 to 5 parts by weight of a release agent, 0.1 to 5 parts by weight of a primary antioxidant and 0.1 to 5 parts by weight of a secondary antioxidant To provide a flexible polyamide compound.

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

1) Eco-friendly flexible polyamide Compound  Composition

The polyamide resin included in the present invention is prepared by adding water (H ₂ O) as a catalyst to caprolactam as a monomer and polymerizing (polymerization) under high pressure (240 to 280 ° C.) under pressure (15 to 18 kg / cm ² ) do. The monomer is ring-opened by water to initiate the reaction, and the molecule is grown by the reaction of the ring-opened monomer with the caprolactam or the terminal of the polymer. After completion of the polymerization reaction, the monomer that has not undergone the reaction (ring opening) is extracted and dried to complete the production of the resin. The polyamide resin may include 40 to 80% by weight based on the total weight of the polyamide resin. If the addition range is lower than the above range, the rigidity, impact strength and heat resistance are lowered. On the other hand, when the addition range is higher than the above range, the mold is not in contact with the mold surface of the extruder or extruder during the manufacturing process. It can fall.

The maleic anhydride-graft-polyolefin elastomer (MAH-g-POE) contained in the present invention is used for imparting flexibility to the polyamide through an imide bond with a polyamide chain.

The maleic anhydride-graft-polyolefin elastomer may include 1 to 10 parts by weight, and the weight average molecular weight thereof is preferably 20,000 to 500,000, based on 100 parts by weight of the polyamide resin. When the maleic anhydride-graft-polyolefin elastomer has a range lower than the above range, the mechanical properties are lowered and the flexibility is lowered. On the other hand, when the elastomer has a higher range than the above range, the mechanical properties are improved, The moldability and workability of the amide are deteriorated.

The nucleating agent included in the present invention enhances the crystallization speed, miniaturizes the crystal size, and improves the mechanical strength of the polyamide as the polyamide provides nuclei that can be easily crystallized. For the above reasons, there is an advantage that the efficiency of the process is increased because the cooling rate is increased during the extrusion molding of the polyamide and the cycle time is reduced.

The nucleating agent may include 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide resin. If the addition range is lower than the above range, the effect of the nucleating agent can not be observed. On the contrary, if the addition range is higher than the above range, the pore diameter of the polyamide becomes larger and its use may be limited.

Herein, the nucleating agent is not particularly limited as to its material, but adipic acid, 1,2,3,4-dibenzylidene sorbitol, 1,2,3,4-bis (p-methylbenzylidene) sorbitol, At least one selected from the group consisting of 2,3,4-bis (p-ethylene sorbitol), bis (4-t-butylphenyl) sodium phosphate, NaH ₂ PO ₄ , Ph ₃ Pb ₃ (PO ₄ ) ₂ , Talc and kaolin Can be used

The releasing agent included in the present invention lubricates a mold surface such as a device surface during processing, molding, or extrusion of a polyamide resin to prevent the working material from sticking, and prevents residue from staying in the extruder or the injection machine to prevent carbonization of the resin For example. Further, since the releasing agent is kneaded with the working material to reduce the melt viscosity, the molding processability is improved, the processing temperature in the manufacturing process is lowered, and the deterioration of the polyamide resin is reduced to improve the quality of the product. It also allows the extrudate to be easily separated from the mold during the extrusion process, which means that it can reduce the cooling time of the extrusion process in particular. During the kneading with the polyamide resin, the releasing agent is applied to the polyamide particles, and when the temperature rises, the polyamide and the releasing agent are simultaneously melted and the releasing agent is impregnated into the polymer.

The release agent may include 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide resin. When the addition range is lower than the above range, the function of the releasing agent can not be exhibited effectively in the resin. On the contrary, when the addition range is higher than the above range, the quality of the product may be greatly deteriorated. The mold release agent may obtain various effects by using a small amount, but it may not be so. In the case of the same release agent, since the function of the same release agent or the production method to be manufactured varies from time to time, This is important.

Here, the releasing agent is not particularly limited, but may be selected from the group consisting of paraffin wax, paraffin wax, paraffin wax and low molecular weight ethyl vinyl acetate (EVA), which are hydrocarboncarbons, and stearic acid and alcohol- Stearyl alcohol, stearyl alcohol and the like and ester stearates such as butyl stearate, glycol monostearate, glycerin monooleate, stearyl stearate and the like and metal salts (carboxylate salts) such as calcium stearate, barium stearate, magnesium Stearamide, amide, stearamide, amide, stearamide, oleamide, erucamide, and pentaerythrityl tetrastearate may be used, and may include one or more selected from the group consisting of However, preferably, erucamide and pentaerythrityl tetras having a structure represented by the following formula Oh, the rate may be mixed.

The pentaerythrityl tetrastearate may have a refractive index of 1.442 to 1.446, a density of 0.87 to 0.88 g / cm3, a viscosity of 18 to 24 mPa.s, and a saponification value of 185 to 200. [

In the case of pentaerythrityl tetrastearate having the above-mentioned physical properties, it is suitable for use in the environmentally friendly flexible polyamide compound of the present invention because of its excellent thermal stability and very low volatility even at high temperatures, The moldability and the productivity of the final product are increased and the smooth surface condition of the final product can be maintained.

The antioxidant included in the present invention is used for the purpose of preventing deterioration of the quality of the polyamide resin when it is produced. The polyamide resin easily oxidizes at the surface when it comes into contact with oxygen in the air. If an oxidation reaction occurs during processing such as extrusion and molding, radicals are generated due to heat, shear force and residual metal. A side reaction such as homo bonding or cross-linking occurs due to the generated radical, so that the polyamide resin becomes unstable or loses its inherent physical properties such as decrease in melt flow index, resulting in deterioration of quality.

The antioxidant should be non-toxic, have stability at the processing temperature, and must have high affinity to the resin without interfering with the processability of the resin.

In the present invention, the antioxidant is divided into a primary antioxidant and a secondary antioxidant. The primary antioxidant acts to reduce hydrogen by supplying hydrogen to the oxidized peroxide radical and the secondary antioxidant dissociates the peroxide hydroperoxide to decompose the peroxide into a stable state. The primary antioxidant may include 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide resin.

Here, the primary antioxidant is not particularly limited in its material, but phenol, monophenol, bisphenol, macromolecular phenol and aromatic amines can be used, preferably aromatic amines, more preferably, (3, 5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide having the structure of Formula 2 or Tetrakis- [3- 5-di-tert-butyl-4-hydroxyphenyl) propionate.

The secondary antioxidant may include 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide resin. Here, the secondary antioxidant is not particularly limited, but thioester and phosphite can be used. Phosphites can be used, and more preferably, Tris (2,4-di- tert- butylphenyl) phosphite having the structure of

If the addition range is lower than the above range of addition of the primary and secondary antioxidants, it is impossible to function as an antioxidant, and side reactions such as crosslinking or homogeneous bonding may be caused to lower the melting index of the resin. Conversely, If the addition range is higher than the above range, the efficiency of the polyamide polymerization reaction proceeding through the extrusion reaction may be impaired.

2) Maleic anhydride - Graft - Of a polyolefin elastomer  Manufacturing method

The maleic anhydride-graft-polyolefin elastomer included in the present invention can be produced through grafting by introducing a reactive monomer having a reactive group to the polyolefin side chain.

Usually, the grafting reaction is usually performed by a solution grafting method using a solvent or a melt grafting method without using a solvent. However, in the present invention, separation of a product without using an organic solvent It is preferable to select a graft process by reactive extrusion which is easy and can significantly reduce the reaction time and which is advantageous for the continuous process and requires relatively low equipment cost.

The reactive monomer is not particularly limited, but maleic anhydride, (meth) acrylate ester, (meth) acrylic acid and the like can be used, and maleic anhydride can be preferably used.

[Reaction Scheme 1]

Referring to Scheme 1, maleic anhydride is introduced into the polyolefin side chain by adding radicals to side chains of the polyolefin through the initiator and then adding maleic anhydride. At the same time as maleic anhydride is introduced, a new radical is formed in the maleic anhydride molecule, which takes away the proton of the nearest polyolefin chain and creates a new radical. The new radical reacts again with another maleic anhydride.

Through the above process, a continuous maleic anhydride graft reaction takes place. Such a graft polymerization method has a disadvantage in that a large amount of a polar monomer can not be introduced into a polyolefin main chain and thus there is a limitation in an amount of a graft. However, the graft polymerization method has an advantage that its characteristics can be well preserved without substantially changing the main chain of the polyolefin main chain. The reaction may require cooling below the Tm or Tg of the polymer used to provide dimensional stability of the product.

The maleic anhydride graft rate of the maleic anhydride-graft-polyolefin elastomer may be affected by the kind and molecular weight of the polyolefin elastomer to be added.

Preferably, the polyolefin elastomer may be a low molecular weight polyethylene wax (PEW), a low-density polyethylene (LDPE), or a linear low-density polyethylene (LLDPE) More preferably, linear low-density polyethylene (LLDPE) in which ethylene is copolymerized with butene, hexene or octene can be used, and still more preferably, Metallocene linear low density polyethylene, which is a linear low density polyethylene produced under a metallocene catalyst, can be used.

Since the metallocene linear low density polyethylene has a MWD of about 2 and the comonomer is homogeneous and close to amorphous, the metallocene linear low density polyethylene has a high tensile strength and can be easily extruded to increase process efficiency.

In addition, the maleic anhydride graft rate of the maleic anhydride-graft-polyolefin elastomer may be affected by the content ratio of maleic anhydride added to the reaction. The content of maleic anhydride may be 1 to 10 parts by weight based on 100 parts by weight of the polyolefin elastomer.

When the addition range is lower than the above range, the maleic anhydride graft rate is too low. On the contrary, when the addition range is higher than the above range, since the graft ratio has already reached the steady state, It may be ineffective in terms of.

In addition, the maleic anhydride graft ratio of the maleic anhydride-graft-polyolefin elastomer may be influenced by the content ratio of the initiator added to the reaction. The content ratio of the initiator may be 0.1 to 3 parts by weight based on 100 parts by weight of the polyolefin elastomer.

When the addition range is lower than the above range, the maleic anhydride graft rate is too low. On the contrary, when the addition range is higher than the above range, since the graft ratio has already reached the steady state, Can be inefficient, and can induce homogeneous bonding with the cross-linking reaction of the polymer to produce side products. The initiator is not particularly limited, but preferably dicumyl peroxide can be used.

3) Eco-friendly flexible polyamide Compound  Manufacturing method

First, referring to FIG. 1, a polyamide resin is prepared by using caprolactam, and a monomer extraction step for removing unreacted materials and by-products is performed to produce a polyamide resin. The resulting polyamide resin and maleic anhydride-graft-polyolefin elastomer are reacted and extruded to finally produce a flexible polyamide compound.

Hereinafter, a method for producing an environmentally friendly flexible polyamide compound will be described in detail.

The polyamide resin included in the present invention is prepared by adding water (H ₂ O) as a catalyst to caprolactam as a monomer and polymerizing (polymerization) under high pressure (240 to 280 ° C.) under pressure (15 to 18 kg / cm ² ) do.

[Reaction Scheme 2]

Referring to Reaction Scheme 2, the caprolactam monomer is ring-opened by water to initiate the reaction, and the molecule is grown by the reaction of the ring-opened monomer with the caprolactam of the adjacent caprolactam or the terminal of the polymer, After the polymerization reaction is terminated, unreacted caprolactam monomers are separated and dried to produce a polyamide resin.

The polyamide resin and the maleic anhydride-graft-polyolefin elastomeric nucleating agent, the release agent, the primary antioxidant and the secondary antioxidant prepared through the above-mentioned method are reactively extruded using a twin-screw extruder.

[Reaction Scheme 3]

Referring to Reaction Scheme 3, it can be seen that an imide bond is formed between the amino end group of the polyamide resin and the maleic anhydride-graft-polyolefin elastomer in the main chain amino group of the polyamide.

The extrusion reaction temperature is suitably 150 to 300 캜, preferably 200 to 270 캜, and the extrusion reaction pressure is suitably 100 to 1000 psig, preferably 400 to 800 psig. If the temperature is lower than the above range, the melt kneading can not be effectively performed in the extruder. On the contrary, when the temperature is higher than the above range, additives such as a nucleating agent, a releasing agent and an antioxidant are thermally decomposed, There is a possibility that the function may not be performed properly.

It is also important to effectively control the residence time of the extrudate in the extruder during extrusion. In the present invention, additives such as a nucleating agent, a releasing agent, and an antioxidant are used to control the residence time. However, additives such as a flame retardant, a lubricant, and a plasticizer may be added depending on the user's circumstances, .

2, there is shown an extruder device comprising a first extruding section 10, a second extruding section 20, a third extruding section 30, a discharge opening 40 and a pressurizing section 50. First, the first extruding section 10 includes a step of melting the polyamide resin, the nucleating agent, and the releasing agent injected through the supply port 11 through the melting section 12. The housing of the first extrusion section may be designed with a heating element (not shown). The molten polyamide resin is conveyed to the second extrusion section through a screw. The housing of the second extruding section 20 can be designed with a heating element (not shown) to suck and remove the volatile components generated from the polyamide resin decomposed in the first extruding section 10, The antioxidant is injected through the supply port 22 and the extrudate is mixed through the mixing section 23 and the mixture is injected through the screw of the mixing section 23 To the third extrusion section. The housing of the third extruding section 30 can be designed with a heating element (not shown), which removes the volatile components generated in the second extruding section 20 and provides a gas for applying the interior of the extruder in a vacuum atmosphere An additive such as a flame retardant and an endurance agent which can be used in the range not exceeding the object of the present invention can be additionally injected through the outlet 31 through the inlet 32. [

Subsequently, the extrudate is mixed through the mixing portion 33 and can be moved to the discharge section 40 through the screw of the mixing portion 33. The outlet section 40 includes a gas outlet 41 for sucking and removing the volatile components generated in the third extruding section 30 and applying the inside of the extruder in a vacuum atmosphere and the pressure section 50 ). ≪ / RTI > The pressurizing section 5 is a preparation step for finally discharging the flexible polyamide resin.

In producing the flexible polyamide through the above-described extrusion method, the shear rate, the action time, and the viscosity of the resin may be factors that influence the mixing.

Process variable effect Remarks Dispersive  mixing Distributive mixing Shear rate ○ ○ ○: Rising effect as variable increases
X: Decreases the effect as the variable increases Residence time △ ○ Viscosity of fluid △ X

Referring to Table 1, it is possible to increase the shear rate in the case of the shear rate of the extruder by increasing the rotation speed of the screw or by lowering the depth of the screw channel. However, if the depth of the screw channel is decreased, The free volume of the polyamide resin can be reduced and the discharge amount or production amount of the polyamide resin can be reduced. For this purpose, a mixing section with a narrow gap between the extruder sections can be installed or a kneading block can be installed. And may be 50 RPM to 300 RPM for the rotation speed.

In the case of the residence time of the extruder, if the amount of polyamide resin is increased, the average residence time may be reduced. However, if the screw rotation speed is increased, the filling rate is lowered due to the decrease of the discharge amount per unit of rotation, Shortening. For this purpose, the average residence time may be increased by installing a mixing part or a kneading block in the extruder.

Generally, the lower the temperature, the higher the viscosity of the resin. Conversely, the higher the temperature, the lower the viscosity of the resin. Since the resin temperature is increased by the shear force from the beginning of the screw to have the highest rising distribution at the end of the screw, the mixing part necessary for dispersive mixing is installed at the beginning of the screw so that the mixing action occurs at the high viscosity condition. The effect of lowering the viscosity can be seen.

Hereinafter, preferred embodiments and comparative examples are provided to facilitate understanding of the present invention. However, the following examples illustrate the present invention, but the scope of the present invention is not limited to the following examples.

<Examples>

Maleic anhydride - Graft - Polyolefin elastomer  Produce

The following materials are prepared for the examples.

Polyolefin: metallocene linear low density polyethylene having a molecular weight of 1000 to 2000.

Maleic anhydride: grade 1, 98% purity, manufactured by DAE JUNG CHEMICAL.

Initiator: Dicumyl Peroxide, manufactured by Sigma Aldrich

Washing solution: Acetone (grade 1, 99.5% purity), Daedong Chemical

A maleation reaction was carried out by introducing maleic anhydride into the side chain of the metallocene linear low density polyethylene through graft polymerization using an extruder. First, 10 weight% of metallocene linear low density polyethylene was added to the weight of the water solvent. At this time, the reaction temperature was set to the temperature within the vaporization point of the solvent, and the reaction was carried out until the internal temperature of the reactor reached the set temperature of 240 占 폚. When the reaction temperature was reached, a certain amount of maleic acid and an initiator were introduced into the reactor and the graft polymerization reaction proceeded for 3 hours. After completion of the reaction, acetone was added to remove unreacted residues and byproducts. The precipitate was washed twice, left at room temperature for one day, and dried in a vacuum drier at 80 ° C for 24 hours to prepare crystals.

Comparative Example  1 to 6

In Comparative Examples 1 to 6, maleic anhydride-graft-polyolefin elastomer was prepared by changing the content ratio of maleic anhydride in the course of the examples.

Comparative Example  7 to 12

In Comparative Examples 7 to 12, maleic anhydride-graft-polyolefin elastomer was prepared by changing the content ratio of the initiator in the course of the examples.

Linear low density polyethylene Maleic anhydride Initiator Example 100 5 0.2 Comparative Example 1 100 2 0.2 Comparative Example 2 100 7 0.2 Comparative Example 3 100 9 0.2 Comparative Example 4 100 14 0.2 Comparative Example 5 100 16 0.2 Comparative Example 6 100 18 0.2

Linear low density polyethylene Maleic anhydride Initiator Example 100 7 0.2 Comparative Example 7 100 7 0.4 Comparative Example 8 100 7 0.6 Comparative Example 9 100 7 0.8 Comparative Example 10 100 7 1.0 Comparative Example 11 100 7 1.2 Comparative Example 12 100 7 1.4

Eco-friendly flexible polyamide Compound  Produce

The following materials are prepared for the examples.

Polyamide resin: nylon 6 having caprolactam monomer content ratio within 0.5%

Maleic anhydride-graft-polyolefin elastomer

Nucleating agent: kaolin

Release agents: erucamide, pentaerythrityl tetrastearate

Primary antioxidant: 3,3'-Bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide

Secondary antioxidant: Tris (2,4-di- tert- butylphenyl) phosphite

Comparative Example  13

Comparative Example 13 was prepared by changing the content ratio of the maleic anhydride-graft-polyolefin elastomer in the process of the embodiment, thereby producing an environmentally flexible polyamide compound.

Comparative Example  14

Comparative Example 14 was prepared by changing the content ratio of maleic anhydride-graft-polyolefin elastomer in the process of the embodiment, thereby preparing an environmentally flexible polyamide compound.

Comparative Example  15

Comparative Example 15 was prepared by changing the content ratio of the nucleating agent in the course of the examples to prepare an environmentally friendly flexible polyamide compound.

Comparative Example  16

Comparative Example 16 is a preparation of an environmentally friendly flexible polyamide compound by varying the content ratio of the nucleating agent in the course of the examples.

Comparative Example  17

Comparative Example 17 was prepared by changing the content ratio of the release agent in the course of the examples to prepare an environmentally flexible polyamide compound.

Comparative Example  18

Comparative Example 18 was prepared by changing the content ratio of the release agent in the course of the examples to prepare an environmentally flexible polyamide compound.

Comparative Example  19

Comparative Example 19 was prepared by changing the content ratio of the first antioxidant in the course of the examples to prepare an environmentally flexible polyamide compound.

Comparative Example  20

In Comparative Example 20, the content of the first antioxidant was varied in the course of the examples to prepare an environmentally flexible polyamide compound.

Comparative Example  21

Comparative Example 21 was prepared by changing the content ratio of the second antioxidant in the course of the examples to prepare an environmentally flexible polyamide compound.

Comparative Example  22

Comparative Example 22 was prepared by changing the content ratio of the second antioxidant in the course of the examples to prepare an environmentally flexible polyamide compound.

Polyamide
MAH -g-POE
Nucleophilic agent
Release agent Primary
Antioxidant Secondary
Antioxidant Example 100 5 0.5 0.5 0.5 0.5 Comparative Example 13 100 One 0.5 0.5 0.5 0.5 Comparative Example 14 100 15 0.5 0.5 0.5 0.5 Comparative Example 15 100 5 0.1 0.5 0.5 0.5 Comparative Example 16 100 5 5 0.5 0.5 0.5 Comparative Example 17 100 5 0.5 0.1 0.5 0.5 Comparative Example 18 100 5 0.5 5 0.5 0.5 Comparative Example 19 100 5 0.5 0.5 0.1 0.5 Comparative Example 20 100 5 0.5 0.5 5 0.5 Comparative Example 21 100 5 0.5 0.5 0.5 0.1 Comparative Example 22 100 5 0.5 0.5 0.5 5

Referring to Table 4, the respective content ratios according to Examples and Comparative Examples are specified.

<Test Results>

Using FT-IR MAH -g-POE MAH Graft rate  Measure

 FT-IR analyzes of Examples and Comparative Examples 1 to 12 were conducted in order to confirm whether MAH functional groups were introduced into the metallocene linear low density polyethylene through the graft reaction.

A _λ is the area at _λ cm ^-1 of the FT-IR spectra.

The formula 1 is a formula for measuring the graft ratio of maleic anhydride by substituting the results obtained by FT-IR analysis of the maleic anhydride-graft-polyolefin elastomer.

Maleic anhydride-grafted-on the FT-IR results of a polyolefin elastomer, 1,784 ^cm-1 absorption band appears in is symmetrical or asymmetrical expansion of the spectrum peak due to the carbonyl group of the anhydride groups of maleic anhydride, shown in 1,710 cm ^-1 The strong absorption band is the spectral peak which is converted into the carboxyl group by the ring opening phenomenon of the anhydride group. As the grafting rate of maleic anhydride increased, the peak appeared stronger at 1,710 cm ^-1 , and the carbonyl group due to the anhydride group was more strongly observed at the grafting rate of from 5% to 1,784 cm ^-1 . When the maleic anhydride was grafted onto the linear low density polyethylene, the maleic anhydride group was present in the carboxyl group state to a considerable extent, and the maleic anhydride group coexisted with the anhydride group in the high graft efficiency region.

Referring to FIG. 3, it can be seen that as the maleic anhydride content added increases, the grafting rate also increases, because the maleic anhydride increases the probability of reacting with the reactive radical sites of the polymer. However, when the content of maleic anhydride is further increased, it shows a steady-state that converges to a grafting rate of about 3%, because maleic anhydride monomers not participating in the reaction cause homo-bonding By-product.

Referring to FIG. 4, it can be seen that as the content of added initiator increases, the grafting rate also tends to increase because the initiator increases the probability of forming a reactive radical site of the polymer and promotes the chain transfer reaction. However, when the content of the initiator is further increased, it shows a steady-state that converges to a graft rate of about 4% because initiators that do not participate in the reaction cause homogeneous bonding to form by-products.

The maleic anhydride graft rate of the maleic anhydride-graft-polyolefin elastomer is preferably in the range of 1 to 10% in terms of graft ratio in producing the environmentally flexible polyamide of the present invention, And a graft rate of 1 to 4% in order to lower the production cost.

If the maleic anhydride graft ratio of the maleic anhydride-graft-polyolefin elastomer is out of the range of 1 to 10%, flexibility of the produced flexible polyamide may be deteriorated.

Eco-friendly flexible polyamide Compound Morphology  And mechanical properties analysis

Examples and Comparative Examples 13 to 18 were subjected to a standard test method of the American Society for Testing and Materials (ASTM) to analyze the number of sheets, tensile strength, elongation and flexural strength.

Melt index: The melt index of the flexible polyamide compound was measured using a standard reference material (SRM) in accordance with the appropriate test procedure of the standard test method for melt flow rate of thermoplastics by extrusion plastometer.

Tensile Strength: The tensile strength of the flexible polyamide compound was measured by following the appropriate test procedure of Standard Test Method for Tensile Properties of Plastics, which is International Standard ASTM D638.

Elongation Ratio: The elongation percentage of the flexible polyamide compound was measured in accordance with the appropriate test procedure of the Standard Test Method for Tensile Properties of Plastics, which is an international standard ASTM D638.

Flexural Strength: The flexural strength of the flexible polyamide compound was measured by following the appropriate test procedure of International Standard ASTM D790 Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials.

Melt Index
(g / 10 min) Tensile strength (kg / cm ² ) Elongation rate (%) Flexural strength (kg / cm ² ) Example 5 347 445 2,478 Comparative Example 13 4.8 342 381 2,235 Comparative Example 14 4.7 300 387 2,458 Comparative Example 15 4.8 345 440 2,469 Comparative Example 16 4.8 343 439 2,462 Comparative Example 17 4.7 347 440 2,465 Comparative Example 18 4.6 330 427 2,423 Comparative Example 19 3.9 342 435 2,468 Comparative Example 20 4.5 338 436 2,465 Comparative Example 21 3.7 346 440 2,477 Comparative Example 22 4.3 341 435 2,471

Referring to Table 5, Comparative Examples 13 to 22 are examples of the case where the additive used in the present invention is out of the usable range, and when compared with the present invention, the property value is less than expected value.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. The present invention is not limited to the drawings.

10: first extrusion section 20: second extrusion section
30: Third extrusion section 40: Discharge opening
50: pressurizing portion 11:
12: melting portion 21: gas outlet
22: feed port 23: mixing section
31: gas outlet port 32:
33: mixing portion 41: gas outlet
51:

Claims (10)

With respect to 100 parts by weight of the polyamide resin,
1 to 10 parts by weight of a maleic anhydride-graft-polyolefin elastomer;
0.1 to 5 parts by weight of a nucleating agent;
0.1 to 5 parts by weight of a release agent;
0.1 to 5 parts by weight of the primary antioxidant and the secondary antioxidant, respectively,
The maleic anhydride-graft-polyolefin elastomer is produced through a graft reaction between metallocene linear low density polyethylene, maleic anhydride and peroxydicperum, an initiator, wherein the maleic anhydride has a graft ratio of 1 to 10% Features environment friendly flexible polyamide compound. delete The method according to claim 1,
Wherein the maleic anhydride is used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the metallocene linear low density polyethylene, and the peroxide diluent is 0.1 to 5 parts by weight. The method according to claim 1,
Wherein the weight-average molecular weight of the maleic anhydride-graft-polyolefin elastomer is 20,000 to 500,000.
The method according to claim 1,
The nucleating agent is selected from the group consisting of adipic acid, 1,2,3,4-dibenzylidene sorbitol, 1,2,3,4-bis (p-methylbenzylidene) sorbitol, 1,2,3,4-bis (Ethylene sorbitol), bis (4-t-butylphenyl) sodium phosphate, sodium phosphate (NaH ₂ PO ₄ ), phosphine lead phosphate (Ph ₃ Pb ₃ (PO ₄ ) ₂ ), talc and kaolin Wherein at least one of the polyamide compounds is used.
The method according to claim 1,
The release agent may be selected from the group consisting of paraffin wax, oxidized paraffin wax, low molecular weight ethyl vinyl acetate (EVA), stearic acid, cetyl alcohol, stearyl alcohol, butyl stearate, glycol monostearate, glycerin monooleate, stearyl stearate, calcium Wherein at least one selected from the group consisting of stearate, barium stearate, magnesium stearate, stearamide, oleamide, erucamide and pentaerythrityl tetrastearate is used. The method according to claim 1,
The primary antioxidant is 3,3'-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylene dipropionamide Butyl-4-hydroxyphenyl) - N, N'-hexamethylenedipropionamide) or tetrakis- [3- (3,5-di- tert- butyl-4-hydroxyphenyl)] propionate - [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate) is used singly or in combination.
The method according to claim 1,
Wherein the secondary antioxidant is tris (2,4-di-tert-butylphenyl) phosphite. 2. The eco-friendly flexible polyamide compound according to claim 1, wherein the secondary antioxidant is tris (2,4-di-tert-butylphenyl) phosphite.
Condensing the caprolactam monomer to prepare a polyamide resin;
A monomer extracting step of removing unreacted materials and byproducts; And
Adding a polyamide resin, a maleic anhydride-graft-polyolefin elastomer, a nucleating agent, a releasing agent, a primary antioxidant, and a secondary antioxidant to the polyamide resin,
The maleic anhydride-graft-polyolefin elastomer is produced through a graft reaction between metallocene linear low density polyethylene, maleic anhydride and peroxydicperum, an initiator, wherein the maleic anhydride has a graft ratio of 1 to 10% Wherein said polyamide compound is a polyamide compound.
10. The method of claim 9,
Wherein the extrusion pressure of the reaction extrusion step is 100 to 1000 psig, the screw rotation speed is 50 to 300 RPM, and the extrusion temperature is 150 to 300 ° C.

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