KR101593938B1 - Preparatiom method for nylon tpe possessing good mechanical, elastomeric properties and shape memory effect - Google Patents

Abstract

The nylon thermoplastic elastomer comprises 10 to 40% by weight of a nylon resin; And nylon resin obtained by polymerizing lactam having 4 to 12 carbon atoms or amino acid monomer having 4 to 12 carbon atoms or diamine having 4 to 12 carbon atoms and dicarboxylic acid And a nylon resin obtained by melt polymerization of an acid, wherein the ethylenic copolymer has a vinyl acetate content of 20 to 40 wt%.
(A) ring-opening polymerization of a lactam having 4 to 12 carbon atoms or condensation polymerization of an amino acid having 4 to 12 carbon atoms or a diamine having 4 to 12 carbon atoms with a dicarboxylic acid to obtain a nylon-based thermoplastic elastomer Obtaining a resin; (B) melt-blending 10 to 40% by weight of the nylon resin obtained in the step (A) and 60 to 90% by weight of an ethylene-vinyl acetate copolymer at 200 to 260 ° C using a twin-screw extruder And thermoplastic melt-blending to produce a nylon-based thermoplastic elastomer. According to the present invention, the nylon resin and the polyolefin elastomer are melt-blended, which facilitates the production. Further, a continuous processing step is possible, which is economical. Further, it has excellent rubber elasticity and mechanical properties, and at the same time exhibits shape memory characteristics.

Description

TECHNICAL FIELD [0001] The present invention relates to a nylon thermoplastic elastomer having excellent mechanical strength, rubber elasticity, and shape memory properties, and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel nylon thermoplastic elastomer which is transparent using a nylon / ethylene-vinyl acetate copolymer blend and has good rubber elasticity and mechanical strength and exhibits shape memory characteristics, and a method for producing the same.

Thermoplastic Elastomer (TPE) is a material that simultaneously exhibits excellent processability of thermoplastic resin and softness and elasticity of vulcanized rubber. It is excellent in processability, recyclability, rubber elasticity, bending fatigue resistance, chemical resistance and heat resistance. It is used in various fields such as automobile parts, sporting goods, medical supplies, leisure, toys and the like.

A thermoplastic elastomer is a block copolymer composed of a soft segment which is flexible with rubber and which exhibits entropy deformation against external stress and a hard segment which has a crystallinity such as a general hard plastic and performs a physical crosslinking point and is composed of a soft segment and a hard segment There are various kinds according to kinds. Three general purpose thermoplastic elastomers such as polyolefin, polystyrene, and PVC, and three engineering plastics based thermoplastic elastomers such as polyester, polyurethane, and polyamide, are also typical examples. They are also manufactured by chemical modification and polymer blend. The physical properties of the thermoplastic elastomer are greatly influenced by the melting point (T _m ) of the hard segment and the glass transition temperature (T _g ) of the soft segment, so that the rubber elasticity of the thermoplastic elastomer is exerted between T _m and T _g . At a temperature of T _m or higher, the thermoplastic elastomer is melted and flows, and therefore, the thermoplastic elastomer is in a formable state. When it is below T _g , it softens and loses rubber elasticity.

Of the representative engineering plastic thermoplastic elastomers, nylon thermoplastic elastomers are produced in the form of a polyether-amide multiblock copolymer in which a crystalline polyamide forms a hard segment and a rubber phase polyether having a low glass transition temperature forms a soft segment. These polyether-amides have a high temperature limit of use among thermoplastic elastomer materials due to the polyamide constituting the hard segment and have excellent flexural fatigue failure properties, abrasion resistance, and chemical resistance, and can be used as thermoplastic elastomers such as polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, Silicone rubber, etc., and is currently applied to sporting goods, fuel hoses for automobiles, hydraulic and pneumatic devices, medical tubes, and the like, and is a high value-added engineering elastic material that can be applied in various fields by giving various functions.

Such a nylon thermoplastic elastomer can be produced by blending rubber and nylon, and can be manufactured by appropriately combining rubber and nylon resin, which have already been commercialized, compared with a copolymerization system thermoplastic elastomer obtained by polymerization. Therefore, it is more economical, It is relatively easy to control the melt processing temperature to a desired level. However, in order for the nylon thermoplastic elastomer to exhibit rubber elasticity and melt processability, the rubber and the thermoplastic resin must have sufficient compatibility so that a sufficient amount of rubber can be finely dispersed in a relatively small amount of nylon resin.

Shape memory polymers are smart materials that can actively and actively respond to changes in external environmental conditions. Specifically, a shape memory polymer is a substance that is able to self-adjust and react to stimulation or environmental conditions by mechanical, thermal, chemical, electrical, magnetic, or other causes, and to respond to such changes in environmental conditions. Shape memory polymers are lighter than shape memory alloys, have higher shape recovery rates, are easier to process, can be dyed, and are more economical. Shape memory polymers generally consist of two phases, reversible phase and temperature sensitive shape memory resin, which can be deformed in shape, and reversible phase, which can deform most of the shape, and fixed phase, which memorizes the original shape. Crystal phase, glass phase, crosslinking point, or entanglement of physical chains are used as the stationary phase. The glass transition temperature or the melting point of the crystalline phase is used as the shape recovery temperature since the reversible phase should have a property of rapidly decreasing the modulus when heated above a certain temperature (shape recovery temperature). The shape memory polymer can be manufactured by blending resins having appropriate compatibility, and can regulate the shape recovery temperature and mechanical properties by controlling the composition ratio of the resins in the blend, and can be applied to various fields.

Disclosure of Invention Technical Problem [8] The present invention is directed to a thermoplastic elastomer for solving the problems of the prior art described above, and it is an object of the present invention to provide a thermoplastic elastomer using a nylon system.

The nylon-based thermoplastic elastomer for achieving the above-

10 to 40% by weight of a nylon resin; And nylon resin obtained by polymerizing lactam having 4 to 12 carbon atoms or amino acid monomer having 4 to 12 carbon atoms or diamine having 4 to 12 carbon atoms and dicarboxylic acid And a nylon resin obtained by melt polymerization of an acid, wherein the ethylenic copolymer has a vinyl acetate content of 20 to 40 wt%.

In another method for producing a nylon-based thermoplastic elastomer,

(A) ring-opening polymerization of a lactam having 4 to 12 carbon atoms or condensation polymerization of an amino acid having 4 to 12 carbon atoms or a diamine having 4 to 12 carbon atoms with a dicarboxylic acid to obtain a nylon resin; (B) melt-blending 10 to 40% by weight of the nylon resin obtained in the step (A) and 60 to 90% by weight of an ethylene-vinyl acetate copolymer at 200 to 260 ° C using a twin-screw extruder And thermoplastic melt-blending to produce a nylon-based thermoplastic elastomer.

In the present invention, the nylon resin is a nylon polymer obtained by polymerizing a lactam having 4 to 12 carbon atoms, an amino acid monomer having 4 to 12 carbon atoms or a diamine having 4 to 12 carbon atoms and a dicarboxylic acid having 4 to 12 carbon atoms, Nylon 6, nylon 9, nylon 10, nylon 11, nylon 12, nylon 46, nylon 49, nylon 410, nylon 411, nylon 412, and nylon 66 manufactured by using lactam or amino acid or diamine and dicarboxylic acid. , Nylon 610, nylon 612, nylon 1010, nylon 1012 and nylon 4-nylon 9, nylon 4-nylon 10, nylon 4-nylon 11, nylon 4-nylon 12 or the like, and has an intrinsic viscosity of 0.8 to 1.2 ml / g and a melting temperature of 170 to 240 ° C. .

For production of the nylon resin, a lactam or an amino acid having 4 to 12 carbon atoms may be used. The lactam may be 2-pyrrolidone (4 C atoms), 2-piperidone (5 C atoms) (C atoms 6), omega-oenan lactam (7 C atoms), 8-capryllactam (8 C atoms), 9-nonanlactam (9 C atoms), 10- Aminobutanoic acid (4 C atoms), 5-aminopentanoic acid (5 C atoms), 6-aminocaproic acid (5 C atoms) -Aminohexanoic acid (6 C atoms), 7-aminoheptanoic acid (7 C atoms), 8-aminooctanoic acid (8 C atoms), 9-aminonanoic acid, Undecanoic acid (11 C atoms), 12-aminododecanoic acid (12 C atoms), and the like.

For the production of the nylon resin, diamines and dicarboxylic acids having 4 to 12 carbon atoms can be used. The diamines include 1,4-diaminobutane (4 C atoms), 1,5-diaminopentane (C atoms Diaminohexane (6 C atoms), 1,7-diaminoheptane (7 C atoms), 1,8-diaminooctane (8 C atoms), 1,9- Diaminodecane (C atom 9), 1,10-diaminodecane (C atom 10), 1,11-diaminoundecane (C atom 11), 1,12-diaminododecane (C (12 atoms), and the dicarboxylic acid is 1,4-butanedioic acid (4 C atoms), 1,5-pentanedioic acid (5 C atoms), 1,6-hexanedioic acid Octane dioic acid (8 C atoms), 1,9-nonanedioic acid (9 C atoms), 1,10-hexanedioic acid (7 C atoms) Decanedioic acid (C atoms 10), 1,11-undecanedioic acid (C atoms 11), and 1,12-dodecanedioic acid (C atoms 12).

The properties of such physical properties are mainly due to the difference in the content of the resin composition in the blend, and in particular, the physical properties of the nylon thermoplastic elastomer produced by the manufacturing method exemplified in the following examples are excellent as described above I could confirm.

All or at least a part of the blending conditions and the content ratio of the resin composition in the blend proposed in the present invention plays a very important role in the production of the thermoplastic elastomer desired in the present invention.

INDUSTRIAL APPLICABILITY As described above, the present invention has an effect of facilitating the production by melt blending nylon resin and polyolefin elastomer.

Further, the present invention is economically effective because a continuous machining process is possible.

Further, the present invention is excellent in rubber elasticity and mechanical properties, and at the same time, exhibits shape memory characteristics.

1 is a stress-strain curve graph of a nylon-based polyamide thermoplastic elastomer.
2 is a graph showing changes in storage elastic modulus of a nylon-based polyamide thermoplastic elastomer with temperature.
3 is an image showing shape memory characteristics of a nylon thermoplastic elastomer.

Hereinafter, the present invention will be described in detail with reference to specific examples.

Manufacturing example

Production of nylon resin 1

50 g (0.232 mol) of 11-aminoundecanoic acid as a monomer was reacted in a 250 ml glass reactor under nitrogen atmosphere at 200 ° C for 1 hour, 220 ° C for 1 hour and 240 ° C for 2 hours And then dried in a vacuum oven at 60 DEG C for 24 hours to prepare a nylon resin. The nylon resin thus prepared was dried in a vacuum oven at 80 ° C for 4 hours and then dissolved in meta-gramolysol at 40 ° C to measure the intrinsic viscosity and the melting temperature was measured using a differential scanning calorimeter. Table 1].

Production of nylon resin 2

In a 250 ml glass reactor, 50 g (0.232 mol) of 12-aminorauric acid as a monomer was reacted at 200 ° C for 1 hour, 230 ° C for 1 hour and 260 ° C for 2 hours under a nitrogen atmosphere, And dried in a vacuum oven for 24 hours to prepare a nylon resin. The prepared nylon resin was dried in a vacuum oven at 80 ° C. for 4 hours and then dissolved in metacresol at 40 ° C. to measure its concentration and intrinsic viscosity and the melting temperature was measured using a differential scanning calorimeter. [Table 1].

Intrinsic viscosity (ml / g) Melting temperature (캜) Production of nylon resin 1 0.83 184 Production of nylon resin 2 0.92 180

Example 1

The nylon resin and ethylenic copolymer obtained in Preparation 1 of the nylon sapphire of the above Preparation Example were melted and mixed at 200 rpm and 60 rpm using an internal mixer so that the weight ratio of the nylon resin and the ethylenic copolymer was 70:30, To prepare a thermoplastic elastomer.

The mechanical properties, tensile strain, and shape memory characteristics of the film were measured using a hot press to a thickness of 1 cm. The results are shown in Table 2.

Example 2

Except that the nylon resin and the ethylenic copolymer obtained in Preparation 1 of the nylon resin of the above-mentioned Production Example were melted and mixed at a weight ratio of 20:80 as in the composition of the following [Table 2] And the results are shown in Table 2.

Example 3

Except that the nylon resin obtained in Production Example 1 of the nylon resin of the Production Example and the ethylenic copolymer were melted and mixed at a weight ratio of 10:90 as in the composition of the following [Table 2] And the results are shown in Table 2.

Example 4

Except that the nylon resin obtained in Production Example 2 of the nylon resin of the above Production Example and the ethylenic copolymer were melted and mixed at a weight ratio of 30:70 as in the composition of the following [Table 2] And the results are shown in Table 2.

Example 5

Except that the nylon resin and ethylenic copolymer obtained in Preparation 2 of the nylon resin of the preparation example of the preparation example were melt-mixed in a weight ratio of 20:80 as in the composition of the following [Table 2] And the results are shown in Table 2.

Example 6

Except that the nylon resin obtained in Production Example 2 of the nylon resin of the above Production Example and the ethylenic copolymer were melted and mixed at a weight ratio of 10:90 as in the composition of the following [Table 2] And the results are shown in Table 2.

division Composition (% by weight) Properties nylon
Suzy Ethylene-based
Copolymer The tensile strength
(Kg / cm2) Elongation at break
(%) Tensile strain
(%) Shape fixation rate
(%) Shape recovery rate
(%) Example 1 30 70 10.1 900 17 96 97 Example 2 20 80 11.5 920 12 97 97 Example 3 10 90 13.8 900 9 96 97 Example 4 30 70 9.6 910 15 94 96 Example 5 20 80 11.0 930 10 96 97 Example 6 10 90 13.4 910 8 97 97

In the present invention, the proper amount of the nylon resin used for producing the nylon thermoplastic elastomer is 10 to 50% by weight, preferably 10 to 40% by weight. When the content of the nylon thermoplastic elastomer is less than 10% by weight, it is difficult to exhibit excellent mechanical strength, processability and shape memory characteristics of the thermoplastic elastomer produced. When the content of the nylon thermoplastic elastomer is more than 50% by weight, excellent rubber elasticity it's difficult.

The ethylenic copolymer, which is a constituent component of the nylon thermoplastic elastomer, is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 20 to 40 wt% and a melting temperature of 45 to 90 ° C.

  The suitable content of vinyl acetate in the ethylenic copolymer is 10 to 40% by weight, preferably 20 to 40% by weight. When the content of the vinyl acetate is less than 10% by weight, the thermoplastic elastomer can not be produced because of insufficient compatibility with nylon. When the content of the vinyl acetate exceeds 40% by weight, the melting temperature of the ethylenic copolymer is too low. The shape memory characteristic of the memory cell is deteriorated.

  The suitable content of the ethylenic copolymer is 60 to 95% by weight, preferably 70 to 90% by weight. When the content of the polyolefin elastomer in the nylon thermoplastic elastomer produced by the present invention is 70 to 90% by weight, the nylon thermoplastic elastomer PEBAX 2533 (hard segment (nylon 12) / soft segment (Polytetramethylene glycol) = 23 mol% / 73 mol%), and has excellent mechanical properties and excellent dynamic characteristics.

  (A) a step of condensing a lactam having 4 to 12 carbon atoms or an amino acid having 4 to 12 carbon atoms or a diamine having 4 to 12 carbon atoms with a carboxylic acid to obtain a nylon resin, (B) 10 to 40% by weight of a nylon resin and 60 to 90% by weight of a polyethylene copolymer are melt-blended at 200 to 260 DEG C and 60 to 150 rpm using a twin-screw extruder, .

The nylon thermoplastic elastomer according to the present invention, in particular, the nylon thermoplastic elastomer produced according to the above production method, has a tensile strength of 9.6-13.8 MPa, a elongation at break of 900-930%, a permanent tensile strain of 8-17% -97%, a shape recovery capability of 95-97%, and a shape recovery temperature of 45-70 ° C.

Hereinafter, the evaluation according to the embodiment will be described.

Evaluation example 1

The stress-strain curves of the nylon thermoplastic elastomers produced by Examples 4 to 6 are shown in Fig. The stress-strain curves of the nylon thermoplastic elastomers produced by Examples 4 to 6 showed rubber-like behavior, and the content of nylon in the nylon-based polyamide thermoplastic elastomer produced by the blend increased 100% modulus increased and tensile strength decreased, but elongation at break was almost similar. In particular, the nylon thermoplastic elastomer produced in Example 6 had a tensile strength of 13.4 MPa, a tensile elongation of 910% and a tensile strain of 10%, PEBAX 2533 (tensile strength 17.5 MPa, tensile elongation 1000%, tensile strain 5% And the like.

Evaluation example 2

The change of the storage elastic modulus of the nylon thermoplastic elastomer produced by Examples 4 to 6 with the temperature was measured using a DMA (TA Instrument Co., DMA 2980) at a measurement temperature range of -100 ° C to 200 ° C, 2 [deg.] C / min, frequency 1 Hz, amplitude 10 [mu] m, and the results are shown in Fig.

The storage elastic modulus in the nylon thermoplastic elastomer prepared within the measurement temperature range increased with increasing nylon resin content. The nylon thermoplastic elastomers produced by Examples 4 to 6 exhibit a rapid storage modulus change in the vicinity of -40 ° C to 0 ° C due to the glass transition of the rubbery polyethylene copolymer, It shows a rapid decrease of the storage elastic modulus again near to the melting of the ethylenic copolymer of the rubber phase. Also, it was found that the storage elastic modulus of the nylon thermoplastic elastomers prepared within the measurement temperature range increased as the content of nylon increased.

Fig. 3 shows the shape memory characteristics of the nylon thermoplastic elastomer produced by Example 6 above. The nylon thermoplastic elastomer sample prepared in Example 6 was heated to 60 DEG C to be deformed and quenched at 0 DEG C to remove the external force to maintain the deformed state. When the sample is heated again to 70 ° C, it returns to the initial film form within 5 seconds. From this, it can be seen that a new nylon thermoplastic elastomer having excellent shape memory characteristics can be produced by blending nylon resin and rubber.

The mechanical properties, tensile strain, and shape memory characteristics of the nylon thermoplastic elastomers prepared according to the above examples were measured as follows. The conditions of each test property were as follows.

1. Mechanical properties

Mechanical properties were evaluated by measuring tensile strength and tensile elongation. The tensile strength and tensile elongation were measured at room temperature using a universal tester (UTM, United Co., Model STM-10E) at a rate of 10 mm / The average value was taken after the experiment.

2. Tensile strain

The tensile strain was measured by measuring the initial length (L0) of the sample and then changing the initial length to 100% of the initial length by applying an external force, fixing it for 10 minutes, measuring the changed length (Lt) L0) / L0 x 100).

3. Shape Memory Characteristics

In the case of the shape memory property, shape fixability and shape restoration ability were measured and evaluated. The shape fixability and shape restoration ability were calculated by [Equation 1] and [Equation 2] same.

[Equation 1]

Shape Fixation Ratio (%) = 竜 u / 竜 m x 100

&Quot; (2) "

Shape restoration ratio (%) = (? M-? P) /? M x 100

The specimen is subjected to 100% strain (εm) at a temperature not lower than the melting temperature (Tm) of the soft segment polyolefin elastomer. When the specimen is quenched below the melting temperature (Tm) of the polyolefin elastomer while maintaining this deformation, the deformed shape is maintained and the deformed shape (εu) is maintained. When the polyolefin elastomer is heated to a temperature above the melting temperature (Tm) of the polyolefin elastomer, it shrinks to? P. The shape fixation rate and the shape restoration rate were calculated by calculating the values obtained by the above-described method using equations (1) and (2).

The foregoing description is merely illustrative of the technical idea of the present invention and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (10)

A nylon thermoplastic elastomer which is controllable in a shape recovery temperature range of 45-70 占 폚,
10 to 40% by weight of a nylon resin; And
60 to 90% by weight of ethylene-vinyl acetate,
A nylon resin obtained by polymerizing a lactam having 4 to 12 carbon atoms or an amino acid monomer having 4 to 12 carbon atoms, or a nylon resin obtained by melt-polymerizing a diamine having 4 to 12 carbon atoms with a dicarboxylic acid,
Wherein the ethylene-vinyl acetate has a vinyl acetate content of 20 to 40% by weight. The method according to claim 1,
Wherein the nylon resin is a nylon polymer obtained by polymerizing a lactam selected from a lactam having 4 to 12 carbon atoms and a mixture thereof;
The nylon resin is a nylon polymer obtained by polymerizing an amino acid selected from an amino acid having 4 to 12 carbon atoms and a mixture thereof;
The nylon resin is a nylon polymer obtained by polymerizing a dicarboxylic acid with a diamine selected from a diamine having 4 to 12 carbon atoms and a dicarboxylic acid and a mixture thereof;
Said nylon resin being a copolymer of said nylon polymers; And
And mixtures of said nylon polymers. ≪ RTI ID = 0.0 > 21. < / RTI > The method according to claim 1,
Wherein the nylon resin has an intrinsic viscosity of 0.6 to 1.2 ml / g. The method according to claim 1,
Wherein the nylon resin has a melting temperature of 160 to 240 占 폚. delete The method according to claim 1,
Wherein the ethylene-vinyl acetate has a melting temperature of 45 to 90 占 폚. The method according to claim 1,
Wherein the thermoplastic elastomer has a tensile strength of 9.6-13.8 MPa, a tensile elongation of 900-930%, a permanent tensile strain of 8-17%, a shape fixation ratio of 94-97%, and a shape recovery ratio of 95-97%. delete A method for producing a new nylon thermoplastic elastomer which is controllable in a shape recovery temperature range of 45-70 DEG C,
(A) ring-opening polymerization of a lactam having 4 to 12 carbon atoms or condensation polymerization of an amino acid having 4 to 12 carbon atoms or a diamine having 4 to 12 carbon atoms with a dicarboxylic acid to obtain a nylon resin; And
(B) melt-blending 10 to 40% by weight of the nylon resin obtained in the step (A) and 60 to 90% by weight of an ethylene-vinyl acetate copolymer at 200 to 260 ° C using a twin-screw extruder And thermoplastic melt-blending to produce a nylon-based thermoplastic elastomer,
Wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 20 to 40% by weight. ≪ RTI ID = 0.0 > 21. < / RTI > The method of claim 9,
Wherein the nylon resin is a nylon polymer obtained by polymerizing a lactam selected from a lactam having 4 to 12 carbon atoms and a mixture thereof;
A nylon polymer obtained by polymerizing an amino acid selected from amino acids having 4 to 12 carbon atoms and a mixture thereof;
A nylon polymer obtained by polymerizing a dicarboxylic acid with a diamine selected from a diamine having 4 to 12 carbon atoms and a dicarboxylic acid and a mixture thereof;
Copolymers of said nylon polymers; And
And mixtures of the nylon polymers. ≪ RTI ID = 0.0 > 21. < / RTI >

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