KR20220003689A - Thermoplastic resin with supramolecular structure and Carbon Fiber Reinforced Thermal Plastic comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin having a supramolecular structure, which includes a reactive group-bound thermoplastic resin containing a thermoplastic resin and a reactive group forming a dynamic bond at the end of the thermoplastic resin, wherein the reactive group-bound thermoplastic resin is present in plurality, a dynamic bond is formed between the reactive groups among the plural reactive group-bound thermoplastic resins, and the dynamic bond is a thermally cleavable bond and is any one selected from hydrogen bonding, host-guest interaction, ionic interaction and π-π interaction. The present invention also relates to a carbon fiber-reinforced plastic including the thermoplastic resin. The thermoplastic resin having a supramolecular structure according to the present invention shows excellent tensile properties, and the carbon fiber-reinforced plastic including the thermoplastic resin shows improved interfacial properties between the carbon fibers and the polymer, low porosity and improved tensile properties.

Description

Thermoplastic resin with supramolecular structure and Carbon Fiber Reinforced Thermal Plastic comprising the same

The present invention relates to a thermoplastic resin having a supramolecular structure and a carbon fiber-reinforced plastic comprising the same, and more particularly, to a supramolecular structure by introducing a reactive group that forms a dynamic bond such as hydrogen bonding at the end of the thermoplastic resin, It relates to carbon fiber-reinforced plastics having improved tensile properties by impregnating carbon fibers.

Carbon Fiber Reinforced Plastic (CFRP) has a higher specific gravity and higher rigidity than existing lightweight materials such as high-strength steel and aluminum alloy. Since then, it has been applied to sports materials such as fishing rods, tennis racquets, and golf shafts, and in the aviation field. In the automobile sector, there is the LTD sedan announced by Ford in 1979, which is the world's first car with a body that is 544 kg lighter than the previous model. After that, GM, BMW, Toyota Motors, and Nissan Motors applied it, but there was a limit to the full-scale application of CFRP due to the high cost of the manufacturing process of thermosetting composites and low recycling of thermosetting resins.

Therefore, CFRTP (Carbon Fiber Reinforced Thermoplastic), which uses a thermoplastic resin advantageous in terms of productivity, cost reduction, and recycling as a matrix resin to which carbon fiber is applied, has recently attracted attention. Key factors driving the growth of the CFRTP market are the growing demand for fuel-efficient vehicles, the use of CFRTP in aerospace applications, and the ease of application of complex designs.

However, for CFRTP research and development using thermoplastic resins, it is necessary to improve the physical properties of the resin, increase the interfacial adhesion with carbon fibers, and optimize the design. In particular, in order to apply the thermoplastic resin to structural CFRTP, it must have excellent rigidity and strength. Such a thermoplastic resin exhibits high viscosity characteristics due to its high molecular weight, and the high viscosity characteristics have a problem in that when CFRTP is manufactured, a low interaction force acts at the interface with carbon fibers, or the internal porosity increases due to carbon fiber impregnation, resulting in deterioration of physical properties. .

Korean Patent Publication No. 10-1470803

An object of the present invention is to solve the above problems, and various dynamic bonds, that is, hydrogen bonds, host-guest interactions, ionic interactions, and π-π interactions, etc. An object of the present invention is to provide a thermoplastic resin having a supramolecular structure with improved tensile properties by supramolecularization through it.

Another object of the present invention is to produce CFRTP (Carbon Fiber Reinforced Thermoplastic) by impregnating carbon fibers in a thermoplastic resin having a supramolecular structure, thereby improving the interfacial properties between the thermoplastic resin and carbon fibers, reducing the porosity significantly, and improving tensile properties. Our goal is to provide superior Carbon Fiber Reinforced Thermoplastic (CFRTP).

According to one aspect of the present invention,

A thermoplastic resin, and a reactive group comprising a reactive group that forms dynamic bonds at the ends of the thermoplastic resin;

A plurality of thermoplastic resins to which the reactive groups are bound exist, and a dynamic bond is formed between the reactive groups of the thermoplastic resins to which a plurality of the reactive groups are bound,

The dynamic bond is a bond broken by heat, and a thermoplastic resin having a supramolecular structure, which is any one selected from hydrogen bonds, host-guest interactions, ionic interactions, and π-π interactions provided

The thermoplastic resin may be any one selected from polyamide, polyethylene, polypropylene, and polystyrene.

The thermoplastic resin may be polyamide.

The polyamide may be any one selected from polyamide 6, polyamide 12, polyamide 66, polyamide 6/66, polyamide 6/12, polyamide 6/6T, polyamide 6/6I, and copolymers thereof have.

The dynamic bonding may be hydrogen bonding.

The hydrogen bonding may be multiple hydrogen bonding.

The reactive group for forming the dynamic bond is Upy-NCO (2 (6-isocyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-pyrimidinone), DAN (2,7-diamido-1,8-naphthyridine), UTr (ureidotriazine) , DDA-AAD (cytosine-guanine), 2-acrylamidopyridine (2-acrylamidopyridine), 3-N-methyl-6-tridecyluracil (3-N-methyl-6-tridecyluracil), having a cis-amide group Any one selected from bis(acyloamino)triazine with cis-amide groups, and bis(acylamino)pyridine with trans-amide groups It may be a reactor derived from

According to another aspect of the present invention,

Thermoplastic resin layer of supramolecular structure; and

Including; a carbon fiber layer comprising carbon fibers impregnated in the thermoplastic resin of the supramolecular structure;

The thermoplastic resin layer of the supramolecular structure,

A thermoplastic resin, and a reactive group comprising a reactive group that forms dynamic bonds at the ends of the thermoplastic resin;

A plurality of thermoplastic resins to which the reactive groups are bound exist, and a dynamic bond is formed between the reactive groups of the thermoplastic resins to which a plurality of the reactive groups are bound,

The dynamic bond is a bond broken by heat, and carbon fiber, characterized in that it is any one selected from hydrogen bonds, host-guest interactions, ionic interactions, and π-π interactions A reinforced plastic is provided.

The carbon fiber-reinforced plastic may have a structure in which a thermoplastic resin layer and a carbon fiber layer are alternately repeatedly laminated.

According to another aspect of the present invention,

(a) preparing a reactant to form a dynamic bond with the thermoplastic resin; and

(b) reacting a reactant that forms a dynamic bond with the thermoplastic resin to introduce a reactive group that forms a dynamic bond at the end of the thermoplastic resin, and forms a dynamic bond between the reactive groups to produce a thermoplastic resin having a supramolecular structure There is provided a method for producing a thermoplastic resin having a supramolecular structure comprising;

The thermoplastic resin may be any one selected from polyamide, polyethylene, polypropylene, and polystyrene.

Preferably, the thermoplastic resin may be polyamide.

The polyamide may be any one selected from polyamide 6, polyamide 12, polyamide 66, polyamide 6/66, polyamide 6/12, polyamide 6/6T, polyamide 6/6I, and copolymers thereof have.

The reactant forming the dynamic bond is Upy-NCO (2 (6-isocyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-pyrimidinone), DAN (2,7-diamido-1,8-naphthyridine), UTr (ureidotriazine) ), DDA-AAD (cytosine-guanine), 2-acrylamidopyridine, 3-N-methyl-6-tridecyluracil, cis-amide group Bis (acryloamino) triazine with bis (acyloamino) triazine with cis-amide groups, and bis (acryloamino) pyridine with trans-amide groups, any one selected from can be one

More preferably, the polyamide is polyamide 12, and the reactant is Upy-NCO,

Based on 100 parts by weight of polyamide 12, Upy-NCO 4 to 20 parts by weight may be reacted.

The thermoplastic resin may have a carboxyl group (-COOH) bonded to a terminal thereof.

According to another aspect of the present invention,

(1) forming a first mixed powder layer of a reactant that forms a dynamic bond with a thermoplastic resin;

(2) forming a carbon fiber layer by placing carbon fibers on the mixed powder layer;

(3) preparing a mixed powder/carbon fiber laminate by forming a second mixed powder layer of a reactant that forms a dynamic bond with a thermoplastic resin on the carbon fiber layer; and

(4) manufacturing a carbon fiber reinforced plastic (CFRTP) by applying heat to the mixed powder/carbon fiber laminate by pressing; a method for manufacturing carbon fiber reinforced plastic (CFRTP) comprising a is provided.

Steps (2) and (3) may be repeated 2 to 10 times to prepare a mixed powder/carbon fiber laminate.

The thermoplastic resin having a supramolecular structure of the present invention is a supramolecular resin through various dynamic bonds to the thermoplastic resin, that is, hydrogen bonding, host-guest interactions, ionic interactions, and π-π interactions. It is possible to improve the tensile properties by

In addition, the carbon fiber-reinforced plastic of the present invention improves the interfacial properties between the thermoplastic resin and the carbon fiber by impregnating carbon fibers in a thermoplastic resin having a supramolecular structure to produce CFRTP (Carbon Fiber Reinforced Thermoplastic), and the porosity is significantly low. , the tensile properties can be improved.

1 is a 1H-NMR analysis result of Upy-NCO.
2 is a synthesis schematic of the supramolecular polyamide 12 of Example 1.
3 is an ATR-IR analysis result of Experimental Example 1.
4 is a DSC thermal analysis result of Experimental Example 2.
5 is a TGA thermal analysis result of Experimental Example 2.
6 is a measurement result of tensile properties of a film according to Experimental Example 3.
7 is a measurement result of the tensile modulus of a film according to Experimental Example 3.
8 is a measurement result of tensile modulus of a film according to Experimental Example 3.
9 is a porosity measurement photograph of CFRTP according to Experimental Example 4.
10 is a measurement result of tensile strength of CFRTP according to Experimental Example 5.
11 is a measurement result of tensile modulus of CFRTP according to Experimental Example 5;
12 is a measurement result of tensile modulus of CFRTP according to Experimental Example 5;
13 is a side SEM image of CFRTP according to Experimental Example 6.
14 is an interlayer shear strength (ILSS) measurement result of CFRTP according to Experimental Example 6.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention. However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that detailed descriptions of related known technologies may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, and includes one or more other features or It should be understood that the possibility of the presence or addition of numbers, steps, acts, elements, or combinations thereof is not precluded in advance.

Hereinafter, the thermoplastic resin of the supramolecular structure of the present invention will be described.

The thermoplastic resin of the supramolecular structure of the present invention includes a thermoplastic resin and a reactive group that forms dynamic bonds at the ends of the thermoplastic resin, a reactive group comprising a thermoplastic resin, the reactive group is bound to the thermoplastic resin exists in plurality, and the thermoplastic resin to which the plurality of reactive groups are bonded forms a dynamic bond between the reactive groups with each other, and the dynamic bond is a bond that is broken by heat, hydrogen bonding, host-guest interaction (Host-guest interaction) interactions), ionic interactions, and π-π interactions may be selected.

The thermoplastic resin is preferably any one selected from polyamide, polyethylene, polypropylene, and polystyrene, and more preferably polyamide.

The polyamide may be any one selected from polyamide 6, polyamide 12, polyamide 66, polyamide 6/66, polyamide 6/12, polyamide 6/6T, polyamide 6/6I, and copolymers thereof and most preferably polyamide 12.

Among the thermoplastic resins, polyamide 12 is the most suitable for application to carbon fiber-reinforced plastics because of its low melting point, processing convenience, low water absorption, and high dimensional stability.

The dynamic bonding may be hydrogen bonding, preferably multiple hydrogen bonding between reactors. More preferably, it may be a triple or quadruple hydrogen bond, and even more preferably, it may be a quadruple hydrogen bond.

The reactant forming the dynamic bond is Upy-NCO (2 (6-isocyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-pyrimidinone), DAN (2,7-diamido-1,8-naphthyridine), UTr (ureidotriazine) ), DDA-AAD (cytosine-guanine), 2-acrylamidopyridine, 3-N-methyl-6-tridecyluracil, cis-amide group Bis (acryloamino) triazine with bis (acyloamino) triazine with cis-amide groups, and bis (acryloamino) pyridine with trans-amide groups, any one selected from One derived from one is preferable, and more preferably, it may be Upy-NCO that forms a quadruple hydrogen bond.

Next, the carbon-reinforced fiber plastic of the present invention will be described.

Carbon-reinforced fiber plastic of the present invention is a thermoplastic resin layer of a supramolecular structure; and a carbon fiber layer including carbon fibers impregnated in the thermoplastic resin of the supramolecular structure.

The thermoplastic resin layer of the supramolecular structure,

A thermoplastic resin, and a reactive group comprising a reactive group that forms dynamic bonds at the ends of the thermoplastic resin, the reactive group comprises a bound thermoplastic resin, the reactive group is bound to the thermoplastic resin exists in plural, a plurality of the In the thermoplastic resin to which the reactive groups are bonded, a dynamic bond is formed between the reactive groups, and the dynamic bond is a bond that is broken by heat, hydrogen bonding, host-guest interactions, ionic interactions ) and may be any one selected from π-π interactions.

Since the contents of the dynamic bonding with the thermoplastic resin are the same as those described in the above-described thermoplastic resin having a supramolecular structure, the details thereof will be referred to.

The carbon fiber may be used without limitation as long as it is applicable to carbon fiber-reinforced plastics.

In general, carbon fibers included in CFRP can be divided into rayon-based, PAN-based, pitch-based and the like depending on the precursor. Pitch-based carbon fibers can be divided into liquid crystal pitch-based carbon fibers and isotropic pitch-based carbon fibers according to the type of pitch that is a precursor. Isotropic pitch-based carbon fiber is called general-purpose carbon fiber because it has a low price compared to high-performance quality.

The carbon fiber-reinforced plastic may have a structure in which a thermoplastic resin layer and a carbon fiber layer are alternately repeatedly laminated, and preferably may be manufactured in a form in which the thermoplastic resin layer is exposed at upper and lower parts.

Hereinafter, a method for producing a thermoplastic resin having a supramolecular structure of the present invention will be described.

First, a reactant that forms a dynamic bond with a thermoplastic resin is prepared (step a).

The thermoplastic resin is preferably any one selected from polyamide, polyethylene, polypropylene, and polystyrene, and more preferably polyamide.

The polyamide may be any one selected from polyamide 6, polyamide 12, polyamide 66, polyamide 6/66, polyamide 6/12, polyamide 6/6T, polyamide 6/6I, and copolymers thereof and most preferably polyamide 12.

Among the thermoplastic resins, polyamide 12 is the most suitable for application to carbon fiber-reinforced plastics.

Based on 100 parts by weight of polyamide 12, Upy-NCO 4 to 20 parts by weight

The thermoplastic resin preferably has any one selected from a carboxyl group (-COOH), a hydroxyl group (-OH), and an amine group (-NH _{2 ) bonded to a terminal thereof.} If a carboxyl group is bonded to the terminal, it may be easy to introduce a reactive group that binds to the reactant to form a dynamic bond at the terminal.

The dynamic bonding may be hydrogen bonding, preferably multiple hydrogen bonding between reactors. More preferably, it may be a triple or quadruple hydrogen bond, and even more preferably, it may be a quadruple hydrogen bond.

The reactant forming the dynamic bond is Upy-NCO (2 (6-isocyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-pyrimidinone), DAN (2,7-diamido-1,8-naphthyridine), UTr (ureidotriazine) ), DDA-AAD (cytosine-guanine), 2-acrylamidopyridine, 3-N-methyl-6-tridecyluracil, cis-amide group Bis (acryloamino) triazine with bis (acyloamino) triazine with cis-amide groups, and bis (acryloamino) pyridine with trans-amide groups, any one selected from It is preferable that there is one, and more preferably, it may be Upy-NCO which forms a quadruple hydrogen bond.

Next, a reactive material that forms a dynamic bond with the thermoplastic resin is reacted to introduce a reactor that forms a dynamic bond at the end of the thermoplastic resin, and a dynamic bond is formed between the reactive groups to prepare a thermoplastic resin having a supramolecular structure (step b).

Most preferably, the polyamide is polyamide 12, and the reactant may be Upy-NCO. At this time, it is preferable to react 4 to 20 parts by weight of Upy-NCO based on 100 parts by weight of polyamide 12, more preferably 5 to 16 parts by weight, and still more preferably 6 to 12 parts by weight. When the content of Upy-NCO is out of the range of 4 to 20 parts by weight, tensile properties may be significantly reduced.

The reaction is preferably carried out at a temperature of 200 to 260 °C, more preferably 220 to 250 °C, even more preferably 225 to 245 °C. If it is less than 200 ℃, the introduction of the reactor at the end of the thermoplastic resin is not sufficiently made, and if it exceeds 260 ℃, the process cost may increase due to unnecessary heat supply.

When the thermoplastic resin of the supramolecular structure is prepared, the thermoplastic resin of the film-type supramolecular structure may be prepared by applying heat while simultaneously pressing.

In particular, although not explicitly described in the following examples, in the method for producing a thermoplastic resin having a supramolecular structure according to the present invention, the type of the thermoplastic resin, the type of reactant forming a dynamic bond, and the content of the thermoplastic resin and the reactant A thermoplastic resin with a supramolecular structure was prepared while varying the ratio and reaction temperature. As a result of confirming the tensile properties of the thus-prepared supramolecular thermoplastic resin, unlike other conditions, only when all of the following conditions were satisfied, the tensile properties were specified to be remarkably excellent.

The thermoplastic resin is polyamide 12, the reactant is Upy-NCO, Upy-NCO is 8 to 12 parts by weight based on 100 parts by weight of polyamide 12, and the reaction temperature is 225 to 245°C.

Next, a method for manufacturing carbon fiber reinforced plastic (CFRTP) will be described.

First, a first mixed powder layer of a reactant that forms a dynamic bond with a thermoplastic resin is formed (step 1).

Thereafter, a carbon fiber layer is formed by placing carbon fibers on the mixed powder layer (step 2).

Next, a second mixed powder layer of a reactant that forms a dynamic bond with a thermoplastic resin is formed on the carbon fiber layer to prepare a mixed powder/carbon fiber laminate (step 3).

The mixed powder/carbon fiber laminate is pressurized while applying heat to prepare carbon fiber reinforced plastic (CFRTP) (step 4).

Steps (2) and (3) may be repeated 2 to 10 times to prepare a mixed powder/carbon fiber laminate, and more preferably, repeated 3 to 4 times to obtain a mixed powder/carbon fiber laminate can be manufactured. If it is not repeated, it is difficult to sufficiently realize the strengthening effect of the thermoplastic resin by carbon fiber. difficult to do

In particular, although not explicitly described in the following examples, in the method for producing a thermoplastic resin having a supramolecular structure according to the present invention, the type of the thermoplastic resin, the type of reactant forming a dynamic bond, and the content of the thermoplastic resin and the reactant A thermoplastic resin having a supramolecular structure was prepared while varying the ratio, reaction temperature, carbon fiber type, number of repeated laminations, and pressurization pressure. As a result of confirming the tensile properties of the thus-prepared supramolecular thermoplastic resin, unlike other conditions, only when all of the following conditions were satisfied, the tensile properties were specified to be remarkably excellent.

The thermoplastic resin is polyamide 12, the reactant is Upy-NCO, Upy-NCO is 8 to 12 parts by weight based on 100 parts by weight of polyamide 12, the reaction temperature is 225 to 245° C., and the carbon fiber is T700 carbon A fiber fabric is used, the number of repetitions of lamination is set to 3, the carbon fiber layer is formed in 3 layers, and the thermoplastic resin layer is formed in 4 layers, and the pressurization pressure is 18 to 22 MPa.

Hereinafter, examples according to the present invention will be described in detail.

[Example]

Example 1: Supramolecular Polyamide 12

In order to implement polyamide 12 having a supramolecular structure, reactive groups are required at both ends of polyamide 12. Evonik's VESTOSINT 2159 product uses Evonik's VESTOSINT 2159 product, which is polyamide 12 containing carboxylic acid at both ends, and has the advantage of being able to provide various reactive groups to both ends. The molecular weight of VESTOSINT 2159 was analyzed through THF GPC analysis, and number average molecular weight (Mn) = 7,560, weight average molecular weight (Mw) = 149,00, PDI = 1.96.

Meanwhile, 2(6-isocyanatohexylaminocarbonylamino)-6-methyl-4[1H]-pyrimidinone (Upy-NCO), which is a reactant for quadruple hydrogen bonding, was synthesized according to the prior art. Specifically, 2-ureido-4-[1H]pyrimidinone (UPy, 1.0 equiv, 40 mmol, 5 g) and HDI (hexamethyleneiisocyanate) (7.0 equiv, 280 mmol, 47 g) were mixed at 100° C. for 16 hours in a nitrogen atmosphere. After the reaction, 100 ml of hexane was added, and the precipitate was obtained by filtration, purified three times with hexane (20 ml), and dried in a vacuum atmosphere at 50° C. (yield = 90%). ^{The results of 1} H-NMR analysis of Upy-NCO thus prepared are shown in FIG. 1 .

The ideal 1:1 reaction weight ratio of polyamide 12 and Upy-NCO predicted through calculation is 100:7.76. Accordingly, the weight ratio of polyamide 12 powder and Upy-NCO powder was set to 100:4, and A mixture of polyamide 12 and Upy-NCO was prepared by mixing for 10 minutes, and reacted in an oven at 240° C. for 1 hour. The synthesis overview of the thus prepared supramolecular polyamide 12 is shown in FIG. 2 .

Example 2: Supramolecular Polyamide 12

Supramolecular polyamide 12 was synthesized in the same manner as in Example 1, except that the weight ratio of polyamide 12 and Upy-NCO was 100:8 instead of 100:4.

Example 3: Supramolecular Polyamide 12

Supramolecular polyamide 12 was synthesized in the same manner as in Example 1, except that the weight ratio of polyamide 12 and Upy-NCO was 100:12 instead of 100:4.

Example 4: Supramolecular Polyamide 12 Film

5 g of polyamide 12 and Upy-NCO powder mixed with a Thinky mixer in a weight ratio of 100:4 for 10 minutes is placed in a 12 cm x 12 cm hot press mold covered with polyimide film, and 10 bar A film having a thickness of 100 μm was prepared by applying pressure.

Example 5: Supramolecular Polyamide 12 Film

A film was prepared under the same conditions as in Example 4, except that a mixed powder in which polyamide 12 and Upy-NCO powder were mixed in a weight ratio of 100:8 instead of 100:4 was used.

Example 6: Supramolecular Polyamide 12 Film

A film was prepared under the same conditions as in Example 4, except that a mixed powder in which polyamide 12 and Upy-NCO powder were mixed in a weight ratio of 100:12 instead of 100:4 was used.

Example 7: Supramolecular Polyamide 12 Film

A film was prepared under the same conditions as in Example 4, except that a mixed powder in which polyamide 12 and Upy-NCO powder were mixed in a weight ratio of 100:16 instead of 100:4 was used.

Example 8: Carbon Fiber Reinforced Plastic (CFRTP)

2.5 g of the mixed powder of Example 4 was evenly distributed in a 12 cm x 12 cm CFRTP manufacturing mold, and a T700 carbon fiber fabric having a size of 12 cm x 12 cm was placed on the mixed powder. By repeating evenly distributing 2.5 g of the mixed powder again on the carbon fiber fabric, a CFRTP laminated structure including five mixed powder layers and four T700 carbon fiber fabric layers formed therebetween was formed. Thereafter, CFRTP was prepared by pressing at 230° C. at 20 MPa pressure for 10 minutes, and after cooling, the mold was disassembled to obtain CFRTP.

Example 9: Carbon Fiber Reinforced Plastic (CFRTP)

A carbon fiber reinforced plastic was prepared under the same conditions as in Example 8, except that the mixed powder of Example 5 was used instead of the mixed powder of Example 4.

Example 10: Carbon Fiber Reinforced Plastic (CFRTP)

A carbon fiber reinforced plastic was prepared under the same conditions as in Example 8, except that the mixed powder of Example 6 was used instead of the mixed powder of Example 4.

Example 11: Carbon Fiber Reinforced Plastic (CFRTP)

A carbon fiber reinforced plastic was prepared under the same conditions as in Example 8, except that the mixed powder of Example 7 was used instead of the mixed powder of Example 4.

Comparative Example 1: Polyamide 12

Polyamide 12 of Example 1 was prepared.

Comparative Example 2: Polyamide 12 film

A film was prepared under the same conditions as in Example 4, except that polyamide 12 powder was used instead of polyamide 12 and Upy-NCO mixed powder.

Comparative Example 3: Carbon fiber reinforced plastic (CFRTP)

A carbon fiber reinforced plastic was prepared under the same conditions as in Example 8, except that polyamide 12 powder was used instead of polyamide 12 and Upy-NCO mixed powder.

[Test Example]

Experimental Example 1. ATR-IR analysis

Attenuated total reflection (ATR)-IR analysis of the supramolecular polyamide 12 of Example 2 is shown in FIG. 3 . Here, the red graph is the curve before the reaction of Upy-NCO, and the blue graph is the curve after the reaction of Upy-NCO.

According to this, the absorption peak at 2280 cm-1 means the presence of -NCO, and the characteristic peak of Upy-NCO completely disappeared after 1 hour of reaction. Thus, it was confirmed that supramolecular polyamide 12 was synthesized.

Experimental Example 2: DSC and TGA thermal analysis

For the samples of Examples 1 to 3 and Comparative Example 1, changes in crystallinity of the samples were observed through DSC analysis, and the results are shown in FIG. 4 . According to this, as the content of Upy-NCO increased, the crystallization temperature decreased and the temperature range increased. This means that Upy-NCO inhibits the degree of crystallinity inside polyamide 12, and the decrease in crystallinity may act as a factor inhibiting physical properties.

Meanwhile, the results of TGA thermal analysis of the samples of Examples 1 to 3 and Comparative Example 1 are shown in FIG. 5 . According to this, it was confirmed that the thermal decomposition temperature was lowered as the content of Upy-NCO increased, which means that the Upy-NCO group was decomposed by heat.

Experimental Example 3: Evaluation of tensile properties of the film

For the measurement of mechanical properties of the films prepared according to Comparative Example 2 and Examples 4 to 7, a dog-bone type specimen was prepared, and the tensile properties were measured using a universal material tester, and the results were obtained 6 to 8, the horizontal axis means parts by weight of Upy-NCO with respect to 100 parts by weight of polyamide.

6 is a result of measuring tensile strength. According to this, the film of Comparative Example 2 prepared only with polyamide 12 without Upy-NCO had a tensile strength of 48.9 MPa, whereas for the film of Example 5 containing 8 parts by weight of Upy-NCO, the tensile strength was 61.1 It was shown to improve up to MPa. However, the films of Example 6 in which the Upy-NCO content is 12 parts by weight and the films of Example 7 in an excess of 16 parts by weight show that the tensile strength of Upy-NCO decreases.

7 is a measurement result of a tensile modulus (Modulus). According to this, the film of Example 7 containing 16 parts by weight of Upy-NCO was found to be the highest at 1560 MPa.

8 is a tensile rate (Strain) measurement result. According to this, the film of Comparative Example 2 prepared only with polyamide 12 showed 159%, and Comparative Examples 4, 5 and 6 containing Upy-NCO in 4, 8, and 12 parts by weight were each 203%, It showed improved values of 201% and 182%. However, the film of Example 7 containing 16 parts by weight of Upy-NCO exhibited a sharp decrease to 12%. It is predicted that excessive Upy-NCO formed a cross-linked structure inside the resin through a side reaction with residual moisture. As a result of the experiment, the film of Example 5 showed the best tensile strength and tensile modulus, and it was confirmed that it was most suitable to mix polyamide 12 and Upy-NCO in a weight ratio of 100:8 in the supramolecular polyamide 12 film. .

Experimental Example 4: Measurement of porosity of CFRTP

Micro-CT analysis was performed to measure the porosity of CFRTP containing supramolecular polyamide 12 prepared according to Example 10, and the porosity was measured to be very low as 3.4%. A photograph of CFRTP containing supramolecular polyamide 12 prepared in this way is shown in FIG. 9 .

Experimental Example 5: Evaluation of tensile properties of CFRTP

Tensile properties were evaluated for the CFRTP specimens prepared according to Comparative Example 3 and Examples 8 to 11, respectively, the tensile strength measurement result is shown in Fig. 10, the tensile modulus measurement result is shown in Fig. 11, and the tensile modulus measurement result is shown in Fig. 12, respectively. indicated.

According to FIG. 10, the tensile strength of CFRTP was measured to increase from 594 to a maximum of 800 MPa as the content of Upy-NCO increased. Through this, it was confirmed that Upy-NCO significantly increased the tensile strength of CFRTP.

According to FIG. 11 , the tensile modulus of CFRTP increased to 63.9 GPa in Example 10 with 12 parts by weight of Upy-NCO, whereas CFRTP of Comparative Example 3 without Upy-NCO was 52.3 GPa. Example 11, in which Upy-NCO was 16 parts by weight, was 56.2 GPa, and it was measured that the tensile modulus was rather decreased. Through this, it was confirmed that Upy-NCO not only increased the tensile strength of CFRTP, but also had a significant effect on the increase of the tensile modulus.

According to FIG. 11, the tensile modulus of CFRTP exhibited a value between 1.9 and 2.3% regardless of the content of Upy-NCO in the supramolecular polyamide 12, and this tensile rate is greatly affected by the intrinsic tensile properties of CFRTP. Because.

Unlike the supramolecular polyamide 12 film through the evaluation of the tensile properties of CFRTP, Example 10 containing 12 parts by weight of Upy-NCO compared to 100 parts by weight of polyamide 12 showed the best physical properties in CFRTP.

Experimental Example 6: Interlaminar Shear Strength (ILSS) Measurement of CFRTP

For CFRTP prepared according to Comparative Example 3 and Examples 8 to 10, interlaminar shear strength was measured through a universal testing machine to confirm the interface characteristics between carbon fibers and supramolecular polyamide 12. The side SEM images of the CFRTP prepared according to Comparative Example 3 and Examples 8 to 10 are shown in FIG. 13 , and the measurement result of the interlayer shear strength is shown in FIG. 14 .

According to this, the interlayer shear strength of CFRTP of Comparative Example 3 without Upy-NCO was 165 MPa, whereas the CFRTP of Example 10 containing 12 parts by weight of Upy-NCO increased by about 85% to 306 MPa. It is understood that the isocyanate group of some Upy-NCO reacts with the hydroxyl group on the surface of the carbon fiber, and the quadruple hydrogen bonding group introduced on the surface of the carbon fiber bonds with the supramolecular polyamide 12, resulting in excellent interlayer shear strength. Through this, it was confirmed that supramolecular polyamide 12 is an excellent resin capable of not only improving the tensile properties of CFRTP, but also greatly improving the interlaminar shear strength.

In the above, although embodiments of the present invention have been described, those of ordinary skill in the art can add, change, delete or add components within the scope that does not depart from the spirit of the present invention described in the claims. The present invention may be variously modified and changed by, etc., and this will also be included within the scope of the present invention.

Claims (18)

A thermoplastic resin, and a reactive group comprising a reactive group that forms dynamic bonds at the ends of the thermoplastic resin;
A plurality of thermoplastic resins to which the reactive groups are bound exist, and a dynamic bond is formed between the reactive groups of the thermoplastic resins to which a plurality of the reactive groups are bound,
The dynamic bond is a bond that is broken by heat, and a thermoplastic resin having a supramolecular structure that is any one selected from hydrogen bonds, host-guest interactions, ionic interactions, and π-π interactions. According to claim 1,
The thermoplastic resin has a supramolecular structure, characterized in that any one selected from polyamide, polyethylene, polypropylene, and polystyrene. According to claim 1,
The thermoplastic resin is a thermoplastic resin with a supramolecular structure, characterized in that the polyamide. 4. The method of claim 3,
The polyamide is any one selected from polyamide 6, polyamide 12, polyamide 66, polyamide 6/66, polyamide 6/12, polyamide 6/6T, polyamide 6/6I, and copolymers thereof A thermoplastic resin with a supramolecular structure. According to claim 1,
The dynamic bonding is a thermoplastic resin with a supramolecular structure, characterized in that hydrogen bonding. According to claim 1,
The hydrogen bond is a thermoplastic resin of a supramolecular structure, characterized in that multiple hydrogen bonds. According to claim 1,
The reactive group for forming the dynamic bond is Upy-NCO (2 (6-isocyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-pyrimidinone), DAN (2,7-diamido-1,8-naphthyridine), UTr (ureidotriazine) , DDA-AAD (cytosine-guanine), 2-acrylamidopyridine (2-acrylamidopyridine), 3-N-methyl-6-tridecyluracil (3-N-methyl-6-tridecyluracil), having a cis-amide group Any one selected from bis(acyloamino)triazine with cis-amide groups, and bis(acylamino)pyridine with trans-amide groups A thermoplastic resin with a supramolecular structure, characterized in that it is a reactive group derived from Thermoplastic resin layer of supramolecular structure; and
Including; a carbon fiber layer comprising carbon fibers impregnated in the thermoplastic resin of the supramolecular structure;
The thermoplastic resin layer of the supramolecular structure,
A thermoplastic resin, and a reactive group comprising a reactive group that forms dynamic bonds at the ends of the thermoplastic resin;
A plurality of thermoplastic resins to which the reactive groups are bound exist, and a dynamic bond is formed between the reactive groups of the thermoplastic resins to which a plurality of the reactive groups are bound,
The dynamic bond is a bond that is broken by heat, and carbon fiber, characterized in that it is any one selected from hydrogen bonds, host-guest interactions, ionic interactions, and π-π interactions reinforced plastic. 9. The method of claim 8,
The carbon fiber-reinforced plastic is carbon fiber-reinforced plastic, characterized in that the structure in which a thermoplastic resin layer and a carbon fiber layer are alternately repeatedly laminated. (a) preparing a reactant to form a dynamic bond with the thermoplastic resin; and
(b) reacting the thermoplastic resin with a reactant forming a dynamic bond to introduce a reactive group that forms a dynamic bond at the end of the thermoplastic resin, and forming a dynamic bond between the reactive groups to produce a thermoplastic resin having a supramolecular structure A method for producing a thermoplastic resin having a supramolecular structure, comprising the steps of: 11. The method of claim 10,
The thermoplastic resin is a method for producing a thermoplastic resin with a supramolecular structure, characterized in that any one selected from polyamide, polyethylene, polypropylene, and polystyrene. 12. The method of claim 11,
The thermoplastic resin is a method for producing a thermoplastic resin with a supramolecular structure, characterized in that the polyamide. 13. The method of claim 12,
The polyamide is any one selected from polyamide 6, polyamide 12, polyamide 66, polyamide 6/66, polyamide 6/12, polyamide 6/6T, polyamide 6/6I, and copolymers thereof Method for producing a thermoplastic resin with a supramolecular structure, characterized in that. 12. The method of claim 11,
The reactant forming the dynamic bond is Upy-NCO (2 (6-isocyanatohexylaminocarbonylamino)-6-methyl-4 [1H]-pyrimidinone), DAN (2,7-diamido-1,8-naphthyridine), UTr (ureidotriazine) ), DDA-AAD (cytosine-guanine), 2-acrylamidopyridine, 3-N-methyl-6-tridecyluracil, cis-amide group Bis (acryloamino) triazine with bis (acyloamino) triazine with cis-amide groups, and bis (acryloamino) pyridine with trans-amide groups, any one selected from Method for producing a thermoplastic resin of a supramolecular structure, characterized in that one. 12. The method of claim 11,
The polyamide is polyamide 12, the reactant is Upy-NCO,
A method for producing a thermoplastic resin having a supramolecular structure, characterized in that 4 to 20 parts by weight of Upy-NCO are reacted based on 100 parts by weight of polyamide 12. 13. The method of claim 12,
The thermoplastic resin is a method for producing a thermoplastic resin, characterized in that any one selected from a carboxyl group (-COOH), a hydroxyl group (-OH), an amine group (-NH _{2 ) is bonded to the terminal.} (1) forming a first mixed powder layer of a reactant that forms a dynamic bond with a thermoplastic resin;
(2) forming a carbon fiber layer by placing carbon fibers on the mixed powder layer;
(3) preparing a mixed powder/carbon fiber laminate by forming a second mixed powder layer of a reactant that forms a dynamic bond with a thermoplastic resin on the carbon fiber layer; and
(4) manufacturing the carbon fiber reinforced plastic (CFRTP) by applying heat to the mixed powder/carbon fiber laminate by pressing; 18. The method of claim 17,
Steps (2) and (3) are repeated 2 to 10 times to prepare a mixed powder/carbon fiber laminate.

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