阅读说明：本技术 低摩擦树脂复合体 (Low friction resin composite ) 是由 安起镐 朴钟星 金相佑 于 2019-08-14 设计创作，主要内容包括：本发明涉及低摩擦树脂复合体。所述低摩擦树脂复合体具有优异的耐热性和低摩擦系数,并因此,可以提供具有优异的耐久性和低摩擦特性的相对摩擦组件材料。(The present invention relates to a low-friction resin composite. The low-friction resin composite has excellent heat resistance and a low friction coefficient, and therefore, a relative friction member material having excellent durability and low friction characteristics can be provided.)

1. A low friction resin composite comprising:

a binder containing a phthalonitrile-based resin; and

three or more fillers dispersed in the binder.

2. The low friction resin composite of claim 1, wherein the filler is three or more additives selected from the group consisting of graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fiber.

3. The low friction resin composite of claim 2, wherein the filler comprises graphite, and

the filler further comprises two or more additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fibers.

4. The low friction resin composite of claim 1, wherein the filler is a powder additive having a longest diameter of 0.01 to 100 μ ι η.

5. The low friction resin composite of claim 1, comprising

100 parts by weight of the binder containing a phthalonitrile-based resin; and

1 to 100 parts by weight of the filler.

6. The low-friction resin composite according to claim 3, wherein the composite comprises, based on 100 parts by weight of the binder containing a phthalonitrile-based resin:

15 to 30 parts by weight of graphite;

10 to 40 parts by weight of two additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide and milled carbon fibers.

7. The low-friction resin composite according to claim 1, wherein the adhesive containing a phthalonitrile-based resin is obtained by curing a composition containing a phthalonitrile compound via one or more curing agents selected from the group consisting of an amine-based compound, a hydroxyl-based compound, and an imide-based compound.

8. The low-friction resin composite body according to claim 7, wherein the phthalonitrile compound is a compound represented by the following chemical formula P1:

[ chemical formula P1]

In the chemical formula P1, R^P11To R^P16Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, a group of the formula P2 below or a group of the formula P3 below, and R^P11To R^P16Are the group of the following formula P2 or the group of the following formula P3,

[ chemical formula P2]

In the chemical formula P2, the chemical formula P,

L^P2is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O) -, or-S (═ O)₂-，

R^P21To R^P25Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl or cyano, and R^P21To R^P25Two or more of which are cyano groups,

[ chemical formula P3]

In the chemical formula P3, the chemical formula P,

L^P3is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(CH₃)₂-、-C(CF₃)₂-or-C (═ O) NH-,

R^P31to R^P35Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl or a group of the formula P2, and R^P31To R^P35One or more of which are groups of the formula P2.

9. The low friction resin composite of claim 6, wherein the curing agent is an imide-based compound represented by the following chemical formula 9:

[ chemical formula 9]

In the chemical formula 9, the first and second organic solvents,

m is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound,

X¹and X²Each independently an alkylene group, an alkylidene group, or a divalent group derived from an aromatic compound, and

n is a number equal to or greater than 1.

10. The low-friction resin composite body according to claim 9, wherein M in chemical formula 9 is a tetravalent group derived from an alkane, alkene, or alkyne, or a tetravalent group derived from a compound represented by any one of the following chemical formulae 10 to 15:

[ chemical formula 10]

In the chemical formula 10, R¹⁰¹To R¹⁰⁶Each independently is hydrogen, alkyl, alkoxy or aryl;

[ chemical formula 11]

In the chemical formula 11, R¹¹¹To R¹¹⁸Each independently is hydrogen, alkyl, alkoxy or aryl;

[ chemical formula 12]

In the chemical formula 12, the chemical formula is shown,

R¹²⁰to R¹²⁹Each independently hydrogen, alkyl, alkoxy or aryl,

x is a single bond, alkylene, alkylidene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹-O-C(＝O)-、-L²-C(＝O)-O-L³-、-L⁴-O-C(＝O)-L⁵-or-L⁶-Ar¹-L⁷-Ar²-L⁸-，L¹To L⁸Each independently a single bond, -O-, alkylene or alkylidene, and Ar¹And Ar²Each independently is an arylene group;

[ chemical formula 13]

In the chemical formula 13, the first and second organic solvents,

R¹³¹to R¹³⁴Each independently is hydrogen, alkyl or alkoxy, and R¹³¹To R¹³⁴May be linked to each other to form an alkylene group,

a is alkylene or alkenylene, and the alkylene or alkenylene of a may contain one or more oxygen atoms as heteroatoms:

[ chemical formula 14]

In the chemical formula 14, the first and second organic solvents,

R¹⁴¹to R¹⁴⁴Each independently of the others is hydrogen, alkyl or alkoxy, and

a is an alkylene group;

[ chemical formula 15]

In the chemical formula 15, the first and second compounds,

R¹⁵⁰to R¹⁵⁹Each independently hydrogen, alkyl or alkoxy.

11. The low-friction resin composite according to claim 9, wherein n is a number in the range of 2 to 200 in chemical formula 9.

12. The low-friction resin composite body according to claim 1, wherein the low-friction resin composite body has a PV value of 2.3 MPa-m/sec of 1.3cm to a carbon steel friction object material according to ASTM D3702²The thrust washer test specimen of contact area measured a coefficient of friction of 0.175 or less under no lubrication (self-lubricating) conditions.

13. The low-friction resin composite body according to claim 1, wherein the low-friction resin composite body has a PV value of 4.6 MPa-m/sec of 1.3cm to a carbon steel friction object material according to ASTM D3702²The thrust washer test specimen of (1) has a coefficient of friction measured under a lubricated (lubricant: automotive lubricating oil) condition of 0.060 or less.

14. A relative friction member material prepared using the low friction resin composite of claim 1.

15. The relative friction assembly material of claim 14, wherein the relative friction assembly material is a bearing, bushing, thrust washer, oil seal, piston ring, sliding member, or roller.

Technical Field

Cross Reference to Related Applications

This application claims the benefits of korean patent application No. 10-2018-.

The present invention relates to a resin composite having not only low friction characteristics but also excellent heat resistance, and a relative friction member material using the same.

Background

In recent years, in the automotive industry, many efforts are being made to reduce friction at energy transmission components (e.g., a power train, a drive train, etc.) in order to improve energy efficiency along with light weight. This is because only 15% of the fuel used in the automobile is transferred to the wheels, and 10% of it is lost due to friction of the driving parts.

Therefore, in order to reduce friction of the driving part, a plastic material is used in addition to a metal product. Since the friction member made of plastic material has self-lubricating properties, it contributes significantly to reducing losses due to friction. However, in an environment where high rotation and pressure are generated, the friction member made of a plastic material may be deformed or melted due to frictional heat.

Therefore, high heat-resistant super engineering plastics (e.g., PEEK (polyether ether ketone), PAI (polyamide imide), PI (polyimide), etc.) having high heat resistance and exhibiting low friction characteristics are mainly used as the relative friction components (e.g., bearings, bushes, thrust washers (oil seals), etc.). However, PEEK is still not suitable as a component exposed to ultra-high pressure and ultra-high speed environments due to relatively low heat resistance, and PAI and PI are limited in application as a component due to low processability and productivity and high cost.

Disclosure of Invention

Technical problem

An object of the present invention is to provide a low-friction resin composite having not only high heat resistance and excellent workability but also exhibiting improved low-friction characteristics.

It is another object of the present invention to provide a relative friction pack material prepared using the low friction resin composite.

Technical scheme

According to the present invention, there is provided a low-friction resin composite comprising a binder containing a phthalonitrile-based resin and three or more fillers on the binder.

In accordance with the present invention, there is also provided a relative friction pack material prepared using the low friction resin composite.

Hereinafter, a low friction resin composite and a relative friction member material using the same according to an embodiment of the present invention will be described in detail.

First, the technical terms used herein are merely used to explain specific embodiments, and are not intended to limit the present invention.

The singular forms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise.

As used herein, the term "comprising" is intended to specify the presence of stated features, numbers, steps, constituents, or combinations thereof, and it is not intended to preclude the possibility of one or more other features, numbers, steps, constituents, or combinations thereof, being present or added.

I. Low friction resin composite

In accordance with one embodiment of the present invention,

provided is a low-friction resin composite comprising: a binder containing a phthalonitrile-based resin; and three or more fillers dispersed in the binder.

As a result of the continuous research of the present inventors, it was confirmed that a resin composite comprising a binder containing a phthalonitrile-based resin and three or more fillers dispersed in the binder has not only excellent heat resistance and workability, but also exhibits improved low-friction characteristics.

The low friction resin composite can provide a relative friction member material having excellent durability and low friction characteristics even under a very high pressure and a very high speed environment.

(1) Adhesive agent

In the low-friction resin composite, a phthalonitrile-based resin is contained as a binder.

Specifically, the adhesive containing a phthalonitrile-based resin may be obtained by curing a composition containing a phthalonitrile-based compound via one or more curing agents selected from the group consisting of an amine-based compound, a hydroxyl-based compound, and an imide-based compound.

The phthalonitrile compound may be a compound containing 2 or more, or 2 to 20, or 2 to 16, or 2 to 12, or 2 to 8, or 2 to 4 phthalonitrile structures capable of forming a phthalonitrile resin by reaction with a curing agent.

Preferably, the phthalonitrile compound may be one or more compounds selected from the group consisting of compounds represented by the average composition formula of the following chemical formula 1 or by the average composition formula of the following chemical formula 5:

[ chemical formula 1]

[R¹¹R¹² ₂SiO_1/2]_a[R¹¹R¹²SiO_2/2]_b[R¹² ₂SiO_2/2]_c[R¹¹SiO_3/2]_d[R¹²SiO_3/2]_e[SiO_4/2]_f

In the chemical formula 1, the first and second,

R¹¹each independently a substituent of the following chemical formula 2,

R¹²each independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl,

a. b and c are each a positive number,

d. e and f are each 0 or a positive number, and

a + b + c + d + e + f is 1;

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

x is a group bonded to the silicon atom of chemical formula 1, and is a single bond, an oxygen atom, a sulfur atom, -S (═ O)₂-, carbonyl, alkylene, alkenylene, alkynylene, -C (═ O) -X¹-or-X¹-C (═ O) -, and X¹Is an oxygen atom, a sulfur atom, -S (═ O)₂-, alkylene, alkenylene, or alkynylene,

R²¹to R²⁵Each independently hydrogen, alkyl, alkoxy, hydroxy, cyano or a substituent of the following chemical formula 3, and R²¹To R²⁵At least one of which is a substituent of the following chemical formula 3;

[ chemical formula 3]

In the chemical formula 3, the first and second,

y is a single bond, oxygen atom, sulfur atom, -S (═ O)₂-, carbonyl, alkylene, alkenylene, alkynylene, -C (═ O) -X¹-or-X¹-C (═ O) -, and X¹Is an oxygen atom, a sulfur atom, -S (═ O)₂-, alkylene, alkenylene or alkynylene,

R³¹to R³⁵Each independently is hydrogen, alkyl, alkoxy, hydroxy or cyano, and R³¹To R³⁵Two or more of which are cyano groups.

Throughout the specification, the description of the phthalonitrile compound represented by a specific average composition formula means that the phthalonitrile compound is a single compound represented by the composition formula.

Also, the description that the phthalonitrile compound is represented by a specific average composition formula means that the phthalonitrile compound is a mixture of two or more different compounds, and if the average composition of the mixture is taken, the compound is represented by the composition formula.

The compound represented by the average composition formula of chemical formula 1 may be a compound in the form of a polymer or oligomer, and for example, the weight average molecular weight (Mw) may be in the range of 1000g/mol to 50000g/mol, or 2500g/mol to 35000g/mol, or 4000g/mol to 20000g/mol, or 6000g/mol to 9000 g/mol.

The compound represented by the average composition formula of chemical formula 1 has a weight average molecular weight in the above range, and thus can prepare a polymerizable composition having a low processing temperature and/or a wide processing window.

Throughout the specification, the term "weight average molecular weight" is a numerical value in terms of standard polystyrene measured by GPC (gel permeation chromatography), and unless otherwise described, the term "molecular weight" means a weight average molecular weight,

for example, molecular weight was measured using Agilent PL-GPC220 equipped with a PLgel MIXED-B column (Polymer Laboratories) 300mm long. The measurement temperature was 160 ℃ and 1,2, 4-trichlorobenzene was used as a solvent at a flow rate of 1 mL/min. Samples were prepared at a concentration of 10mg/10mL and then injected in an amount of 200. mu.L. The Mw and Mn values were derived with reference to a calibration curve formed using polystyrene standards. As the molecular weight (g/mol) of the polystyrene standard, 2000/10000/30000/70000/200000/700000/2000000/4000000/10000000 kinds of 9 were used.

Preferably, the compound represented by the average composition formula of chemical formula 1 may be a compound represented by the average composition formula of chemical formula 4 below:

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R¹¹and R¹²As defined in chemical formula 1,

n and m are numbers selected from the range of 1 to 100, respectively, and satisfy 2. ltoreq. n + m. ltoreq.100.

Preferably, in chemical formula 4, n + m is 2 to 100, or 2 to 80, or 2 to 50. The compound satisfying the range of n + m enables to prepare a polymerizable composition having excellent processability.

[ chemical formula 5]

R⁵¹ _aR⁵² _bSiO_(4-a-b)/2

In the chemical formula 5, the first and second organic solvents,

R⁵¹is a substituent of the following chemical formula 6,

R⁵²each independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl,

a is a number in the range of 0.01 to 0.4,

b is a number in the range of 0.5 to 4;

[ chemical formula 6]

In the chemical formula 6, the first and second,

x' is a group bonded to the silicon atom of chemical formula 5, and is a single bond, an oxygen atom, a sulfur atom, -S (═ O)₂-, carbonyl, alkylene, alkenylene, alkynylene, -C (═ O) -X¹-or-X¹-C (═ O) -, and X¹Is an oxygen atom, a sulfur atom, -S (═ O)₂-, alkylene, alkenylene or alkynylene,

R⁶¹to R⁶⁵Each independently hydrogen, alkyl, alkoxy, hydroxy, cyano or a substituent of the following chemical formula 7, and R⁶¹To R⁶⁵At least one of which is a substituent of the following chemical formula 7;

[ chemical formula 7]

In the chemical formula 7, the first and second,

y' is a single bond, oxygen atom, sulfur atom, -S (═ O)₂-, carbonyl, alkylene, alkenylene, alkynylene, -C (═ O) -X¹-or-X¹-C (═ O) -, and X¹Is an oxygen atom, a sulfur atom, -S (═ O)₂-, alkylene, alkenylene or alkynylene,

R⁷¹to R⁷⁵Each independently is hydrogen, alkyl, alkoxy, hydroxy or cyano, and R⁷¹To R⁷⁵Two or more of which are cyano groups.

The compound represented by the average composition formula of chemical formula 7 may be a compound in the form of a polymer or oligomer, and for example, the weight average molecular weight (Mw) may be in the range of 700g/mol to 7000g/mol, or 700g/mol to 6500g/mol, or 700g/mol to 5800g/mol, or 700g/mol to 5000 g/mol.

The compound represented by the average composition formula of chemical formula 7 has a weight average molecular weight in the above range, and thus can prepare a polymerizable composition having a low processing temperature and/or a wide processing window.

Preferably, the compound represented by the average composition formula of chemical formula 7 may be a compound represented by the following chemical formula 8:

[ chemical formula 8]

In the chemical formula 8, the first and second,

R⁵¹and R⁵²As defined in chemical formula 5, and

n is a number in the range of 3 to 100.

In chemical formula 8, n may be 5 or more, or 7 or more; and 95 or less, or 90 or less, or 85 or less, or 80 or less, or 75 or less, or 70 or less, or 65 or less, or 60 or less.

Preferably, the phthalonitrile compound may be a compound represented by the following chemical formula P1:

[ chemical formula P1]

In the formula P1, R^P11To R^P16Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, a group of the formula P2 below or a group of the formula P3 below, and R^P11To R^P16Two or more of which are a group of the following formula P2 or a group of the following formula P3,

[ chemical formula P2]

In the chemical formula P2, the chemical formula P,

L^P2is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O) -, or-S (═ O)₂-，

R^P21To R^P25Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl or cyano, and R^P21To R^P25Two or more of which are cyano groups,

[ chemical formula P3]

In the chemical formula P3, the chemical formula P,

L^P3is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(CH₃)₂-、-C(CF₃)₂-or-C (═ O) NH-,

R^P31to R^P35Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl or a group of the formula P2, and R^P31To R^P35One or more of which are groups of formula P2.

Throughout the specification, "alkyl" may be a linear or branched chain. Preferably, the alkyl group has a carbon number of 1 to 5 or a carbon number of 1 to 3. Specifically, the alkyl group may be a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, or the like.

Throughout the specification, "aryl" may be monocyclic aryl or polycyclic aryl. Preferably, the aryl group has a carbon number of 6 to 30. Specifically, the aryl group may be phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, or the like,A base,

And fluorenyl and the like.

Throughout the specification, "direct bond" means that no atom is present in the corresponding group, and groups on both sides are directly connected to each other.

According to an embodiment of the present invention, the phthalonitrile compound may be a compound represented by the following chemical formula P1'.

[ chemical formula P1' ]

In the chemical formula P1', the chemical formula P,

L^P2and L^P3Each independently is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(CH₃)₂-、-C(CF₃)₂-or-C (═ O) NH-.

As a non-limiting example, where L is^P2Each independently is-O-and L^P3The compound of formula P1', which is a direct bond or methylene, is used as the phthalonitrile compound.

In addition to the above-mentioned phthalonitrile compounds, as examples of phthalonitrile compounds, compounds described in U.S. Pat. No. 4,408,035, U.S. Pat. No. 5,003,039, U.S. Pat. No. 5,003,078, U.S. Pat. No. 5,004,801, U.S. Pat. No. 5,132,396, U.S. Pat. No. 5,139,054, U.S. Pat. No. 5,208,318, U.S. Pat. No. 5,237,045, U.S. Pat. No. 5,292,854, or U.S. Pat. No. 5,350,828, and the like may be mentioned, and various compounds known in the art may be included in addition to those described in the literature.

Meanwhile, the curing agent for the phthalonitrile compound is not particularly limited as long as it can react with the phthalonitrile compound to form a phthalonitrile resin.

For example, as the curing agent, one or more selected from the group consisting of an amine-based compound, a hydroxyl-based compound, and an imide-based compound may be used. The amine-based compound, the hydroxyl-based compound, and the imide-based compound mean a compound containing at least one amino group, hydroxyl group, and imide group in a molecule, respectively.

Preferably, the curing agent may be an imide-based compound represented by the following chemical formula 9:

[ chemical formula 9]

In the chemical formula 9, the first and second,

m is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound,

X¹and X²Each independently an alkylene group, an alkylidene group, or a divalent group derived from an aromatic compound, and

n is a number equal to or greater than 1.

Such an imide-based compound represented by chemical formula 9 exhibits excellent heat resistance due to its inclusion of an imide structure in a molecule, and thus, even if it is included in an excessive amount in a polymerizable composition, or the polymerizable composition is processed or cured at high temperature, a polymerizable composition that does not generate defects such as voids that may have an adverse effect on characteristics can be prepared.

In chemical formula 9, M may be a tetravalent group derived from an aliphatic compound, an alicyclic compound, or an aromatic compound, and M may have such a structure: wherein groups formed by dehydrogenation of 4 hydrogen atoms in the molecule of the aliphatic compound, the alicyclic compound or the aromatic compound are respectively attached to carbon atoms of the carbonyl group of chemical formula 9.

In particular, as aliphatic compounds, mention may be made of linear or branched alkanes, alkenes or alkynes. As the aliphatic compound, C2-20, C2-16, C2-12, C2-8 or C2-4 alkane, alkene or alkyne can be used. An alkane, alkene, or alkyne can be optionally substituted with one or more substituents.

As the alicyclic compound, there may be mentioned a hydrocarbon compound containing a C3-20, C3-16, C3-12, C3-8 or C3-4 non-aromatic ring structure. Such alicyclic hydrocarbon compounds may contain at least one heteroatom such as oxygen or nitrogen as a ring member, and if necessary, may be optionally substituted with one or more substituents.

Also, as the aromatic compound, benzene, a benzene-containing compound, or a derivative thereof may be mentioned. By benzene-containing compound is meant a compound in which two or more benzene rings are fused, or directly connected, or connected through an appropriate connecting group while sharing one or two or more carbon atoms.

As the linking group for linking two benzene rings, there may be mentioned alkylene, alkylidene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹-O-C(＝O)-、-L²-C(＝O)-O-L³-、-L⁴-O-C(＝O)-L⁵-, or-L⁶-Ar¹-L⁷-Ar²-L⁸-and the like.

L¹To L⁸Each independently being a single bond, -O-, alkylene or alkylidene, and Ar¹And Ar²Each may independently be an arylene group.

The aromatic compound may contain, for example, 6 to 30, 6 to 28, 6 to 27, 6 to 25, 6 to 20, or 6 to 12 carbon atoms, and may be substituted with one or more substituents, if necessary. In the case where the aromatic compound contains the above-mentioned linking group, the number of carbon atoms of the aromatic compound is a number including the carbon atom present in the linking group.

Specifically, for example, in chemical formula 9, M may be a tetravalent group derived from an alkane, alkene, or alkyne; or a tetravalent group derived from a compound represented by any one of the following chemical formulas 10 to 15:

[ chemical formula 10]

In chemical formula 10, R¹⁰¹To R¹⁰⁶Each independently is hydrogen, alkyl, alkoxy or aryl;

[ chemical formula 11]

In chemical formula 11, R¹¹¹To R¹¹⁸Each independently is hydrogen, alkyl, alkoxy or aryl;

[ chemical formula 12]

In the chemical formula 12, the first and second,

R¹²⁰to R¹²⁹Each independently hydrogen, alkyl, alkoxy or aryl,

x is a single bond, alkylene, alkylidene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹-O-C(＝O)-、-L²-C(＝O)-O-L³-、-L⁴-O-C(＝O)-L⁵-or-L⁶-Ar¹-L⁷-Ar²-L⁸-，L¹To L⁸Each independently a single bond, -O-, alkylene or alkylidene, and Ar¹And Ar²Each independently is an arylene group.

Here, a single bond means that no atom is present at the moiety. Therefore, in chemical formula 12, if X is a single bond, it means that there is no atom at the portion represented by X, and in this case, benzene rings at both sides of X may be directly connected to form a biphenyl structure.

In X in chemical formula 12, at-C (═ O) -O-L¹-O-C(＝O)-、-L²-C(＝O)-O-L³-or-L⁴-O-C(＝O)-L⁵In (L)¹To L⁵Each may independently be a C1-12, C1-8, or C1-4 alkylene or alkylidene group, and the alkylene or alkylidene group may be substituted or unsubstituted.

And, in X in chemical formula 12, at-L⁶-Ar¹-L⁷-Ar²-L⁸Middle and L⁶And L⁸Can be-O-, L⁷May be a C1-12, C1-8 or C1-4 alkylene or alkylidene group, and the alkylene or alkylidene group may be substituted or unsubstituted. Ar (Ar)¹And Ar²May be phenylene and, in this case, is based on L⁷，L⁶And L⁸Each may be attached in ortho, meta or para positions relative to the phenylene group.

[ chemical formula 13]

In the chemical formula 13, the first and second carbon atoms are represented by,

R¹³¹to R¹³⁴Each independently is hydrogen, alkyl or alkoxy, and R¹³¹To R¹³⁴May be linked to each other to form an alkylene group,

a is alkylene or alkenylene, and the alkylene or alkenylene of a may contain one or more oxygen atoms as heteroatoms:

[ chemical formula 14]

In chemical formula 14, R¹⁴¹To R¹⁴⁴Each independently is hydrogen, alkyl or alkoxy, and A is alkylene;

[ chemical formula 15]

In chemical formula 15, R¹⁵⁰To R¹⁵⁹Each independently hydrogen, alkyl or alkoxy.

The tetravalent group derived from the compound represented by any one of chemical formulas 10 to 15 may be formed by directly removing the substituent of chemical formulas 10 to 15, or may be formed by dehydrogenation of a hydrogen atom of an alkyl group, an alkoxy group, an aryl group, an alkylene group, or an alkenylene group in the substituent.

For example, in the case where the tetravalent group is derived from the compound of chemical formula 10, R of chemical formula 10¹⁰¹To R¹⁰⁶One or more, two or more, three or more, or four of them may form a group, or R¹⁰¹To R¹⁰⁶The hydrogen atoms of the alkyl, alkoxy or aryl groups present in (a) may be removed to form a group. As described above, the formation of a group means that the moiety is attached to the carbon atom of the carbonyl group of chemical formula 9.

And, in case that the tetravalent group is derived from the compound of chemical formula 12, R of chemical formula 12¹²⁰To R¹²⁹Each independently is hydrogen, alkyl, alkoxy, or aryl, and one or more, two or more, three or more, or four of the foregoing may form a group attached to formula 9. Each of the above-mentioned unformed groups may be hydrogen, alkyl or alkoxy, or may be hydrogen or alkyl. For example, in chemical formula 12, R¹²⁷To R¹²⁹Two of (1) and R¹²²To R¹²⁴May form a group and the other substituents may independently be hydrogen, alkyl, alkoxy or aryl, or may be hydrogen, alkyl or alkoxy, or may be hydrogen or alkyl.

As a non-limiting example, the compound represented by chemical formula 10 may be benzene or 1,2,4, 5-tetraalkylbenzene.

As a non-limiting example, the compound represented by chemical formula 12 may be biphenyl, or a compound represented by any one of the following chemical formulae a to F:

[ chemical formula A ]

[ chemical formula B ]

[ chemical formula C ]

[ chemical formula D ]

[ chemical formula E ]

[ chemical formula F ]

Also, the compound represented by chemical formula 13 may be C4-8 cycloalkane such as cyclohexane and the like, C4-8 cycloalkene such as cyclohexene and the like which may be substituted with one or more alkyl groups, or a compound represented by any one of the following chemical formulae G to I:

[ chemical formula G ]

[ chemical formula H ]

[ chemical formula I ]

Also, the compound represented by chemical formula 14 may be a compound represented by chemical formula J below, or a compound represented by chemical formula J below in which at least one hydrogen is substituted with an alkyl group.

[ chemical formula J ]

In chemical formula 9, X¹And X²Each may independently be a divalent group derived from an aromatic compound. For example, X¹And X²Each may independently be a divalent radical derived from a C6-40 aromatic compound. The divalent group derived from an aromatic compound is as described above.

Specifically, in chemical formula 9, X¹And X²Each may independently be a divalent group derived from a compound represented by any one of the following chemical formulas 16 to 18:

[ chemical formula 16]

In chemical formula 16, R¹⁶¹To R¹⁶⁶Each independently is hydrogen, alkyl, alkoxy, aryl, hydroxy or carboxy;

[ chemical formula 17]

In the chemical formula 17, the reaction mixture is,

R¹⁷⁰to R¹⁷⁹Each independently hydrogen, alkyl, alkoxy, aryl, hydroxy or carboxy,

x' is a single bond, alkylene, alkylidene, -O-, -S-, -C (═ O) -, -NR^a-、-S(＝O)-、-S(＝O)₂-、-L⁹-Ar³-L¹⁰-or-L¹¹-Ar⁴-L¹²-Ar⁵-L¹³-，R^aIs hydrogen, alkyl, alkoxy or aryl, L⁹To L¹³Each independently a single bond, -O-, alkylene or alkylidene, and Ar³To Ar⁵Each independently is an arylene group;

[ chemical formula 18]

In chemical formula 18, R¹⁸⁰To R¹⁸⁹Each independently hydrogen, alkyl, alkoxy, aryl, hydroxy or carboxy.

The divalent group derived from the compound represented by any one of chemical formulas 16 to 18 may be formed by directly removing the substituent of chemical formulas 16 to 18, or may be formed by dehydrogenation of a hydrogen atom of an alkyl group, an alkoxy group, an aryl group, an alkylene group, or an alkenylene group among examples of the substituent.

For example, in the case where the divalent group is derived from the compound of chemical formula 16, e.g., phenylene, based on X of chemical formula 9¹The substituent position of the amine group may be ortho, meta, or para with respect to the moiety attached to N in (1), and X based on chemical formula 9²The substitution position of the amino group in the moiety attached to N may be ortho, meta or para.

And, in the case where the divalent group is derived from the compound of chemical formula 17, R of chemical formula 17¹⁷⁷To R¹⁷⁹And R of chemical formula 17¹⁷²To R¹⁷⁴May form a group connected to the nitrogen atom of chemical formula 9. Other substituents than those forming a group may independently be hydrogen, alkyl, alkoxy or aryl, or hydrogen, alkyl or alkoxy, or hydrogen or alkyl.

As a non-limiting example, the compound represented by chemical formula 16 may be benzene which may be substituted with at least one hydroxyl group or carboxyl group.

Also, the compound represented by chemical formula 17 may be biphenyl which may be substituted with at least one hydroxyl group or carboxyl group, a compound represented by any one of chemical formulae a to F which may be substituted with at least one hydroxyl group or carboxyl group, or a compound represented by the following chemical formula K or M which may be substituted with at least one hydroxyl group or carboxyl group.

[ chemical formula K ]

[ chemical formula L ]

[ chemical formula M ]

Also, the compound represented by chemical formula 18 may be a compound represented by the following chemical formula N, or a compound represented by the following chemical formula N in which at least one hydrogen is substituted with a hydroxyl group or a carboxyl group:

[ chemical formula N ]

Throughout the specification, unless otherwise described, an alkyl group may be a C1-20, C1-16, C1-12, C1-8 or C1-4 alkyl group. The alkyl group may be linear, branched or cyclic, and may be substituted with one or more substituents, if necessary.

Unless otherwise described, alkoxy groups may be C1-20, C1-16, C1-12, C1-8, or C1-4 alkoxy groups. The alkoxy group may be linear, branched or cyclic, and may be substituted with one or more substituents, if necessary.

Unless otherwise stated, aryl means a monovalent residue derived from the above aromatic compound.

Unless otherwise described, alkylene and alkylidene groups may be C1-20, C1-16, C1-12, C1-8, or C1-4 alkylene and alkylidene groups. The alkylene and alkylidene groups may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents, if necessary.

Throughout the specification, as a substituent which may optionally substitute an aliphatic compound, an alicyclic compound, an aromatic compound, an alkyl group, an alkoxy group, an aryl group, an alkylene group, an alkylidene group, or the like, there may be mentioned a halogen (e.g., chlorine or fluorine, etc.), an epoxy group (e.g., a glycidyl group, an epoxyalkyl group, a glycidoxyalkyl group, an alicyclic epoxy group, or the like), an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, an aryl group, or the like, but not limited thereto.

And, in chemical formula 9, n means the number of imide repeating units, and it may be a number ranging from 2 to 200, 2 to 150, 2 to 100, 2 to 90, 2 to 80, 2 to 70, 2 to 60, 2 to 50, 2 to 40, 2 to 30, to 20, or 2 to 10.

If n in chemical formula 9 is 2 or more, that is, if the compound of chemical formula 9 is a polyimide-based compound, it may be more advantageous in terms of heat resistance and strength. Therefore, the opposite friction member material including the phthalonitrile resin cured using the polyimide-based compound has higher heat resistance, thereby preventing the phthalonitrile resin from being deformed and melted under high-speed and high-pressure conditions, and can exhibit low wear and high durability due to higher strength.

As a non-limiting example, the curing agent may be a compound represented by the following chemical formula C1 or the following chemical formula C2.

[ chemical formula C1]

[ chemical formula C2]

In the chemical formulas C1 and C2,

x and X' are each independently a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹-O-C(＝O)-、-L²-C(＝O)-O-L³-、-L⁴-O-C(＝O)-L⁵-or-L⁶-Ar¹-L⁷-Ar²-L⁸-；L¹To L⁸Each independently is a direct bond, -O-or C_1-5An alkylene group; and Ar¹And Ar²Each independently is C_6-30An arylene group, a cyclic or cyclic alkylene group,

R⁹⁰to R⁹⁹Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, hydroxyl or carboxyl.

Meanwhile, the compound represented by chemical formula 9 may be synthesized by any known synthetic method of organic compounds, and the specific method is not particularly limited. For example, the compound represented by chemical formula 9 may be formed by dehydration condensation of a dianhydride compound and a diamine compound, or the like.

Also, the compound represented by chemical formula 9 is not volatilized or decomposed at high temperature due to a high boiling point, and thus curability of the polymerizable composition is stably maintained, and voids, which may have an adverse effect on characteristics, are not formed during high-temperature processing or a curing process. Thus, for example, the decomposition temperature of the compound can be 300 ℃ or greater, 350 ℃ or greater, 400 ℃ or greater, or 500 ℃ or greater. The decomposition temperature means a temperature at which the decomposition rate of the compound represented by chemical formula 9 is maintained in the range of 10% or less, 5% or less, or 1% or less. The upper limit of the decomposition temperature is not particularly limited, but it may be, for example, about 1000 ℃ or less.

And, the compound represented by chemical formula 9 may pass through the core M or the linking group X¹Or X²To easily control the reactivity or processing window of the polymerizable composition itself (i.e., to control the amount of the polymerizable compositionThe difference between the melting temperature and the curing temperature of the polymerizable composition or a prepolymer formed therefrom), and thus functions as a curing agent having various characteristics depending on the use.

(2) Filler material

In the low-friction resin composite, a filler dispersed in a binder is contained as an additive.

The filler is dispersed in the binder to reduce corrosion of the opposite sides and to exhibit wear resistance in ultra-high pressure and ultra-high speed environments.

Preferably, three or more fillers are used in the low friction resin composite, thereby ensuring appropriate wear resistance and a low friction coefficient.

In order to exhibit the above characteristics, it is preferable to use a material selected from graphite, Polytetrafluoroethylene (PTFE), and tungsten disulfide (WS)₂) Molybdenum disulfide (MoS)₂) And milled carbon fiber (mCF) as a filler.

More preferably, it is advantageous for the above-mentioned properties to comprise graphite; and further comprising two or more additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fibers as fillers.

Graphite may be preferably used because graphite has relatively low density and cost among the above fillers, and at the same time, excellent low friction characteristics and appropriate wear resistance may be achieved.

As non-limiting examples, in the low friction resin composite, the following may be included as fillers:

graphite, polytetrafluoroethylene, and tungsten disulfide; or

Graphite, polytetrafluoroethylene and molybdenum disulfide; or

Graphite, polytetrafluoroethylene, and milled carbon fiber; or

Graphite, tungsten disulfide and molybdenum disulfide; or

Graphite, tungsten disulfide and milled carbon fiber; or

Graphite, molybdenum disulfide and milled carbon fiber; or

Graphite, polytetrafluoroethylene, tungsten disulfide and molybdenum disulfide; or

Graphite, polytetrafluoroethylene, tungsten disulfide, and ground carbon fibers; or

Graphite, polytetrafluoroethylene, molybdenum disulfide, and ground carbon fibers; or

Graphite, tungsten disulfide, molybdenum disulfide, and ground carbon fibers; or

Graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and ground carbon fibers;

if necessary, the low-friction resin composite may contain, in addition to the above-described filler, one or more particles selected from the group consisting of: glass fibers, titanium oxides, antimony trisulfide, antimony trioxide, barium sulfate, calcium hydroxide, calcium carbonate, magnesium oxide, calcium fluoride, silica, alumina, iron oxides, chromium oxides, zirconium oxide, boron nitride, carbon nanotubes, carbon fibers, and graphene.

Preferably the filler is a powder additive consisting of the above materials and having a longest diameter of 0.01 μm to 100 μm. Wherein, in the case where the fine particles constituting the powder are spherical, the longest diameter means the diameter of the fine particles. In the case where the fine particles constituting the powder are not spherical, the longest diameter means the longest diameter at the center cutting plane of the fine particles.

The particle size of the fine particles can be measured using a particle size analyzer (representatively, available from HORIBA Company, etc.) according to ASTM E799-03 (standard for measurement data and standard practice for droplet size analysis processing).

If the size of the fine particles constituting the powder is too small, aggregation may be liable to occur when producing the low-friction resin composite, and therefore, it may be difficult to achieve uniform characteristics. Also, if the size of the fine particles is too small, the number of inner layers of particles capable of lubrication may decrease, and thus may not fully exert the function as a lubricant.

In the case where the size of the fine particles constituting the powder is too large, it may be difficult to uniformly disperse the filler in preparing the low-friction resin composite, and therefore, it may be difficult to achieve the target low-friction characteristics.

The filler may be included in a content of 1 to 100 parts by weight, based on 100 parts by weight of the adhesive containing the phthalonitrile-based resin.

Specifically, the filler may be included at the following contents based on 100 parts by weight of the adhesive: 1 part by weight or greater, or 5 parts by weight or greater, or 10 parts by weight or greater, or 20 parts by weight or greater, or 30 parts by weight or greater, or 40 parts by weight or greater; and 100 parts by weight or less, or 90 parts by weight or less, or 80 parts by weight or less, or 70 parts by weight or less, or 60 parts by weight or less, or 50 parts by weight or less.

Preferably, the filler may be included at the following contents based on 100 parts by weight of the adhesive: 1 to 100 parts by weight, or 5 to 90 parts by weight, or 10 to 80 parts by weight, or 15 to 80 parts by weight, or 20 to 70 parts by weight, or 30 to 60 parts by weight, or 40 to 60 parts by weight.

If the content of the filler is too low, the low-friction resin composite may not have a sufficiently low friction coefficient and appropriate wear resistance. Whereas if the content of the filler is too high, it may not provide sufficient strength to the low-friction resin composite, and thus, it may be damaged under high-speed and high-pressure conditions or due to impact.

For one example, the low friction resin composite may include, based on 100 parts by weight of the binder containing the phthalonitrile-based resin: 15 to 30 parts by weight of graphite; and 10 to 40 parts by weight of two additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fibers.

For another example, the low friction resin composite may include, based on 100 parts by weight of the binder containing the phthalonitrile-based resin: 20 to 25 parts by weight of graphite; and 15 to 35 parts by weight of two additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fibers.

(3) Characteristics of Low-Friction resin composite

To determine whether the above-described low friction resin composite exhibits low friction characteristics, the coefficient of friction may be measured according to ASTM D3702 (standard test method for wear rate and coefficient of friction of materials in self-lubricating frictional contacts using a thrust washer tester).

In particular, as determined in the following examples, the low-friction resin composite exhibits a low friction coefficient with respect to the friction object material even under high pressure and high rotation speed conditions, and thus can be used as a material for a counter friction member of an automobile.

Here, the ASTM D3702 standard measures the coefficient of friction and the wear rate of a thrust washer test sample to determine whether it is suitable for use as a self-lubricating material.

In the present invention, the friction coefficient and the wear rate according to ASTM D3702 are measured using a friction coefficient measuring device as shown in fig. 1.

Specifically, the method of calculating the friction coefficient and wear rate according to ASTM D3702 is as follows:

1) the low friction resin composite was prepared into test samples having the dimensions and thickness specified in ASTM D3702.

2) The prepared test sample was mounted in the upper rotary sample holder of the friction coefficient measuring device.

3) In the lower fixed sample holder of the friction coefficient measuring device, a friction object material was mounted (in fig. 1, a steel washer was mounted as the object material).

4) The specific pressure (P) and the rotation speed (V) are set in the friction coefficient measuring device, and the friction coefficient (f) at a desired PV value (product of pressure and speed) can be calculated according to the following equation 1.

[ equation 1]

f＝T/rW

In the case of the equation 1, the,

t is the torque applied to the test specimen (N m), r is the radius of the test specimen (mm), and W is the vertical force (kg).

Also, the wear rate can be calculated as follows: measuringWeight change before/after experiment and divided by density to obtain wear volume, the obtained volume change was divided by the area of the ring to obtain reduced thickness, and based on this, wear rate was calculated as thickness reduction per second (10)^-10m/sec).

Has a PV value of 1.3cm relative to a carbon steel target material measured at a PV value of 2.3 MPa-m/sec according to ASTM D3702²The friction coefficient of the sample was measured using the thrust washer having the contact area of (1), the low-friction resin composite was not thermally deformed. That is, the low friction resin composite according to one embodiment can withstand a speed and pressure in a non-lubricated environment with a PV value of 2.3MPa · m/sec.

Specifically, the low friction resin composite has a PV value of 1.3cm to a carbon steel target material at 2.3MPa · m/sec according to ASTM D3702²The contact area of the thrust washer test sample may have a coefficient of friction of 0.175 or less in a non-lubricated (self-lubricating) condition.

Specifically, the coefficient of friction under non-lubricated (self-lubricating) conditions may be 0.175 or less, or 0.170 or less, or 0.165 or less. Preferably, the coefficient of friction may be from 0.050 to 0.175, or 0.055 to 0.170, or 0.060 to 0.165, or 0.065 to 0.165, or 0.070 to 0.165, or 0.075 to 0.165, or 0.080 to 0.165, or 0.085 to 0.165.

The low-friction resin composite may have a lower friction coefficient under the lubrication conditions where a conventional lubricant is applied. Among them, the kind and application method of the lubricant are not particularly limited.

Specifically, the low friction resin composite has a PV value of 1.3cm at 4.6MPa · m/sec according to ASTM D3702 for a carbon steel target material²The coefficient of friction under lubricated (lubricant: automotive oil) conditions measured for the thrust washer test specimen of contact area of (c) may be 0.060 or less.

Specifically, the coefficient of friction under lubricating conditions may be 0.060 or less, or 0.057 or less, or 0.055 or less. Preferably, the coefficient of friction may be 0.035 to 0.060, or 0.040 to 0.057, or 0.045 to 0.055.

Here, a PV value of 2.3MPa · m/sec can be achieved by a pressure (P) of 1.63MPa and a rotational speed (V) of 1.41 m/sec, and a PV value of 4.6MPa · m/sec can be achieved by a pressure (P) of 1.63MPa and a rotational speed (V) of 2.82 m/sec.

Meanwhile, the processing temperature of the low friction resin composite may be in the range of 150 ℃ to 350 ℃.

The processing temperature means a temperature at which the low-friction resin composite exists in a processable state. Such processing temperatures may be, for example, the melting temperature (Tm) or the glass transition temperature (Tg).

In this case, the absolute value of the processing window of the low friction resin composite body, i.e., the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) of the phthalonitrile compound and the curing agent may be 30 ℃ or more, 50 ℃ or more, or 100 ℃ or more. For example, the curing temperature (Tc) may be higher than the processing temperature (Tp). Such a range may be advantageous to ensure proper workability during the process of preparing the relative friction member material described below. The upper limit of the processing window is not particularly limited, but for example, the absolute value of the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) may be 400 ℃ or less, or 300 ℃ or less.

Meanwhile, the low-friction resin composite may be provided in a prepolymer state.

The prepolymer state means a state in which: in which the reaction of the phthalonitrile compound constituting the binder with the curing agent has occurred to some extent (for example, a-stage or B-stage polymerization has occurred), but not in a completely polymerized state, and which exhibits appropriate fluidity and thus can be processed.

As a non-limiting example, the state of the prepolymer may mean a state in which the melt viscosity measured in the range of about 150 ℃ to 250 ℃ is 10Pa · s to 100000Pa · s, 10Pa · s to 10000Pa · s, or 10Pa · s to 5000Pa · s.

For example, the processing temperature of the prepolymer can be from 150 ℃ to 350 ℃. The processing temperature means the temperature at which the prepolymer is present in a processable state.

Relative friction component material

In accordance with another embodiment of the present invention, a relative friction component material is provided that is prepared using a low friction resin composite.

As described above, the low friction resin composite can provide a relative friction member material having durability and low friction characteristics even under a very high pressure and a very high speed environment.

As the relative friction member material, a bearing, a bush, a thrust washer, an oil seal, a piston ring, a sliding member, a roller, or the like can be mentioned. The relative friction component can be applied to automobiles, airplanes or other industrial materials and the like.

The relative friction member material may be prepared by molding a prepolymer of the low friction resin composite into a target shape by heating, and then curing. The processing and curing process for preparing the relative friction component may be carried out according to known methods.

Advantageous effects

The low friction resin composite according to the present invention has low friction characteristics and excellent heat resistance, and thus, a counter friction member material having excellent durability and low friction characteristics can be prepared.

Drawings

FIG. 1 is an exploded perspective view of a friction coefficient measuring device for measuring a friction coefficient according to ASTM D3702.

FIGS. 2 to 4 show 1H-NMR data of the compounds prepared in preparation examples 1 to 3, respectively.

Detailed Description

Hereinafter, preferred examples are provided for a better understanding of the present invention. However, these examples are provided only as illustrations of the present invention, and the scope of the present invention is not limited thereto.

¹H-NMR (nuclear magnetic resonance) analysis

NMR analysis of the compound prepared below was performed using a 500MHz NMR apparatus of Agilent inc. Samples for NMR measurement were prepared by dissolving the compounds in DMSO (dimethyl sulfoxide) -d 6.

Preparation example 1 Synthesis of phthalonitrile Compound (PN1)

A compound of the following chemical formula a1 (PN1) was synthesized as follows.

32.7g of the compound of the following chemical formula A2 and 120g of DMF (dimethylformamide) were introduced into 3RBF (3 packard bottom flash, three-necked round bottom flask) and stirred at room temperature to dissolve it. Subsequently, 51.9g of the compound of the following chemical formula a3 was added, and 50g of DMF was added, followed by stirring to dissolve it. Subsequently, 62.2g of potassium carbonate and 50g of DMF were introduced together, and the temperature was raised to 85 ℃ while stirring. After about 5 hours of reaction, the solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to be neutralized and precipitated, and after filtration, washed with water. Thereafter, the filtered reaction was dried in a vacuum oven at 100 ℃ for one day, water and the remaining solvent were removed, and then the compound of the following chemical formula a1 (PN1) was obtained in a yield of about 80 wt%. Of the obtained Compound of formula A1 (PN1)¹The results of H-NMR analysis are shown in FIG. 2.

[ chemical formula A1]

[ chemical formula A2]

[ chemical formula A3]

Preparation example 2 Synthesis of curative Compound (CA1)

A compound of the following chemical formula a14 (CA1) was synthesized by dehydration condensation of diamine and dianhydride. 24g of 4,4' -oxydianiline and 40g of NMP (N-methyl-pyrrolidone) were introduced into 3RBF (3 neutral round bottom flash, three-necked round bottom flask) and stirred at room temperature to dissolve it. Cooling the solution with water bath, and adding 8.7g or lessThe compound of formula a15 was gradually introduced in three portions together with 40g of NMP. When the introduced compound was completely dissolved, 16g of toluene was added to the reaction to form an azeotrope. A Dean-Stark apparatus and a reflux condenser were installed, and toluene was charged into the Dean-Stark apparatus. 4.2mL of pyridine was introduced as a dehydration condensation catalyst, the temperature was raised to 170 ℃ and the solution was stirred for 3 hours. While removing water generated with the formation of an imide ring with a Dean-Stark apparatus, the solution was stirred for an additional 2 hours, and the remaining toluene and pyridine were removed. The reaction product was cooled to room temperature and precipitated in methanol for recovery. The recovered precipitate was extracted with methanol to remove residual reactants, and dried in a vacuum oven to obtain the compound of formula a14 (CA1) in a yield of about 85 wt%. Of the Compound of formula A14 obtained (CA1)¹The results of H-NMR analysis are shown in FIG. 3.

[ chemical formula A14]

[ chemical formula A15]

Preparation example 3 Synthesis of curative Compound (CA2)

A compound of the following chemical formula a18 (CA2) was synthesized by dehydration condensation of diamine and dianhydride. 8.1g of the compound of the following chemical formula A16 (m-phenylenediamine) and 50g of NMP (N-methyl-pyrrolidone) were introduced into 3RBF (3 rock roundbottom flash, three-necked round-bottomed flask) and stirred at room temperature to dissolve it. The solution was cooled with a water bath, and 26g of the compound of the following formula A17 was gradually introduced in three portions together with 60g of NMP. When the introduced compound was completely dissolved, 23g of toluene was added to the reaction to form an azeotrope. A Dean-Stark apparatus and a reflux condenser were installed, and toluene was charged into the Dean-Stark apparatus. 5.2mL of pyridine was introduced as a dehydration condensation catalyst, the temperature was raised to 170 ℃ and the solution was stirred for 3 hours. Removal of acyl groups with formation in Dean-Stark apparatusWhile water was generated by imine ring formation, the solution was stirred for an additional 2 hours, and the remaining toluene and pyridine were removed. The reaction product was cooled to room temperature and precipitated in methanol for recovery. The recovered precipitate was subjected to Soxhlet (Soxhlet) extraction with methanol to remove residual reactants, and dried in a vacuum oven to obtain a compound of formula a18 (CA2) in a yield of about 93 wt%. Of the Compound of formula A18 obtained (CA2)¹The results of H-NMR analysis are shown in FIG. 4.

[ chemical formula A16]

[ chemical formula A17]

[ chemical formula A18]

In formula a18, n is about 3.