KR101557547B1 - Dianhydride monomer with side group, polyimide with side group and manufacturing method thereof - Google Patents

Abstract

상기 측쇄기 R은 적어도 하나의 제3급 탄소 원자를 갖는 α 치환 시클로알켄, 하나의 제3급 탄소 원자를 갖는 시클로알칸, 적어도 하나의 제3급 탄소 원자를 갖는 시클로알켄, 페닐, α 치환 페닐, 나프탈렌, α 치환 나프탈렌, 페난트렌, α 치환 페난트렌, 안트라센, α 치환 안트라센, α 치환 방향족 탄화수소 유도체, 방향족 탄화수소 유도체, 아다만탄, α 치환 아다만탄, 다이아만틴, α 치환 다이아만틴으로 구성된 군에서 선택된 기이다.In the present invention, dihydric monomers having a side chain are provided, because the dihydric monomer has a large side chain group R, thereby increasing the asymmetry and arrangement irregularity of the structure of the dianhydride monomer. The dianhydride monomer has the following structure,

The side chain group R may be an? -Substituted cycloalkene having at least one tertiary carbon atom, a cycloalkane having one tertiary carbon atom, a cycloalkene having at least one tertiary carbon atom, phenyl, , Naphthalene, alpha-substituted naphthalene, phenanthrene, alpha-substituted phenanthrene, anthracene, alpha-substituted anthracene, alpha-substituted aromatic hydrocarbon derivatives, aromatic hydrocarbon derivatives, adamantane, alpha-substituted adamantane, ≪ / RTI >

Description

TECHNICAL FIELD The present invention relates to a diimide monomer having a side chain group, a side chain group-containing diimide monomer, a polyimide having a side chain group, and a process for producing the diimide monomer, a diimide monomer group having a side chain group,

The present invention relates to a dianhydride monomer, a polyimide and a preparation method thereof, and more particularly to a dianhydride monomer having a side chain group, a polyimide and a process for producing the same.

Polyimide is the most common industrial plastic currently used, and is widely used in the semiconductor industry, the photoelectric industry and the mechanical industry because of its good mechanical properties, relatively high glass transition temperature and relatively high pyrolysis temperature. However, polyimides have low solubility in organic solvents and therefore affect the processability of polyimides. Therefore, many studies on the properties of polyimides at present are aimed at improving the solubility of polyimide as well as maintaining the constant mechanical properties thereof.

U.S. Patent Application Publication No. US 2011/0263791 A1 (Oct. 27, 2011) U.S. Pat. No. 3,956,320 B2 (May 11, 1976) Chinese Patent Application Publication CN 102504295 A (June 20, 2012)

The present invention provides dianhydride monomers, which have side chain groups.

The present invention provides a process for producing dianhydride monomers, which produces the dianhydride monomers.

In the present invention, a polyimide compound is provided, which has a side chain group.

The present invention provides a method for producing a polyimide compound, which produces the polyimide.

The present invention provides a dianhydride monomer having a side chain, and since it has a large side chain group, such a dianhydride monomer has relatively low structural symmetry and alignment regularity. The side chain group R may be an? -Substituted cycloalkene having at least one tertiary carbon atom, a cycloalkane having one tertiary carbon atom, a cycloalkene having at least one tertiary carbon atom , Phenyl, alpha-substituted phenyl, naphthalene, alpha-substituted naphthalene, phenanthrene, alpha-substituted phenanthrene, anthracene, alpha-substituted anthracene, alpha-substituted aromatic hydrocarbon derivatives, aromatic hydrocarbon derivatives, But is a group selected from the group consisting of adamantane, alpha-substituted adamantane, diamantine, and alpha-substituted diamantine.

The present invention provides a process for producing dianhydride monomers, which produces the dianhydride monomers. The method for producing the dianhydride monomer comprises the following steps. That is, (I) a bromo compound, a hydroquinone compound and benzene are heated and recirculated to precipitate a hydroquinone compound solid. (3,4-dicyano-phenoxy) compound (bis (3,4-dicyano-phenoxy)) compound was prepared by heating the compound (II) hydroquinone compound and 4-nitrophthalonitrile with a methanol aqueous solution as a precipitant. 3,4-dicyanophenoxy) compound. (3,4-dicarboxyphenoxy) compound (bis (3,4-dicyanophenoxy) compound, potassium hydroxide (KOH) and methanol was heated and refluxed to obtain bis , 4-dicarboxyphenoxy) compound. (IV) bis (3,4-dicarboxyphenoxy) compound, glacial acetic acid and acetic anhydride are subjected to a dehydrating cyclization reaction to form dianhydride monomers.

In the present invention, a polyimide compound having a side chain is provided, which is prepared by using the dianhydride monomer. Such a polyimide compound has a relatively low structural symmetry and regularity because it has a large side chain group. The side chain group R may be an? -Substituted cycloalkene having at least one tertiary carbon atom, a cycloalkane having one tertiary carbon atom, a cycloalkene having at least one tertiary carbon atom, phenyl, , Naphthalene, alpha-substituted naphthalene, phenanthrene, alpha-substituted phenanthrene, anthracene, alpha-substituted anthracene, alpha-substituted aromatic hydrocarbon derivatives, aromatic hydrocarbon derivatives, adamantane, alpha-substituted adamantane, ≪ / RTI >

The present invention provides a method for producing a polyimide compound, which produces the polyimide. The method for producing the polyimide compound comprises the following steps. (I) Under anhydrous conditions, dianhydride monomers and diamine monomers are dissolved in cresol and stirred to form polyamic acid compounds. (II) 5-10 drops of isoquinoline are added dropwise to the polyamic acid compound solution, followed by heating and reflux to form a polyimide compound solution. (III) The polyimide compound solution is cooled and put into ethanol to form a precipitate to precipitate a polyimide compound solid.

As described above, the present invention provides a dianhydride monomer having a side chain, a polyimide compound having a side chain, and a process for producing the same. Since the dianhydride monomer has a large side chain group, the structure symmetry and alignment regularity of the polyimide compound prepared using such a dianhydride monomer is relatively low, and the intermolecular force of the polyimide compound is relatively low. Therefore, such a polyimide compound has a relatively good solubility for various solvents.

BRIEF DESCRIPTION OF THE DRAWINGS For a more complete understanding of the features and technical features of the present invention, reference will now be made, by way of example only, to the detailed description and diagram of the invention, but are not intended to limit the scope of the invention.

In the present invention, a dianhydride monomer (e) having a side chain group is provided, and its structural formula is as follows.

The side chain group R may be an? -Substituted cycloalkene having at least one tertiary carbon atom, a cycloalkane having one tertiary carbon atom, a cycloalkene having at least one tertiary carbon atom, phenyl, alpha-substituted phenyl , Naphthalene, alpha-substituted naphthalene, phenanthrene, alpha-substituted phenanthrene, anthracene, alpha-substituted anthracene, alpha-substituted aromatic hydrocarbon derivatives, aromatic hydrocarbon derivatives, adamantane, alpha-substituted adamantane, ≪ / RTI >

Hereinafter, a method for producing the dianhydride monomer (e) will be described. Four major steps are involved in the preparation of the dianhydride monomer (e). (3,4-dicarboxyphenoxy) compound (d) is formed, and the hydroquinone compound (d) To form a water monomer (e). It should be noted that R, mentioned below, is one of the various types of large groups listed above, and redundant description thereof is omitted.

In the step of forming the hydroquinone compound (b), the bromine compound (a), the hydroquinone compound and benzene are put into a reactor such as a three-necked flask under aeration, and the mixture is heated and refluxed for 3-4 days. It should be noted that venting is to avoid unnecessary effects of air and water vapor on the reaction. The reaction temperature for heating and refluxing is about 80-85 DEG C, which is the boiling point of benzene. After the reaction is completed, the hydroquinone compound (b) is formed and precipitated, and a solid of the hydroquinone compound (b) can be obtained by a direct filtering method. The structural formula of the bromine compound (a) is as follows.

The structural formula of the hydroquinone compound (b) is as follows.

Continuing with the above, the hydroquinone compound (b) obtained by filtering is washed with hot water to wash excess hydroquinone and by-product hydrogen bromide. The temperature of the hot water is about 50-70 ° C. Subsequently, vacuum drying is performed to remove the solvent and moisture to obtain the hydroquinone compound (b). Finally, the hydroquinone compound (b) is recrystallized to increase the purity of the hydroquinone compound (b). The reaction formula for forming the hydroquinone compound (b) is as follows.

In the step of forming the bis (3,4-dicyano phenoxy) compound (c), the purified hydroquinone compound (b), anhydrous potassium carbonate (K ₂ CO ₃ ), methanol and dimethylformamide , DMF) are placed in the reactor and heated for 4 to 5 hours and refluxed. Then, the hydroquinone compound (b) is ionized into a negative ion by dehydration using an azeotropic method, and the azeotropic temperature at this time is 150-160 ° C. The structural formula of the ionized hydroquinone compound (b) is as follows.

Continuing with the above discussion, a heating reaction was carried out on the subsequently ionized hydroquinone compound (b) and 4-nitrophthalonitrile for 6-12 hours. The heating temperature was 70-85 ° C., and the bis (3, 4-dicyanophenoxy) compound (c). Subsequently, using ethanol as a precipitant, a bis (3,4-dicyano phenoxy) compound (c) is precipitated. Then, the bis (3,4-dicyanophenoxy) compound (c) solid is washed with distilled water to wash away excess solvent and unreacted material. Vacuum drying is then performed to obtain a bis (3,4-dicyano phenoxy) compound (c) powder. Finally, the bis (3,4-nitrophenoxy) compound (c) is recrystallized to increase the purity of the bis (3,4-nitrophenoxy) compound (c), and its structural formula is as follows.

The reaction formula of the bis (3,4-nitrophenoxy) compound (c) is as follows.

In the step of forming the bis (3,4-dicarboxyphenoxy) compound (d), bis (3,4-nitrophenoxy) compound (c), potassium hydroxide and methanol are placed in a reactor, And reflux. Methanol is a solvent of bis (3,4-nitrophenoxy) compound (c) and potassium hydroxide, and the reaction temperature for heating and refluxing is about 70-85 ° C., which is the boiling point of methanol.

After completion of the reaction, an aqueous solution of bis (3,4-dicarboxyphenoxy) compound (d) is filtered. The aqueous PH value of the bis (3,4-dicarboxyphenoxy) compound (d) is adjusted to 2-3 by using an aqueous solution of hydrogen chloride. As a result, the bis (3,4-dicarboxyphenoxy) compound (d) precipitates a solid. Then, the bis (3,4-dicarboxyphenoxy) compound (d) solid is washed with distilled water to remove the excess solution. The structural formula of the bis (3,4-dicarboxyphenoxy) compound (d) is as follows.

The reaction formula for forming the bis (3,4-dicarboxyphenoxy) compound (d) is as follows.

(D), glacial acetic acid and anhydrous acetic acid are placed in a reactor to carry out a dehydration cyclization reaction to obtain a dianhydride monomer (e). The dianhydride monomer (e) . The dehydration cyclization reaction is carried out by heating and refluxing for 1 to 6 hours, and the reaction temperature is 130 to 140 ° C. The structural formula of the dianhydride monomer (e) is as follows.

The reaction formula for forming the dianhydride monomer (e) is as follows.

Hereinafter, the adamantane is referred to as a large side chain group and the dihydroxyl monomer (e) of the present invention is described as an example, but the present invention is not limited thereto.

Example 1

The dianhydride monomer (e) of Example 1 of the present invention is 1,4-bis (3,4-dicyano phenoxy) -2-adamantylbenzene, and its structural formula is as follows.

The preparation of this dianhydride monomer involves four main steps: 2-adamantyl hydroquinone, 1,4-bis (3,4-dicyanophenoxy) -2-adamantane Bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene (1,4-bis (3,4-dicyanophenoxy) Bis (3,4-dicarboxyphenoxy) -2-adamantyl benzene) and 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride ) -2-adamantyl benzene dianhydride.

In the step of forming 2-adamantylhydroquinone, 15 grams (69.77 mmol) of 1-bromoadamantane, 15.35 grams (139.5 mmol) of hydroquinone and 75 milliliters of benzene are introduced into a 250 milliliter three- And the mixture is heated and refluxed for 72 hours. The reaction temperature includes about 80-85 deg. C which is the boiling point of benzene. It should be noted that a large amount of white smoke is produced in the course of the reaction and the color of the solution is relatively high.

After the reaction, a 2-adamantylhydroquinone solid precipitates. The precipitated 2-adamantylhydroquinone solid can be directly filtered. After filtering and separating, the obtained solid can be washed several times with hot water to remove excess hydroquinone. Thereafter, it is vacuum dried and recrystallized to increase the purity of the 2-adamantyl hydroquinone. The final product of 2-adamantyl hydroquinone is 12.21 grams of yellow transparent needle crystal, with a yield of 71.73% and mp 217-219 [deg.] C. Its properties are as follows.

In the step of forming 1,4-bis (3,4-dicyanophenoxy) -2-adamantylbenzene, 2 g (8.197 mmol) of 2-adamantylhydroquinone, 1.25 g ) And 40 milliliters of methanol into a 150 milliliter three-necked flask through which nitrogen is passed. Then, a reflux reaction is carried out at a temperature of 150-160 ° C. for 4-5 hours, and a dehydration reaction is carried out in a methanol-water azeotropic manner to ionize the 2-adamantylhydroquinone into a negatively charged anion.

Three grams (17.34 mmol) of 4-nitropthalonitrile are then added and the reaction is allowed to proceed at 75-80 占 폚 for 12 hours. Subsequently, a pale yellow solid initial product is obtained using an aqueous methanol solution as a precipitant. Washed several times with distilled water and vacuum dried, and then recrystallized to increase the purity of 1,4-bis (3,4-dicyanophenoxy) -2-adamantylbenzene. Finally 3.08 grams of a pale yellow crystalline product of the light brown 1,4-bis (3,4-dicyano phenoxy) -2-adamantylbenzene was formed, yield 75.8% and mp 260-261 ° C to be. Its properties are as follows.

In the step of forming 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene, in a 250 ml three-necked flask through which nitrogen is passed 1,4-bis Phenoxy) -2-adamantylbenzene, 5.0 grams (36.2 mmol) of potassium hydroxide, and 100 milliliters of methanol. Then, heating and refluxing reaction is carried out for 4-5 days. The heated and refluxed aqueous solution was directly filtered and the PH value was adjusted to 2-3 using a hydrogen chloride aqueous solution to obtain 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene solid To precipitate. (3,4-dicarboxyphenoxy) -2-adamantylbenzene solid was washed with distilled water and dried to obtain 1,4-bis (3,4-dicarboxyphenoxy) -2- Only tilobenzene is obtained.

In the step of forming 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) 2-adamantylbenzene, 30-40 milliliters of glacial acetic acid and anhydrous acetic acid are placed in a three-necked flask, and heated and refluxed at 130-140 DEG C to conduct a dehydration cyclization reaction. 1.81 grams of 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride was obtained after stoppage cooling, and the yield was 83.7% and mp270-271 ° C. Its properties are as follows.

The above description relates to the dianhydride monomer (e) provided in the present invention, followed by the polyimide compound (h) formed using the dianhydride monomer (e), and its structural formula is as follows .

R 'is selected from the group consisting of:

As can be seen from the structure of the polyimide compound (h), the polyimide compound (h) of the present invention has a large side chain group. The large side chain group R can lower the structural symmetry and the ordered regularity of the polyimide compound.

Hereinafter, a method for producing the polyimide compound (h) will be described. The polyimide compound (h) may be produced by a method using thermal cyclization or a method using chemical cyclization. It should be noted that R 'mentioned below is one of the eight groups I to VIII listed above, and redundant description thereof is omitted. First, a method of producing a polyimide (h) by a method using a thermal cyclization method will be introduced. The process for producing the polyimide (h) by a thermal cyclization method includes two main steps, that is, the formation of the polyimide compound (g) and the formation of the polyimide compound (h).

In the step of forming the polyimide (g), the diamine monomer (f) is dissolved in anhydrous N-methyl-2-pyrrolidone (NMP) and stirred in an ice bath, Lt; RTI ID = 0.0 > 0 C < / RTI > Then, dianhydride monomer (e) is added and stirred for 1-2 hours. The diamine monomer (f) and dianhydride monomer (e) have the same molar number. Then, the diamine monomer (f) and the dianhydride monomer (e) aqueous solution are stirred at room temperature for 4-5 hours to form a polyimide compound (g). The structural formula of the diamine monomer (f) is as follows.

The structural formula of the polyimide compound (g) is as follows.

The step of forming the polyimide compound (h) solid includes coating the polyimide compound (g) on a glass plate to form a film. The baking temperature is then 100-300 ° C. Finally, it is cyclized to a polyimide compound (h) solid at a high temperature, and the reaction temperature is about 300-350 ° C. The structural formula of the polyimide compound (h) solid is as follows.

The polyimide compound (h) is formed by reacting the dianhydride (e) prepared in Example 1 and one of the diamine monomers (f) of the above group to produce a polyimide compound h ). However, the present invention is not limited thereto.

Example  2

The polyimide compound according to Example 2 of the present invention is obtained by using 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride as the dianhydride monomer (e) Group is the main chain of the diamine monomer (fIII). It should be noted that since the group III is a group of a diamine monomer, compounds having a group III, for example, a diamine monomer (fIII), a polyimide compound (gIII) and a polyimide compound (hIII) The structural formula of the polyimide compound (hIII) according to Example 2 of the present invention is as follows.

Since the method for producing the polyimide compound (g III), that is, the thermal cyclization method, has been described in detail above, a detailed description thereof will be omitted here.

The present invention also provides a method for producing a polyimide compound by a chemical cyclization method, which includes three main steps: forming a polyimide compound (g), forming a polyimide compound (h) solution, (H) solids.

The step of forming the polyimide compound (g) includes dissolving the dianhydride monomer (e), the diamine monomer (f) in cresol and stirring to form a sticky solution of the polyimide compound (g) under anhydrous environment . The reaction temperature is 20-30 ° C, and the reaction time is 6-7 hours.

In the step of forming the polyimide compound (h) solution, 5-10 drops of isoquinoline are added dropwise to the polyimide compound (g) and heated and refluxed at 100-200 ° C, -12 hours, and forming the polyimide compound (h). Here, isoquinoline is a dehydrating agent.

It should be noted that since the step of forming the polyimide compound (h) is a dehydration step, it must proceed in an anhydrous environment. Generally, nitrogen or other inert gas is passed through to remove moisture. The cresol may be p-cresol or m-cresol, but the present invention is not limited thereto. The step of heating and refluxing the polyimide compound (g) and the isoquinoline can be classified into three steps. First, the polyimide compound and the isoquinoline solution are heated and refluxed at 90-100 ° C for 2-4 hours. The temperature is then raised to 140-150 DEG C and then heated and refluxed for 2-4 hours. Finally, the reaction temperature is raised to 200-210 캜 and then heated and refluxed for 2-4 hours.

Continuing with the above, the polyimide compound (h) is then cooled to 20-30 ° C and poured into ethanol. A direct polyimide compound (h) solid precipitates. The polyimide compound (h) solid can be heated and refluxed again with ethanol to increase the purity of the polyimide compound (h) solid by an extraction method. The reaction temperature is the boiling point of ethanol, i.e., 70-80 DEG C, and the reaction time is 4-6 hours. Finally, the vacuum drying is carried out to obtain the polyimide compound (h).

The polyimide compound (h) is formed by reacting the dianhydride (e) prepared in Example 1 and one of the diamine monomers (f) described below to form the polyimide compound (h) by the chemical cyclization method of the present invention The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.

Example  3

The polyimide compound according to Example 3 of the present invention is obtained by using 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride as the dianhydride monomer (e) Group is the main chain of the diamine monomer (fI). The structural formula of the polyimide compound (hI) according to Example 3 of the present invention is as follows.

The method of producing the polyimide (hI), that is, the chemical cyclization has been described in detail in the above, so that the detailed description thereof will be omitted here. Since the group I is a group of the diamine monomer, the compounds having the group I, for example, the diamine monomer (f), the polyimide compound (g), and the polyimide compound (h) The following II and IV-VIII groups can be deduced from the same principle, and a detailed description thereof will be omitted.

Example  4

The polyimide compound according to Example 4 of the present invention is obtained by reacting 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride of the present invention as dianhydride monomer (e) Group is the main chain of the diamine monomer (fII). The structural formula of the polyimide compound (hII) according to Example 4 of the present invention is as follows.

Example  5

The polyimide compound according to Example 5 of the present invention is obtained by reacting 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride with dianhydride monomer (e) Group is the main chain of the diamine monomer (fIV). The structural formula of the polyimide compound (hIV) according to Example 5 of the present invention is as follows.

Example  6

The polyimide compound according to Example 6 of the present invention is obtained by using 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride as the dianhydride monomer (e) Group is the main chain of the diamine monomer (fV). The structural formula of the polyimide compound (hV) according to Example 6 of the present invention is as follows.

Example  7

The polyimide compound according to Example 7 of the present invention can be obtained by using 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride as the dianhydride monomer (e) Group is the main chain of the diamine monomer (fVI). The structural formula of the polyimide compound (hVI) according to Example 7 of the present invention is as follows.

Example  8

The polyimide compound according to Example 8 of the present invention can be obtained by using 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride as the dianhydride monomer (e) Group is used as the main chain of the diamine monomer (f VII). The structural formula of the polyimide compound (h VII) according to Example 8 of the present invention is as follows.

Example  9

The polyimide compound according to Example 9 of the present invention can be obtained by using 1,4-bis (3,4-dicarboxyphenoxy) -2-adamantylbenzene dianhydride as the dianhydride monomer (e) Group is used as the main chain of the diamine monomer (f VIII). The structural formula of the polyimide compound (h VIII) according to Example 9 of the present invention is as follows.

Examples 2 to 9 were subjected to a physical property analysis including viscosity test, molecular weight test (for example, number average molecular weight Mn, weight average molecular weight Mw and polymerization degree Mw / Mn), solubility (E.g., glass transition temperature (Tg), thermal decomposition temperature in nitrogen, and thermal decomposition temperature in oxygen (e.g., Etc.). Table 1 shows the viscosity and molecular weight test results of the polyimides (hl to hll). Table 2 shows the solubility test results of the polyimides (hl to hwi). Table 3 shows the results of the mechanical properties test of the polyimide (hl to hwi). Table 4 shows the test results of the thermal properties of the polyimides (hI to hVII). Table 1 is as follows.

As a result of Table 1, the viscosity of the polyimide (g III) was 0.53 dL / g and the inherent viscosity range of the remaining soluble polyimides (h I, h II and h IV to h VIII) was 0.42 to 1.06 dL / g, (hI to hVII) has a number average molecular weight ranging from 42,000 to 112,000.

In the solubility test, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), o- The solubility of polyimides (hl to hwi) is tested using solvents such as chlorophenol, m-cresol, chloroform and tetrahydrofuran (THF). The results are shown in Table 2. It should be noted that "++" in Table 2 means completely dissolved in a room temperature environment, "+" means completely dissolved at 60 DEG C, Means that it is partially dissolved at 60 ° C, and "-" means that it can not be dissolved at 60 ° C.

As can be seen from the results in Table 2, the most important reason that the polyimides (hV and hVI) have relatively good solubility for various solvents is that they have a "-CF ₃ " group. Since the F atoms are relatively large, solubility of polyimides (hV and hVI) is increased because the arrangement of molecules is not tight and the solvent can penetrate easily between molecules.

Since the polyimide (hIII) is synthesized with paraphenylenediamine, the monomer has a linear symmetrical structure and the arrangement between the molecules is comparatively tight and the solubility is comparatively excellent. The polyimide (hI to hVII) has a comparatively good solubility in solvents such as N-methyl-2-pyrrolidone, o-chlorophenol, m-cresol and chloroform.

Table 3 shows the results of the mechanical properties test of the polyimide (hI to hviii) thin film. As can be seen from Table 3, the breaking strength range of the polyimide (hI to hVII) is between 95.4 and 141.6 MPa, the elongation at break is between 5.4 and 22.4%, and the initial elastic modulus is between 2.2 and 2.4 GPa. Further, the breaking strength of the polyimide (h VI) is less than 100 MPa, and the breaking strengths of the other polyimides (h I to h V and h VII to h VIII) are all 110 MPa or more.

May be due to a-polyimide (hⅠ and hⅡ) is relatively large flexible chain structure (-O-, -CH ₂₎ in bar, polyimide (hⅠ and hⅡ) having excellent elongation at break of 20% or more. Therefore, the degree of winding of the molecules is relatively high, so that the thin film has a relatively large amount of stretch deformation. Although the polyimide (h Ⅶ) has a relatively large number of soft chains, it has no asymmetric structure of 1,3-diamantine on the main chain, and thus does not have a phenomenon of elongation change of polyimides (h Ⅰ and h Ⅱ).

As can be seen from Table 4, the polyimides (hI to hVII) have comparatively excellent heat resistance. The polyimide (hI to hVII) has a main pyrolysis temperature in the range of 507 to 529 DEG C in nitrogen gas. The polyimide (hI to hVII) has a main pyrolysis temperature in the range of 507 to 543 DEG C in air. As can be seen from the above results, the aliphatic polyimide (hI to hVII) has excellent mechanical properties.

According to the results through DSC, the glass transition temperature range of polyimide (hI to hVII) is between 268 and 331 ° C. Structures containing a rigid polycyclic aliphatic group allow the polymer to have a relatively high glass transition temperature. The glass transition temperature of the polyimide (hI to VI) is about 290 DEG C and the glass transition temperature of the polyimide (hIII) reaches 331 DEG C. Since the polyamide (h VII) has relatively low glass transition temperature and has relatively flexible groups and asymmetric structures such as an ether having a relatively large molecular chain, it is possible to lower the action force between molecules, Temperature.

As described above, the present invention provides a dianhydride monomer, a polyimide compound, and a process for producing the same. The dihydrophthalate monomer has a large side chain group, and the polyimide compound prepared using such dianhydride monomer has relatively low structural symmetry and alignment regularity. As can be seen from the solubility test of the present invention, the polyimide compound having a large side chain group has excellent solubility in various solvents. And these polyimide compounds still have relatively good mechanical and thermal properties.

The above description is not intended to limit the scope of protection of the present invention merely as a preferred embodiment of the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (18)

A dianhydride monomer having a side chain group and having the following structural formula:

Wherein R is a cycloalkane group having at least one tertiary carbon atom. delete delete A process for preparing a dianhydride monomer having a side chain group, comprising the steps of:
(I) a step of heating and refluxing a solution containing a bromine compound (a), a hydroquinone compound and benzene to precipitate a solid of the hydroquinone compound (b)
The heating and reflux temperature is 80-85 deg. C, the heating and refluxing period is 3-4 days,
The bromine compound (a) has the following structural formula,

Wherein the hydroquinone compound (b) has the following structural formula:

;
(3,4-dicyano phenoxy) compound (c) by heating reaction of (II) hydroquinone compound (b) with 4-nitrophthalonitrile and using methanol aqueous solution as a precipitant ,
The reaction temperature is 75-80 占 폚, the reaction time is 6-12 hours,
The bis (3,4-dicyanophenoxy) compound (c) has the following structural formula:

;
(3,4-dicyanophenoxy) compound (c), potassium hydroxide and methanol is heated and refluxed to precipitate a bis (3,4-dicarboxyphenoxy) compound (d) , ≪ / RTI &
The reflux temperature is 70-85 ° C., the reflux time is 4-5 days,
The bis (3,4-dicarboxyphenoxy) compound (d) has the following structural formula:

; And
(E) by subjecting a solution containing (IV) bis (3,4-dicarboxyphenoxy) compound (d), glacial acetic acid and acetic anhydride to a dehydration cyclization reaction,
The reaction temperature is 130-140 占 폚, the reaction time is 1-6 hours,
The dianhydride monomer (e) has the following structural formula,

Wherein R is a cycloalkane group having at least one tertiary carbon atom. delete delete 5. The process according to claim 4, wherein the hydroquinone compound (b) and 4-nitrophthalonitrile are subjected to the following steps:
Heating and refluxing anhydrous potassium carbonate, methanol and dimethylformamide, and ionizing the hydroquinone compound (b) with a negatively charged anion in an azeotropic manner,
Wherein the azeotropic temperature is 150-160 < 0 > C and the reaction time is 4-5 hours;
≪ / RTI > wherein the dihydroxy monomer has a side chain group. 5. The process of claim 4, wherein after forming the hydroquinone compound (b) solids,
Washing the hydroquinone compound (b) solid with hot water, wherein the temperature of the hot water is 70-80 占 폚; And
Recrystallizing the hydroquinone compound (b);
≪ / RTI > wherein the dihydroxy monomer has a side chain group. 5. The method according to claim 4, wherein after forming the bis (3,4-dicyano phenoxy) compound (c)
Washing the bis (3,4-dicyanophenoxy) compound (c) with distilled water; And
Recrystallizing the bis (3,4-dicyanophenoxy) compound (c);
≪ / RTI > wherein the dihydroxy monomer has a side chain group. A polyimide compound having a side chain group and having the following structural formula:

Wherein R is a cycloalkane group having at least one tertiary carbon atom,
R '

,

,

,

,

,

,

And

≪ / RTI > delete delete A process for producing a polyimide compound having a side chain group, comprising the steps of:
(I) dissolving a dianhydride monomer and a diamine monomer in cresol and stirring to form a polyamic acid compound solution under anhydrous environment,
Wherein the dianhydride monomer has the following structural formula,

The diamine monomer has the following structural formula,

The polyamic acid compound has the following structural formula,

Wherein R is a cycloalkane group having at least one tertiary carbon atom,
R '

,

,

,

,

,

,

And

≪ / RTI >
Wherein the reaction temperature is from 20 to 30 DEG C and the reaction time is from 6 to 7 hours;
(II) 5-10 drops of isoquinoline are added dropwise to the polyamic acid compound solution, followed by heating and refluxing to form a polyimide compound solution,
Wherein the heating and refluxing temperature is 100-200 DEG C and the heating and refluxing time is 8-12 hours; And
(III) A step of cooling a polyimide compound solution and adding it to ethanol to form a precipitate to precipitate a polyimide compound solid,
Wherein the polyimide compound has the structure:

. delete delete 14. The method according to claim 13, wherein the cresol comprises p-cresol or m-cresol. 14. The method of claim 13, further comprising, after forming the polyimide compound solid,
Heating and refluxing a polyimide compound solid, ethanol,
Wherein the reaction temperature is from 70 to 80 캜, and the reaction time is from 4 to 6 hours. 14. The method according to claim 13, wherein the polyimide compound solution and the isoquinoline solution are heated and refluxed,
Heating and refluxing the polyimide compound solution and the isoquinoline solution at 90-100 占 폚, wherein the reaction time is 2-4 hours;
Heating and refluxing the polyimide compound solution and the isoquinoline solution at 140-150 캜 by raising the reaction temperature, wherein the reaction time is 2-4 hours; And
Heating and refluxing the polyimide compound solution and the isoquinoline solution at 200-210 캜 by raising the reaction temperature again, the reaction time being 2-4 hours;
Wherein the polyimide compound has a side chain group.