WO2017074096A1

WO2017074096A1 - Polyimide comprising isosorbide and method for preparing same

Info

Publication number: WO2017074096A1
Application number: PCT/KR2016/012240
Authority: WO
Inventors: 정민경; 조대희; 박상윤; 김승환; 김인범; 조상현
Original assignee: 에스케이이노베이션 주식회사; 에스케이종합화학 주식회사
Priority date: 2015-10-30
Filing date: 2016-10-28
Publication date: 2017-05-04
Also published as: KR20170050216A

Abstract

The present invention relates to a polyimide comprising isosorbide and a method for preparing the same. The polyimide comprising isosorbide according to the present invention is environmentally friendly, and is excellent in stable solubility, processability and optical properties. In particular, since the polyimide according to the present invention has a low linear thermal expansion coefficient and high temperature stability, the polyimide is applicable to flexible display optical members or electrical and electronic circuit members.

Description

Polyimide containing isosorbide and preparation method thereof

The present invention relates to a polyimide comprising isosorbide and a process for producing the same.

In general, polyimide resins are widely applied in the field of insulating substrates for circuit and device formation because of excellent heat, mechanical, electrical, and chemical properties, and recently, optical members for displays (color filters for organic light emitting devices) that require optical properties. Transparent polyimide resins are attracting attention as next-generation materials that can replace glass materials with base and cover substrates for flexible or bendable flexible devices, which are one of the next-generation displays.

Such variously applied polyimide resins generally have a disadvantage in that moldability is poor because the imide bonds are thermosetting. Polyetherimide with ether bond is thermoplastic and has excellent heat resistance, flame retardancy, and mechanical properties as well as moldability which is an advantage of ether bond.

The existing bisphenol A based polyetherimide (Ultem) has various environmental and environmental hormone problems due to bisphenol A that can be eluted when used. In order to solve chemical structures and environmental problems that can impart moldability to such polyimide, the inventors have introduced aliphatic diols, that is, isosorbide.

Recently, isosorbide has attracted attention as a monomer necessary for the synthesis of next-generation high-performance, eco-friendly materials. Isosorbide is manufactured from biomass-derived sorbitol and is used as a highly safe substance in the pharmaceutical industry. In the cosmetics industry, esters and ethers of isosorbide are also used as raw materials for nonionic surfactants.

Isosorbide is a compound having a structure in which two tetrahydrofuran rings are bonded at an angle of 120 °, having a hydroxyl group at carbon positions 2 and 6, and having a rigid structure having optical asymmetry. Isosorbide based products are biodegradable and can be used as renewable resources by the plastics manufacturing industry. In addition, there is an excellent advantage such as transparency and surface hardness, the application has been attempted to optical electronic products such as optical disk substrate, optical fiber or lens utilizing optical characteristics.

Accordingly, there is a demand for a method for producing a polyimide containing isosorbide, which is not only a substitute for bisphenol, which is a raw material of polyetherimide, but also has excellent optical and thermal properties, and is known as a substance having no risk of elution such as environmental hormone. .

In order to solve the above problems, polyimide and its polyisoimide are not only substitute for bisphenol, which is a raw material of polyetherimide, but also have excellent optical and thermal properties. It is intended to provide a manufacturing method.

The present invention relates to a polyimide comprising isosorbide and a process for producing the same. The polyimide of the present invention relates to a polyimide containing a repeating unit represented by the following formula (1).

[Formula 1]

(In Formula 1,

Is a substituted or unsubstituted trivalent (C6-C12) aromatic ring;

R is at least one selected from substituted or unsubstituted (C1-C7) alkylene, substituted or unsubstituted (C4-C12) alicyclic ring, substituted or unsubstituted (C6-C12) aromatic ring and AXB-; It is the top;

A and B are independently of each other a (C6-C12) aromatic ring;

X is a single bond, -O-, -S-, -C (= O)-, -SO ₂ -,-C (CF ₃ ) ₂ - _or- (C _y H _2y )-(y is 1 to 5 An integer);

n is an integer between 1 and 1,000.)

Polyimide containing isosorbide according to the present invention is environmentally friendly, excellent in stable solubility, processability and optical properties. In particular, the polyimide according to the present invention has a low coefficient of thermal expansion and high temperature stability, and thus can be applied as a flexible display optical member or an electric and electronic circuit member.

Hereinafter, the present invention will be described in detail. The embodiments and drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. In addition, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may be unnecessarily blurred are omitted.

Polyimide according to the present invention may have a repeating unit represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

Is a substituted or unsubstituted trivalent (C6-C12) aromatic ring;

R is at least one selected from substituted or unsubstituted (C1-C7) alkylene, substituted or unsubstituted (C4-C12) alicyclic ring, substituted or unsubstituted (C6-C12) aromatic ring, and AXB-; It is the top;

A and B are independently of each other a (C6-C12) aromatic ring;

X is a single bond, -O-, -S-, -C (= O)-, -SO ₂ -,-C (CF ₃ ) ₂ - _or- (C _y H _2y )-(y is 1 to 5 Integer).

remind

Or substituted in R is halogen, nitro, hydroxy, (C1-C7) alkyl, (C1-C7) alkoxy, (C1-C7) alkylcarbonyl, (C1-C7) alkoxycarbonyl, and formyl group (- CHO) may be substituted with one or more substituents selected from.

remind

Is not limited so long as it is a group containing an aromatic group, specifically

And one or more trivalent groups selected from and the like, and the bonding position in the repeating unit may be located in an aromatic ring.

E.g,

Can be.

R may be an alkylene group, and specifically, methylene, ethylene, propylene, 1-methylethylene 1,1-dimethylethylene, 1,1-dimethylpropylene, butylene, 1-methylpropylene, 1-methylbutylene, It may be one or more divalent selected from 2-methyl-propylene, pentylene, hexylene, heptylene and the like.

In addition, R may be an alicyclic ring, specifically, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene It may be at least one divalent selected from monocyclic or polycyclic cycloalkylenes, such as dicyclopentylene, dicyclohexylene, tricyclodekalene, norbornylene.

In addition, the R may be an aromatic ring, specifically

It may be at least one divalent selected from the back.

Polyimide n of the present invention may comprise a structural unit of 1 to 1,000 or more, preferably 30 to 500.

The polyimide of the present invention may be prepared by condensation of anhydride and diamine containing isosorbide, and specifically from polyamic acid prepared by condensation of dianhydride and diamine containing isosorbide. Can be prepared.

The polyamic acid according to the present invention may have a repeating unit represented by Chemical Formula 2.

[Formula 2]

In Chemical Formula 2,

Is a substituted or unsubstituted trivalent (C6-C12) aromatic ring;

A and B are independently of each other a (C6-C12) aromatic ring;

m is an integer between 1 and 1,000.

The polyamic acid may include a repeating unit in which some of the repeating units constituting the polyamic acid are imidated. Specifically, a part of the amic acid present in the repeating unit of the polyamic acid during the condensation reaction of anhydride and diamine may be imidized through dehydration, and the resulting polyamic acid is poly (amic acid-co-imide) It may include the form of.

The polyimide according to the present invention may be prepared by the following method, but is not limited thereto.

a) reacting isosorbide with 4-nitrophthalonitrile to produce an anhydride of formula (3);

b) condensing an anhydride of Formula 3 with a diamine of H ₂ NR-NH ₂ to prepare a polyamic acid of Formula 2; And

c) imidating the polyamic acid of Formula 2 to prepare a polyimide;

[Formula 1]

[Formula 2]

[Formula 3]

(In Chemical Formulas 1 to 3,

Is a substituted or unsubstituted trivalent (C6-C12) aromatic ring;

A and B are independently of each other a (C6-C12) aromatic ring;

n and m are integers between 1 and 1,000.)

In step a) of the present invention, a bis (3,4-dicyanophenoxy) compound is prepared by reacting isosorbide with 4-nitrophthalonitrile, and a bis (3,4-dicyanophenoxy) compound A bis (3,4-dicarboxyphenoxy) compound may be prepared by reacting a solution containing potassium hydroxide and ethanol, followed by a dehydration cyclization reaction in a solution containing acetic anhydride to prepare an anhydride of Chemical Formula 3 have.

Isosorbides of the present invention may comprise isosorbide, isosorbide mixtures, mixtures of isomers of isosorbide and / or individual isomers of isosorbide. Specifically, isosorbide may be represented by the following formula (4).

[Formula 4]

The stereochemistry of isosorbide is also not particularly limited. The diol may be prepared by dehydration of the corresponding hexitol. Hexitol can be produced commercially from the corresponding sugar (aldohexose). Isosorbide of formula (4) is a 1,4: 3,6- dianhydro-D-glucitol structure of formula (5), and 1,4: 3,6- dianhydro-L-iditol of formula (6); 1,4: 3,6-dianhydro-D-mannitol of Formula 7 and any combination thereof.

[Formula 5]

[Formula 6]

[Formula 7]

In step b) of the present invention, the polyamic acid of Formula 2 may be prepared by condensation reaction of the anhydride of Formula 3 prepared in step a) with a diamine of H ₂ NR—NH ₂ .

[Formula 2]

[Formula 3]

The diamine which is H ₂ NR-NH ₂ may be an aromatic group R, preferably meta-phenylenediamine (m-PDA), para-phenylenediamine (p-PDA), 4,4-methylenedianiline ( MDA), 3,4-oxydianiline (3,4-ODA), 4,4'-biphenyldiamine (BPA), metabisaminophenoxydiphenylsulfone (m-BAPS), 2,2-bisamino Phenylhexafluoropropane (HFDA), 4,4-oxydianiline (4,4-ODA), 3,5-bis (trifluoromethyl) -1,2-diaminobenzene (TFDB), parabis Aminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenyl Propane (BAPP), 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP), 4- (4- (4-aminophenylsulfonyl) phenoxy) benzeneamine, 5-diaminobenzoic acid, 2, 4-diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 2,2-diaminobenzenedisulfonic acid, and the like may be included, but is not limited thereto.

The content of the anhydride and diamine of the general formula (3) of the present invention can be variously adjusted as necessary. For example, the molar ratio of the anhydride and diamine of Formula 3 may be 1: 0.5 to 1: 1.5, preferably 1: 1. By-products can be prevented in the above range, and a high molecular weight resin can be obtained.

The solvent for producing the anhydride of Formula 3 and the polyamic acid of Formula 2 of the present invention is not particularly limited as long as it is a substance capable of dissolving anhydride and diamine. Known reaction solvents include, for example, m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl One or more polar solvents selected from acetates can be used.

In addition, low-boiling solvents such as tetrahydrofuran (THF) and chloroform or low-absorbent solvents such as γ-butyrolactone or low-boiling solutions such as tetrahydrofuran (THF) and chloroform or low-absorbing solvents such as γ-butyrolactone can be used. Can be. The content of the solvent is not particularly limited, but 50 to 95% by weight, preferably 70 to 90% by weight of the total solution may smoothly proceed with the overall polymerization.

The polyamic acid polymerization reaction of the present invention can proceed in a conventional manner. For example, the reaction temperature is a temperature of 20 to 200 ℃, the reaction time may be carried out under the conditions of 1 to 48 hours, may be prepared in nitrogen or argon atmosphere, but is not limited thereto.

The polyamic acid of the present invention may include one or more other components except the polymer. Examples include light stabilizers (for example, 2-hydroxybenzophenone, 2-hydroxyphenylbenzotriazole, etc.), catalysts, plasticizers, dyes, colorants, organic dyes, inorganic dyes, flame retardants, antistatic agents, bio stabilizers ( biostabilizer), foaming agents, adhesion promoters, compatibilizers, curing agents, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet absorbers and the like.

In step c) of the present invention, a polyimide may be prepared by imidizing the polyamic acid prepared in step b).

The imidation can be prepared by applying both chemical and thermal methods, and in the chemical method, acetic anhydride and pyridine are further added to the prepared polyamic acid, and then heated at 60 to 150 ° C., toluene is added to the precursor, and then toluene There is a method of heating at the boiling point of. The thermal method may be a method of heating the precursor stepwise at 50 to 400 ℃. In the present invention, a thermal method is preferably used, but is not limited thereto.

The polyimide may apply a solution containing polyamic acid, which is a precursor of polyimide, and proceed with imidization at a high temperature. Specifically, it may be produced by applying to one surface of the support for forming a polyimide film and then curing.

In this case, glass, a metal substrate or a plastic substrate may be used as the support without particular limitation, and excellent thermal and chemical stability with respect to polyamic acid, and without any separate release agent treatment, is easy without damage to the formed polyimide film. Preference is given to glass substrates which can be easily separated.

In addition, the coating process may be carried out according to a conventional coating method, specifically, spin coating method, bar coating method, roll coating method, air-knife method, gravure method, reverse roll method, kiss roll method, doctor blade method, Spray method, dipping method, etc. can be used.

The coated polyimide may be subjected to a drying process for removing the organic solvent present in the polyamic acid solution prior to the curing process.

The drying process may be carried out according to a conventional method, it may be carried out at a temperature of 50 to 140 ℃ to form a polyimide film of a uniform thickness. The curing process may be performed by heat treatment at a temperature of 80 to 400 ℃. The curing process may be carried out in a multi-step heat treatment within the above temperature range.

The weight average molecular weight of the polyimide including the isosorbide structure of the present invention may be 10,000 to 500,000g / mol. At this time, the weight average molecular weight was measured by using Agilent Technologies' 1260 Infinity (standard sample: Polystyrene), column was used PL gel Olexis, sample was 100ml LiCl (concentration) using DMAc as a solvent : 0.5wt%) contained 4mg. The weight average molecular weight of the polyimide produced through the present invention is not particularly limited thereto, but if the above-mentioned range is satisfied, it has mechanical, electrical and heat resistance properties suitable for use as a member in the field of electrical electronics and mechanical materials. Deformation does not occur at, and at the same time, mechanical properties such as strength, elasticity and surface hardness can be exhibited, which is preferable.

In addition, the present invention may include a display optical member or a member for an electronic circuit containing a polyimide. It can be prepared by controlling the properties of the polymers produced in connection with the high glass transition temperature, thermal stability, flame retardancy, chemical resistance and melt processability of the polyimide polymer itself. Members for electronic circuits may be manufactured by any known processing method of radio, television sets and computers and electrical wiring coatings, or may be used as dielectrics in printed wiring boards, semiconductors and flexible electrical networks. In addition, polyimides can be used in a variety of electronic adhesive applications, such as lead frame adhesives and aircraft interiors.

In addition, polyimides may be used in mechanical operating devices, medical devices, sensing devices, free-standing films, fibers, foams, nonwoven materials (eg separators), semipermeable membranes, ion exchange membranes, fuel cell devices, It can be applied to photoluminescence or electroluminescent devices.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the embodiments, and various other modifications and changes may be possible.

EXAMPLE

1. Preparation of isosorbide dianhydride compound.

[Formula 8]

The dianhydride monomer of the present invention [Formula 8] was prepared through the reaction of three steps as follows.

1) Preparation of Bis (3,4-dicyanophenoxy) Compound

10.2 g of isosorbide and 21.2 g of anhydrous potassium carbonate were added to a 250 ml three-necked flask, followed by nitrogen replacement. Then, 100 ml of N, N-dimethylformamide (DMF) was added and stirred. 25.3 g of 4-nitrophthalonitrile were added at room temperature, and the reaction was performed at 80 ° C for 12 hours. The reaction mixture was added to aqueous methanol solution to precipitate, and the resulting solid compound was filtered, washed several times with distilled water and dried. The resulting solid compound was recrystallized using acetonitrile and methanol mixed solvent to obtain 17.8 g (yield: 60%) of bis (3,4-dicyanophenoxy) compound.

2) Preparation of Bis (3,4-Dicarboxyphenoxy) Compound

100.3 g of potassium hydroxide was added to a 1 L three-necked flask, and 180 ml of ethanol and 180 ml of distilled water were added and dissolved. 38.1 g of the bis (3,4-dicyanophenoxy) compound obtained in 1) was added thereto, followed by heating to reflux for 12 hours. The solution was cooled to room temperature, filtered, and the bis (3,4-dicarboxyphenoxy) compound was precipitated by adjusting the pH value to 2-3 using an aqueous solution of hydrogen chloride. Then, the solid obtained in distilled water was washed and dried to obtain 42.8 g (yield: 100%) of bis (3,4-dicarboxyphenoxy) compound.

3) Preparation of isosorbide dianhydride compound (Formula 8)

40 g of the bis (3,4-dicarboxyphenoxy) compound obtained in the above 2) was placed in a 1 L three-necked flask, followed by nitrogen replacement, and 340 ml of anhydrous tetrahydrofuran was added to dissolve completely. 160 ml of acetic anhydride was added, followed by heating and refluxing for 12 hours to proceed with dehydration cyclization. The solution was cooled to room temperature, concentrated under reduced pressure to remove tetrahydrofuran to precipitate an isosorbide dianhydride compound. The obtained solid was filtered, washed with diethyl ether and dried to give 32.2 g (yield: 87%) of isosorbide dianhydride compound.

2. Preparation of Polyimide

After 240 g of N, N-dimethylacetamide (DMAc) was charged while passing through a 5,000 ml reactor, 11.87 g (109.79 mmol) of mPD (m-phenylene diamine) was dissolved while maintaining the temperature of the reactor at 40 ° C. . 48.12 g (109.79 mmol) of the prepared ISDA (isosorbide dianhydride) was added three times, and stirred for 10 hours to react, followed by a polyamic acid having a solid content of 20% by weight and a viscosity (25 ° C) of 6,000 cps. A solution was obtained.

The obtained solution was cast on a glass substrate at 150 μm of coater gap and the coating speed was 5 mm / min, followed by hot air drying at 80 ° C. for 20 minutes, followed by heating up to 300 ° C. at a heating rate of 2 ° C./min, and heating for 30 minutes to obtain polyimide. A film was obtained. Physical properties of the prepared samples are shown in Table 1 below.

[Measurement of properties]

1. Coefficient of Thermal Expansion (CTE)

The coefficient of linear thermal expansion was measured using a Hitachi TMA7100 thermomechanical analyzer. The polyimide film was heated to 50 ° C to 250 ° C to complete the first measurement. In the measurement process, the tension was 30 mN, and the temperature rising / lowing rate was maintained at 10 ° C./min, cooled to 50 ° C., and then heated to 250 ° C. to complete the second measurement.

2. Glass Transition Temperature, Storage Modulus (Tg)

Tg and Storage Moulus values were measured using a SDTA861e instrument from Mettler Toledo. The measurement temperature was 30 deg. C to 400 deg. C, the temperature increase rate was 5 deg. C per minute, and the tension was applied to a film having a thickness of 50 mu m.

CTE(ppm/℃) CTE (ppm / ° C)	Tg(℃) Tg (℃)	Modulus(GPa) Modulus (GPa)
54 54	263 263	4.0 4.0

Looking at the physical properties of the PI film containing isosorbide, it can be seen that the CTE physical properties are 60 ppm / ° C. or less and Tg is 250 ° C. or more.

The polyimide of the present invention has a glass transition temperature of 250 ℃ or more, it was confirmed that the form of the film changes from the temperature of 300 ℃ or more. Through this, the polyimide of the present invention was found to be effectively improved heat resistance compared to the glass transition temperature of 217 ℃ of the existing Ultem.

In addition, it has been confirmed that the elastic modulus is excellent in the elasticity of 4.0GPa, and can be applied to the process for manufacturing substrate materials such as flexible displays and active display devices.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and changes can be made without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.

Claims

Polyimide containing a repeating unit represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

Is a substituted or unsubstituted trivalent (C6-C12) aromatic ring;

R is at least one selected from substituted or unsubstituted (C1-C7) alkylene, substituted or unsubstituted (C4-C12) alicyclic ring, substituted or unsubstituted (C6-C12) aromatic ring, and AXB-; It is the top;

A and B are independently of each other a (C6-C12) aromatic ring;

X is a single bond, -O-, -S-, -C (= O)-, -SO 2 -,-C (CF 3 ) 2 - or- (C y H 2y )-(y is 1 to 5 An integer);

n is an integer between 1 and 1,000.
The method of claim 1,

remind
silver

At least one trivalent group selected from the group wherein the bonding position in the repeating unit is located in an aromatic ring.
The method of claim 1,

R is

Polyimide which is at least 1 sort (s) divalent selected from among.
a) reacting isosorbide with 4-nitrophthalonitrile to produce an anhydride of formula (3);

b) condensing an anhydride of Formula 3 with a diamine of H 2 NR-NH 2 to prepare a polyamic acid of Formula 2; And

c) imidating the polyamic acid of Chemical Formula 2 to prepare a polyimide.

[Formula 1]

[Formula 2]

[Formula 3]

(In Chemical Formulas 1 to 3,

Is a substituted or unsubstituted trivalent (C6-C12) aromatic ring;

R is at least one selected from substituted or unsubstituted (C1-C7) alkylene, substituted or unsubstituted (C4-C12) alicyclic ring, substituted or unsubstituted (C6-C12) aromatic ring, and AXB-; It is the top;

A and B are independently of each other a (C6-C12) aromatic ring;

X is a single bond, -O-, -S-, -C (= O)-, -SO 2 -,-C (CF 3 ) 2 - or- (C y H 2y )-(y is 1 to 5 An integer);

n and m are integers between 1 and 1,000.)
The method of claim 4, wherein

The diamine in step b) is meta-phenylenediamine (m-PDA), para-phenylenediamine (p-PDA), 4,4-methylenedianiline (MDA), 3,4-oxydianiline (3, 4-ODA), 4,4'-biphenyldiamine (BPA), metabisaminophenoxydiphenylsulfone (m-BAPS), 2,2-bisaminophenylhexafuluropropane (HFDA), 4,4 -Oxydianiline (4,4-ODA), 3,5-bis (trifluoromethyl) -1,2-diaminobenzene (TFDB), parabisaminophenoxydiphenylsulfone (p-BAPS), 1, 4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxy Phenylhexafluoropropane (HFBAPP), 4- (4- (4-aminophenylsulfonyl) phenoxy) benzeneamine, 5-diaminobenzoic acid, 2,4-diaminobenzene sulfonic acid, 2,5-dia A method for producing a polyamide, which is at least one selected from minobenzene sulfonic acid and 2,2-diaminobenzenedisulfonic acid.
The method of claim 4, wherein

The molar ratio of the anhydride and diamine in step b) is 1: 0.5 to 1: 1.5 method of producing a polyimide.
The method of claim 4, wherein

In the step b), the reaction temperature is a temperature of 20 to 200 ℃ and the reaction time is a method for producing a polyimide 1 to 48 hours.
The method of claim 4, wherein

The imidation in step c) is a method of producing a polyimide is heat treatment at a temperature of 50 to 400 ℃.