CN101392059B - A kind of colorless transparent aromatic polyimide film and preparation method thereof - Google Patents

Abstract

The invention discloses a colorless and transparent aromatic polyimide film, the general formula of molecular structure is as follows; its preparation includes: using aromatic primary amine and aromatic acid anhydride with specific molecular structure in a strong polar aprotic organic solvent system , Polymerization reaction is carried out in the temperature range of 0°C-35°C to obtain a colorless and transparent homogeneous viscous polyamic acid solution. Adjust viscosity, cast film, heat up, remove solvent, and at the same time, partial imidization reaction occurs, stripping and stretching, further deep thermal imidization, winding, to obtain colorless and transparent aromatic polyimide film. The invention does not need special production equipment, can be produced on a traditional polyimide film production line, and is suitable for industrialized production.

Description

A kind of colorless transparent aromatic polyimide film and preparation method thereof

technical field

The invention relates to a preparation method of a colorless and transparent organic polymer film, in particular to a colorless and transparent aromatic polyimide film and a preparation method thereof.

Background technique

Polyimide is a kind of polymer with excellent comprehensive performance, which has excellent heat resistance, low temperature resistance, solvent resistance, self-lubricating property and flame retardancy. At the same time, it also has very good mechanical properties and Dielectric properties. Therefore, it is widely used in photovoltaic materials, nonlinear optical materials; high temperature resistant materials for spacecraft, satellites or space vehicles; advanced structural composite materials in aerospace, automobiles, electromechanical, etc.; Insulating materials, high temperature resistant adhesives, etc.; and FPC or PCB substrate materials in the field of electronic microelectronics, IC interlayer insulating materials, VLSI passivation coatings and alpha particle barrier coating materials, etc.

Japanese patent JP H05-0175175A discloses the molecular structure and preparation method of colorless transparent polyimide, and its main feature is: 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and polyimide The ether-type diamine reacts to obtain fluorine-containing polyamic acid, and then obtains colorless and transparent polyimide through chemical imidization or thermal imidization.

Chul Ha Ju etc. (Synthesis and Characterization of Colorless Polyimide Nanocomposite Films, Journal of Applied Polymer Science, 2007, 106: 4192-4201) discloses a preparation method of a colorless polyimide nanocomposite film, the main features of which are: 2 , 2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride reacts with 2,2'-bis(trifluoromethyl)biphenyldiamine to prepare a precursor polymer, and then mixes with inorganic (such as mica etc.) Nano-particle hybridization to obtain a colorless polyimide nano-hybrid composite film.

The molecular structure and preparation method of the colorless and transparent aromatic polyimide film disclosed by the present invention have not yet been published in literature or patent reports.

Contents of the invention

The object of the present invention is to provide a method for preparing a colorless and transparent aromatic polyimide film. The method is simple in process, low in cost, friendly to the environment, can be prepared in general-purpose equipment, and is suitable for industrial production.

The chemical reaction equation of the present invention is as follows:

Among them, p is an integer not less than 1; q is an integer not less than 0, and p and q are independent and uncorrelated;

A colorless and transparent aromatic polyimide film, the general formula of molecular structure is shown in Figure 1, wherein p is an integer not less than 1; q is an integer not less than 0, and p and q are independent of each other and not related to each other . In particular, molecular structures involving the following: (1)

A preparation method of a colorless and transparent aromatic polyimide film, comprising:

Aromatic primary amines and aromatic anhydrides with specific molecular structures are used to carry out polymerization reactions in a strong polar aprotic organic solvent system at a temperature range of 0°C-35°C to obtain a colorless and transparent homogeneous viscous polymer Amic acid solution; adjust viscosity, cast film, heat up, remove solvent, and part of imidization reaction occurs at the same time, film release stretching, further deep thermal imidization, winding, to obtain colorless and transparent aromatic polyamide imide film.

The aromatic primary amines with a specific molecular structure are aromatic four-element primary amines and aromatic two-element primary amines.

The aromatic quaternary primary amine of the specific molecular structure is selected from 2,2-bis[4-(2,4-diaminophenoxy)phenyl]propane, 2,2-bis[4-(2, One or more of 4-diaminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(2,4-diaminophenoxy)diphenyl sulfide.

The aromatic dibasic primary amine of the specific structure is selected from 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4 -aminophenoxy)benzene, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl Base-4-aminophenoxy)phenyl]hexafluoropropane, 2,5-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,5-bis(2-trifluoromethyl -4-aminophenoxy) tert-butylbenzene, 2,5-di-tert-butyl-1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 4,4'-bis (2-trifluoromethyl-4-aminophenoxy)diphenylsulfone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)-3,3'5,5'- Tetramethyldiphenylsulfone, 4,4′-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl, 4,4′-bis(2-trifluoromethyl-4-aminophenoxy base)-3,3'5,5'-tetramethylbiphenyl, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether, 4,4'-bis( 4-aminophenoxy)diphenyl ether, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , 2,2-bis[4-(4-diaminophenoxy)phenyl]hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) One or more of oxy)benzene and 1,4-bis(4-aminophenoxy)benzene, wherein the molar ratio of aromatic dibasic primary amines to aromatic quaternary primary amines is 1:0.1 ~10.

The aromatic acid anhydrides are aromatic monoanhydrides and aromatic dianhydrides.

The aromatic monoanhydride is selected from one or more of phthalic anhydride, 4-fluorophthalic anhydride, and tetrafluorophthalic anhydride, wherein the aromatic monoanhydride and specific molecular structure The molar ratio of the aromatic quaternary primary amine is 2:1.

The aromatic dianhydride is selected from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)benzene base] propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy ) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl One or more of dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 3,3',4,4'-tetracarboxydiphenyl ether dianhydride, among which aromatic The number of moles of the aromatic dianhydride is equal to the sum of the number of moles of the aromatic quaternary primary amine and the aromatic dibasic primary amine of a specific molecular structure.

The highly polar aprotic organic solvent is selected from N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, One or more of dimethyl sulfoxide.

The volume-to-weight ratio of the described strong polar aprotic organic solvent to the total reactant is 3 milliliters to 10 milliliters: 1 gram, wherein the weight of the total reactant refers to the aromatic quaternary primary amine, aromatic di The sum of the weights of primary amines, aromatic monoanhydrides and aromatic dianhydrides.

The reaction temperature of the monoanhydride and the aromatic tetravalent primary amine with a specific molecular structure is 0° C. to 35° C., and the reaction time is 0.5 hours to 2 hours.

The reaction temperature of the aromatic dibasic anhydride and the aromatic primary amine is 0° C. to 35° C., and the reaction time is 1 hour to 5 hours.

Beneficial effect:

(1) The present invention discloses a molecular structure of a colorless and transparent aromatic polyimide film and a preparation method thereof, which is an industrial method for preparing a colorless and transparent aromatic polyimide film, and the product has excellent comprehensive performance;

(2) The reaction conditions of the synthetic resin solution are mild, the operation is simple, the reaction process is carried out under normal pressure, does not involve and does not produce corrosive substances, has no special requirements for equipment, and has less investment, which is conducive to reducing production costs;

(3) There are few types of organic solvents, and they are easy to recycle, can be recycled repeatedly, have less waste, and are environmentally friendly;

(4) The molecular weight of the resin is easy to control, and the molecular structure is also easy to adjust, which is conducive to the preparation of polyimide products with ideal properties;

(5) The resulting polyimide product has excellent dimensional stability, low water absorption and excellent electrical properties, mechanical properties and heat resistance;

(6) The source of reaction raw materials for synthesizing polyimide resin is convenient, the cost is low, and it is convenient for further popularization and application.

(7) used resin synthesis process equipment and film-forming equipment are all general-purpose, can utilize the existing complete set of equipment for producing polyimide film to implement the present invention, be very conducive to the industrialization of product;

Description of drawings

Figure 1 is the general molecular structure formula of colorless and transparent aromatic polyimide film.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

440.5 grams (1.0 moles) of 2,2-bis[4-(2,4-diaminophenoxy)phenyl]propane and 23200 milliliters of N,N-dimethylacetamide were added to the reaction kettle, at room temperature Stir and dissolve completely, cool in an ice-water bath to 0°C, add 440.0 grams (2.0 moles) of tetrafluorophthalic anhydride, stir and react within the temperature range of 0°C-35°C, and continue to react for 0.5 hours after a homogeneous solution is formed , add 400.0 grams (1.0 moles) of 4,4'-bis(4-aminophenoxy) diphenyl sulfide, stir, after completely dissolving, cool to 0°C in an ice-water bath, add 1040.0 grams (2.0 moles) of 2, 2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride was stirred in the temperature range of 0°C-35°C, and after it was completely dissolved, the reaction was maintained for 5 hours to obtain a colorless and transparent homogeneous Viscous solution, filter, remove mechanical impurities, adjust viscosity, cast on a casting machine to form a film with a predetermined thickness, devolatilize in the temperature range of 80°C-150°C, remove most of the organic solvent (recycling can be reused) And carry out partial imidization reaction, demoulding, stretching, enter the imidization sintering furnace, the furnace temperature is 150°C-350°C, and wind up to obtain a colorless, transparent and tough polyimide film with a glass transition temperature of At 212°C, the tensile strength is 130 MPa, and has obvious infrared characteristic absorption peaks of imine structure (1720.12cm ^-1 , 1742.32cm ^-1 ), and no infrared characteristic absorption peaks of anhydride groups, carboxyl groups, and primary amino groups. The molecular structure is as follows:

Example 2

54.8 grams (0.1 mol) of 2,2-bis[4-(2,4-diaminophenoxy)phenyl]hexafluoropropane and 500 milliliters of N,N-dimethylformamide and 3000 milliliters of N- Add methyl-2-pyrrolidone into the reaction kettle, stir at room temperature, after completely dissolving, cool in an ice-water bath to 0°C, add 22.0 grams (0.1 moles) of tetrafluorophthalic anhydride and 14.8 grams (0.1 moles) of phthalic anhydride Formic anhydride, stirred and reacted within the temperature range of 0°C-35°C. After a homogeneous solution was formed, the reaction was continued for 2 hours, and 29.2 grams (0.1 moles) of 1,3-bis(4-aminophenoxy)benzene, 385.2 grams of (0.9 mol) 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, stirring, after completely dissolving, cooling to 0°C in an ice-water bath, adding 628.0 g (1.0 mol) 2,2- Bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride and 31.0 grams (0.1 moles) of 3,3',4,4'-tetracarboxylic acid diphenyl ether dianhydride powder, in Stir in the temperature range of 0°C-35°C. After completely dissolving, keep the reaction for 1 hour to obtain a colorless and transparent homogeneous viscous solution. Filter it to remove mechanical impurities, adjust the viscosity, and cast it on a casting machine to form a film with a predetermined thickness. The film is devolatilized in the temperature range of 80°C-150°C, most of the organic solvents are removed (recycled and reused) and part of the imidization reaction is carried out, the film is stripped, stretched, and the imidization sintering furnace is carried out at a temperature of 150 ℃-350℃, roll up, and obtain a colorless, transparent and tough polyimide film with a glass transition temperature of 235℃, a tensile strength of 110MPa, and an obvious infrared characteristic absorption peak of imide structure (1722.51cm ^{- 1} , 1745.32cm ^-1 ), there are no infrared characteristic absorption peaks of anhydride group, carboxyl group, and primary amino group, and its molecular structure is as follows:

Example 3

440.5 grams (1.0 moles) of 2,2-bis[4-(2,4-diaminophenoxy)phenyl]propane and 6000 milliliters of N,N-dimethylacetamide were added to the reaction kettle, at room temperature Stir and dissolve completely, cool in an ice-water bath to 0°C, add 440.0 grams (2.0 moles) of tetrafluorophthalic anhydride, stir and react within the temperature range of 0°C-35°C, and continue to react for 0.5 hours after a homogeneous solution is formed , to get A component.

54.8 grams (0.1 moles) of 2,2-bis[4-(2,4-diaminophenoxy)phenyl]hexafluoropropane and 4000 milliliters of N,N-dimethylacetamide were added to the reactor, Stir at room temperature, after completely dissolving, cool in an ice-water bath to 0°C, add 16.6 grams (0.1 mole) of 4-fluorophthalic anhydride and 14.8 grams (0.1 mole) of phthalic anhydride, at a temperature of 0°C-35°C The reaction was stirred within a certain range, and after a homogeneous solution was obtained, the reaction was continued for 0.5 hours to obtain component B.

After mixing components A and B evenly, add 200.0 grams (0.5 moles) of 4,4'-bis(4-aminophenoxy) diphenyl sulfide, 54.7 grams (0.1 moles) of 2,2-bis [4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane and 42.8 grams (0.1 moles) of 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene , stir, after completely dissolving, ice-water bath is cooled to 0 ℃, adds 624.0 grams (1.2 mole) 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride and 186.0 grams ( 0.6 mol) 3,3′,4,4′-tetracarboxylic diphenyl ether dianhydride powder, stirred in the temperature range of 0°C-35°C, after completely dissolving, the reaction was maintained for 3 hours to obtain a colorless and transparent homogeneous viscous Thick solution, filter, remove mechanical impurities, adjust viscosity, cast on a casting machine to form a film with a predetermined thickness, devolatilize in the temperature range of 80°C-150°C, remove most of the organic solvent (recycling can be reused) and carry out Partial imidization reaction, demoulding, stretching, into the imidization sintering furnace, the furnace temperature is 150 ℃ -350 ℃, winding, to obtain a colorless, transparent and tough polyimide film, the tensile strength is 100MPa, its The molecular structure is as follows:

Example 4

43.1 grams (0.1 mole) of 4,4'-bis(2,4-diaminophenoxy) diphenyl sulfide and 8500 milliliters of N-methyl-2-pyrrolidone were added to the reaction kettle, stirred at room temperature, completely After dissolving, cool in an ice-water bath to 0°C, add 44.0 grams (0.2 moles) of tetrafluorophthalic anhydride, stir and react within the temperature range of 0°C-35°C, after a homogeneous solution, continue the reaction for 1 hour, add 200.0 gram (0.5 mol) of 4,4'-bis(4-aminophenoxy)diphenyl sulfide, stirred, after completely dissolving, cooled to 0°C in an ice-water bath, added 780.0 gram (1.5 mol) of 2,2-bis [4-(3,4-Dicarboxyphenoxy)phenyl]propane dianhydride powder, stirred in the temperature range of 0°C-35°C, after completely dissolving, keep the reaction for 2 hours to obtain a colorless and transparent homogeneous viscous Thick solution, filter, remove mechanical impurities, adjust viscosity, cast on a casting machine to form a film with a predetermined thickness, devolatilize in the temperature range of 80°C-150°C, remove most of the organic solvent (recycling can be reused) and carry out Partial imidization reaction, demoulding, stretching, into the imidization sintering furnace, the furnace temperature is 150°C-350°C, and winding, to obtain a colorless, transparent and tough polyimide film with a tensile strength of 85MPa. The molecular structure is as follows:

Claims (9)

1. A colorless and transparent aromatic polyimide film, the general formula of molecular structure is:

in,

Wherein, p is an integer not less than 1; q is an integer not less than 0, and p and q are independent and uncorrelated with each other. 2. A kind of colorless transparent aromatic polyimide film according to claim 1, is characterized in that: described molecular structure relates to any one in following structure:

3. A preparation method for a colorless and transparent aromatic polyimide film, comprising: Using aromatic primary amines and aromatic anhydrides, in a strong polar aprotic organic solvent system, polymerize at a temperature range of 0°C-35°C to obtain a colorless and transparent homogeneous viscous polyamic acid solution; Adjust viscosity, cast film, heat up, remove solvent, and at the same time, partial imidization reaction occurs, film release stretching, further deep thermal imidization, winding, to obtain colorless and transparent aromatic polyimide film; The aromatic primary amines are aromatic quadrature primary amines and aromatic dibasic primary amines; Among them, the aromatic quaternary primary amine is selected from 2,2-bis[4-(2,4-diaminophenoxy)phenyl]propane, 2,2-bis[4-(2,4-diaminobenzene One or more of oxy)phenyl]hexafluoropropane, 4,4'-bis(2,4-diaminophenoxy)diphenyl sulfide; Aromatic dibasic primary amines are selected from 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4-aminophenoxy) Benzene, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl] Oxy)phenyl]hexafluoropropane, 2,5-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,5-bis(2-trifluoromethyl-4-aminophenoxy Base) tert-butylbenzene, 2,5-di-tert-butyl-1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 4,4'-bis(2-trifluoromethane Base-4-aminophenoxy)diphenylsulfone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)-3,3'5,5'-tetramethyldiphenylsulfone , 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)-3,3 '5,5'-tetramethylbiphenyl, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether, 4,4'-bis(4-aminophenoxy ) diphenyl ether, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [4-(4-Diaminophenoxy)phenyl]hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 , one or more of 4-bis(4-aminophenoxy)benzene, wherein the molar ratio of aromatic dibasic primary amines to aromatic quaternary primary amines is 1:0.1-10; The aromatic acid anhydrides are aromatic monoanhydrides and aromatic dianhydrides. 4. the preparation method of colorless transparent aromatic polyimide film according to claim 3 is characterized in that: described aromatic monoanhydride is selected from phthalic anhydride, 4-fluorophthalic anhydride One or more of acid anhydrides and tetrafluorophthalic anhydrides, wherein the molar ratio of aromatic monoanhydrides to aromatic quaternary primary amines is 2:1. 5. the preparation method of colorless transparent aromatic polyimide film according to claim 3 is characterized in that: described aromatic dianhydride is selected from 2,2-bis(3,4-dicarboxyphenyl ) hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy base) phenyl] hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy base) diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyldianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, One or more of 3,3',4,4'-tetracarboxy diphenyl ether dianhydrides, wherein the number of moles of aromatic dianhydrides is equal to the number of moles of aromatic quaternary primary amines and aromatic binary primary amines Sum. 6. the preparation method of colorless transparent aromatic polyimide film according to claim 3 is characterized in that: described strongly polar aprotic organic solvent is selected from N, N-dimethylformamide, N , one or more of N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and dimethyl sulfoxide. 7. the preparation method of colorless transparent aromatic polyimide film according to claim 3 is characterized in that: the volume-to-weight ratio of described highly polar aprotic organic solvent and total reactant is 3 milliliters～10 Milliliter: 1 gram, wherein the weight of the total reactants refers to the sum of the weight of aromatic quaternary primary amine, aromatic dibasic primary amine, aromatic monoanhydride and aromatic dianhydride. 8. The method for preparing a colorless and transparent aromatic polyimide film according to claim 3, characterized in that: the reaction temperature of the monoanhydride and the aromatic quaternary primary amine is 0° C. to 35° C. The time is 0.5 hours to 2 hours. 9. The method for preparing a colorless and transparent aromatic polyimide film according to claim 3, characterized in that: the reaction temperature of the aromatic dianhydride and the aromatic primary amine is 0° C. to 35° C. The time is 1 hour to 5 hours.

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