CN101392059A - Colorless transparent aromatic polyimide film and preparation method thereof - Google Patents
Colorless transparent aromatic polyimide film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a colorless and transparent aromatic polyimide film which has the general formula of molecular structure as follows; the preparation thereof includes: aromatic primary amine and aromatic acid anhydride with specific molecular structures are adopted for polymerization in a strong polar aprotic organic solvent system within the temperature range of 0 DEG C to 35 DEG C to prepare a colorless and transparent viscous polyamide acid solution with homogeneous phase. Viscosity adjustment, casting for forming the film, heating for rising temperature and solvent removal are carried out simultaneously when partial imidization reaction is carried out, and then demoulding and stretching, further deep thermal imidization and rolling are carried out to obtain the colorless and transparent aromatic polyimide film. No special production equipment is required by the invention so that production can be carried out on the conventional production line of the polyimide film and the polyimide film is applicable to industrialized production.
Description
Technical field
The present invention relates to the preparation method of water white transparency organic polymer thin film, particularly relate to a kind of colorless transparent aromatic polyimide film and preparation method thereof.
Background technology
Polyimide is the very excellent polymkeric substance of a class over-all properties, has very good thermotolerance, lower temperature resistance, solvent resistance, self lubricity and characteristic such as fire-retardant, simultaneously, also has very excellent mechanical property and dielectric properties.Therefore, it is widely used in photovoltaic material, nonlinear optical material; The high temperature material of spaceship, satellite or space craft etc.; The advanced configuration matrix material of aspects such as aerospace, automobile, electromechanics, C level or 200 higher level insulating materials, high-temperature resistance adhesive etc.; And interlayer dielectic, super large-scale integration passivating coating and the alpha-particle blocking layer coating material etc. of the body material of the FPC of electronics microelectronic or PCB, IC.
Japanese Patent JP H05-0175175A discloses molecular structure of transparent polyimide and preparation method thereof, be primarily characterized in that: 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride and multiple ether type diamine reactant obtain fluorine-containing polyamic acid, obtain water white polyimide by chemical imidization or hot imidization subsequently.
(Synthesis and Characterization of Colorless Polyimide NanocompositeFilms such as Chul Ha Ju, Journal of Applied Polymer Science, 2007,106:4192-4201) preparation method of colorless polyimide nano hybridization composite membrane is disclosed, be primarily characterized in that: 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride and 2,2 '-two (trifluoromethyl) benzidine reaction makes precursor polymer, with inorganic (as mica etc.) nano particle hybridization, make colorless polyimide nano hybridization composite membrane again.
Molecular structure of colorless transparent aromatic polyimide film disclosed in this invention and preparation method thereof is not seen disclosed document or patent report as yet.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of colorless transparent aromatic polyimide film, this method technology is simple, cost is low, environmental friendliness, can finish preparation process in general-purpose equipment, is applicable to industrial production.
Chemical equation of the present invention is as follows:
Wherein, p is no less than 1 integer; Q is not less than 0 integer, and p, q are separate, and be uncorrelated mutually;
A kind of colorless transparent aromatic polyimide film, general formula of molecular structure are shown in Figure 1, and wherein p is no less than 1 integer; Q is not less than 0 integer, and p, q are separate, and be uncorrelated mutually.Particularly relate to following molecular structure:
A kind of preparation method of colorless transparent aromatic polyimide film comprises:
Adopt the primary aromatic amine and the aromatic anhydride of specific molecular structure, in strong polar non-proton organic solvent system, in 0 ℃ of-35 ℃ of temperature range, carry out polyreaction, make the thick polyamic acid solution of water white homogeneous phase; Regulate viscosity, casting film-forming, heat temperature raising removes solvent, and the part imidization takes place simultaneously, and demoulding stretches, further degree of depth hot imidization, rolling obtains colorless transparent aromatic polyimide film.
The primary aromatic amine of described specific molecular structure is aromatic series quaternary primary amine and aromatic dicarboxylic primary amine.
The aromatic series quaternary primary amine of described specific molecular structure is selected from 2, two [4-(2, the 4-diamino phenoxy) phenyl] propane, 2 of 2-, 2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa, 4,4 '-in two (2, the 4-diamino phenoxy) diphenyl sulfide one or more.
The aromatic dicarboxylic primary amine of described ad hoc structure is selected from 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-diamino phenoxy) phenyl] HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, in two (4-amino-benzene oxygen) benzene of 4-one or more, wherein the aromatic dicarboxylic primary amine is 1:0.1～10 with the ratio of the mole number of aromatic series quaternary primary amine.
Described aromatic anhydride is aromatic series list acid anhydride and aromatic series dianhydride.
Described aromatic series list acid anhydride be selected from Tetra hydro Phthalic anhydride, 4-fluoro Tetra hydro Phthalic anhydride, tetrafluoro in the Tetra hydro Phthalic anhydride one or more, wherein aromatic series list acid anhydride is 2:1 with the ratio of the mole number of the aromatic series quaternary primary amine of specific molecular structure.
Described aromatic series dianhydride is selected from 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 3,3 ', 4,4 '-in the tetracarboxylic phenyl ether dianhydride one or more, wherein the mole number of aromatic series dianhydride equals the mole number sum of the aromatic series quaternary primary amine and the aromatic dicarboxylic primary amine of specific molecular structure.
Described strong polar non-proton organic solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO).
The envelope-bulk to weight ratio of described strong polar non-proton organic solvent and total reactant is 3 milliliters～10 milliliters: 1 gram, wherein the weight of total reactant is meant the weight sum of aromatic series quaternary primary amine, aromatic dicarboxylic primary amine, aromatic series list acid anhydride and the aromatic series dianhydride of specific molecular structure.
The temperature of reaction of the aromatic series quaternary primary amine of described single acid anhydride and specific molecular structure is 0 ℃～35 ℃, and the reaction times is 0.5 hour～2 hours.
The temperature of reaction of described aromatic dicarboxylic acid anhydride and primary aromatic amine is 0 ℃～35 ℃, and the reaction times is 1 hour～5 hours.
Beneficial effect:
(1) the invention discloses the molecular structure and preparation method thereof of colorless transparent aromatic polyimide film, it is the commercial run of preparation colorless transparent aromatic polyimide film, and the The comprehensive performance excellence;
(2) the reaction conditions gentleness of synthetic resin solution is simple to operate, and reaction process is carried out under normal pressure, does not relate to also not producing corrosives, and equipment is not had particular requirement, and less investment helps reducing production costs;
(3) organic solvent uses kind few, and reclaims conveniently, Recycling repeatedly, and the three wastes are few, and are environmentally friendly;
(4) molecular weight of resin is controlled easily, and molecular structure is also adjusted easily, helps preparing the polyimide product of ideal performance;
(5) gained polyimide product has excellent size stability, low water-intake rate and excellent electric property, mechanical property and thermotolerance;
(6) the reaction raw materials convenient sources of synthesis of polyimides resin, cost is lower, is convenient to further apply.
(7) used synthetic technology of resins equipment and film-forming apparatus are universal, can utilize the suite of equipment of existing production Kapton to implement the present invention fully, are very beneficial for the industrialization of product;
Description of drawings
Fig. 1 is the general formula of molecular structure of colorless transparent aromatic polyimide film.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 2 of 440.5 grams (1.0 moles), 2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane and 23200 milliliters of N, the N-N,N-DIMETHYLACETAMIDE adds in the reactor, stir under the room temperature, fully after the dissolving, ice-water bath is cooled to 0 ℃, add 440.0 gram (2.0 moles) ptfe phthalic anhydrides, stirring reaction in 0 ℃ of-35 ℃ of temperature range, after being homogeneous phase solution, continue reaction 0.5 hour, 4,4 of adding 400.0 grams (1.0 moles) '-two (4-amino-benzene oxygen) diphenyl sulfide, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, adds 1040.0 gram (2.0 moles) 2, and 2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, in 0 ℃ of-35 ℃ of temperature range, stir, after the dissolving, keep reaction 5 hours fully, obtain the thick solution of water white homogeneous phase, filter, remove mechanical impurity, regulate viscosity, curtain coating becomes the film of pre-determined thickness on casting machine, devolatilization in 80 ℃ of-150 ℃ of temperature ranges is removed most of organic solvent (reclaiming recycling) and is carried out part imidization, demoulding, stretch, advance the imidization sintering oven, furnace temperature is 150 ℃-350 ℃, rolling, obtain the tough and tensile Kapton of water white transparency, second-order transition temperature is 212 ℃, and tensile strength is 130MPa, and has the infrared signature absorption peak (1720.12cm of tangible imine structure
-1, 1742.32cm
-1), the infrared signature absorption peak of acid anhydride base, carboxyl, primary amine groups does not appear, and its molecular structure is as follows:
Embodiment 2
With 2 of 54.8 grams (0.1 mole), 2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa and 500 milliliters of N, dinethylformamide and 3000 milliliters of N-N-methyl-2-2-pyrrolidone N-s add in the reactor, stir under the room temperature, fully after the dissolving, ice-water bath is cooled to 0 ℃, add 22.0 gram (0.1 mole) ptfe phthalic anhydrides and 14.8 gram (0.1 mole) Tetra hydro Phthalic anhydrides, stirring reaction in 0 ℃ of-35 ℃ of temperature range, after being homogeneous phase solution, continue reaction 2 hours, add 29.2 gram (0.1 moles) 1, two (4-amino-benzene oxygen) benzene of 3-, 385.2 gram (0.9 mole) 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, add 628.0 gram (1.0 moles) 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride and 31.0 the gram (0.1 moles) 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride powder, in 0 ℃ of-35 ℃ of temperature range, stir, after the dissolving, keep reaction 1 hour fully, obtain the thick solution of water white homogeneous phase, filter, remove mechanical impurity, regulate viscosity, curtain coating becomes the film of pre-determined thickness on casting machine, devolatilization in 80 ℃ of-150 ℃ of temperature ranges is removed most of organic solvent (reclaiming recycling) and is carried out part imidization, demoulding, stretch, advance the imidization sintering oven, furnace temperature is 150 ℃-350 ℃, rolling, obtain the tough and tensile Kapton of water white transparency, second-order transition temperature is 235 ℃, and tensile strength is 110MPa, and has the infrared signature absorption peak (1722.51cm of tangible imine structure
-1, 1745.32cm
-1), the infrared signature absorption peak of acid anhydride base, carboxyl, primary amine groups does not appear, and its molecular structure is as follows:
Embodiment 3
With 2 of 440.5 grams (1.0 moles), two [4-(2, the 4-diamino phenoxy) phenyl] propane of 2-and 6000 milliliters of N,N-dimethylacetamide add in the reactor, stir under the room temperature, after the dissolving, ice-water bath is cooled to 0 ℃ fully, adds 440.0 gram (2.0 moles) ptfe phthalic anhydrides, stirring reaction in 0 ℃ of-35 ℃ of temperature range, after being homogeneous phase solution, continue reaction 0.5 hour, get the A component.
With 2 of 54.8 grams (0.1 mole), two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2-and 4000 milliliters of N,N-dimethylacetamide add in the reactor, stir under the room temperature, after the dissolving, ice-water bath is cooled to 0 ℃ fully, adds 16.6 gram (0.1 mole) 4-difluorophthalic anhydrides and 14.8 gram (0.1 mole) Tetra hydro Phthalic anhydrides, stirring reaction in 0 ℃ of-35 ℃ of temperature range, after being homogeneous phase solution, continue reaction 0.5 hour, get the B component.
After A component and B component mixed, add 4 of 200.0 grams (0.5 mole), 4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 54.7 gram (0.1 mole) 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-and 42.8 gram (0.1 moles) 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, add 624.0 gram (1.2 moles) 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydrides of 2-and 186.0 gram (0.6 moles) 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride powder, in 0 ℃ of-35 ℃ of temperature range, stir, fully after the dissolving, keep reaction 3 hours, obtain the thick solution of water white homogeneous phase, filter, remove mechanical impurity, regulate viscosity, curtain coating becomes the film of pre-determined thickness on casting machine, and devolatilization in 80 ℃ of-150 ℃ of temperature ranges is removed most of organic solvent (reclaiming recycling) and carried out the part imidization, demoulding, stretch, advance the imidization sintering oven, furnace temperature is 150 ℃-350 ℃, rolling, obtain the tough and tensile Kapton of water white transparency, tensile strength is 100MPa, and its molecular structure is as follows:
Embodiment 4
With 4 of 43.1 grams (0.1 mole), 4 '-two (2, the 4-diamino phenoxy) diphenyl sulfide and 8500 milliliters of N-N-methyl-2-2-pyrrolidone N-s add in the reactor, stir under the room temperature, fully after the dissolving, ice-water bath is cooled to 0 ℃, add 44.0 gram (0.2 mole) ptfe phthalic anhydrides, stirring reaction in 0 ℃ of-35 ℃ of temperature range, after being homogeneous phase solution, continue reaction 1 hour, add 4 of 200.0 grams (0.5 mole), 4 '-two (4-amino-benzene oxygen) diphenyl sulfide, stir, after the dissolving, ice-water bath is cooled to 0 ℃ fully, adds 780.0 gram (1.5 moles) 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride powder, stir in 0 ℃ of-35 ℃ of temperature range, fully after the dissolving, keep reaction 2 hours, obtain the thick solution of water white homogeneous phase, filter, remove mechanical impurity, regulate viscosity, curtain coating becomes the film of pre-determined thickness on casting machine, and devolatilization in 80 ℃ of-150 ℃ of temperature ranges is removed most of organic solvent (reclaiming recycling) and carried out the part imidization, demoulding, stretch, advance the imidization sintering oven, furnace temperature is 150 ℃-350 ℃, rolling, obtain the tough and tensile Kapton of water white transparency, tensile strength is 85MPa, and its molecular structure is as follows:
Claims (12)
1. colorless transparent aromatic polyimide film, general formula of molecular structure is:
Wherein p is no less than 1 integer; Q is not less than 0 integer, and p, q are separate, and be uncorrelated mutually.Particularly relate to following molecular structure:
2. the preparation method of a colorless transparent aromatic polyimide film comprises:
Adopt the primary aromatic amine and the aromatic anhydride of specific molecular structure, in strong polar non-proton organic solvent system, in 0 ℃ of-35 ℃ of temperature range, carry out polyreaction, make the thick polyamic acid solution of water white homogeneous phase; Regulate viscosity, casting film-forming, heat temperature raising removes solvent, and the part imidization takes place simultaneously, and demoulding stretches, further degree of depth hot imidization, rolling obtains colorless transparent aromatic polyimide film.
3. the preparation method of colorless transparent aromatic polyimide film according to claim 2, it is characterized in that: the primary aromatic amine of described specific molecular structure is aromatic series quaternary primary amine and aromatic dicarboxylic primary amine.
4. the preparation method of colorless transparent aromatic polyimide film according to claim 3, it is characterized in that: the aromatic series quaternary primary amine of described specific molecular structure is selected from 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa, 4,4 '-in two (2, the 4-diamino phenoxy) diphenyl sulfide one or more.
5. the preparation method of colorless transparent aromatic polyimide film according to claim 3, it is characterized in that, the aromatic dicarboxylic primary amine of described ad hoc structure is selected from 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-diamino phenoxy) phenyl] HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, in two (4-amino-benzene oxygen) benzene of 4-one or more, wherein the aromatic dicarboxylic primary amine is 1:0.1～10 with the ratio of the mole number of aromatic series quaternary primary amine.
6. the preparation method of colorless transparent aromatic polyimide film according to claim 2, it is characterized in that: described aromatic anhydride is aromatic series list acid anhydride and aromatic series dianhydride.
7. the preparation method of colorless transparent aromatic polyimide film according to claim 6, it is characterized in that: described aromatic series list acid anhydride be selected from Tetra hydro Phthalic anhydride, 4-fluoro Tetra hydro Phthalic anhydride, tetrafluoro in the Tetra hydro Phthalic anhydride one or more, wherein aromatic series list acid anhydride is 2:1 with the ratio of the mole number of the aromatic series quaternary primary amine of specific molecular structure.
8. the preparation method of colorless transparent aromatic polyimide film according to claim 6, it is characterized in that: described aromatic series dianhydride is selected from 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 2-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 4-, 3,3 ', 4,4 '-in the tetracarboxylic phenyl ether dianhydride one or more, wherein the mole number of aromatic series dianhydride equals the mole number sum of the aromatic series quaternary primary amine and the aromatic dicarboxylic primary amine of specific molecular structure.
9. the preparation method of colorless transparent aromatic polyimide film according to claim 2, it is characterized in that: described strong polar non-proton organic solvent is selected from N, in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO) one or more.
10. the preparation method of colorless transparent aromatic polyimide film according to claim 2, it is characterized in that: the envelope-bulk to weight ratio of described strong polar non-proton organic solvent and total reactant is 3 milliliters～10 milliliters: 1 gram, wherein the weight of total reactant is meant the weight sum of aromatic series quaternary primary amine, aromatic dicarboxylic primary amine, aromatic series list acid anhydride and the aromatic series dianhydride of specific molecular structure.
11. preparation method according to claim 2 or 7 described colorless transparent aromatic polyimide films, it is characterized in that: the temperature of reaction of the aromatic series quaternary primary amine of described single acid anhydride and specific molecular structure is 0 ℃～35 ℃, and the reaction times is 0.5 hour～2 hours.
12. the preparation method of colorless transparent aromatic polyimide film according to claim 2 is characterized in that: the temperature of reaction of described aromatic dicarboxylic acid anhydride and primary aromatic amine is 0 ℃～35 ℃, and the reaction times is 1 hour～5 hours.
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