CN100336849C - Preparation method of polyimide siloxanel polyimide two face different property composite film - Google Patents
Preparation method of polyimide siloxanel polyimide two face different property composite film Download PDFInfo
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Abstract
The present invention belongs to the field of high molecular materials, and particularly relates to a novel perparation method for polyimide siloxane/polyimide double-face isomerism complex films. The method comprises: preparing polyamic acid siloxane prepolymer; preparing polyamic acid prepolymer; preparing the polyimide siloxane / polyimide double-face isomerism complex films. The present invention utilizes synthetic polyamic acid siloxane and polyamic acid as raw materials, and utilizes tetrahydrofuran, N, N-dimethyl formamide, N, N-dimethyl acetamide or N-methyl pyrrolidone as a component solvent. PDMS chain segment parts move to the upper surfaces of the films in the process of volatilizing the solvent when low-boiling THF volatilizes under low temperature. The complex films prepared by the present invention use block copolymer and pure PI making films, have good compatibility, and eliminate interface effect. When the complex films change surface properties, the main body property of polyimide is maintained well.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of preparation method of novel Polyimidesiloxane/polyimide double-sided anisotropic composite membrane.
Background technology
Polyimide (PI) is widely used in numerous areas such as machinery, electronics, aviation owing to having excellent thermostability, electrical insulating property, physical and mechanical properties and chemical stability etc.But insoluble, infusibility that its rigid structure has caused, character such as higher water absorbability and high surface energy have limited its application at electric insulation lacquer, buffering coating, interlayer packaged material etc.
Characteristics such as yet silicone resin has good solvability, and low water absorption hangs down dielectric constant, and cohesiveness is good.Because the needs of electronics, electrical equipment industry development, for example be used for the materials such as substrate that insulation film, passive film and printed IC use and all require to have higher cohesiveness, resistant of high or low temperature and wet fastness etc., the scientific research personnel synthesizes siliceous polyimide resin by methods such as copolymerization, blending, combine both characteristics, to satisfy the needs in market.The surface properties of siliceous polyimide resin has obtained extensive studies, in homopolymer, add the blend material that a spot of polydimethylsiloxane (PDMS) just can obtain low surface energy, but owing to both have caused phenomenon of phase separation in qualitative difference.Therefore, investigators have designed the segmented copolymer of a kind of polyimide/polydimethylsiloxane (PDMS), PDMS is easy to form surface enrichment in this segmented copolymer, this is because PDMS has low-down surface energy, PDMS is to the surface transport of material when having caused in many polymeric systems material cured, form the surface enrichment layer of PDMS, and do not changed the character of body of material.But in aviation field was used, the linear expansivity of this segmented copolymer and other material differed big and has caused that the contraction of storeroom causes peeling off phenomenon.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of novel Polyimidesiloxane/polyimide double-sided anisotropic composite membrane, it simultaneously is a polyimide-silicone block copolymer, and one side is a polyimide.
Utilized polyimide/polydimethylsiloxaneblock block copolymers and pure polyimide (PI) system film in this composite membrane, eliminated interfacial effect thereby have better consistency.In addition, a large amount of polyimide resin composition that exists in a small amount of polydimethylsiloxane composition that exists in the composite membrane surface and the main body makes the main nature of composite membrane its polyimide when changing surface properties obtain better maintenance.
The preparation method of Polyimidesiloxane involved in the present invention/polyimide double-sided anisotropic composite membrane comprises following three steps: aggressiveness is synthetic before the polyimide-silicone block copolymer, polyamic acid prepolymer synthetic, the preparation of Polyimidesiloxane/polyimide composite film.
(1) aggressiveness before the preparation polyimide-silicone block copolymer
Aggressiveness is with dianhydride promptly 3 before the polyimide-silicone block copolymer, 4,3 ', 4 '-BPDA (s-BPDA), 2,3 ', 3,4 '-BPDA (a-BPDA), 2,2 ', 3,3 '-BPDA (i-BPDA), phenyl ether tetracarboxylic dianhydride (ODPA) or pyromellitic acid dianhydride (PMDA); Diamines is 4,4 '-diamines yl diphenyl ether (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 3,3 '-diaminodiphenyl oxide (3,3 '-ODA) or 1,4 ,-(3-amino-benzene oxygen) benzene (1,4,3-APB), it is raw material that the present invention adopts the end capped polydimethylsiloxane of aminopropyl, with N, N-N,N-DIMETHYLACETAMIDE (DMAc), N, dinethylformamide (DMF) or N-Methyl pyrrolidone (NMP) are the solvent synthetic.
The structural formula of dianhydride monomer involved in the present invention is as follows:
The structural formula of diamine monomer involved in the present invention is as follows:
The structural formula of the end capped polydimethylsiloxane of aminopropyl involved in the present invention is as follows:
PDMS p＝1，2，3，4，5，6，9
M
w＝252，334，406，475，550，600，813g/mol
The concrete preparation technology of composite membrane of the present invention is: under magnetic agitation, taking by weighing diamines is dissolved in N is housed, N-N,N-DIMETHYLACETAMIDE (DMAc), N, in the beaker of dinethylformamide (DMF) or N-Methyl pyrrolidone (NMP), slowly add dianhydride, adding finishes, under agitation condition room temperature reaction 0.5-3 hour; Add the end capped polydimethylsiloxane of aminopropyl again, add reaction 4-10 hour that finishes (experimental result shows 6 hours better), obtain the preceding aggressiveness of polyimide-silicone block copolymer in our design, wherein the mol ratio of dianhydride, diamines and the end capped polydimethylsiloxane of aminopropyl is 2: 1: 1, solid content in the solvent is 8-20%, the quality of solute in solid content=solvent/(quality of the quality+solvent of solute) %.
The end capped polydimethylsiloxane of aminopropyl that is suitable in the above-mentioned steps can have different polymerization degree p=1,2,3,4,5,6,9, and corresponding molecular-weight average is respectively M
w=252,334,406,475,550,600,813g/mol.
Below only with 3,4,3 ', 4 '-BPDA (s-BPDA), 4,4 '-diamines yl diphenyl ether (4,4 '-ODA) for example to polyimide-silicone block copolymer of the present invention before the preparation method of aggressiveness describe, rather than limitation of the invention, its building-up reactions formula is as follows:
(2) preparation polyamic acid prepolymer
The polyamic acid prepolymer is with dianhydride promptly 3,4,3 ', 4 '-BPDA (s-BPDA), 2,3 ', 3,4 '-BPDA (a-BPDA), 2,2 ', 3,3 '-BPDA (i-BPDA), phenyl ether tetracarboxylic dianhydride (ODPA) or pyromellitic acid dianhydride (PMDA), diamines are 4,4 '-diamines yl diphenyl ether (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 3,3 '-diaminodiphenyl oxide (3,3 '-ODA) or 1,4 ,-(3-amino-benzene oxygen) benzene (1,4,3-APB) be raw material, with N,N-dimethylacetamide (DMAc), N, dinethylformamide (DMF) or N-Methyl pyrrolidone (NMP) are the solvent synthetic.
Concrete preparation technology comprises: under magnetic agitation, take by weighing diamines and be dissolved in N,N-dimethylacetamide (DMAc), N are housed, in the beaker of dinethylformamide (DMF) or N-Methyl pyrrolidone (NMP), after treating that diamines dissolves fully, in beaker, slowly add dianhydride; Under whipped state, room temperature reaction 2-6 hour (experimental result shows 4 hours better), obtain the polyamic acid prepolymer, wherein the mol ratio of dianhydride and diamines is 1: 1, the concentration of solute is 10-40g/ml in the solvent.
Below only with 3,4,3 ', 4 '-BPDA, 4, to be example describe the preparation method of polyamic acid prepolymer of the present invention 4 '-diaminodiphenyl oxide, rather than limitation of the invention, shown in the following reaction formula of its synthetic route:
(3) preparation of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane
The synthetic method of Polyimidesiloxane among the present invention/polyimide double-sided anisotropic composite membrane is as follows: with aggressiveness and polyamic acid prepolymer before the aforesaid method synthetic polyimide-silicone block copolymer is raw material, with tetrahydrofuran (THF) (THF) and N, N-N,N-DIMETHYLACETAMIDE (or N, dinethylformamide or N-Methyl pyrrolidone) as mixed solvent, the use of lower boiling tetrahydrofuran (THF) is because the solvability of PDMS in THF is better, the solvability of polyamic acid (PAA) in THF is then relatively poor, so the part of the PDMS segment among the PAA-PDMS better is dissolved among the THF.When subzero treatment, along with lower boiling THF volatilization, the PDMS segment part among the PAA-PDMS is along with the upper surface of solvent evaporates process migration to film, thereby prepared the composite film material of this Polyimidesiloxane/polyimide double-sided anisotropic.
Specific embodiment: the ratio that we have prepared Polyimidesiloxane/polyimide respectively is 0.2%, 0.3%, 0.5% composite membrane.
Concrete preparation process is as follows: aggressiveness before the polyimide-silicone block copolymer for preparing in the above-mentioned steps is dissolved in the tetrahydrofuran (THF), mix (N with the polyamic acid prepolymer then, the N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide or N-Methyl pyrrolidone use when preparing before polyamic acid prepolymer and the polyimide-silicone block copolymer aggressiveness in above-mentioned steps, in this step, do not need to add again this kind solvent), add aggressiveness before the polyimide-silicone block copolymer of 0.05g-0.5g in every milliliter of tetrahydrofuran (THF), the mass ratio of aggressiveness and polyamic acid prepolymer consumption is 0.001-0.01 before the polyimide-silicone block copolymer: 1, after it is mixed, casting film-forming on sheet glass (also claiming the cast film); Room temperature leaves standstill 0.5-3 hour (experimental result show 1 hour better), puts into baking oven then and ℃ handles respectively 1-5 hour (experimental result shows 3 hours better) in 35-45 ℃, 55-65; Be transferred to again in the vacuum drying oven and ℃ handle 0.5-3 hour (experimental result shows 1 hour better) respectively in 75-85 ℃, 95-105 ℃, 115-125 ℃, 145-155 ℃, 175-185 ℃, 245-255 and carry out hot imidization.After disposing, taking off film from sheet glass promptly is the composite membrane that we prepare.
The present invention has prepared the preceding aggressiveness of polyimide-silicone block copolymer, and with this segmented copolymer and the blend of polyamic acid prepolymer, in the imidization process, utilize similar mix principle and the different solubility of each component in different solvents to prepare the composite membrane of polyimide-silicone block copolymer/polyimide double-sided anisotropic, by the sign of XPS and water droplet contact angle, can prove the double-sided anisotropic of this composite membrane.And it has been carried out the research of thermal characteristics and mechanical property etc., the result has shown that this composite membrane has excellent thermal characteristics and mechanical property.Because a side surface of this composite membrane has advantages such as ageing-resistant, long lifetime, dirt-resistant self-cleaning, anti-solvent of organosilicon itself, good cohesiveness and waterproof, and the opposite side surface has heat, mechanical property and the dielectric properties etc. of polyimide excellence, has wide practical use in fields such as electronics, chemical industry.
Description of drawings
Fig. 1: be the Polyimidesiloxane/polyimide double-sided anisotropic composite membrane synoptic diagram of the present invention's preparation;
Fig. 2: the sem photograph of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane;
(A) be the scanned photograph of Polyimidesiloxane layer;
(B) be the scanned photograph of polyimide layer;
Fig. 3: the X-photoelectron spectral data of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane;
(A) the X-photoelectron spectral data of the air surface of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane;
(B) the X-photoelectron spectral data of the glass surface of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane;
Fig. 4: the thermal weight loss thetagram of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane;
As shown in Figure 1,1 is the Polyimidesiloxane layer, and 2 is polyimide layer.
Composite membrane among Fig. 2 is that the Polyimidesiloxane of the described polyamic acid prepolymer preparation of aggressiveness before the described polyimide-silicone block copolymer of embodiment 1-1, embodiment 2-1 and polyimide ratio are the scanned photograph of 0.5% double-sided anisotropic composite membrane.As shown in Figure 2, the clear existence of seeing the organosilicon particle of energy in the scanned photograph of polyimide layer does not see that in the scanned photograph of polyimide layer this particle exists.
Composite membrane among Fig. 3 is to be the X-photoelectron spectral data of 0.2% double-sided anisotropic composite membrane by the Polyimidesiloxane of aggressiveness before the described polyimide-silicone block copolymer of embodiment 1-1, the described polyamic acid prepolymer preparation of embodiment 2-1 and polyimide ratio.(A), (B) is respectively the x-ray photoelectron spectroscopy figure of the air surface and the glass surface of composite membrane.As seen from the figure: in air surface, the peak of Si is about 1425 by force, and the peak of C is about 15742 by force, and the peak of N is about 5310 by force, and the peak of O is about 16012 by force; Yet in glass surface, the peak of Si is about 1277 by force, and the peak of C is about 16912 by force, and the peak of N is about 7798 by force, and the peak of O is about 15839 by force.The peak of Si and O by force in air surface than glass surface height, yet the peak of C and N is lower than glass surface in air surface by force.This is because the surface enrichment of Polyimidesiloxane causes, and air surface shows as more high-load Si and O owing to more silicone component exists, and the content of C and N is higher and lower surface is owing to contain more polyimide composition.Thereby proved in this Polyimidesiloxane/polyimide composite film of our synthetic that the surface enrichment of Polyimidesiloxane has proved the double-sided anisotropic of this composite membrane.
Table 1 is the contact angle data of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane, and this composite membrane is to be 0%, 0.2%, 0.3%, 0.5% double-sided anisotropic composite membrane by the Polyimidesiloxane of aggressiveness before the described polyimide-silicone block copolymer of embodiment 1-1, the described polyamic acid prepolymer preparation of embodiment 2-1 and polyimide ratio.Silicone based have the good hydrophobic performance, and polyimide is good hydroaropic substance, so can characterize the distribution situation of two kinds of materials in composite membrane with the water droplet contact angle.From table 1 data as seen, pure polyimide has less water droplet contact angle, along with the increase of the add-on of Polyimidesiloxane multipolymer, the water droplet contact angle of the air surface of composite membrane increases, the water droplet contact angle of glass surface changes little.Especially when the content of Polyimidesiloxane multipolymer reaches 0.5%, the water droplet contact angle on the two sides of our synthetic composite membrane changes the most obvious.This has also illustrated in polyimide-silicone block copolymer/polyimide composite film, Polyimidesiloxane more is enriched in the upper surface (with the air contact surface) of film, its contact angle is increased, and the more composition of the lower surface of film (with the glass contact face) is a polyimide.Contact angle experiments has further proved the double-sided anisotropic of this composite membrane.
Table 1: the contact angle data of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane
| Polyimidesiloxane/ | 0％ | 0.2％ | 0.3％ | 0.5％ | |
| Contact angle | Air surface (Air side) | 73 | 92 | 93 | 100 |
| Glass surface (Glass side) | 79 | 74 | 83 | 65 | |
By above sign, proved target product---the double-sided anisotropic of Polyimidesiloxane/polyimide composite film.
Table 2 is second-order transition temperature data of measuring Polyimidesiloxane/polyimide double-sided anisotropic composite membrane by the DSC scan method.This composite membrane is to be 0%, 0.2%, 0.3%, 0.5% double-sided anisotropic composite membrane by the Polyimidesiloxane of aggressiveness before the described polyimide-silicone block copolymer of embodiment 1-1, the described polyamic acid prepolymer preparation of embodiment 2-1 and polyimide ratio.As seen, the second-order transition temperature of pure polyimide is 281 ℃, and this high glass transition is that the rigid structure owing to polyimide causes.When the content of Polyimidesiloxane multipolymer was 0.2%-0.5%, along with the increase of the content of Polyimidesiloxane multipolymer, the second-order transition temperature of its composite membrane descended gradually as can be seen, and this is that increase owing to flexible siloxane bond causes.When content was 0.5%, its second-order transition temperature was 272 ℃.The second-order transition temperature of this composite film material is compared with pure polyimide, has only descended 9 ℃, has illustrated that this composite membrane has kept the outstanding high temperature resistance of polyimide.
Table 2: the second-order transition temperature data of measuring PI-PDMS/PI double-sided anisotropic composite membrane by the DSC scan method
| Polyimidesiloxane/ | 0％ | 0.2％ | 0.3％ | 0.5％ |
| T g (℃) | 281 | 279 | 275 | 272 |
Composite membrane among Fig. 4 is to be the thermogravimetric curve figure of 0.5% double-sided anisotropic composite membrane by the Polyimidesiloxane of aggressiveness before the described polyimide-silicone block copolymer of embodiment 1-1, the described polyamic acid prepolymer preparation of embodiment 2-1 and polyimide ratio.As seen from the figure, 5% thermal weight loss temperature of pure polyimide is 579 ℃, and the carbonization conservation rate is 63%; The content of Polyimidesiloxane is that 0.5% composite membrane 5% thermal weight loss temperature is 564 ℃, and the carbonization conservation rate is respectively 61%.Its thermal weight loss temperature is compared with pure polyimide, has only descended 15 ℃, has illustrated that this composite film material has kept the good thermostability of polyimide.
Table 3 is data of the mechanical property of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane.This composite membrane is to be 0%, 0.2%, 0.3%, 0.5% double-sided anisotropic composite membrane by the Polyimidesiloxane of aggressiveness before the described polyimide-silicone block copolymer of embodiment 1-1, the described polyamic acid prepolymer preparation of embodiment 2-1 and polyimide ratio.By the data in the table as seen: its modulus remains on more than the 2.8GPa, and tensile strength is more than 123MPa, and elongation at break surpasses 17%.This composite film material is compared with pure polyimide material, its modulus does not have to change substantially, maximum breaking tenacity remains on more than the 120MPa, elongation at break has also obtained good maintenance, has illustrated that the adding of polyimide-silicone block copolymer does not have influence on the mechanical property of the original excellence of polyimide.
Table 3: the data of the mechanical property of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane
| Polyimidesiloxane/polyimide | Modulus (GPa) | Maximum breaking tenacity (MPa) | Elongation at break (%) |
| 0％ 0.2％ 0.3％ 0.5％ | 2.9 2.8 2.8 2.8 | 147 149 170 123 | 36 29 39 17 |
To sum up, by structural characterization, proved the double-sided anisotropic of this composite membrane to Polyimidesiloxane/polyimide double-sided anisotropic composite membrane.Sign by to the performance of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane has proved that Polyimidesiloxane/polyimide double-sided anisotropic composite membrane has kept the heat and the mechanical property of polyimide excellence.
Embodiment
One, the embodiment of polyamic acid prepolymer preparation:
Embodiment 1-1:
With 4 of 0.20mol (40g), 4 '-diaminodiphenyl oxide is dissolved in the beaker of the DMAc that is placed with 946mL (889g), under magnetic agitation, treat 4, after the dissolving of 4 '-diaminodiphenyl oxide finishes, slowly add 0.20mol (58.8g) 3,4,3 ', 4 '-BPDA, adding finishes, in confined conditions, reaction is 4 hours under the magnetic agitation, and the solid content that promptly obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 1.
Embodiment 1-2:
Identical with the step of embodiment 1-1, just dianhydride monomer is changed to 0.20mol (58.8g) 2,3 ', 3,4 '-BPDA, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 2.
Embodiment 1-3:
Identical with the step of embodiment 1-1, just dianhydride monomer is changed to 0.20mol (58.8g) 2,2 ', 3,3 '-BPDA, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 3.
Embodiment 1-4:
Identical with the step of embodiment 1-1, just dianhydride monomer is changed to 0.20mol (62g) phenyl ether tetracarboxylic dianhydride, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 4.
Embodiment 1-5:
Identical with the step of embodiment 1-1, just dianhydride monomer is changed to 0.20mol (43.6g) pyromellitic acid dianhydride, the solid content that obtains 950ml is 9% slightly lurid polyamic acid prepolymer solution A 5.
Embodiment 1-6:
With 3 of 0.20mol (40g), 4 '-diaminodiphenyl oxide is dissolved in the beaker of the DMAc that is placed with 946mL, under magnetic agitation, treat 3, after the dissolving of 4 '-diaminodiphenyl oxide finishes, slowly add 0.20mol (58.8g) 3,4,3 ', 4 '-BPDA, adding finishes, in confined conditions, reaction is 4 hours under the magnetic agitation, and the solid content that promptly obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 6.
Embodiment 1-7:
Identical with the step of embodiment 1-6, just dianhydride monomer is changed to 0.20mol (58.8g) 2,3 ', 3,4 '-BPDA, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 7.
Embodiment 1-8:
Identical with the step of embodiment 1-6, just dianhydride monomer is changed to 0.20mol (58.8g) 2,2 ', 3,3 '-BPDA, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 8.
Embodiment 1-9:
Identical with the step of embodiment 1-6, just dianhydride monomer is changed to 0.20mol (62g) phenyl ether tetracarboxylic dianhydride, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 9.
Embodiment 1-10:
Identical with the step of embodiment 1-6, just dianhydride monomer is changed to 0.20mol (43.6g) pyromellitic acid dianhydride, the solid content that obtains 950ml is 9% slightly lurid polyamic acid prepolymer solution A 10.
Embodiment 1-11:
With 3 of 0.20mol (40g), 3 '-diaminodiphenyl oxide is dissolved in the beaker of the DMAc that is placed with 946mL, under magnetic agitation, treat 3, after the dissolving of 3 '-diaminodiphenyl oxide finishes, slowly add 0.20mol (58.8g) 3,4,3 ', 4 '-BPDA, adding finishes, in confined conditions, reaction is 4 hours under the magnetic agitation, and the solid content that promptly obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 11.
Embodiment 1-12:
Identical with the step of embodiment 1-11, just dianhydride monomer is changed to 0.20mol (58.8g) 2,3 ', 3,4 '-BPDA, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 12.
Embodiment 1-13:
Identical with the step of embodiment 1-11, just dianhydride monomer is changed to 0.20mol (58.8g) 2,2 ', 3,3 '-BPDA, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 13.
Embodiment 1-14:
Identical with the step of embodiment 1-11, just dianhydride monomer is changed to 0.20mol (62g) phenyl ether tetracarboxylic dianhydride, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 14.
Embodiment 1-15:
Identical with the step of embodiment 1-11, just dianhydride monomer is changed to 0.20mol (43.6g) pyromellitic acid dianhydride, the solid content that obtains 950ml is 9% slightly lurid polyamic acid prepolymer solution A 15.
Embodiment 1-16:
With 1,4 of 0.20mol (58.4g) ,-(3-amino-benzene oxygen) benzene is dissolved in the beaker of the DMAc that is placed with 946mL, under magnetic agitation, treat 1,4, after the dissolving of-(3-amino-benzene oxygen) benzene finishes, slowly add 0.20mol (58.8g) 3,4,3 ', 4 '-BPDA, adding finishes, in confined conditions, reaction is 4 hours under the magnetic agitation, and the solid content that promptly obtains 950ml is 12% slightly lurid polyamic acid prepolymer solution A 16.
Embodiment 1-17:
Identical with the step of embodiment 1-16, just dianhydride monomer is changed to 0.20mol (58.8g) 2,3 ', 3,4 '-BPDA, the solid content that obtains 950ml is 12% slightly lurid polyamic acid prepolymer solution A 17.
Embodiment 1-18:
Identical with the step of embodiment 1-16, just dianhydride monomer is changed to 0.20mol (58.8g) 2,2 ', 3,3 '-BPDA, the solid content that obtains 950ml is 12% slightly lurid polyamic acid prepolymer solution A 18.
Embodiment 1-19:
Identical with the step of embodiment 1-16, just dianhydride monomer is changed to 0.20mol (62g) phenyl ether tetracarboxylic dianhydride, the solid content that obtains 950ml is 12% slightly lurid polyamic acid prepolymer solution A 19.
Embodiment 1-20:
Identical with the step of embodiment 1-16, just dianhydride monomer is changed to 0.20mol (43.6g) pyromellitic acid dianhydride, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 20.
Embodiment 1-21:
Identical with the step of embodiment 1-1, just solvent DMAc is changed to DMF, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 21.
Embodiment 1-22:
Identical with the step of embodiment 1-1, just solvent DMAc is changed to NMP, the solid content that obtains 950ml is 10% slightly lurid polyamic acid prepolymer solution A 22.
Two, the embodiment of aggressiveness preparation before the polyimide-silicone block copolymer:
Embodiment 2-1:
Under magnetic agitation, with 4 of 0.04mol (8g), 4 '-diaminodiphenyl oxide is dissolved in the beaker that is placed with 530mL (499.68g) DMAc, treats 4, after the dissolving of 4 '-diaminodiphenyl oxide finishes, slowly add 0.08mol (23.52g) 3,4,3 ', 4 '-BPDA, react after 2 hours, add the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl again
w=600g/mol), adding finishes, and in confined conditions, reaction is 6 hours under the magnetic agitation, promptly obtains the 550ml solid content and be aggressiveness solution B 1 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-2:
Identical with the step of embodiment 2-1, just dianhydride monomer is changed to 0.08mol (23.52g) 2,3 ', 3,4 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 2 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-3:
Identical with the step of embodiment 2-1, just dianhydride monomer is changed to 0.08mol (23.52g) 2,2 ', 3,3 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 3 before 10% the slightly lurid polyimide-silicone block copolymer.
Embodiment 2-4:
Identical with the step of embodiment 2-1, just dianhydride monomer is changed to 0.08mol (24.8g) phenyl ether tetracarboxylic dianhydride, obtain the 550ml solid content and be aggressiveness solution B 4 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-5:
Identical with the step of embodiment 2-1, just dianhydride monomer is changed to 0.08mol (17.44g) pyromellitic acid dianhydride, obtaining the 550ml solid content is aggressiveness solution B 5 before the 9.5% water white polyimide-silicone block copolymer.
Embodiment 2-6:
Under magnetic agitation, with 3 of 0.04mol (8g), 4 '-diaminodiphenyl oxide is dissolved in the beaker that is placed with 530mL (499.68g) DMAc, treats 3, after the dissolving of 4 '-diaminodiphenyl oxide finishes, slowly add 0.08mol (23.52g) 3,4,3 ', 4 '-BPDA, react after 2 hours, add the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl again
w=600g/mol), adding finishes, and in confined conditions, reaction is 6 hours under the magnetic agitation, promptly obtains the 550ml solid content and be aggressiveness solution B 6 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-7:
Identical with the step of embodiment 2-6, just dianhydride monomer is changed to 0.08mol (23.52g) 2,3 ', 3,4 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 7 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-8:
Identical with the step of embodiment 2-6, just dianhydride monomer is changed to 0.08mol (23.52g) 2,2 ', 3,3 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 8 before 10% the slightly lurid polyimide-silicone block copolymer.
Embodiment 2-9:
Identical with the step of embodiment 2-6, just dianhydride monomer is changed to 0.08mol (24.8g) phenyl ether tetracarboxylic dianhydride, obtain the 550ml solid content and be aggressiveness solution B 9 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-10:
Identical with the step of embodiment 2-6, just dianhydride monomer is changed to 0.08mol (17.44g) pyromellitic acid dianhydride, obtaining the 550ml solid content is aggressiveness solution B 10 before the 9.5% water white polyimide-silicone block copolymer.
Embodiment 2-11:
Under magnetic agitation, with 0.04mol (8g) 3,3 '-diaminodiphenyl oxide is dissolved in the beaker of the DMAc that is placed with 530mL (499.68g), treats 3, after the dissolving of 3 '-diaminodiphenyl oxide finishes, slowly add 0.08mol (23.52g) 3,4,3 ', 4 '-BPDA, react after 2 hours, add the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl again
w=600g/mol), adding finishes, and in confined conditions, reaction is 6 hours under the magnetic agitation, promptly obtains the 550ml solid content and be aggressiveness solution B 11 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-12:
Identical with the step of embodiment 2-11, just dianhydride monomer is changed to 0.08mol (23.52g) 2,3 ', 3,4 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 12 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-13:
Identical with the step of embodiment 2-11, just dianhydride monomer is changed to 0.08mol (23.52g) 2,2 ', 3,3 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 13 before 10% the slightly lurid polyimide-silicone block copolymer.
Embodiment 2-14:
Identical with the step of embodiment 2-11, just dianhydride monomer is changed to 0.08mol (24.8g) phenyl ether tetracarboxylic dianhydride, obtain the 550ml solid content and be aggressiveness B14 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-15:
Identical with the step of embodiment 2-11, just dianhydride monomer is changed to 0.08mol (17.44g) pyromellitic acid dianhydride, obtain the 550ml solid content and be aggressiveness solution B 15 before 9.5% the water white polyimide-silicone block copolymer.
Embodiment 2-16:
Under magnetic agitation, with 0.04mol (11.68g) 1,4,-(3-amino-benzene oxygen) benzene is dissolved in the beaker of the DMAc that is placed with 530mL (499.68g), treat 1,4, after the dissolving of-(3-amino-benzene oxygen) benzene finishes, slowly add 0.08mol (23.52g) 3,4,3 ', 4 '-BPDA, react after 2 hours, add the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl again
w=600g/mol), adding finishes, and in confined conditions, reaction is 6 hours under the magnetic agitation, promptly obtains the 550ml solid content and be aggressiveness solution B 16 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-17:
Identical with the step of embodiment 2-16, just dianhydride monomer is changed to 0.08mol (23.52g) 2,3 ', 3,4 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 17 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-18:
Identical with the step of embodiment 2-16, just dianhydride monomer is changed to 0.08mol (23.52g) 2,2 ', 3,3 '-BPDA obtains the 550ml solid content and is aggressiveness solution B 18 before 10% the slightly lurid polyimide-silicone block copolymer.
Embodiment 2-19:
Identical with the step of embodiment 2-16, just dianhydride monomer is changed to 0.08mol (24.8g) phenyl ether tetracarboxylic dianhydride, obtain the 550ml solid content and be aggressiveness solution B 19 before 11% the water white polyimide-silicone block copolymer.
Embodiment 2-20:
Identical with the step of embodiment 2-16, just dianhydride monomer is changed to 0.08mol (17.44g) pyromellitic acid dianhydride, obtain the 550ml solid content and be aggressiveness solution B 20 before 10% the water white polyimide-silicone block copolymer.
Embodiment 2-21:
Identical with the step of embodiment 2-1, just solvent DMAc is changed to DMF, the solid content that obtains 550ml is 10% the preceding aggressiveness solution B 21 of water white polyimide-silicone block copolymer.
Embodiment 2-22:
Identical with the step of embodiment 2-1, just solvent DMAc is changed to NMP, the solid content that obtains 550ml is 10% the preceding aggressiveness solution B 22 of water white polyimide-silicone block copolymer.
Embodiment 2-23:
Identical with the step of embodiment 2-1, just with the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl
w=600g/mol) be changed to the end capped polydimethylsiloxane (M of 0.04mol (10.08g) aminopropyl
w=252g/mol), the solid content that obtains 550ml is 8% the preceding aggressiveness solution B 23 of water white polyimide-silicone block copolymer.
Embodiment 2-24:
Identical with the step of embodiment 2-1, just with the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl
w=600g/mol) be changed to the end capped polydimethylsiloxane (M of 0.04mol (13.36g) aminopropyl
w=334g/mol), the solid content that obtains 550ml is 8% the preceding aggressiveness solution B 24 of water white polyimide-silicone block copolymer.
Embodiment 2-25:
Identical with the step of embodiment 2-1, just with the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl
w=600g/mol) be changed to the end capped polydimethylsiloxane (M of 0.04mol (16.24g) aminopropyl
w=406g/mol), the solid content that obtains 550ml is 9% the preceding aggressiveness solution B 25 of water white polyimide-silicone block copolymer.
Embodiment 2-26:
Identical with the step of embodiment 2-1, just with the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl
w=600g/mol) be changed to the end capped polydimethylsiloxane (M of 0.04mol (19g) aminopropyl
w=475g/mol), the solid content that obtains 550ml is 9% the preceding aggressiveness solution B 26 of water white polyimide-silicone block copolymer.
Embodiment 2-27:
Identical with the step of embodiment 2-1, just with the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl
w=600g/mol) be changed to the end capped polydimethylsiloxane (M of 0.04mol (22g) aminopropyl
w=550g/mol), the solid content that obtains 550ml is an aggressiveness solution B 27 before the 9.6% water white polyimide-silicone block copolymer.
Embodiment 2-28:
Identical with the step of embodiment 2-1, just with the end capped polydimethylsiloxane (M of 0.04mol (24g) aminopropyl
w=600g/mol) be changed to the end capped polydimethylsiloxane (M of 0.04mol (32.52g) aminopropyl
w=813g/mol), the solid content that obtains 550ml is 11% the preceding aggressiveness solution B 28 of water white polyimide-silicone block copolymer.
Three, the embodiment of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane preparation:
Embodiment 3-1:
Aggressiveness B1 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mix with 50g polyamic acid prepolymer A1 again, the ratio of aggressiveness and polyamic acid prepolymer is respectively 0.2%, 0.3%, 0.5% before the polyimide-silicone block copolymer, films on sheet glass then.Room temperature was placed 1 hour, put into 40 ℃ in baking oven, 60 ℃ again and handled respectively 3 hours.Being transferred in the vacuum drying oven 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 250 ℃ again handles respectively and carried out hot imidization in 1 hour.After disposing, taking off film from sheet glass promptly is the composite membrane that we prepare, and the composite membrane that obtains has the good transparency and thermotolerance.
Embodiment 3-2:
Aggressiveness B2 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A2 again, and method is with embodiment 3-1.The composite membrane that obtains has better thermotolerance and mechanical property than the composite membrane of embodiment 3-1.
Embodiment 3-3:
Aggressiveness B3 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A3 again, and method is with embodiment 3-1.The composite membrane that obtains has better thermotolerance than the composite membrane of embodiment 3-1 but mechanical property is relatively poor.
Embodiment 3-4:
Aggressiveness B4 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A4 again, and method is with embodiment 3-1.The composite membrane that obtains is than the poor heat resistance of the composite membrane of embodiment 3-1.
Embodiment 3-5:
Aggressiveness B5 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A5 again, and method is with embodiment 3-1.The composite membrane that obtains is than the good heat resistance of the composite membrane of embodiment 3-1.
Embodiment 3-6:
Aggressiveness B6 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A6 again, and method is with embodiment 3-1.The composite membrane that obtains is than the good mechanical property of the composite membrane of embodiment 3-1.
Embodiment 3-7:
Aggressiveness B7 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A7 again, and method is with embodiment 3-1.The composite membrane that obtains is than the good mechanical property of the composite membrane of embodiment 3-1.
Embodiment 3-8:
Aggressiveness B8 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A8 again, and method is with embodiment 3-1.The composite membrane that obtains is than the good heat resistance of the composite membrane of embodiment 3-1.
Embodiment 3-9:
Aggressiveness B9 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A9 again, and method is with embodiment 3-1.The composite membrane that obtains is than the poor heat resistance of the composite membrane of embodiment 3-1, but the transparency is better.
Embodiment 3-10:
Aggressiveness B10 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A10 again, and method is with embodiment 3-1.The composite membrane that obtains is than the good heat resistance of the composite membrane of embodiment 3-1.
Embodiment 3-11:
Aggressiveness B11 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A11 again, and method is with embodiment 3-1.The composite membrane that obtains is transparent better than the composite membrane of embodiment 3-1.
Embodiment 3-12:
Aggressiveness B12 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A12 again, and method is with embodiment 3-1.The composite membrane that obtains is better than the thermotolerance and the transparency of the composite membrane of embodiment 3-1.
Embodiment 3-13:
Aggressiveness B13 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A13 again, and method is with embodiment 3-1.The composite membrane that obtains is good but bad mechanical property than the transparency of the composite membrane of embodiment 3-1.
Embodiment 3-14:
Aggressiveness B14 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A14 again, and method is with embodiment 3-1.The composite membrane that obtains is good but poor heat resistance than the transparency of the composite membrane of embodiment 3-1.
Embodiment 3-15:
Aggressiveness B15 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A15 again, and method is with embodiment 3-1.The composite membrane that obtains is than the transparency and the good heat resistance of the composite membrane of embodiment 3-1.
Embodiment 3-16:
Aggressiveness B16 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A16 again, and method is with embodiment 3-1.The composite membrane that obtains is than the composite membrane poor heat resistance of embodiment 3-1 but water-intake rate is low.
Embodiment 3-17:
Aggressiveness B17 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A17 again, and method is with embodiment 3-1.The composite membrane that obtains is lower than composite membrane good mechanical property and the water-intake rate of embodiment 3-1.
Embodiment 3-18:
Aggressiveness B18 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A18 again, and method is with embodiment 3-1.The composite membrane that obtains is than the composite membrane bad mechanical property of embodiment 3-1 but water-intake rate is low.
Embodiment 3-19:
Aggressiveness B19 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A19 again, and method is with embodiment 3-1.The composite membrane that obtains is than the composite membrane poor heat resistance of embodiment 3-1 but water-intake rate is low.
Embodiment 3-20:
Aggressiveness B20 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A20 again, and method is with embodiment 3-1.The composite membrane that obtains is than the composite membrane poor heat resistance of embodiment 3-1 but water-intake rate is low.
Embodiment 3-21:
Aggressiveness B21 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A21 again, and method is with embodiment 3-1.The composite membrane that obtains has the good transparency and thermotolerance.
Embodiment 3-22;
Aggressiveness B22 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A22 again, and method is with embodiment 3-1.The composite membrane that obtains has the good transparency and thermotolerance.
Embodiment 3-23;
Step just changes 1 hour into 40 ℃, 60 ℃ treatment times with embodiment 3-1.Above film is tested, and clear this film of data sheet is compared with embodiment 3-1 does not have good double-sided anisotropic, and this may be that the subzero treatment time is shorter, and the run duration of siloxanes segment is short to be caused.
Embodiment 3-24;
Step is with embodiment 3-1, and just 40 ℃, 60 ℃ are put on the hot-plate and handle.Obtain the relatively poor composite membrane of uniformity coefficient, this is because the local heating of handling on the hot-plate makes that the uniformity coefficient of film is relatively poor.
Embodiment 3-25:
Step does not just add tetrahydrofuran (THF) in the mixing process with embodiment 3-1.Above film is tested, and clear this film of data sheet is compared with embodiment 3-1 does not have good double-sided anisotropic.This may be that in the process of solvent evaporates, Polyimidesiloxane and polyimide solubleness do not have difference, so do not reach good separating effect because Polyimidesiloxane and polyimide all are dissolved in the same solvent.
Embodiment 3-26:
Step is just changed on the stainless steel plate and is filmed with embodiment 3-1.Above film is tested, and clear this film of data sheet is compared with embodiment 3-1 does not have good double-sided anisotropic.This may be because Polyimidesiloxane and polyimide when filming on stainless steel plate, and the power that has certain effect between polysiloxane and the stainless steel plate is so caused the double-sided anisotropic of composite membrane not obvious.
Embodiment 3-27:
Step just is placed on film on the aluminium foil when pyroprocessing with embodiment 3-1.Above film is tested, and clear this film of data sheet is compared with embodiment 3-1 does not have good double-sided anisotropic.This may be because Polyimidesiloxane and polyimide are placed on the aluminium foil, when pyroprocessing, certain reaction is arranged between polysiloxane and the aluminium foil, so caused the double-sided anisotropic of composite membrane not obvious.In addition, aluminium foil takes place to curl when pyroprocessing, has also caused the ununiformity of composite membrane.
Embodiment 3-28:
Step is with embodiment 3-1, and just when room temperature was placed, a disk took off disk on the last face shield when changing pyroprocessing over to.Obtain the relatively poor composite membrane of uniformity coefficient, because when subzero treatment, handle in confined conditions, solvent evaporates is not gone out, thereby gutters down the another fixed influence of film.So caused the ununiformity of film.
Embodiment 3-29:
Aggressiveness B23 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A1 again, and method is with embodiment 3-1.The double-sided anisotropic of the composite membrane that obtains is relatively poor.This is because shorter segmental Polyimidesiloxane is unfavorable for that it moves in according to the imide segment, thereby causes the double-sided anisotropic of film relatively poor.
Embodiment 3-30:
Aggressiveness B24 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A1 again, and method is with embodiment 3-1.Obtain with embodiment 3-29 in the similar relatively poor composite membrane of double-sided anisotropic.This is because shorter segmental Polyimidesiloxane is unfavorable for that it moves in according to the imide segment, thereby causes the double-sided anisotropic of film relatively poor.
Embodiment 3-31:
Aggressiveness B25 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A1 again, and method is with embodiment 3-1.Obtain with embodiment 3-28 in the similar relatively poor composite membrane of double-sided anisotropic.This is because shorter segmental Polyimidesiloxane is unfavorable for that it moves in according to the imide segment, thereby causes the double-sided anisotropic of film relatively poor.
Embodiment 3-32:
Aggressiveness B26 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A1 again, and method is with embodiment 3-1.Obtain with embodiment 3-28 in the similar relatively poor composite membrane of double-sided anisotropic.This is because shorter segmental Polyimidesiloxane is unfavorable for that it moves in according to the imide segment, thereby causes the double-sided anisotropic of film relatively poor.
Embodiment 3-33:
Aggressiveness B27 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A1 again, and method is with embodiment 3-1.Obtain with embodiment 3-28 in the similar relatively poor composite membrane of double-sided anisotropic.This is because shorter segmental Polyimidesiloxane is unfavorable for that it moves in according to the imide segment, thereby causes the double-sided anisotropic of film relatively poor.
Embodiment 3-34:
Aggressiveness B28 is dissolved in the 1mL tetrahydrofuran (THF) before getting 0.1g, 0.15g, 0.25g polyimide-silicone block copolymer respectively, mixes with 50g polyamic acid prepolymer A1 again, and method is with embodiment 3-1.Obtain and the similar double-sided anisotropic of embodiment 3-1 composite membrane preferably.This is because the segment sufficiently long of Polyimidesiloxane helps it to move in according to the imide segment, thereby has obtained double-sided anisotropic film preferably.
Claims (4)
1, the preparation method of a kind of Polyimidesiloxane/polyimide double-sided anisotropic composite membrane, comprise 3 steps of preparation of synthetic, Polyimidesiloxane/polyimide composite film of synthetic, the polyamic acid prepolymer of aggressiveness before the polyimide-silicone block copolymer, it is characterized in that:
(1) under magnetic agitation, take by weighing diamines and be dissolved in the beaker that organic solvent is housed, slowly add dianhydride, adding finishes, under agitation condition room temperature reaction 0.5-3 hour; Add the end capped polydimethylsiloxane of aminopropyl again, add reaction 4-10 hour that finishes, obtain the preceding aggressiveness of polyimide-silicone block copolymer, wherein the mol ratio of dianhydride, diamines and the end capped polydimethylsiloxane of aminopropyl is 2: 1: 1, and solid content is 8-20%;
(2) under magnetic agitation, take by weighing diamines and be dissolved in the beaker that organic solvent is housed, treat that diamines dissolves fully after, in beaker, slowly add dianhydride; Under whipped state, room temperature reaction 2-6 hour, obtain the polyamic acid prepolymer, wherein the mol ratio of dianhydride and diamines is 1: 1, solid content is 8-20%;
(3) aggressiveness before the polyimide-silicone block copolymer for preparing in the above-mentioned steps is dissolved in the tetrahydrofuran (THF), mix with the polyamic acid prepolymer then, add aggressiveness before the polyimide-silicone block copolymer of 0.05g-0.5g in every milliliter of tetrahydrofuran (THF), the mass ratio of aggressiveness and polyamic acid prepolymer consumption is 0.001-0.01 before the polyimide-silicone block copolymer: 1, after it is mixed, casting film-forming on sheet glass; Room temperature left standstill 0.5-3 hour, put into baking oven then and ℃ handled respectively 1-5 hour in 35-45 ℃, 55-65; Be transferred to again in the vacuum drying oven ℃ to handle respectively and carried out hot imidization in 0.5-3 hour in 75-85 ℃, 95-105 ℃, 115-125 ℃, 145-155 ℃, 175-185 ℃, 245-255, after disposing, taking off film from sheet glass promptly is Polyimidesiloxane/polyimide double-sided anisotropic composite membrane;
Diamines in the above-mentioned steps is 4,4 '-diamines yl diphenyl ether, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide or 1,4, a kind of in-(3-amino-benzene oxygen) benzene; Dianhydride is 3,4,3 ', 4 '-BPDA, 2,3 ', 3,4 '-BPDA, 2,2 ', 3, a kind of in 3 '-BPDA, phenyl ether tetracarboxylic dianhydride or the pyromellitic acid dianhydride; Organic solvent is N, a kind of in dinethylformamide, N,N-dimethylacetamide or the N-Methyl pyrrolidone.
2, the preparation method of Polyimidesiloxane as claimed in claim 1/polyimide double-sided anisotropic composite membrane is characterized in that: the polymerization reaction time that the end capped polydimethylsiloxane of dianhydride, diamines and aminopropyl prepares the preceding aggressiveness of polyimide-silicone block copolymer is 6 hours.
3, the preparation method of Polyimidesiloxane as claimed in claim 1/polyimide double-sided anisotropic composite membrane is characterized in that: the polymerization reaction time that dianhydride and diamines prepare the polyamic acid prepolymer is 4 hours.
4, the preparation method of Polyimidesiloxane as claimed in claim 1/polyimide double-sided anisotropic composite membrane, it is characterized in that: the time that room temperature leaves standstill behind casting film-forming on the sheet glass is 1 hour, putting into baking oven is 3 hours in 35-45 ℃, the 55-65 ℃ time of handling respectively, and being transferred in the vacuum drying oven in 75-85 ℃, 95-105 ℃, 115-125 ℃, 145-155 ℃, 175-185 ℃, the 245-255 ℃ time of handling respectively again is 1 hour.
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| CN101824159B (en) * | 2009-03-06 | 2011-11-09 | 北京化工大学 | Preparation method of polyimide/ladder-like polysiloxane double-sided anisotropic composite thin film |
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
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| US4853452A (en) * | 1988-02-09 | 1989-08-01 | Occidental Chemical Corporation | Novel soluble polyimidesiloxanes and methods for their preparation using a flourine containing anhydride |
| CN1092448A (en) * | 1993-03-16 | 1994-09-21 | 西方化学公司 | Three-layer polyimidesiloxane adhesive tape |
| JP2005146213A (en) * | 2003-11-19 | 2005-06-09 | Arakawa Chem Ind Co Ltd | Method for producing silane-modified polyimide siloxane resin containing methoxysilyl group, the resin, the resin composition, cured film, and metal foil laminated product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853452A (en) * | 1988-02-09 | 1989-08-01 | Occidental Chemical Corporation | Novel soluble polyimidesiloxanes and methods for their preparation using a flourine containing anhydride |
| CN1092448A (en) * | 1993-03-16 | 1994-09-21 | 西方化学公司 | Three-layer polyimidesiloxane adhesive tape |
| JP2005146213A (en) * | 2003-11-19 | 2005-06-09 | Arakawa Chem Ind Co Ltd | Method for producing silane-modified polyimide siloxane resin containing methoxysilyl group, the resin, the resin composition, cured film, and metal foil laminated product |
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