CN102140106B - Novel oligomerization silsesquioxane polymer and preparation method thereof - Google Patents
Novel oligomerization silsesquioxane polymer and preparation method thereof Download PDFInfo
- Publication number
- CN102140106B CN102140106B CN201010118322.8A CN201010118322A CN102140106B CN 102140106 B CN102140106 B CN 102140106B CN 201010118322 A CN201010118322 A CN 201010118322A CN 102140106 B CN102140106 B CN 102140106B
- Authority
- CN
- China
- Prior art keywords
- solvent
- oligomeric silsesquioxane
- silsesquioxane
- polymer
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N O=C(c(c1c2)cc(C(O3)=O)c2C3=O)OC1=O Chemical compound O=C(c(c1c2)cc(C(O3)=O)c2C3=O)OC1=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N O=C(c(cc1)cc(C(O2)=O)c1C2=O)c(cc1C(O2)=O)ccc1C2=O Chemical compound O=C(c(cc1)cc(C(O2)=O)c1C2=O)c(cc1C(O2)=O)ccc1C2=O VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- YSFOQCREJKDJJX-UHFFFAOYSA-N O=C(c1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)cc(CC(O3)=O)c2C3=O)cc11)OC1=O Chemical compound O=C(c1ccc(C(C(F)(F)F)(C(F)(F)F)c(cc2)cc(CC(O3)=O)c2C3=O)cc11)OC1=O YSFOQCREJKDJJX-UHFFFAOYSA-N 0.000 description 1
- DYSOZVIDEKOCOW-UHFFFAOYSA-N O=C(c1ccc(COc(cc2C(O3)=O)ccc2C3=O)cc11)OC1=O Chemical compound O=C(c1ccc(COc(cc2C(O3)=O)ccc2C3=O)cc11)OC1=O DYSOZVIDEKOCOW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention belongs to the field of new materials and discloses a novel oligomerization silsesquioxane polymer. The polymer takes oligomerization silsesquioxane as a monomer and dianhydride as a bridging molecule. The oligomerization silsesquioxane polymer provided by the invention has a regular silica cagelike structure and a reactive organic group with an adjustable outer end. Meanwhile, the invention provides a preparation method of the novel polymer. According to the preparation method disclosed by the invention, a polymer with an ordered adjustable nanometer structure can be obtained conveniently, the macro-performance of the type of materials can be realized by adjusting the molecular level, and an unusual chemical or physical property is presented. Furthermore, the method provided by the invention has a simple process, has a reaction condition similar to that of the conventional industrial technology, and is easy for realizing industrialization.
Description
Technical field
The invention belongs to field of new, be specifically related to a kind of Novel oligomerization silsesquioxane polymer and preparation method thereof.
Background technology
Along with the progress of nano material, there is the nano material of ordered structure to show unusual chemistry or physical properties.And the approach of preparation two dimension or three-dimensional ordered nano structure material is conventionally all very complicated, and the macro property that can control material by the adjusting of molecular level is that this class ordered structural material is in the most important application of field of nanometer technology.
Oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) is the inorganic nano material that a class has cage structure, and molecular diameter is about 1～3nm, has the features such as heat-resisting, fire-retardant, density is low.POSS itself is with SiO
2for inorganic core, add in polymkeric substance and can give the heat-resisting and mechanical property that material is good, and the reactive organic group of its periphery not only can improve the consistency between POSS and polymkeric substance, can also realize the chemical bonding effect between oligomeric silsesquioxane and polymkeric substance, give polymkeric substance better performance.As utilized the reactivity of POSS terminal amino group and dicarboxylic anhydride group is dispersed in POSS in polyimide matrix in patent (CN200710133643.3), improve the second-order transition temperature of material; And the heat of the middle polyimide/POSS hybrid material of patent (CN200710130841.4) and dielectric properties all improve because of the introducing of POSS.In research at majority about POSS, the excessive rear dispersion variation of the addition of POSS and cannot further improve substrate performance.Document (Macromolecules 2009,42,3489) in, first passage bridge formation molecule has been prepared POSS autopolymer, realize the preparation of the micro-nanometer ordered structure material of high POSS content, but owing to having used the bridge formation molecule (Succinic anhydried) only with an anhydride group in building-up process, cause using condensing agent to carry out condensation, and in follow-up purge process, must remove unnecessary condensing agent and by product, technique is comparatively complicated.
Summary of the invention
The object of this invention is to provide a kind of Novel oligomerization silsesquioxane polymer, and prepare the micro-nanometer ordered structure material of high-content oligomeric silsesquioxane by a kind of simple process.
Another object of the present invention is to provide the preparation method of above-mentioned oligomerization silsesquioxane polymer.
Object of the present invention can reach by following measures:
Oligomerization silsesquioxane polymer, by oligomeric silsesquioxane and the molecule condensation of dicarboxylic anhydride class bridge formation and obtain; Wherein the mol ratio of dicarboxylic anhydride class bridge formation molecule and oligomeric silsesquioxane is 8: 1.2～2.5;
Oligomeric silsesquioxane used is prepared voluntarily by the method (Journal of the AmericanChemical Society, 2001,123:12416) of having reported, has the structure of formula (I):
formula (I).
Described dicarboxylic anhydride class bridge formation molecule can be selected from pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride (6FDA), biphenyl dianhydride (ODPA), tetramethylene tetracarboxylic acid dianhydride (CBDA) or 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) etc.Different types of dicarboxylic anhydride can give final polymkeric substance different physical and chemical performances, as use 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride (6FDA) is as bridge formation molecule, and the oligomerization silsesquioxane polymer of gained can be used for low dielectric packaged material or hydrophobic, hates oily film etc.Consider film-forming properties and the over-all properties of resulting polymers, thus the preferred pyromellitic acid anhydride of the present invention, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride or 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride.
Anhydrides
Pyromellitic acid anhydride, PMDA 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, ODPA
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, BTDA 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride, 6FDA
The anhydride group at dicarboxylic anhydride bridge formation molecule two ends reacts with the amino of oligomeric silsesquioxane cages shape end respectively, a large amount of bridge formation molecules is connected different oligomeric silsesquioxane cages shape structures, and the polymkeric substance of gained has suc as formula the schematic diagram shown in (III).Oligomeric silsesquioxane in adjustment reaction system and the ratio of bridge formation molecule, the reaction ratio respective change of each oligomeric silsesquioxane cages shape end group, the crosslinking degree of polymkeric substance changes thus, and the performance of polymkeric substance shows as thereupon and changes.Therefore, the performance of this oligomerization silsesquioxane polymer can be adjusted by the ratio that changes reactant.
formula (III)
Wherein:
Wherein: Ar1:
R：
A kind of method of preparing described oligomerization silsesquioxane polymer is also provided in the present invention, and it comprises the following steps:
(1) oligomeric silsesquioxane is divided into A, B two portions, the mol ratio of A and B is 1: 0.2～1.5;
(2) oligomeric silsesquioxane A is dissolved in solvent 1 to wiring solution-forming 1;
(3) under the protection of rare gas element, dicarboxylic anhydride class bridge formation molecule is added in solvent 2, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 10～35 DEG C, react 12～24 hours, obtain solution 2;
(4) oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 10～35 DEG C, react 12～24 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5), by the pre-gathering solutions desolventizing of oligomeric silsesquioxane, then at 260～350 DEG C, carry out, after the imidization reaction of 2～4 hours, obtaining oligomerization silsesquioxane polymer.
Wherein, solvent 1 is selected from N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Solvent 2 is selected from N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Solvent 1 and solvent 2 can identical can be not identical yet.
Consider the toxicity of solvability and solvent, the preferred of solvent 1 is N,N-dimethylacetamide or N-Methyl pyrrolidone; The preferred of solvent 2 is N,N-dimethylacetamide or N-Methyl pyrrolidone; Solvent 1 and solvent 2 can identical can be not identical yet.
In above-mentioned steps (1), considering the snappiness of material and the reason of film-forming properties, A and B mol ratio be preferably 1: 0.2～and 1.0.The variation of A and B mol ratio can cause the reaction ratio respective change of each oligomeric silsesquioxane cages shape end group, and the crosslinking degree of polymkeric substance changes thus, and the structure of resulting polymers and physical and chemical performance can be realized by adjusting this mol ratio.Dicarboxylic anhydride class bridge formation molecule is preferably 8: 1 with the mol ratio of oligomeric silsesquioxane in step (3), be in order to ensure the end of oligomeric silsesquioxane in this step is reacted can with bridge formation molecular reaction and system in there is not the bridge formation molecule of free state.Using the object stirring is the homogeneity for whole system, and viscosity that can reference frame is selected mechanical stirring or magnetic agitation.Make the method for oligomeric silsesquioxane pre-gathering solutions desolventizing comprise casting film-forming 60-80 DEG C of desolventizing or oligomeric silsesquioxane pre-gathering solutions is slowly splashed into Precipitation in the precipitation agent such as water or methyl alcohol then on substrate; Also can use other Desolventizing methods of the prior art.
Oligomeric silsesquioxane in this reaction has the structure of formula (II):
formula (II).
Described dicarboxylic anhydride class bridge formation molecule can be selected from pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride (6FDA), biphenyl dianhydride (ODPA), tetramethylene tetracarboxylic acid dianhydride (CBDA) or 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) etc.Different types of dicarboxylic anhydride can give final polymkeric substance different physical and chemical performances, as use 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride (6FDA) is as bridge formation molecule, and the oligomerization silsesquioxane polymer of gained can be used for low dielectric packaged material or hydrophobic, hates oily film etc.Consider film-forming properties and the over-all properties of resulting polymers, thus the preferred pyromellitic acid anhydride of the present invention, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride or 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride.
Anhydrides
Pyromellitic acid anhydride, PMDA 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, ODPA
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, BTDA 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride, 6FDA
The oligomerization silsesquioxane polymer of present method gained can be by making oligomeric silsesquioxane pre-gathering solutions in sheet glass, stainless steel plate, silicon chip, aluminium foil, polyfluortetraethylene plate or other stromal surface film forming or be molded into then solidifying formation of mould.Conventional manufacturing process is film forming on sheet glass or stainless steel plate.
Oligomeric silsesquioxane used in the present invention, has the adjustable reactive organic group in regular silica cagelike structure and outer end.According to preparation method of the present invention, can obtain easily having the polymkeric substance of orderly adjustable nanostructure, the macro property of this class material can be realized by the adjusting of molecular level, shows unusual chemistry or physical properties.
Again, method technique provided by the invention is simple, reaction conditions is similar to existing industrial technology, is easy to realize industrialization.
Because this polymer materials has the adjustable reactive organic group of a large amount of regular silica cagelike structures and outer end, make it realize the control to material macro property by the adjusting of molecular level easily.As according to its good film-forming properties and special cagelike structure, this polymer materials can be used for interlayer wiring board or the high-performance dielectric film etc. of microelectronic industry.
Brief description of the drawings
Fig. 1 is the reaction schematic diagram that the embodiment of the present invention 1 is prepared oligomerization silsesquioxane polymer.
Fig. 2 is the fourier variation infrared rays spectrogram that the embodiment of the present invention 1 is reacted each step product.
As can be seen from the figure, in the composition of solution 2, there is new carboxyl and amide group, corresponding with reaction schematic diagram; In oligomerization silsesquioxane polymer, carboxyl disappears, corresponding with reaction schematic diagram.Verify thus to react and carried out according to setting.
Embodiment
The present invention can obtain further elaboration by the embodiment of preferred embodiment below, but these embodiment are only to illustrate, and scope of the present invention is not made and being defined.
The starting material that use in embodiment:
A) oligomeric silsesquioxane, preparation method:
5g eight nitrophenyl silsesquioxanes and 2g Fe/C supported catalyst are added in 80ml tetrahydrofuran (THF), be uniformly mixed, be warming up to 60 DEG C; Slowly drip the hydrazine hydrate that 8ml concentration is 80%, be added dropwise to complete rear backflow 5 hours.Be down to room temperature, filter, add ethyl acetate extraction, in sherwood oil, precipitate, be isolated to white or field gray precipitation slightly, be eight described aminocarbonyl phenyl silsesquioxanes.
Wherein eight nitrophenyl silsesquioxanes are pressed document (Journal of the American ChemicalSociety, 2001,123:12416) method preparation, in eight aminocarbonyl phenyl silsesquioxane preparation process, agents useful for same is all from Chemical Reagent Co., Ltd., Sinopharm Group.
B) dicarboxylic anhydride: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA): Co., Ltd in SIGMA-ALDRICH; 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride (6FDA): Co., Ltd in SIGMA-ALDRICH; Pyromellitic acid anhydride (PMDA): Chemical Reagent Co., Ltd., Sinopharm Group.
C) solvent: N,N-dimethylacetamide (DMAc): Chemical Reagent Co., Ltd., Sinopharm Group; N-Methyl pyrrolidone (NMP): Chemical Reagent Co., Ltd., Sinopharm Group; Dimethyl sulfoxide (DMSO) (DMSO): Chemical Reagent Co., Ltd., Sinopharm Group; DMF (DMF): Chemical Reagent Co., Ltd., Sinopharm Group.
The measuring method of oligomerization silsesquioxane polymer structure and other performance in embodiment:
A) material structure is confirmed: fourier changes infrared spectrum (FTIR8400s Japan);
B) second-order transition temperature: differential scanning calorimeter (the TA DSC Q100 U.S.), test atmosphere: nitrogen atmosphere, heating schedule: room temperature～300 DEG C, 10 DEG C/point of heat-up rates; 300～0 DEG C, 20 DEG C/point of heat-up rates; 0～300 DEG C, 10 DEG C/point of heat-up rates.The object that the first round heats up is to eliminate the thermal history of sample, and second takes turns intensification can obtain the second-order transition temperature of sample.
C) thermal weight loss: thermal gravimetric analyzer (the TA SDT Q600 U.S.), test atmosphere: nitrogen atmosphere, probe temperature: room temperature～900 DEG C, 20 DEG C/point of heat-up rates.Test specimen in use be film forming on sheet glass, then take off, choose appropriate sample and test.Reading the corresponding temperature spot of weightless 5wt% is the comparative parameter of T5% as thermostability.
D) Dielectric Coefficient: at 25 DEG C, Novocontrol wideband dielectric and impedance spectrometer (BDS-40 Germany), adopt 2 centimetres of electrode diameters, test frequency scope: 0.01Hz～10MHz.Test specimen in use film forming is on stainless steel plate, and sample surfaces is tested after good to ensure sample and contacting between test electrode through metalized (sputter or brush elargol) after cured.Given dielectric result is the mean value of three samples.
Embodiment 1
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.5g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.25g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent DMSO to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.5588gBTDA is added in solvent DMSO, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 30 DEG C, react 20 hours, obtain solution 2;
(4) 0.25g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 30 DEG C, react 12 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 1.5ml of oligomeric silsesquioxane is dripped to casting film-forming on stainless steel plate, carry out, after the curing reaction of 4 hours, obtaining oligomerization silsesquioxane polymer film after desolventizing at 280 DEG C, thickness is 85 microns.
The schematic diagram of this reaction as shown in Figure 1.Structure changes infrared spectrum by fourier to be confirmed, as shown in Figure 2.The second-order transition temperature that the sample that takes a morsel records this polymkeric substance is 171.7 DEG C, and T5% is 495.2 DEG C.
Directly surface sputtering a layer thickness is about the gold layer of 0.1 micron thereon, carries out dielectric properties test, and specific inductivity is under 3.50,100kHz to be 3.45 under 100Hz.
Embodiment 2
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.375g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.125g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent DMF to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.5588gBTDA is added in solvent DMF, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 20 DEG C, react 12 hours, obtain solution 2;
(4) 0.125g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 20 DEG C, react 15 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 6.5ml of oligomeric silsesquioxane is dripped to casting film-forming on sheet glass, carry out, after the curing reaction of 3 hours, obtaining oligomerization silsesquioxane polymer film after desolventizing at 300 DEG C, thickness is 76 microns.The second-order transition temperature that the sample that takes a morsel records this polymkeric substance is 202.5 DEG C, and T5% is 477.4 DEG C.Film is taken off, and the each sputter a layer thickness of lower surface is about the gold layer of 0.1 micron thereon, carries out dielectric properties test, specific inductivity is under 3.61,100kHz to be 3.52 under 100Hz.
Embodiment 3
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.60g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.35g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent DMAc to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.7709g6FDA is added in solvent DMAc, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 25 DEG C, react 20 hours, obtain solution 2;
(4) 0.35g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 25 DEG C, react 15 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 1.5ml of oligomeric silsesquioxane is dripped to casting film-forming on stainless steel plate, after desolventizing, at 320 DEG C, carry out, after the curing reaction of 4 hours, obtaining oligomerization silsesquioxane polymer film.Gained film is imperfect, part cracking, and the second-order transition temperature that records this polymkeric substance through sampling is 146.3 DEG C, T5% is 482.1 DEG C.Directly be about the gold layer of 0.1 micron in film surface sputtering a layer thickness of intact part, carry out dielectric properties test, specific inductivity is under 3.82,100kHz to be 3.74 under 100Hz.
Embodiment 4
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.325g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.125g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent NMP to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.7709g6FDA is added in solvent NMP, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 15 DEG C, react 20 hours, obtain solution 2;
(4) 0.125g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 15 DEG C, react 20 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 1.5ml of oligomeric silsesquioxane is dripped to casting film-forming on stainless steel plate, carry out, after the curing reaction of 4 hours, obtaining oligomerization silsesquioxane polymer film after desolventizing at 320 DEG C, thickness is 92 microns.The second-order transition temperature that the sample that takes a morsel records this polymkeric substance is 247.9 DEG C, and T5% is 459.6 DEG C.
Directly surface brush last layer thickness is about the elargol layer of 0.5 micron thereon, after elargol solidifies completely, carries out dielectric properties test, and specific inductivity is under 3.11,100kHz to be 3.06 under 100Hz.
Embodiment 5
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.325g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.125g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent DMF to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.3783gPMDA is added in solvent DMF, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 10 DEG C, react 24 hours, obtain solution 2;
(4) 0.125g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 10 DEG C, react 24 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 6.5ml of oligomeric silsesquioxane is dripped to casting film-forming on sheet glass, carry out, after the curing reaction of 2 hours, obtaining oligomerization silsesquioxane polymer film after desolventizing at 340 DEG C, thickness is 78 microns.The second-order transition temperature that the sample that takes a morsel records this polymkeric substance is 237.5 DEG C, and T5% is 493.2 DEG C.
Film is taken off, and then the each sputter a layer thickness of lower surface is about the gold layer of 0.1 micron thereon, carries out dielectric properties test, and specific inductivity is under 3.53,100kHz to be 3.42 under 100Hz.
Comparative example 1
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.29g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.04g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent DMSO to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.5588gBTDA is added in solvent DMSO, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 30 DEG C, react 20 hours, obtain solution 2;
(4) 0.04g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 30 DEG C, react 12 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 1.5ml of oligomeric silsesquioxane is dripped to casting film-forming on stainless steel plate, after desolventizing, at 280 DEG C, carry out the curing reaction of 4 hours.Sample can not film forming, is Powdered.
Comparative example 2
(1) be that eight aminocarbonyl phenyl silsesquioxanes are divided into A, B two portions by 0.63g oligomeric silsesquioxane, the amount of A and B is respectively 0.25g, 0.38g;
(2) 0.25g oligomeric silsesquioxane A is dissolved in 4ml solvent DMSO to wiring solution-forming 1;
(3) under the protection of rare gas element, 0.5588gBTDA is added in solvent DMSO, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 30 DEG C, react 20 hours, obtain solution 2;
(4) 0.38g oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 30 DEG C, react 12 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
(5) the pre-gathering solutions 1.5ml of oligomeric silsesquioxane is dripped to casting film-forming on stainless steel plate, after desolventizing, at 280 DEG C, carry out the curing reaction of 4 hours.Sample can not film forming, instant of complete cracking.
Claims (3)
1. a method of preparing oligomerization silsesquioxane polymer, is characterized in that: comprise the following steps:
(1) oligomeric silsesquioxane is divided into A, B two portions, the mol ratio of A and B is 1:0.2～1.5;
(2) oligomeric silsesquioxane A is dissolved in solvent 1 to wiring solution-forming 1;
(3) under the protection of rare gas element, dicarboxylic anhydride class bridge formation molecule is added in solvent 2, stir, slowly add wherein above-mentioned solution 1 after to be dissolved; Afterwards, under the protection of rare gas element, at 10～35 DEG C, react 12～24 hours, obtain solution 2;
(4) oligomeric silsesquioxane B is added in above-mentioned solution 2, stir, to be dissolved after, continue under the protection of rare gas element, at 10～35 DEG C, react 12～24 hours, obtain the pre-gathering solutions of oligomeric silsesquioxane;
By the pre-gathering solutions desolventizing of oligomeric silsesquioxane, then at 260～350 DEG C, carry out, after the imidization reaction of 2～4 hours, obtaining oligomerization silsesquioxane polymer;
Wherein, described oligomeric silsesquioxane has the structure of formula I:
formula I;
Solvent 1 is selected from N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Solvent 2 is selected from N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Solvent 1 and solvent 2 can identical can be not identical yet;
Dicarboxylic anhydride class bridge formation molecule is selected from pyromellitic acid anhydride, 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4, one or more in 4 '-phenyl ether tetracarboxylic dianhydride or 4,4-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride.
2. preparation method according to claim 1, is characterized in that: in step (3), in dicarboxylic anhydride class bridge formation molecule and solution 1, the mol ratio of oligomeric silsesquioxane A is 8:1.
3. preparation method according to claim 1, is characterized in that: described solvent 1 is N,N-dimethylacetamide or N-Methyl pyrrolidone; Solvent 2 is N,N-dimethylacetamide or N-Methyl pyrrolidone; Solvent 1 and solvent 2 can identical can be not identical yet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010118322.8A CN102140106B (en) | 2010-02-02 | 2010-02-02 | Novel oligomerization silsesquioxane polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010118322.8A CN102140106B (en) | 2010-02-02 | 2010-02-02 | Novel oligomerization silsesquioxane polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102140106A CN102140106A (en) | 2011-08-03 |
| CN102140106B true CN102140106B (en) | 2014-07-23 |
Family
ID=44407920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010118322.8A Expired - Fee Related CN102140106B (en) | 2010-02-02 | 2010-02-02 | Novel oligomerization silsesquioxane polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102140106B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949284B (en) * | 2012-02-14 | 2016-03-23 | 长安大学 | For the synthesis of catalysts system and the application of bridged polysilsesquioxane microballoon |
| CN113437361B (en) * | 2021-05-28 | 2022-11-25 | 浙江工业大学 | Polymer electrolyte membrane containing octaaminopropyl POSS hydrochloride and preparation method and application thereof |
| CN116285863B (en) * | 2023-02-17 | 2024-01-23 | 深圳市聚芯源新材料技术有限公司 | Composite engineering plastic with low dielectric constant and preparation method thereof |
| CN116515116B (en) * | 2023-03-15 | 2023-09-19 | 常熟市斯泰普新材料有限公司 | Cage-type oligomeric silsesquioxane flame retardant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060122350A1 (en) * | 2004-01-13 | 2006-06-08 | National Chiao Tung University | Convalently bonded polyhedral oligomeric silsesquioxane/polyimide nanocomposites and process for synthesizing the same |
| US20070027284A1 (en) * | 2004-01-13 | 2007-02-01 | Kuang-Hwa Wei | Covalently bonded polyhedral oligomeric silsesquioxane/polyimide nanocomposites and process for synthesizing the same |
| CN101372534A (en) * | 2007-08-24 | 2009-02-25 | 东丽纤维研究所（中国）有限公司 | Low dielectric coefficient polyimide/oligomeric silsesquioxane nano hybrid film and preparation thereof |
| CN101412847A (en) * | 2007-10-18 | 2009-04-22 | 东丽纤维研究所（中国）有限公司 | Heat resisting polyimides / polyhedral oligomeric silsesquioxane nano hybridization material |
-
2010
- 2010-02-02 CN CN201010118322.8A patent/CN102140106B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060122350A1 (en) * | 2004-01-13 | 2006-06-08 | National Chiao Tung University | Convalently bonded polyhedral oligomeric silsesquioxane/polyimide nanocomposites and process for synthesizing the same |
| US20070027284A1 (en) * | 2004-01-13 | 2007-02-01 | Kuang-Hwa Wei | Covalently bonded polyhedral oligomeric silsesquioxane/polyimide nanocomposites and process for synthesizing the same |
| CN101372534A (en) * | 2007-08-24 | 2009-02-25 | 东丽纤维研究所（中国）有限公司 | Low dielectric coefficient polyimide/oligomeric silsesquioxane nano hybrid film and preparation thereof |
| CN101412847A (en) * | 2007-10-18 | 2009-04-22 | 东丽纤维研究所（中国）有限公司 | Heat resisting polyimides / polyhedral oligomeric silsesquioxane nano hybridization material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102140106A (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101372534B (en) | Low dielectric coefficient polyimide/oligomeric silsesquioxane nano hybrid film and preparation thereof | |
| CN107108926B (en) | Method for producing polyimide film using porous particles and low dielectric constant polyimide film | |
| Zhu et al. | Preparation and properties of organosoluble polyimide/silica hybrid materials by sol–gel process | |
| JP5035830B2 (en) | Hyperbranched polyimide hybrid material | |
| JP5935158B2 (en) | Precursor composition for polyimide and use thereof | |
| JP2007246772A (en) | Multibranched polyimide-based hybrid material | |
| WO2010050491A1 (en) | Polyimide precursor solution composition | |
| CN101412847A (en) | Heat resisting polyimides / polyhedral oligomeric silsesquioxane nano hybridization material | |
| CN102140106B (en) | Novel oligomerization silsesquioxane polymer and preparation method thereof | |
| JP5437604B2 (en) | Polyimide precursor and use thereof | |
| JP6950307B2 (en) | Particle-dispersed polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film | |
| JP2012077144A (en) | Polyamideimide resin, manufacturing method therefor, polyamideimide resin solution, polyamideimide film, and use thereof | |
| JP5985977B2 (en) | Polyimide resin solution | |
| Ye et al. | A simple approach toward low‐dielectric polyimide nanocomposites: Blending the polyimide precursor with a fluorinated polyhedral oligomeric silsesquioxane | |
| Li et al. | Fluorinated polyimide with triphenyl pyridine structure for 5G communications: Low dielectric, highly hydrophobic, and highly transparent | |
| Zhou et al. | Novel acetylene‐terminated polyisoimides with excellent processability and properties comparison with corresponding polyimides | |
| CN113387977A (en) | Diamine and preparation method thereof, and polyimide and preparation method thereof | |
| Zheng et al. | Soluble polyimides containing bulky rigid terphenyl groups with low dielectric constant and high thermal stability | |
| CN101177484B (en) | Bisphenol A-type polyimide material and method for making same | |
| Qin et al. | Double phase separation in preparing polyimide/silica hybrid films by sol–gel method | |
| CN105295374A (en) | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article | |
| Liu et al. | In situ sol–gel route to novel sulfonated polyimide SiO2 hybrid proton‐exchange membranes for direct methanol fuel cells | |
| CN104861162B (en) | Containing the soluble polyimide and preparation method thereof of the tertiary butyl and fluorine-triphenylamine structure | |
| CN103342678A (en) | Aromatic diamine containing triphenylpyridine and tertiary butyl, soluble polyimide prepared from aromatic diamine, and preparation method | |
| Ma et al. | Honeycomb‐Patterned Polyimide Film as a Versatile Coating for High‐Performance Dielectric Material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140723 Termination date: 20180202 |