CN108503867B - Porous low-dielectric-constant diacetylene polymer film and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of integrated circuit manufacturing, in particular to a porous low-dielectric-constant diacetylene polymer film and a preparation method thereof. The preparation method of the porous low-dielectric-constant diacetylene polymer film comprises the following steps: synthesizing a diacetylene polymer; dissolving the diacetylene polymer in an organic solvent, pouring the solution into a film forming container, sealing the film forming container, and volatilizing part of the organic solvent until a diacetylene polymer film is formed; and solidifying the diacetylene polymer film, and evaporating the residual organic solvent to form pores so as to obtain the porous low-dielectric-constant diacetylene polymer film. The basic material has low intrinsic dielectric constant and excellent processing performance, the film forming method is simple, no pollution is generated in the forming process, the micropores are uniformly distributed and the pore diameter is uniform, and the obtained product has ultralow dielectric constant and excellent heat resistance.
Description
Technical Field
The invention relates to the technical field of integrated circuit manufacturing, in particular to a porous low-dielectric-constant diacetylene polymer film and a preparation method thereof.
Background
With the development of science and technology, the performance of electronic chips is rapidly improved, and the sizes of instruments and equipment are continuously reduced. Due to the fact that the integration level of large-scale integrated circuits is higher and higher, the characteristic size of devices is gradually reduced, the number of layers of multilayer wiring and logic interconnection is increased, the resistance of wires and the capacitance between the wires and between layers are increased, RC delay is increased, the transmission speed of the devices is limited, energy consumption is increased, and a series of problems such as noise interference occur. One of the important ways to alleviate this problem is to reduce the dielectric constant of the dielectric material.
At present, introducing a microporous structure into a material is an effective method for reducing the dielectric constant of the material, and the introduction of the microporous structure can increase the free volume of the material, so that the number of polarized groups in a unit volume is reduced, and the dielectric constant is reduced. The main porous media materials studied more at present are: porous silicon-based materials, porous polyimide materials, porous fluoropolymer materials. For porous silicon-based materialsWu Megfeng et al, by sol-gel method, prepared nano-microporous silica film with dielectric constant up to 2.5 using CTAB as template agent. However, porous silicon-based materials are more brittle and have limited application in flexible electronic materials. For the porous polyimide material, the mechanical property, the heat resistance and the like are good, but the intrinsic dielectric constant (2.9-3.6) of the polyimide material is high, so that the dielectric constant of the porous polyimide film obtained by modification is limited. The patent CN 14498900A adopts the plasma enhanced chemical vapor deposition process to prepare the porous polyimide film, and the dielectric constant of the porous polyimide film is between 2.3 and 2.5. The patent CN 104910409A adopts a calcium carbonate template etching method to prepare the porous polyimide film, and the dielectric constant of the porous polyimide film is 2.60-3.15. For porous fluoropolymer materials, the introduction of fluorine can significantly reduce the dielectric constant of the material, but fluorine-containing materials have the following disadvantages: 1. hydrogen fluoride gas is released in the heating process, and the related performance of the base material is influenced; 2. fluoropolymers have poor adhesion to electronic device substrates due to their molecular inertness. 3. The fluorine-containing materials are relatively expensive to manufacture. Thus limiting the development of fluorine-containing porous materials. Patent CN 104201149A and C2F6As a fluorine source, a PEVCD process is adopted to obtain the fluorine-containing porous polyimide film with the dielectric constant of 2.37-2.75.
Most of the methods for forming porous films used at present are relatively complex in process and high in preparation cost, and byproducts generated by certain processes pollute the environment, for example, acid substances such as hydrochloric acid, sulfuric acid and the like used for removing pore-forming substances by a template etching method. Therefore, a porous film base material with low enough intrinsic dielectric constant is sought, a porous film with low enough dielectric constant of the prepared material is prepared, the preparation process is simple, and the porous film base material plays an important role in promoting the development of electronic information technology.
Disclosure of Invention
The invention aims to provide a porous low-dielectric-constant diacetylene polymer film and a preparation method thereof, which are used for solving the problems in the prior art.
The purpose of the invention is realized by the following technical scheme: a preparation method of a porous low-dielectric-constant diacetylene polymer film comprises the following steps: synthesizing a diacetylene polymer; dissolving the diacetylene polymer in an organic solvent, pouring the solution into a film forming container, sealing the film forming container, and volatilizing part of the organic solvent until a diacetylene polymer film is formed; and solidifying the diacetylene polymer film, and evaporating the residual organic solvent to form pores so as to obtain the porous low-dielectric-constant diacetylene polymer film.
Further, the diacetylene-based polymer has the general formula:
wherein: r1And R2Are all non-polar groups;
the organic expression of R4 is:
-O-or-S-;
wherein: r3 is:
r5 and R6 are also both non-polar groups.
Further, R1And R2Are identical groups, as are R5 and R6.
Further, the reaction monomers of the diacetylene polymer are:
r1 and R2 are both non-polar groups;
r3 is:
further, R1And R2Are the same group.
Further, the monomer reaction polymerization ratio is m: n, wherein 0 < m < 1, 0 < n < 1, and the sum of m and n is 1, preferably 0.2 < m < 0.8, 0.2 < n < 0.8, and the sum of m and n is 1, more preferably 0.25 < m < 0.75, 0.25 < n < 0.75, and the sum of m and n is 1.
Further, the diacetylene polymer is dissolved in an organic solvent selected from any one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, ethyl acetate, dichloromethane and toluene.
Further, volatilizing for 2-96h, preferably 18-72 h, and more preferably 24-48 h at room temperature. According to the boiling point of the solvent, when the strong-polarity high-boiling-point solvent is adopted, the solution is only stood for a period of time (2 hours) at room temperature so as to be beneficial to full dissolution.
Further, drying the formed diacetylene polymer film in a vacuum drying oven at the temperature of 30-70 ℃, preferably 35-65 ℃, and more preferably 40-60 ℃; the drying time is 6-72h, preferably 9-60 h, more preferably 12-48 h.
Further, the formed diacetylene polymer film is placed in an air-blowing drying oven for curing, and the curing temperature is 110-250 ℃, preferably 115-200 ℃, and more preferably 110-160 ℃; the curing time is 10-120min, preferably 20-90min, and more preferably 30-60 min.
The porous low-dielectric-constant diacetylene polymer film is obtained by the preparation method of the porous low-dielectric-constant diacetylene polymer film.
Compared with the prior art, the invention has the following advantages:
1. the basic material has low intrinsic dielectric constant and excellent processing performance, the film forming method is simple (curing and pore forming are carried out simultaneously, the process is simple), no pollution is generated in the forming process, the micropores are uniformly distributed and the pore diameter is uniform, the obtained product has ultralow dielectric constant and excellent heat resistance, and as most of the formed pores are closed pores, the water absorption rate of the material is low, and meanwhile, the material meets the required mechanical properties.
2. The temperature of the diacetylene polymer film with the thermal weight loss of 5 wt% is 375 ℃ at most, the storage modulus E' can reach 4.32GPa at room temperature, and the water absorption rate is only 0.2% at least.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Firstly, selecting a diacetylene polymer with low dielectric constant and excellent processability, heat resistance and mechanical property as a film forming base material; secondly, the structural design is carried out on the diacetylene polymer, and a large-volume alkyl side chain is introduced, so that the dielectric property of the material is further reduced; and finally, adopting a polymer solution heating curing pore-forming process, adopting an organic solvent as a polymer solvent and a pore-forming agent, and completing micropore formation while curing the polymer film to prepare the porous low-dielectric dipropargyl polymer film.
The preparation method of the porous low-dielectric-constant diacetylene polymer film comprises the following steps:
(1) synthesis of Diethynyl polymers
Carrying out oxidation copolymerization on dipropargyl ether monomers by a Glaser-Hay oxidation coupling reaction according to the copolymerization ratio m: n of the reaction monomers to obtain the diacetylene polymer.
(2) Forming polymer films
Dissolving diacetylene polymer in an organic solvent by ultrasonic oscillation, pouring a diacetylene polymer solution into a culture dish, sealing the culture dish by using a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing at room temperature, then forming the diacetylene polymer film, and placing the formed film in a vacuum drying oven for drying to remove the organic solvent in the polymer film.
(3) Curing and pore forming of polymer films
And (3) placing the formed diacetylene polymer film in an air-blowing drying oven for heating and curing, and simultaneously evaporating the residual organic solvent in the polymer film to form pores, thereby finally obtaining the porous diacetylene polymer film with low dielectric constant.
The microporous film sealing is adopted to reduce the volatilization speed of the organic solvent and produce gas-liquid equilibrium conditions, so that the uniformity and the flatness of the film can be improved.
The drying process of the film in the vacuum drying oven does not completely volatilize all the solvent, and the residual solvent is used as a subsequent pore-forming agent for pore-forming.
The diacetylene-based polymer has the general formula:
R1and R2Identical or different and are nonpolar groups;
the organic expression of R4 is:
wherein: r3 is:
r5 and R6 are the same or different and are non-polar groups.
The reaction monomers of the diacetylene polymer are as follows:
R1and R2Identical or different and are nonpolar groups;
in the present invention, "nonpolar group" means a group having no polarity. In particular, the non-polar group includes an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkaryl group. The alkyl group may have 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, particularly preferably 3 to 8 carbon atoms, and may be linear or branched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. The alkyl group may contain heteroatoms, such as F. Examples of heteroatom-containing alkyl groups include, but are not limited to, -CF3 and the like. The cycloalkyl group is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. The aryl group may be a C6-C30 aryl group, preferably a C6-C20 aryl group, more preferably a C6-C14 aryl group, such as phenyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, and the like. The aralkyl group may be a C7-C30 aralkyl group, preferably a C7-C20 aralkyl group, more preferably a C7-C15 aralkyl group. The alkylaryl group can be a C7-C30 alkylaryl group, preferably a C7-C20 alkylaryl group, more preferably a C7-C15 alkylaryl group.
When R1 and R2 are alkyl, aralkyl or alkaryl, a polymer having a low dielectric constant can be obtained. Thus, R1 and R2 are preferably alkyl, aralkyl or alkaryl.
R3 is:
the monomer reaction polymerization ratio is m: n, wherein m is more than 0 and less than 1, n is more than 0 and less than 1, the sum of m and n is 1, preferably 0.2 and less than 0.8, n is more than 0.2 and less than 0.8, the sum of m and n is 1, more preferably 0.25 and less than 0.75, n is more than 0.25 and less than 0.75, and the sum of m and n is 1.
Dissolving the diacetylene polymer by using an organic solvent, wherein the organic solvent is selected from any one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, ethyl acetate, dichloromethane and toluene.
Before forming, the diacetylene polymer film is volatilized for 2h to 96h, preferably 18h to 72h, and more preferably 24h to 48h at room temperature. According to the boiling point of the solvent, when the strong-polarity high-boiling-point solvent is adopted, the solution is only stood for a period of time (2 hours) at room temperature so as to be beneficial to full dissolution.
Drying the formed diacetylene polymer film in a vacuum drying oven at the temperature of 30-70 ℃, preferably 35-65 ℃ and more preferably 40-60 ℃; the drying time is 6-72h, preferably 9-60 h, more preferably 12-48 h.
The formed diacetylene polymer film is placed in a forced air drying oven for curing, and the curing temperature is 110-250 ℃, preferably 115-200 ℃, and more preferably 110-160 ℃; the curing time is 10-120min, preferably 20-90min, and more preferably 30-60 min.
Example 1
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and the monomer dipropargyl bisphenol a ether (DPEBA) according to Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 8ml of chloroform, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 12h to further remove excess solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed PEA1-1 film in a forced air drying oven at 120 ℃ for heating and curing for 60min, and simultaneously evaporating the residual organic solvent trichloromethane in the polymer film to form holes; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The following property tests were performed on the polymer PEA1-1 film of example 1:
the cross-sectional morphology of the polymer porous film in example 1 was observed by a scanning electron microscope of model 7800F, Japan Electron Co., Ltd, and the pore size was measured. The micropores are of an ellipsoid shape, and have a long diameter of 4-12 μm and a short diameter of 2-6 μm.
Photoshop is combined with image pro plus picture processing software, the number n of pixel points of holes in the film section electron microscope picture and the number n integer of picture integral pixel points are obtained through analysis and processing, and then the film porosity (%) is calculated to be n holes/n integer multiplied by 100%. The porosity of the polymeric porous film was calculated to be 24.1%.
The polymer porous film of example 1 was subjected to a thermal stability study using a synchronous thermal analyzer model 449Cjupiter of NETZSCH company, germany, and a 5% mass loss temperature of 331 ℃.
A DMA-1 type dynamic thermal mechanical analyzer of Switzerland company is adopted to carry out dynamic mechanical thermal analysis on the polymer film, a sample is in a strip shape with the length of 2cm and the width of 1cm, the temperature range is room temperature-300 ℃, and the heating rate is 5 k/min. The storage modulus E' at room temperature (25 ℃ C.) obtained from the obtained dynamic viscoelasticity curve was 1.35 GPa.
The dielectric constant of the porous polymer film of example 1 was measured using a broadband dielectric spectrometer, model Concopt40 from Novocontrol, germany. The results show that in the range of 100-106In the Hz range, the dielectric constant of the polymer film is in the range of 1.16-1.24. The dielectric constant of the dielectric ceramic is 1.16 under 1MHz, and the dielectric ceramic has excellent dielectric property.
And (3) soaking the porous low-dielectric-constant dipropargyl polymer film in deionized water at 25 ℃ for 7 days, and measuring the water absorption of the polymer film, wherein the water absorption is 0.5%.
Example 2
(1) Synthesis of Polymer PEA3-1
The diacetylene polymer PEA3-1 was obtained by copolymerization of 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and the monomer dipropargyl bisphenol a ether (DPEBA) according to Glaser-Hay oxidative coupling reaction with m: n being 0.75:0.25, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA3-1 film formation
Dissolving 0.3g of PEA3-1 polymer in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 24h to further remove excess solvent from the polymer PEA3-1 film.
(3) Curing and pore formation of polymeric PEA3-1 film
Placing the formed polymer PEA3-1 film in a 130 ℃ forced air drying oven for heating and curing for 60min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a thin film of the porous polymer PEA3-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 2 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoid, the major diameter is 1.0-3.0 μm, the minor diameter is 0.5-1.0 μm, the porosity is 6.2%, the 5% mass loss temperature is 326 deg.C, the storage modulus at room temperature is 3.25GPa, the storage modulus at 100-10 deg.C6In the range of Hz, the dielectric constant of the polymer film is in the range of 2.13-2.16, the dielectric constant is 2.13 at 1MHz, and the water absorption rate is 0.3% at 25 ℃ for 7 days.
Example 3
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of the monomers dipropargyl bisphenol a ether (DPEBA) and 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and placed in a vacuum oven at 40 ℃ for 24h to further remove excess solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed polymer PEA1-1 film in a forced air drying oven at 140 ℃ for heating and curing for 30min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 3 was subjected to the relevant property tests in the same manner as in example 1:
its micropore is ellipsoid type, its major diameter is 3.0-8.0 micrometers, its minor diameter is 1.5-4.0 micrometers, its porosity is 13.8%, 5% mass loss temperature is 331 deg.C, and its storage modulus at room temp. is 2.44GPa, and its storage modulus is 100-10 GPa6In the range of Hz, the dielectric constant of the polymer film is in the range of 1.56-1.61, the dielectric constant is 1.56 at 1MHz, and the water absorption rate is 0.4% at 25 ℃ for 7 days.
Example 4
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of the monomers dipropargyl bisphenol a ether (DPEBA) and 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 8ml of chloroform, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 50 ℃ for 18h to further remove excess solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed PEA1-1 film in a forced air drying oven at 120 ℃ for heating and curing for 50min, and simultaneously evaporating the residual organic solvent trichloromethane in the polymer film to form holes; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 4 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoid, the major diameter is 4.0-10.0 μm, the minor diameter is 1.5-4.5 μm, the porosity is 15.8%, the 5% mass loss temperature is 331 ℃, the storage modulus at room temperature is 1.94GPa, and the storage modulus at 100-106In the Hz range, the dielectric constant of the polymer film is in the range of 1.49-1.53, the dielectric constant is 1.49 at 1MHz, and the water absorption rate is 0.5 percent at 25 ℃ for 7 days.
Example 5
(1) Synthesis of Polymer PEA1-3
The diacetylene polymer PEA1-3 was obtained by copolymerization of 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and the monomer dipropargyl bisphenol a ether (DPEBA) according to Glaser-Hay oxidative coupling reaction with m: n being 0.25:0.75, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-3 film formation
Dissolving 0.3g of PEA1-3 polymer in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 18h to further remove excess solvent from the polymer PEA1-3 film.
(3) Curing and pore formation of polymeric PEA1-3 films
Placing the formed polymer PEA1-3 film in a forced air drying oven at 150 ℃ for heating and curing for 30min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a thin film of the porous polymer PEA1-3 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 5 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoidal, and the major diameter is as follows: 2.0-7.0 μm, short diameter 1.0-3.0 μm, porosity 11.7%, 5% mass loss temperature 341 ℃, storage modulus E' 2.23GPa at room temperature, at 100-106In the Hz range, the dielectric constant of the polymer film is in the range of 1.98-2.05, the dielectric constant is 1.98 under 1MHz, and the water absorption rate is 0.3 percent under 25 ℃ for 7 days.
Example 6
(1) Synthesis of Polymer PEAF1-1
The diacetylene polymer PEAF1-1 was obtained by copolymerization of the monomers 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and dipropargyl bisphenol AF ether (DPEBAF) in a copolymerization ratio m: n of 0.5:0.5 by Glaser-Hay oxidative coupling reaction, and the product was a white fibrous solid.
(2) Polymer PEAF1-1 film formation
Dissolving 0.3g of polymer PEAF1-1 in 8ml of chloroform, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 18h to further remove excess solvent from the polymer PEAF1-1 film.
(3) Curing and pore-forming of polymeric PEAF1-1 films
Placing the formed polymer PEAF1-1 film in a 150 ℃ forced air drying oven for heating and curing for 30min, and simultaneously evaporating the residual organic solvent trichloromethane in the polymer film to form a hole; finally, a film of the porous polymer PEAF1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 6 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoid, the major diameter is 2.5-6.5 μm, the minor diameter is 2.0-4.0 μm, the porosity is 9.1%, the 5% mass loss temperature is 350 ℃, the storage modulus at room temperature is 2.61GPa, the storage modulus at 100-10 ℃ is6In the range of Hz, the dielectric constant of the polymer film is in the range of 1.35-1.38, the dielectric constant is 1.35 at 1MHz, and the water absorption rate is 0.3% at 25 ℃ for 7 days.
Example 7
(1) Synthesis of Polymer PEP3-1
The diacetylene polymer PEP3-1 was obtained by copolymerizing 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and the monomer 4-phenyl-2, 6-bis (4-propargyl-oxy-phenyl) pyridine (PPHPP) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.75:0.25, and the product was a white fibrous solid.
(2) Polymer PEP3-1 film formation
Dissolving 0.3g of polymer PEP1-1 in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and placed in a vacuum oven at 40 ℃ for 18h to further remove excess solvent from the polymer PEP3-1 film.
(3) Curing and pore-forming of polymeric PEP3-1 films
Placing the formed polymer PEP3-1 film in a 150 ℃ forced air drying oven for heating and curing for 30min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a porous polymer PEP3-1 film with the thickness of about 0.1mm is obtained.
The polymer film obtained in example 7 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoidal, and the major diameter is as follows: 1.5-5.0 μm, short diameter 0.5-1.5 μm, porosity 8.1%5% mass loss temperature of 360 ℃, storage modulus at room temperature of 4.32GPa, at 100-10%6In the Hz range, the dielectric constant of the polymer film is in the range of 1.89-1.93, the dielectric constant is 1.89 at 1MHz, and the water absorption rate is 0.4% at 25 ℃ for 7 days.
Example 8
(1) Synthesis of Polymer PEP3-1
The diacetylene polymer PEP3-1 was obtained by copolymerizing 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and the monomer 4-phenyl-2, 6-bis (4-propargyl-oxy-phenyl) pyridine (PPHPP) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.75:0.25, and the product was a white fibrous solid.
(the reaction equation is as in example 8)
(2) Polymer PEP3-1 film formation
Dissolving 0.3g of polymer PEP1-1 in 5ml of N, N-dimethylformamide, and dissolving for 30min by ultrasonic oscillation; then the polymer solution is poured into a culture dish with the diameter of 5cm and sealed by a microporous film, and then the culture dish is placed on a horizontal table, is kept stand for 2 hours at room temperature and is dried for 36 hours in a vacuum drying oven at 50 ℃ to remove excessive solvent in the polymer PEP3-1 film.
(3) Curing and pore-forming of polymeric PEP3-1 films
Placing the formed polymer PEP3-1 film in a 160 ℃ forced air drying oven for heating and curing for 60min, and simultaneously evaporating the residual organic solvent N, N-dimethylformamide in the polymer film to form pores; finally, a porous polymer PEP3-1 film with the thickness of about 0.1mm is obtained.
The polymer film obtained in example 8 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoidal, and the major diameter is as follows: 1.5-3.0 μm, short diameter 1.0-1.5 μm, porosity 12.1%, 5% mass loss temperature 360 deg.C, storage modulus E' 4.12GPa at room temperature, and storage modulus of 100-106In the Hz range, the dielectric constant of the polymer film is in the range of 1.84-1.90, the dielectric constant is 1.84 at 1MHz, and the water absorption rate is 0.6 percent at 25 ℃ for 7 days.
Example 9
(1) Synthesis of Polymer PEF3-1
The diacetylene polymer PEF3-1 was obtained by a Glaser-Hay oxidative coupling copolymerization of the monomers 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and 4- (4-trifluoromethyl) phenyl-2, 6-bis (4-propargyl-oxy-phenyl) pyridine (PFPHPP) at a copolymerization ratio m: n of 0.75:0.25, and the product was a white fibrous solid.
(2) Polymer PEF3-1 film formation
Dissolving 0.3g of polymer PEF3-1 in 4ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 24h to further remove excess solvent from the polymer PEF3-1 film.
(3) Curing and pore-forming of polymeric PEF3-1 films
Placing the formed polymer PEF3-1 film in a forced air drying oven at 150 ℃ to be heated and cured for 50min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a film of the porous polymer PTF3-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 9 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoid, the major diameter is 2.5-4.5 μm, the minor diameter is 1.5-3.0 μm, the porosity is 9.1%, the 5% mass loss temperature is 375 deg.C, the storage modulus at room temperature is 3.59GPa, the storage modulus at 100-106In the range of Hz, the dielectric constant of the polymer film is in the range of 1.54-1.57, the dielectric constant is 1.54 at 1MHz, and the water absorption rate is 0.5% at 25 ℃ for 7 days.
Example 10
(1) Synthesis of Polymer PET1-1
The diacetylene polymer PET1-1 was obtained by copolymerization of the monomers 1, 1 '- (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and 4, 4' -bis (propargyl-oxy) diphenyl sulfide (PTBP) in a Glaser-Hay oxidative coupling reaction at a copolymerization ratio m: n of 0.5:0.5, and was a white fibrous solid.
(2) Polymer PET1-1 film formation
Dissolving 0.3g of polymer PET1-1 in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 18h to further remove excess solvent from the polymer PET1-1 film.
(3) Curing and pore-forming of polymer PET1-1 film
Placing the formed polymer PET1-1 film in a forced air drying oven at 140 ℃ for heating and curing for 40min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form holes; finally, a porous polymer PTE1-1 film with the thickness of about 0.1mm is obtained.
The polymer film obtained in example 10 was subjected to the relevant property test in the same manner as in example 1:
the micropores are ellipsoid, the major diameter is 3.0-5.5 μm, the minor diameter is 2.0-3.5 μm, the porosity is 11.3%, the 5% mass loss temperature is 367 ℃, the storage modulus at room temperature is 3.76GPa, and the storage modulus is 100-10%6In the range of Hz, the dielectric constant of the polymer film is in the range of 1.72-1.77, the dielectric constant is 1.72 at 1MHz, and the water absorption rate is 0.4% at 25 ℃ for 7 days.
Example 11
(1) Synthesis of Polymer PEO1-1
The diacetylene polymer PEO1-1 was obtained by copolymerization of the monomers 1, 1 '- (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and 4, 4' -bis (propargyl-oxy) diphenyl ether (P-ODP) at a copolymerization ratio m: n of 0.5:0.5 by Glaser-Hay oxidative coupling reaction, and the product was a white fibrous solid.
(2) Polymer PEO1-1 film formation
Dissolving 0.3g of polymer PEO1-1 in 8ml of tetrahydrofuran, and dissolving 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and dried under vacuum at 40 ℃ for 18h to further remove excess solvent from the polymer PET1-1 film.
(3) Curing and pore-forming of polymeric PEO1-1 film
Placing the formed polymer PEO1-1 film in a 150 ℃ forced air drying oven for heating and curing for 40min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form holes; finally, a porous polymer PEO1-1 film with the thickness of about 0.1mm is obtained.
The polymer film obtained in example 11 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoidal, have a major diameter of 3.0-5.0 μm and a minor diameter of 1.5-3.5 μm, a porosity of 10.9%, a 5% mass loss temperature of 373 ℃, a storage modulus E' of 3.90GPa at room temperature of 100-10%6In the range of Hz, the dielectric constant of the polymer film is in the range of 1.88 to 1.92, the dielectric constant is 1.88 at 1MHz, and the water absorption rate is 0.2 percent at 25 ℃ for 7 days.
Example 12
(1) Synthesis of Polymer PEO1-1
The diacetylene polymer PEO1-1 was obtained by copolymerization of the monomers 1, 1 '- (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) and 4, 4' -bis (propargyl-oxy) diphenyl ether (P-ODP) at a copolymerization ratio m: n of 0.5:0.5 by Glaser-Hay oxidative coupling reaction, and the product was a white fibrous solid.
(the reaction equation is as in example 11)
(2) Polymer PEO1-1 film formation
Dissolving 0.3g of polymer PEO1-1 in 5ml of N, N-dimethylacetamide, and dissolving for 30min by ultrasonic oscillation; the polymer solution was then cast into a 5cm diameter petri dish and sealed with a microporous film, then placed on a horizontal bench top, allowed to stand at room temperature for 2 hours, and then dried in a 50 ℃ vacuum oven for 36 hours to remove excess solvent from the polymer PEO1-1 film.
(3) Curing and pore-forming of polymeric PEO1-1 film
Placing the formed polymer PEO1-1 film in a 160 ℃ forced air drying oven to be heated and cured for 60min, and simultaneously evaporating the residual organic solvent N, N-dimethylacetamide in the polymer film to form holes; finally, a porous polymer PEO1-1 film with the thickness of about 0.1mm is obtained.
The polymer film obtained in example 12 was subjected to the relevant property test in the same manner as in example 1:
the micropores are ellipsoidal, with a major diameter of 2.0-3.0 μm and a minor diameter of 1.0-2.0 μm, a porosity of 13.1%, a 5% mass loss temperature of 373 deg.C, a storage modulus E' of 3.64GPa at room temperature of 100-10%6In the range of Hz, the dielectric constant of the polymer film is in the range of 1.84-1.87, the dielectric constant is 1.84 at 1MHz, and the water absorption rate is 0.4% at 25 ℃ for 7 days.
Example 13
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of the monomers dipropargyl bisphenol a ether (DPEBA) and 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 8ml of chloroform, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 12 hours at room temperature, and basically shaping the film; the film was then removed and placed in a vacuum oven at 30 ℃ for 72h to further remove excess solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed PEA1-1 film in a forced air drying oven at 250 ℃ for heating and curing for 10min, and simultaneously evaporating the residual organic solvent trichloromethane in the polymer film to form holes; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 3 was subjected to the relevant property tests in the same manner as in example 1:
its micropore is ellipsoid type, its major diameter is 4.5-12.0 micrometers, its minor diameter is 2.5-6.5 micrometers, porosity is 35.3%, 5% mass loss temperature is 331 deg.C, storage modulus at room temp. is 0.98GPa, and its storage modulus is 100-10 GPa6In the range of Hz, the dielectric constant of the polymer film is in the range of 1.11-1.21, the dielectric constant is 1.11 at 1MHz, and the water absorption rate is 1.0% at 25 ℃ for 7 days.
Example 14
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of the monomers dipropargyl bisphenol a ether (DPEBA) and 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 96 hours at room temperature, and basically shaping the film; the film was then removed and placed in a vacuum oven at 70 ℃ for 6h to further remove excess solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed polymer PEA1-1 film in a 110 ℃ forced air drying oven for heating and curing for 90min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 3 was subjected to the relevant property tests in the same manner as in example 1:
the micropores are ellipsoid, the major diameter is 3.5-8.0 μm, the minor diameter is 1.5-4.0 μm, the porosity is 7.3%, the 5% mass loss temperature is 331 ℃, the storage modulus at room temperature is 2.58GPa, and the storage modulus at 100-106In the range of Hz, the dielectric constant of the polymer film is in the range of 2.01-2.06, the dielectric constant is 2.01 under 1MHz, and the water absorption rate is 0.5 percent under 25 ℃ for 7 days.
Comparative example 1
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of the monomers dipropargyl bisphenol a ether (DPEBA) and 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 8ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, sealing the culture dish by adopting a microporous film, then placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and placed in a vacuum oven at 40 ℃ for 7d to further remove the solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed polymer PEA1-1 film in a forced air drying oven at 140 ℃ for heating and curing for 30min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 3 was subjected to the relevant property tests in the same manner as in example 1:
the obtained film is a dense non-porous film, the 5% mass loss temperature is 331 ℃, the storage modulus at room temperature is 4.61GPa, and the storage modulus is 100-10%6In the range of Hz, the dielectric constant of the polymer film is in the range of 2.45-2.51, the dielectric constant is in the range of 2.45-2.51 under 1MHz, and the water absorption rate is 0.1 percent under 25 ℃ for 7 days.
Comparative example 2
(1) Synthesis of Polymer PEA1-1
The diacetylene polymer PEA1-1 was obtained by copolymerization of the monomers dipropargyl bisphenol a ether (DPEBA) and 1, 1' - (1, 3-dimethylbutylidene) bis (4- (2-propynyloxy)) benzene (DBDPE) according to a Glaser-Hay oxidative coupling reaction with m: n being 0.5:0.5, and the product was a white fibrous solid.
(the reaction equation is as in example 1)
(2) Polymer PEA1-1 film formation
Dissolving 0.3g of PEA1-1 polymer in 12ml of tetrahydrofuran, and dissolving for 30min by ultrasonic oscillation; then pouring the polymer solution into a culture dish with the diameter of 5cm, (without a film seal) and placing the culture dish on a horizontal table, naturally volatilizing for 48 hours at room temperature, and basically shaping the film; the film was then removed and placed in a vacuum oven at 40 ℃ for 6h to further remove the solvent from the polymer PEA1-1 film.
(3) Curing and pore formation of polymeric PEA1-1 film
Placing the formed polymer PEA1-1 film in a forced air drying oven at 140 ℃ for heating and curing for 30min, and simultaneously evaporating the residual organic solvent tetrahydrofuran in the polymer film to form pores; finally, a thin film of the porous polymer PEA1-1 with a thickness of about 0.1mm was obtained.
The polymer film obtained in example 3 was subjected to the relevant property tests in the same manner as in example 1:
the resulting film was an open-porous film with through-openings visible to the naked eye, 5% mass loss temperature of 331 ℃ and storage modulus E' of 0.70GPa at room temperature, and the dielectric constant could not be determined due to the through-openings of the film. The water absorption at 25 ℃ for 7 days was 8.2%.
TABLE 1 results of the Performance test of examples 1-14
From the above, the porous diacetylene-based polymer film with low dielectric constant of the invention has an ultra-low dielectric constant, which can be as low as 1.11; the material has higher heat-resistant temperature, and the related process parameters in the embodiment have little influence on the heat-resistant performance of the material except the copolymerization ratio of the monomers and the types of the monomers. The storage modulus of the porous polymer film can reach 4.32 GPa. On the other hand, different process parameters cause the porosity and the pore size of the porous polymer film to be different, the long diameter of the pore size is between 1.0 and 12.0 mu m, the short diameter is between 0.5 and 6.0 mu m, and the porosity is between 6.2 and 35.3 percent. Micropores are uniformly distributed in the film and are of closed pore structures, so that the influence on the water absorption of the polymer film is small, and the water absorption is lower and is between 0.2 and 1.0 percent. Therefore, the porous diacetylene polymer film has potential application value and good application prospect in the field of integrated circuits.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A preparation method of a porous low-dielectric-constant diacetylene polymer film is characterized by comprising the following steps:
synthesizing a diacetylene polymer;
dissolving a diacetylene polymer in an organic solvent, pouring the solution into a film forming container, sealing the film forming container by using a microporous film, naturally volatilizing the solution at room temperature for 2 to 96 hours to form the diacetylene polymer film, and drying the formed film in a drying oven with the vacuum degree of-0.08 to-0.1 MPa, wherein the drying temperature is 30 to 70 ℃, and the drying time is 6 to 72 hours to remove the organic solvent in the polymer film so as to form the diacetylene polymer film;
placing the diacetylene polymer film in a forced air drying oven for curing, evaporating the residual organic solvent to form a hole, wherein the curing temperature is 110-250 ℃, and the curing time is 10-90min, so as to obtain the porous diacetylene polymer film with low dielectric constant;
the diacetylene-based polymer has the general formula:
wherein: r1And R2Are all non-polar groups;
R4the organic expression is as follows:
wherein: r3Comprises the following steps:
R5and R6Are also all non-polar groups.
2. The method of claim 1, wherein R is selected from the group consisting of1And R2Are identical radicals, R5And R6Are also the same groups.
3. The method of claim 1, wherein the reaction monomers of the diacetylene based polymer are:
R1and R2Are all non-polar groups;
R3comprises the following steps:
4. the method of claim 3, wherein the monomer reaction polymerization ratio is m: n, wherein m is more than 0 and less than 1, n is more than 0 and less than 1, and the sum of m and n is 1.
5. The method of claim 1, wherein the organic solvent is selected from the group consisting of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, ethyl acetate, dichloromethane, and toluene.
6. A porous low dielectric constant diacetylene based polymer film obtained by the method of making a porous low dielectric constant diacetylene based polymer film according to any one of claims 1 to 5.
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