CN110527293B - Basalt flake fiber modified polyimide film - Google Patents
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
A basalt flake fiber-modified polyimide film has lower water absorption, higher strength and better heat resistance than an unmodified film of the same kind. The invention aims to solve the technical problems that the basalt scale fibers are easy to agglomerate and not easy to disperse due to the interlaminar acting force of the basalt scale fibers in a polymer matrix, and the basalt scale fibers are subjected to surface modification by using an end aminosilane coupling agent, the surface roughness of the basalt scale fibers is changed by a microwave liquid-phase auxiliary method, so that the infiltration modification effect of the end aminosilane coupling agent is improved, the grafting rate of amino functional groups is improved, amino groups on the surfaces of the modified basalt scale fibers are bonded with monomer dianhydride through in-situ polymerization, inorganic fibers are uniformly and stably dispersed in a polyimide system in a chemical bonding mode, and the agglomeration of the scale fibers is avoided. The invention belongs to the field of modified polyimide films.
Description
Technical Field
The invention relates to a polyimide film modified by basalt flake fibers.
Background
The basalt flake is a novel flake material, has a transparent or dark green sheet-shaped structure, is generally about 3 mu m thick and is generally about 25 mu m-3 mm in size. Because the basalt flakes contain high contents of iron oxide, titanium dioxide, aluminum oxide and calcium oxide and contain less content of alkaline oxide, the basalt flakes not only can generate a shielding effect, but also have unique advantages in the aspects of acid-base resistance and corrosion resistance. The basalt scale fibers belong to lamellar fibers, and the interlayer acting force makes the basalt scale fibers extremely easy to agglomerate and disperse in a polymer matrix.
Disclosure of Invention
The invention aims to solve the technical problem that the interlaminar acting force of basalt flake fibers causes the fibers to be easily agglomerated and not easily dispersed in a polymer matrix, and provides a polyimide film modified by the basalt flake fibers, wherein the method is suitable for in-situ polymerization reaction for preparing PI (polyimide) by taking diamine as a monomer.
The basalt flake fiber modified polyimide film comprises 1-5% by mass of basalt flake fibers subjected to surface modification by an amino-terminated coupling agent.
The preparation method of the basalt flake fiber modified polyimide film comprises the following steps:
firstly, adding basalt flake fibers into absolute ethyl alcohol, and performing ultrasonic dispersion and cleaning to obtain pretreated basalt flake fibers;
adding an amino silane coupling agent into ethanol to prepare a soaking solution, adding the pretreated basalt scale fibers, stirring at a low speed for 1h under an ultrasonic condition, taking out, soaking and washing for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ to obtain the basalt scale fibers treated by the coupling agent;
adding 1 part by mole of diamine monomer and basalt flake fiber treated by a coupling agent into a solvent at 0-5 ℃, wherein the addition amount of the solvent is calculated according to the solid content of the product and the mass fraction of 15%, stirring until the solvent is completely dissolved, then adding 1.1 parts by mole of dianhydride monomer in batches, carrying out in-situ polymerization reaction (noting that the feeding amount of each time is not too large to cause the local monomer to be dissolved and to generate implosion), and continuously reacting for 1-12 hours after the addition is finished to obtain a polyamic acid solution;
and fourthly, filtering the polyamide acid solution by using a 200-mesh copper net, coating a film on a glass plate by using an automatic film coating machine, wherein the thickness of the film is 0.5mm, drying the film in an ultra-clean room at room temperature for 24 hours, and then putting the film in an air drying oven for heating up for hot imidization in a gradient manner to obtain the basalt scale fiber modified polyimide film.
And in the second step, the amino-terminated siloxane is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -aminopropyltriethoxysilane or N-beta (aminoethyl) -aminopropylmethyldiethoxysilane.
The mass fraction of the coupling agent in the ethanol impregnating solution prepared in the second step is 5-10%, and the surface modification method in the second step is a microwave liquid phase auxiliary method.
The adding amount of the modified basalt flake fibers in the third step is 1-5% of the total mass of the added monomers.
The diamine in the third step is diaminodiphenyl ether, p-phenylenediamine, biphenyldiamine or benzophenone tetracarboxylic dianhydride;
the dianhydride in the third step is benzophenone tetracarboxylic dianhydride, pyromellitic anhydride or diphenyl ether tetracarboxylic dianhydride.
The diamine in the third step is fluorine-containing diamine or alicyclic diamine monomer.
The dianhydride in the third step is fluorine-containing dianhydride or alicyclic dianhydride monomer.
And step three, the organic solvent is one or a mixture of several of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran in any ratio.
The invention aims to prepare a basalt flake fiber modified PI film, wherein the modified PI film has better heat resistance and lower water absorption. The dispersibility of the basalt scales in a polymer matrix is improved, the basalt scales need to be subjected to surface modification, the interface compatibility is improved, and chemical bonding is generated. The basalt flake fiber with the surface grafted with the amino group can be subjected to chemical reaction with anhydride in a polyimide monomer and uniformly dispersed in a polyimide system. Because of the labyrinth effect formed by the basalt scale fibers, the permeability resistance and the corrosion resistance of the polymer matrix can be obviously enhanced, so that the water resistance, the permeability resistance, the corrosion resistance and the mechanical property of the polyimide film are improved and enhanced.
The method changes the surface roughness of the basalt scale fibers by a microwave liquid-phase auxiliary method, can improve the effect of wetting modification of an aminosilane-terminated coupling agent, improves the grafting rate of amino functional groups, and uniformly and stably disperses the basalt scale fibers in a polyimide system in a chemical bonding mode by adopting an in-situ polymerization method, thereby avoiding the negative influence on the polymer performance caused by the agglomeration of the scale fibers.
Drawings
FIG. 1 is an infrared spectroscopic analysis chart of basalt fiber before and after modification in the first experiment;
FIG. 2 is a scanning electron microscope photograph of the modified PI film mechanical section basalt fiber distribution in experiment two;
fig. 3 is a TG test chart of the modified polyimide film in experiment two.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the polyimide film modified by the basalt flake fibers comprises 1-5% by mass of basalt flake fibers subjected to surface modification by an amino-terminated coupling agent.
The second embodiment is as follows: detailed description of the inventiona basalt flake fiber-modified polyimide film according to a first embodiment is characterized in that the preparation method of the film is as follows
Firstly, adding basalt flake fibers into absolute ethyl alcohol, and performing ultrasonic dispersion and cleaning to obtain pretreated basalt flake fibers;
adding an amino silane coupling agent into ethanol to prepare a soaking solution, adding the pretreated basalt scale fibers, stirring at a low speed for 1h under an ultrasonic condition, taking out, soaking and washing for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ to obtain the basalt scale fibers treated by the coupling agent;
adding 1 part by mole of diamine monomer and the basalt flake fiber treated by the coupling agent into a solvent at 0-5 ℃, wherein the adding amount of the solvent is calculated according to the solid content of the product, namely the mass fraction of 15%, stirring the mixture until the mixture is completely dissolved, then adding 1.1 parts by mole of dianhydride monomer in batches for in-situ polymerization, and continuously reacting for 1-12 hours after the addition is finished to obtain a polyamide acid solution;
and fourthly, filtering the polyamide acid solution by using a 200-mesh copper net, coating a film on a glass plate by using an automatic film coating machine, wherein the thickness of the film is 0.5mm, drying the film in an ultra-clean room at room temperature for 24 hours, and then putting the film in an air drying oven for heating up for hot imidization in a gradient manner to obtain the basalt scale fiber modified polyimide film.
The third concrete implementation mode: the difference between this embodiment and the second embodiment is that in the second step, the amino-terminated siloxane is γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) -aminopropylmethyldimethoxysilane, N- β (aminoethyl) -aminopropyltriethoxysilane, or N- β (aminoethyl) -aminopropylmethyldiethoxysilane. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the second or third embodiment in that the mass fraction of the coupling agent in the ethanol immersion liquid prepared in the second step is 5-10%, and the surface modification method in the second step is a microwave liquid phase assisted method. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between the embodiment and one of the second to fourth embodiments is that the adding amount of the modified basalt flake fibers in the third step is 1 to 5 percent of the total mass of the added monomers. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: this embodiment is different from one of the second to fifth embodiments in that the diamine described in the third step is diaminodiphenyl ether (ODA), p-phenylenediamine, biphenyldiamine, or benzophenonetetracarboxylic dianhydride; the dianhydride in the third step is benzophenone tetracarboxylic dianhydride, pyromellitic anhydride or diphenyl ether tetracarboxylic dianhydride. . The rest is the same as one of the second to fifth embodiments.
The seventh embodiment: this embodiment is different from any one of the second to sixth embodiments in that the diamine in the third step is a fluorine-containing diamine or an alicyclic diamine monomer. The rest is the same as one of the second to sixth embodiments.
The specific implementation mode is eight: this embodiment is different from one of the second to seventh embodiments in that the dianhydride in step three is a fluorine-containing dianhydride or an alicyclic dianhydride monomer. The rest is the same as one of the second to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the second to eighth embodiments is that the organic solvent in the third step is one or a mixture of several of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran in any ratio. The rest is the same as the second to eighth embodiments.
In the case where the organic solvent is a mixture, the ratio of the components is arbitrary.
The detailed implementation mode is ten: the difference between this embodiment and one of the second to ninth embodiments is that the thermal imidization process in the fourth step is: constant temperature of 120 ℃ for 1.5h, constant temperature of 180 ℃ for 1h, constant temperature of 240 ℃ for 1h, and constant temperature of 280 ℃ for 1 h. The rest is the same as in one of the second to ninth embodiments.
The following experiments are adopted to verify the effect of the invention:
experiment one:
preparing an impregnating solution with the mass fraction of 5% by using aminosilane KH-550 and absolute ethyl alcohol, soaking the basalt scale fibers subjected to ultrasonic dispersion treatment in the impregnating solution, stirring at a low speed for 1h under an ultrasonic condition, taking out the basalt scale fibers, soaking and washing the basalt scale fibers for 3 times by using the absolute ethyl alcohol, and drying a solvent at the temperature of 80 ℃ to obtain the modified basalt scale fibers.
A1000 ml three-necked flask equipped with a stirrer and a thermometer was charged with N2After drying for 3min, adding 39g of diaminodiphenyl ether and modified basalt flake fiber into N, N-dimethylacetamide, stirring and dissolving to obtain a mixed solution, wherein the addition amount of the modified basalt flake fiber is 1% of the total mass of the two reaction monomers, cooling the reaction kettle to 0-5 ℃ by using a low-temperature cooling circulating pump, weighing 44g of pyromellitic dianhydride, adding the pyromellitic dianhydride into the solution in batches, adding the pyromellitic dianhydride into the solution once every 15min according to the viscosity of the reaction kettle until the addition is finished, and reacting for 12h after the addition is finished to obtain a light yellow transparent polyamic acid solution.
Filtering the obtained polyamic acid solution through a 200-mesh copper net, coating a film on a clean glass plate by using an automatic film coating machine, wherein the thickness of the film is 0.5mm, drying the film in a super-clean room at room temperature for 24h, then putting the film into an air-blast drying oven to heat up for imidization in a gradient manner, and obtaining the yellowish transparent polyimide modified film under the process conditions of constant temperature of 120 ℃ for 1.5h, constant temperature of 180 ℃ for 1h, constant temperature of 240 ℃ for 1h and constant temperature of 280 ℃ for 1 h.
Experiment two:
preparing an impregnating solution with the mass fraction of 10% by using aminosilane KH-550 and absolute ethyl alcohol, soaking basalt scale fibers subjected to ultrasonic dispersion treatment in the impregnating solution, stirring at a low speed for 1h under an ultrasonic condition, taking out the basalt scale fibers, soaking and washing the basalt scale fibers for 3 times by using the absolute ethyl alcohol, and drying a solvent at the temperature of 80 ℃ to obtain the modified basalt scale fibers.
A1000 ml three-necked flask equipped with a stirrer and a thermometer was charged with N2After drying for 3min, adding 39g of diaminodiphenyl ether and modified basalt flake fiber into N, N-dimethylacetamide, stirring and dissolving to obtain a mixed solution, wherein the addition amount of the modified basalt flake fiber is 3% of the total mass of the two reaction monomers, cooling the reaction kettle to 0-5 ℃ by using a low-temperature cooling circulating pump, weighing 44g of pyromellitic dianhydride, adding the pyromellitic dianhydride into the solution in batches, adding the pyromellitic dianhydride into the solution once every 15min according to the viscosity of the reaction kettle until the addition is finished, and reacting for 12h after the addition is finished to obtain a light yellow transparent polyamic acid solution.
Filtering the obtained polyamic acid solution through a 200-mesh copper net, coating a film on a clean glass plate by using an automatic film coating machine, wherein the thickness of the film is 0.5mm, drying the film in a super-clean room at room temperature for 24h, then putting the film into an air-blast drying oven to heat up for imidization in a gradient manner, and obtaining the yellowish transparent polyimide modified film under the process conditions of constant temperature of 120 ℃ for 1.5h, constant temperature of 180 ℃ for 1h, constant temperature of 240 ℃ for 1h and constant temperature of 280 ℃ for 1 h.
And (3) carrying out water absorption test, mechanical strength test, SEM (scanning electron microscope) test of film sections, infrared spectrum analysis, thermal weight loss analysis and other tests on the films of the first and second experiments to determine the modification effect of the basalt fibers.
In the figure 1, the upper curve is an infrared spectrogram of unmodified basalt fiber, the lower curve is an infrared spectrogram of basalt fiber modified by KH-550 coupling agent, and the comparison of the upper curve and the lower curve shows that unmodified basalt is 908cm-1The peak has a smooth and wide shape, which is a common characteristic of silicate infrared spectra and belongs to stretching vibration peaks of Si-O and Si-O-Si structures, the wave number of the peak is smaller than that of a normal Si-O vibration peak, and the peak width reaches 400cm-1This is due to basalt fiberAl in the dimension occupies the place of Si, and the vibration frequency of Si-O bonds is reduced and the peak shape is widened due to the poor order degree of Al. The modified basalt fiber is 3300-3600cm-1A plurality of weak absorption peaks which are different from the absorption peaks before modification and are attributed to-NH grafted by the coupling agent appear in the range2And ion formed diffusion peak, 2972cm-1And 2921cm-1The vibration peak is C-H symmetric and antisymmetric stretching vibration peak on methyl, and due to the addition of Si-O bond in the silane coupling agent, the original vibration peak is 908cm-1The single round broad peak at the position is split into 1074cm-1And 959cm-1The bimodal, these features all demonstrate the grafting effect of the modification process of the invention.
Fig. 2 shows a mechanical section SEM scanning electron microscope test chart of the product film obtained in the second experiment, from which it can be seen that the distribution of basalt flake fibers on the film section is very uniform with only a very small amount of particles agglomerated, because the doping amount in the second experiment is larger, the electron microscope photograph of the fiber distribution is more representative, which illustrates that the method used in the present invention has a very good improvement effect on the dispersion of basalt fibers in the resin matrix.
Fig. 3 shows that compared with the PI film heat loss analysis test obtained in the second experiment, theoretically, the addition of basalt fibers should make a positive contribution to the heat resistance of the material, the upper curve of fig. 3 is an unmodified PI film, the temperature of Td 5% (5% loss) is 526 ℃, the lower curve is a modified PI film added with basalt fibers with the mass fraction of 3%, the weight loss temperature Td 5% is 537 ℃, and the heat resistance of the material is improved.
The water absorption test results in table 1 show that the water absorption is significantly reduced as the amount of basalt flake fibers added increases. The tensile strength of the PI film of the example product is listed in Table 2, and the tensile strength of the PI film is increased along with the increase of basalt fibers, and the test results prove that the addition of the basalt fibers can reduce the water absorption of the PI film and enhance the mechanical strength of the PI film.
TABLE 1 comparison of PI film Water absorption data before and after modification
TABLE 2 comparison of tensile Strength of PI films before and after modification
Claims (9)
1. A basalt flake fiber modified polyimide film is characterized in that: the polyimide film comprises 1-5% by mass of basalt flake fibers subjected to surface modification by an amino-terminated coupling agent, and the preparation method of the film comprises the following steps:
firstly, adding basalt flake fibers into absolute ethyl alcohol, and performing ultrasonic dispersion and cleaning to obtain pretreated basalt flake fibers;
adding an amino silane coupling agent into ethanol to prepare a soaking solution, adding the pretreated basalt scale fibers, stirring at a low speed for 1h under an ultrasonic condition, taking out, soaking and washing for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ to obtain the basalt scale fibers treated by the coupling agent;
adding 1 part by mole of diamine monomer and the basalt flake fiber treated by the coupling agent into a solvent at 0-5 ℃, wherein the adding amount of the solvent is calculated according to the solid content of the product, namely the mass fraction of 15%, stirring the mixture until the mixture is completely dissolved, then adding 1.1 parts by mole of dianhydride monomer in batches for in-situ polymerization, and continuously reacting for 1-12 hours after the addition is finished to obtain a polyamide acid solution;
and fourthly, filtering the polyamide acid solution by using a 200-mesh copper net, coating a film on a glass plate by using an automatic film coating machine, wherein the thickness of the film is 0.5mm, drying the film in an ultra-clean room at room temperature for 24 hours, and then putting the film in an air drying oven for heating up for hot imidization in a gradient manner to obtain the basalt scale fiber modified polyimide film.
2. The basalt flake fiber-modified polyimide film of claim 1, wherein in step two the aminosilane-terminated coupling agent is γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) -aminopropylmethyldimethoxysilane, N- β (aminoethyl) -aminopropyltriethoxysilane, or N- β (aminoethyl) -aminopropylmethyldiethoxysilane.
3. The basalt flake fiber-modified polyimide film as claimed in claim 1, wherein the mass fraction of the coupling agent in the ethanol impregnating solution prepared in the second step is 5% to 10%.
4. The basalt scale fiber modified polyimide film according to claim 1, wherein the amount of the basalt scale fiber added after modification in the third step is 1 to 5 percent of the total mass of the added monomers.
5. The basalt flake fiber-modified polyimide film according to claim 1, wherein the diamine in step three is diaminodiphenyl ether, p-phenylenediamine, biphenyldiamine;
the dianhydride in the third step is benzophenone tetracarboxylic dianhydride, pyromellitic anhydride or diphenyl ether tetracarboxylic dianhydride.
6. The basalt flake fiber-modified polyimide film according to claim 1, wherein the diamine in step three is a fluorine-containing diamine or an alicyclic diamine monomer.
7. The basalt flake fiber-modified polyimide film according to claim 1, wherein the dianhydride in step three is a fluorine-containing dianhydride or an alicyclic dianhydride monomer.
8. The basalt flake fiber modified polyimide film according to claim 1, wherein the solvent in step three is one or a mixture of several of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and tetrahydrofuran in any ratio.
9. The basalt scale fiber modified polyimide film according to claim 1, which is characterized in that the thermal imidization process in the four steps comprises: constant temperature of 120 ℃ for 1.5h, constant temperature of 180 ℃ for 1h, constant temperature of 240 ℃ for 1h, and constant temperature of 280 ℃ for 1 h.
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| CN110843294B (en) * | 2019-12-04 | 2021-06-01 | 中国科学院兰州化学物理研究所 | Preparation method of high-speed working condition self-lubricating fabric liner composite material |
| CN112426619A (en) * | 2020-10-26 | 2021-03-02 | 广东泰宝医疗科技股份有限公司 | Quantum energy fiber modified ion induction matrix material |
| CN114656690B (en) * | 2022-02-28 | 2024-03-29 | 海南联塑科技实业有限公司 | Modified basalt flake material, preparation method thereof and HDPE double-wall corrugated pipe containing modified basalt flake material |
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