CN112940254A - Polyimide shell for microcapsule type curing agent and preparation method thereof - Google Patents
Polyimide shell for microcapsule type curing agent and preparation method thereof Download PDFInfo
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 85
- 229920001721 polyimide Polymers 0.000 title claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- 239000003094 microcapsule Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 20
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 150000001345 alkine derivatives Chemical class 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 230000001154 acute effect Effects 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 29
- 239000011347 resin Substances 0.000 abstract description 29
- 239000011159 matrix material Substances 0.000 abstract description 16
- 239000012467 final product Substances 0.000 abstract description 8
- 125000002355 alkine group Chemical group 0.000 abstract 2
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- 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
Abstract
A polyimide shell for a microcapsule type curing agent and a preparation method thereof comprise the following steps of (1) pretreatment: putting aromatic diamine and aliphatic diamine into a polar solution for dissolving; (2) stirring treatment: stirring the obtained dissolved solution, adding aromatic tetracarboxylic dianhydride in the stirring process, and keeping stirring for 24 hours to obtain viscous liquid; (3) and (3) post-treatment: the obtained viscous liquid is filtered, washed and dried to obtain the polyimide. According to the polyimide shell, the aliphatic diamine containing the alkyne structure is introduced, so that the temperature of the polyimide shell during initial melting is reduced, the curing agent in the polyimide shell can be released and contacted with the matrix resin, the polyimide shell can perform a crosslinking reaction at the temperature of 200-300 ℃, the heat resistance of the polyimide shell is improved, the problem that the heat resistance of the resin is deteriorated due to poor heat resistance of the shell is solved, and the dielectric loss of a final product is reduced due to the introduction of the aliphatic diamine containing the alkyne structure.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of polyimide shells and preparation methods thereof, in particular to a polyimide shell for a microcapsule type curing agent and a preparation method thereof.
[ background of the invention ]
The microcapsule curing agent is a curing agent which wraps the curing agent with microcapsules, prevents the curing agent from contacting with matrix resin and reacting at room temperature, prolongs the storage period of the resin, and then releases the curing agent to complete the curing reaction by breaking the microcapsules under certain conditions. However, since the microcapsule wall material must be broken at a high temperature to release the internal curing agent and bring the curing agent into contact with the matrix resin, the wall material part of the microcapsule curing agent is generally composed of a resin having poor heat resistance, and the mixing of the wall material resin having poor heat resistance deteriorates the heat resistance of the final resin, resulting in a problem of poor heat resistance of the matrix resin.
In order to solve the above problems, patent CN95104094.4 discloses a microcapsule type curing agent and a preparation method thereof, wherein the wall material part of the microcapsule type curing agent is composed of aromatic thermoplastic polymer, and has a high heat-resistant temperature, but the aromatic polymer is generally difficult to dissolve, and the resin is not easy to break and release the curing agent inside during curing, which is easy to cause incomplete final curing of the product.
In addition, with the rapid development of electronic equipment and the arrival of the 5G era in recent years, the frequency band used is higher than that of the 4G era, so that the transmission process of signals in electronic devices has higher delay and loss, and therefore, the 5G era puts higher demands on the dielectric loss of electronic device materials. Aromatic polymers generally have high dielectric loss, which is not favorable for reducing the dielectric loss of resins.
[ summary of the invention ]
The present invention is directed to solving the above problems, and an object of the present invention is to provide a polyimide jacket and a method for preparing the same, which solve the problems of the conventional polyimide jacket that the curing agent is not easily melted to release the curing agent, the heat resistance of the polyimide jacket cannot be improved, and the dielectric loss is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyimide shell for a microcapsule-type curing agent having the following structure:
wherein n is1And n2Are all numbers greater than zero, Ar1Is a structural unit of an aromatic tetracarboxylic dianhydride derivative, Ar2Is a structural unit of an aromatic diamine derivative, R1Is an aliphatic structural unit containing alkyne.
Preferably, R1Is a long-chain alkyne of more carbons, R1Is of the general formula CnH2n-4-(NH2)2。
Preferably, n in the polyimide2And n1+n2The ratio of the amounts of the substances in (b) ranges from 0.5 to 0.9.
Preferably, the melting point of the polyimide shell is between 110 and 170 degrees.
Preferably, the polyimide jacket undergoes a self-crosslinking reaction between 200 and 300 deg..
Preferably, the carbon chain length of R is between 4 and 12 carbon atoms.
A preparation method of a polyimide shell for a microcapsule type curing agent comprises the following steps:
(1) and pretreatment: putting aromatic diamine and aliphatic diamine containing alkyne structure into a polar organic solvent for dissolving;
(2) and stirring treatment: stirring the obtained solution, adding aromatic tetracarboxylic dianhydride in the stirring process, and keeping stirring for 24 hours to obtain viscous liquid;
(3) and post-treatment: and filtering, washing and drying the obtained viscous liquid to obtain the required polyimide shell.
Preferably, the polar organic solvent in step (1) is a polar aprotic solvent, and the acute solvent is one or a combination of two or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the aromatic diamine in the step (1) is one or a combination of two of 4,4' -diaminodiphenyl ether and 3- (3-aminophenoxy) aniline, and when the aromatic diamine is a combination of two solvents, the ratio therebetween may be any ratio.
Preferably, the tetracarboxylic dianhydride in the step (2) is one or a combination of two or more of 4,4 '-diphenyl ether dianhydride, 4' -p-phenylene bisphthalic anhydride and pyromellitic dianhydride, and when the tetracarboxylic dianhydride is a combination of two or more, the ratio of the tetracarboxylic dianhydride to the pyromellitic dianhydride can be any ratio.
The contribution of the invention lies in: according to the polyimide shell, the aliphatic diamine containing the alkyne structure is introduced, so that the temperature of the polyimide shell during initial melting is well reduced, the curing agent in the polyimide shell can be fully released and contacted with the matrix resin, the polyimide shell can perform a crosslinking reaction at the temperature of 200-300 ℃, the heat resistance of the polyimide shell is improved, the problem that the heat resistance of a final product is influenced due to the fact that the final product is mixed with components with poor heat resistance is well solved, and the dielectric loss of the final product is well reduced due to the introduction of the aliphatic diamine containing the alkyne structure.
[ description of the drawings ]
FIG. 1 is a schematic diagram of a manufacturing scheme of the present invention;
[ detailed description ] embodiments
The following examples are further illustrative and supplementary to the present invention and do not limit the present invention in any way.
A polyimide shell for a microcapsule-type curing agent, characterized by having the following structure:
wherein n is1And n2Are all numbers greater than zero, Ar1Is a structural unit of an aromatic tetracarboxylic dianhydride derivative, Ar2Is a structural unit of an aromatic diamine derivative, R1Is an aliphatic structure containing an alkyne structureAnd (4) units.
The microcapsule is used for wrapping the curing agent, the curing agent in the microcapsule is released by melting the shell of the microcapsule at a certain temperature, and the shell of the microcapsule is contacted with the external matrix resin, so the traditional shell is usually made of resin with poor heat resistance, but the wall material resin with poor heat resistance is remained in the product after being melted, and the heat resistance of the final product is affected. The shell composed of aromatic thermoplastic polymers is also partially used, but the aromatic thermoplastic polymers have higher heat resistance temperature, the aromatic polymers are generally difficult to melt, the shell is not easy to break to release the internal curing agent during resin curing, and the final curing of the product is incomplete due to insufficient curing agent amount, so that the product quality is affected.
The polyimide shell is obtained by polymerizing aromatic tetracarboxylic dianhydride, aromatic diamine and aliphatic diamine containing an alkyne structure, and part of aromatic compounds are replaced by the aliphatic diamine containing the alkyne structure, so that the melting temperature of the polyimide shell is improved, the polyimide shell can be melted at the temperature of 110-170 ℃, an internal curing agent can be released, the curing agent is reacted with matrix resin to obtain a required product, the situation that the shell is difficult to melt cannot occur, and the final incomplete curing of the product cannot be caused.
On the other hand, the aliphatic diamine containing alkyne structure can generate self-crosslinking reaction along with the rise of temperature, thereby ensuring that the polyimide shell has good heat resistance, and no component with poor heat resistance is mixed in the product to influence the product quality.
In addition, with the rapid development of electronic equipment and the arrival of the 5G era in recent years, the frequency band used is higher than that of the 4G era, so that the transmission process of signals in electronic devices has higher delay and loss, and therefore, the 5G era puts higher demands on the dielectric loss of electronic device materials. The dielectric loss of the aromatic polyimide shell is generally higher, when the aromatic polyimide shell is mixed in matrix resin, the dielectric loss of the resin is not reduced, but the introduced aliphatic diamine structure has a lower dielectric loss value, and the dielectric loss of a product can be reduced well.
According to the polyimide shell, the aliphatic diamine containing the alkyne structure is introduced, so that the temperature of the polyimide shell during initial melting is well reduced, the curing agent in the polyimide shell can be fully released and contacted with the matrix resin, the polyimide shell can generate a crosslinking reaction at the temperature of 200-300 ℃, the heat resistance of the polyimide shell is improved, and the problem that the heat resistance of a final product is influenced due to the fact that the final product is mixed with components with poor heat resistance is well avoided. By introducing the aliphatic diamine containing the alkyne structure, the dielectric loss of the final product is well reduced.
More specifically, the selected diamine is aliphatic diamine containing alkyne structure, and the general formula is CnH2n-2-(NH2)2. The polyimide shell used here is introduced with an alkyne structure, because the carbon-carbon triple bond of alkyne and the carbon-carbon double bond of alkene can generate crosslinking reaction at lower temperature, the crosslinking reaction can be generated at not too high temperature, the heat resistance of the polyimide shell is improved, and if the alkene structure is adopted, the temperature required by the alkene crosslinking is too high (not less than 300 ℃), and the matrix resin begins to generate thermal degradation at the temperature, so that a better effect is not achieved.
To explain further, n in the polyimide2And n1+n2The ratio of the amounts of substances of (a) is in the range of 0.5 to 0.9.
In polyimide n2The structure contains alkyne aliphatic structural units, and compared with the traditional aromatic structure, the melting temperature of the polyimide shell can be effectively reduced, wherein n is2The weight component of (A) is 0.3-0.7 of the total weight component of the polyimide, and if the proportion of the weight component of (A) to the total weight component of the polyimide is too small, the weight component of (A) cannot be well reducedIf the ratio of the melting temperature is too large, the melting temperature is greatly reduced, the polyimide shell is too easy to melt, the polyimide shell is likely to melt in the external environment, the internal curing agent flows out, and the curing agent and matrix resin are not enough to be cured during use, so that the product quality is affected.
Stated further, the melting point of the polyimide shell is between 110 DEG and 170 deg.
The melting point of the polyimide shell is between 110 DEG and 170 DEG, and the melting temperature of the polyimide shell is reduced by replacing part of aromatic structures in the polyimide with aliphatic diamine containing alkyne, so that the curing agent in the polyimide shell can completely flow out to be in contact reaction with the matrix resin.
Stated further, the polyimide jacket undergoes a self-crosslinking reaction between 200 DEG and 300 deg.
When the temperature is continuously increased to 200-300 ℃, the alkyne structure in the polyimide shell generates self-crosslinking reaction, so that the melting temperature of the polyimide shell is increased, the polyimide shell has better heat resistance, the polyimide shell is prevented from being continuously melted, and the final heat resistance of the matrix resin is not influenced.
In a further aspect, R is1Has a carbon chain length of between 4 and 12 carbon atoms.
R1The length of the carbon chain is 4-12 carbon atoms, the melting temperature of the polyimide shell is changed along with the change of the length of the carbon chain, if the length of the carbon chain is too small, the melting temperature of the polyimide shell cannot be reduced, and if the length of the carbon chain is too large, the polyimide shell is easy to melt, and the melting is possibly carried out at normal temperature to a certain extent, so that the loss of the internal curing agent is caused, and the subsequent use is influenced.
A preparation method of a polyimide shell comprises the following steps:
(1) and pretreatment: putting aromatic diamine and aliphatic diamine containing alkyne structure into a polar organic solvent for dissolving;
(2) and stirring treatment: stirring the obtained dissolved solution, adding aromatic tetracarboxylic dianhydride in the stirring process, and keeping stirring for 24 hours to obtain viscous liquid;
(3) and post-treatment: and filtering, washing and drying the obtained viscous liquid to obtain the required polyimide shell.
Wherein, the proportion range of the aromatic diamine and the aliphatic diamine containing alkyne structure is 0.5-0.9.
More specifically, the polar organic solvent in step (1) is a polar aprotic solvent, and the acute solvent is one or a combination of two or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
More specifically, the aromatic diamine in the step (1) is one or a combination of two of 4,4' -diaminodiphenyl ether and 3- (3-aminophenoxy) aniline, and when the aromatic diamine is a combination of two solvents, the ratio therebetween may be any ratio.
More specifically, the tetracarboxylic dianhydride in the step (2) is one or a combination of two or more of 4,4 '-diphenyl ether dianhydride, 4' -p-phenylenedioxydiphthalic anhydride and pyromellitic dianhydride, and when the tetracarboxylic dianhydride is a combination of two or more, the ratio of the tetracarboxylic dianhydride to the pyromellitic dianhydride may be any ratio.
The invention is further illustrated by the following examples.
The polyimide housings and the methods of manufacturing the same in examples 1 to 6 each include the steps of,
examples 1 to 2 were products obtained using a conventional low-temperature resin, examples 3 to 4 were products obtained using a polyimide structure of the present invention, examples 5 to 6 were products obtained using a polyimide containing a high-molecular aromatic structure, and the steps of examples 1 to 6 were those of the above-described method, and the results are shown in the following table.
As can be seen from the above table, in examples 1 and 2, since the resin material with low heat resistance is used as the shell of the microcapsule, the shell has a low melting temperature, and can be melted at about 100 ℃, no self-crosslinking reaction occurs with the temperature rise, and the shell and the matrix resin are almost mixed, which seriously affects the heat resistance of the product, but has a good curing effect;
in the examples 3-4, the curing agent is released by melting at the temperature of 125-133 ℃, and self-crosslinking reaction occurs at the temperature of 245 ℃ and 250 ℃, so that the heat resistance is increased, the continuous melting is avoided, the mixing degree with the matrix resin is low, the requirements of composite products are met, and the curing effect and the heat resistance are good;
examples 5-6 were melted at 205 ℃ of 201 ℃., and the melting rate was slow, the release of the curing agent was slow, and although the shell was rarely mixed with the matrix resin, the product was not cured well, but had good heat resistance.
The preparation steps of examples 7 to 12 were identical to those of example 3 except that the number of carbon atoms in the alkyne was changed, and the results are shown in the following table.
As can be seen from the above table, in examples 7-14, as the number of alkyne carbon atoms increases, the melting temperature of the polyimide shell also increases, and correspondingly, the temperature of the crosslinking reaction also increases, and both the melting temperature and the crosslinking reaction are proportional to the increase of the alkyne carbon atoms.
Furthermore, as the number of alkyne carbon atoms increases, the loss factor of the polyimide shell increases accordingly, so the dielectric loss increases with the increase of carbon atoms, but compared with the aromatic polymer, the aliphatic diamine containing alkyne structure can effectively reduce the dielectric loss.
The procedure of examples 15 to 19 was identical to that of example 3 except that n in the polyimide was changed2And n1+n2The results are shown in the following table.
| Carbon chain length n | n2/n1+n2 | Melting temperature (. degree.C.) | Crosslinking temperature (. degree.C.) |
| Example 15 | 0.5 | 121.5 | 207.1 |
| Example 16 | 0.6 | 132.1 | 228.8 |
| Example 17 | 0.7 | 147.9 | 249.3 |
| Example 18 | 0.8 | 158.2 | 276.9 |
| Example 19 | 0.9 | 169.3 | 295.6 |
As is clear from the above table, in examples 15 to 19, n of the alkyne aliphatic diamine structure in the polyimide2The ratio of the number of the units (a) to the number of the structural units of the polyimide as a whole is from 0.5 to 0.9, and accordingly, the melting temperature of the polyimide shell is also changed from 131.5 ℃ to 169.3 ℃ and the crosslinking temperature is changed from 207.1 ℃ to 295.6 ℃, so that it can be seen that as n is varied2And n1+n2The ratio of (A) to (B) is increased, namely the alkyne structure content is increased, and the melting temperature and the crosslinking temperature of the polyimide are both improved in a direct proportion relationship.
Although the present invention has been described with reference to the above embodiments, the scope of the present invention is not limited thereto, and modifications, substitutions and the like of the above members are intended to fall within the scope of the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A polyimide shell for a microcapsule-type curing agent, characterized by having the following structure:
wherein n is1And n2Are all numbers greater than zero, Ar1Is a structural unit of an aromatic tetracarboxylic dianhydride derivative, Ar2Is a structural unit of an aromatic diamine derivative, R1Is an aliphatic structural unit containing alkyne.
2. The polyimide casing for a microcapsule-type curing agent according to claim 1, wherein: r1Is a long-chain alkyne of more carbons, R1Is of the general formula CnH2n-4-(NH2)2。
3. The polyimide casing for a microcapsule-type curing agent according to claim 1, wherein: n in the polyimide2And n1+n2Of (2)The quantity ratio of (A) is in the range of 0.5-0.9.
4. The polyimide casing for a microcapsule-type curing agent according to claim 1, wherein: the melting point of the polyimide shell is between 110 DEG and 170 deg.
5. The polyimide casing for a microcapsule-type curing agent according to claim 1, wherein: the polyimide shell undergoes a self-crosslinking reaction between 200 DEG and 300 deg.
6. The polyimide casing for a microcapsule-type curing agent according to claim 1, wherein: the carbon chain length of R is between 4 and 12 carbon atoms.
7. A preparation method of a polyimide shell for a microcapsule type curing agent is characterized by comprising the following steps:
(1) and pretreatment: putting aromatic diamine and aliphatic diamine containing alkyne structure into a polar organic solvent for dissolving;
(2) and stirring treatment: stirring the obtained solution, adding aromatic tetracarboxylic dianhydride in the stirring process, and keeping stirring for 24 hours to obtain viscous liquid;
(3) and post-treatment: and filtering, washing and drying the obtained viscous liquid to obtain the required polyimide shell.
8. The method for preparing a polyimide shell for a microcapsule-type curing agent according to claim 7, wherein: the polar organic solvent in the step (1) is a polar aprotic solvent, and the acute solvent is one or a combination of more than two of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
9. The method for preparing a polyimide shell for a microcapsule-type curing agent according to claim 7, wherein: the aromatic diamine in the step (1) is one or a combination of two of 4,4' -diaminodiphenyl ether and 3- (3-aminophenoxy) aniline, and when the aromatic diamine is a combination of two solvents, the proportion of the aromatic diamine can be any proportion.
10. The method for preparing a polyimide shell for a microcapsule-type curing agent according to claim 7, wherein: the tetracarboxylic dianhydride in the step (2) is one or a combination of more than two of 4,4 '-diphenyl ether dianhydride, 4' -p-phenylene dioxy diphthalic anhydride and pyromellitic dianhydride, and when the tetracarboxylic dianhydride is the combination of more than two, the proportion of the tetracarboxylic dianhydride can be any proportion.
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| CN114471391A (en) * | 2022-02-25 | 2022-05-13 | 明士新材料有限公司 | Self-lubricating PI microcapsule and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112142A (en) * | 1994-03-15 | 1995-11-22 | 东丽株式会社 | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
| US5606014A (en) * | 1995-08-04 | 1997-02-25 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom |
| WO2008083258A1 (en) * | 2006-12-29 | 2008-07-10 | Adaptivenergy, Llc. | Polyimide/copolyimide films with low glass transition temperature for use as hot melt adhesives |
| CN102883801A (en) * | 2010-03-12 | 2013-01-16 | 福尔曼化工原料及工艺技术有限公司及两合公司 | Improved microcapsules and production thereof |
| CN103467985A (en) * | 2013-09-22 | 2013-12-25 | 株洲时代电气绝缘有限责任公司 | Polyimide thin film |
| CN104059227A (en) * | 2013-03-21 | 2014-09-24 | 捷恩智株式会社 | Polyamide Acid, Derivation Thereof And Pupose O Thereof, Photo-aligment Liquid Crystal Aligment Layer, Liquid Crystal Display Element And Tetracarboxylic Acid |
| CN109880091A (en) * | 2019-02-26 | 2019-06-14 | 中国科学院化学研究所 | A kind of semi-aromatic thermoset polyimide resin and preparation method thereof and purposes |
| CN111116950A (en) * | 2019-12-13 | 2020-05-08 | 株洲时代华鑫新材料技术有限公司 | High-performance polyimide film and preparation method thereof |
-
2021
- 2021-02-03 CN CN202110147729.1A patent/CN112940254A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112142A (en) * | 1994-03-15 | 1995-11-22 | 东丽株式会社 | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
| US5606014A (en) * | 1995-08-04 | 1997-02-25 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom |
| WO2008083258A1 (en) * | 2006-12-29 | 2008-07-10 | Adaptivenergy, Llc. | Polyimide/copolyimide films with low glass transition temperature for use as hot melt adhesives |
| CN102883801A (en) * | 2010-03-12 | 2013-01-16 | 福尔曼化工原料及工艺技术有限公司及两合公司 | Improved microcapsules and production thereof |
| CN104059227A (en) * | 2013-03-21 | 2014-09-24 | 捷恩智株式会社 | Polyamide Acid, Derivation Thereof And Pupose O Thereof, Photo-aligment Liquid Crystal Aligment Layer, Liquid Crystal Display Element And Tetracarboxylic Acid |
| CN103467985A (en) * | 2013-09-22 | 2013-12-25 | 株洲时代电气绝缘有限责任公司 | Polyimide thin film |
| CN109880091A (en) * | 2019-02-26 | 2019-06-14 | 中国科学院化学研究所 | A kind of semi-aromatic thermoset polyimide resin and preparation method thereof and purposes |
| CN111116950A (en) * | 2019-12-13 | 2020-05-08 | 株洲时代华鑫新材料技术有限公司 | High-performance polyimide film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471391A (en) * | 2022-02-25 | 2022-05-13 | 明士新材料有限公司 | Self-lubricating PI microcapsule and preparation method thereof |
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