CN111621260B - Polyamide acid coating adhesive and preparation method thereof - Google Patents
Polyamide acid coating adhesive and preparation method thereof Download PDFInfo
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- CN111621260B CN111621260B CN202010558046.0A CN202010558046A CN111621260B CN 111621260 B CN111621260 B CN 111621260B CN 202010558046 A CN202010558046 A CN 202010558046A CN 111621260 B CN111621260 B CN 111621260B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a polyamic acid coating adhesive which is mainly formed by polymerizing alicyclic diamine, aliphatic diamine containing siloxane chain segments, aromatic tetracarboxylic dianhydride containing ketone groups and aromatic tetracarboxylic dianhydride containing hydroxyl groups. The preparation method comprises the following steps: (1) dissolving alicyclic diamine and aliphatic diamine containing siloxane chain segment in mixed solvent in inert gas atmosphere; (2) and (2) adding aromatic tetracarboxylic dianhydride containing a ketone group and aromatic tetracarboxylic dianhydride containing a hydroxyl group into the system obtained in the step (1) to react to obtain the polyamic acid coating adhesive. The polyamic acid coating adhesive provided by the invention has the advantages that the polyamic acid coating adhesive molecular chain obtained by random copolymerization of different diamines and dianhydrides contains a large amount of ketone groups, hydroxyl groups and siloxane groups, and the polyamic acid, nickel, aluminum nitride, silicon carbide and other different substrate materials are improved to have good bonding strength on a molecular level.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a polyamic acid coating adhesive and a preparation method thereof.
Background
The polyamic acid adhesive has outstanding heat resistance and film-forming property, and excellent electrical property, mechanical property, irradiation resistance, solvent resistance, optical property and the like, so the polyamic acid adhesive can be coated on the surface of an electronic component to be used as a protective coating, and can also be used for bonding composite materials and common metal materials such as aluminum alloy, stainless steel and the like. However, the prior polyamic acid adhesive has certain influence on heat resistance, adhesive property and performance guarantee of electronic devices.
As disclosed in patent document No. 201210191649, an adhesive film for a semiconductor is provided which can be attached to a semiconductor wafer at a low temperature, and which can sufficiently suppress the occurrence of chip cracks and burrs and can produce semiconductor chips from the semiconductor wafer at a good yield. In this document, the polyamic acid resin contained in the adhesive film for a semiconductor is obtained by reacting s-ODPA and other tetracarboxylic dianhydrides with a siloxane diamine. The glass transition temperature of the polyamic acid resin is within the range of 30-80 ℃, the low-temperature attaching process can be well realized, but the polyamic acid resin has poor heat resistance and is limited in application in the high-temperature process stage of processing a subsequent chip into a device.
Patent document No. 201210548934 discloses a method for preparing polyimide adhesive, which comprises reacting aromatic diamine BAPP, ODA and aromatic dianhydride α -ODPA to generate polyamic acid solution, and chemically imidizing to obtain PI powder. The PI powder greatly reduces the curing temperature (only 170-200 ℃), improves the temperature resistance level (210-. However, the test results show that the adhesive strength of the adhesive is relatively general with copper, aluminum, platinum, stainless steel and the like, and the adhesive can be initially used and popularized in the microelectronic field with low requirements on the adhesive property, but is difficult to be applied in the microelectronic field with more strict requirements on the adhesive property.
The patent document with application number 201010561806 discloses a polyimide electronic packaging material and a synthesis method thereof, which comprises the steps of firstly dissolving 2,3,3 ', 4 ' -biphenyltetracarboxylic dianhydride and 2,2 ' -bis (trifluoromethyl) -4, 4-diaminodiphenyl sulfide in an aprotic polar solvent in an equal molar ratio, and reacting at 10-20 ℃ to prepare polyamic acid; and then putting the prepared polyamic acid into an oven to perform imidization according to the following procedures: and (3) cooling at 80 ℃/3h, 150 ℃/1h, 180 ℃/1h, 250 ℃/1h, 300 ℃/1h and 350 ℃/15min naturally to obtain the electronic packaging polyimide material. The material has the properties of high light transmittance, low water absorption, excellent mechanical property, high temperature resistance and the like, but the glass transition temperature of the material is generally higher than 280 ℃, and the problem of incomplete thermal imidization possibly exists in the process of an electronic packaging process, so that the yield and the production efficiency of electronic devices are influenced.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background art, and provides a preparation method of a polyamic acid coating adhesive, wherein the polyamic acid coating adhesive can be completely cured at a lower temperature (200-260 ℃), and simultaneously shows excellent mechanical strength, heat resistance, electric insulation performance and substrate adhesion performance after being cured, so that good packaging of a chip is realized, interconnection inside a device is protected, the device is prevented from being damaged mechanically and chemically, and the reliability and stability of a power device are improved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a polyamic acid coating adhesive is mainly prepared from alicyclic diamine, aliphatic diamine containing siloxane chain segments, aromatic tetracarboxylic dianhydride containing ketone groups and aromatic tetracarboxylic dianhydride containing hydroxyl groups.
As a general inventive concept, the present invention also provides a preparation method of the polyamic acid coating paste, including the steps of:
(1) dissolving alicyclic diamine and aliphatic diamine containing siloxane chain segment in mixed solvent in inert gas atmosphere;
(2) and (2) adding aromatic tetracarboxylic dianhydride containing a ketone group and aromatic tetracarboxylic dianhydride containing a hydroxyl group into the system obtained in the step (1) to react to obtain the polyamic acid coating adhesive.
In the preparation method, preferably, after the reaction in the step (2) is finished, the adhesion modifier, the defoaming agent and the leveling agent are added into the reaction product, and then the mixture is stirred for 0.5 to 1.0 hour, so that the auxiliaries are uniformly dispersed in the polyamic acid resin to obtain the polyamic acid coating adhesive.
In the above production method, the molar ratio of the alicyclic diamine to the aliphatic diamine having a siloxane segment is preferably (90.0 to 100.0): 1.0; more preferably, the molar ratio is (95.0 to 99.0): 1.0.
The molar ratio of the aromatic tetracarboxylic dianhydride containing the ketone group to the aromatic tetracarboxylic dianhydride containing the hydroxyl group is (0.5-1.2): 1.0; more preferably, the molar ratio is (0.7 to 1.0): 1.0.
In the above production method, preferably, the alicyclic diamine is selected from the group consisting of
One or more of the above;
the aliphatic diamine containing the siloxane segment is selected from
One or more of them.
In the above production process, the aromatic tetracarboxylic dianhydride containing a ketone group is preferably selected from
One or more of the above;
the aromatic tetracarboxylic dianhydride containing hydroxyl is selected from
One or more of them.
In the above production method, in the step (1), the mixed solvent is preferably a mixed solvent of a polar aprotic solvent and a ketone solvent in a mass ratio of (2.0 to 8.0):1.0, and more preferably, in a mass ratio of (3.5 to 6.0): 1.0; the polar aprotic solvent is selected from one or more of Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO), and the ketone solvent is selected from one or more of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone.
In the preparation method, preferably, the addition amount of the mixed solvent accounts for 80.0-90.0% of the polyamic acid coating adhesive; more preferably, 85.0-87.0%;
the total adding amount of the diamine monomer and the dianhydride monomer accounts for 10.0-20.0% of the polyamic acid coating adhesive, and is further preferably 13.0-15.0%.
In the above production method, preferably, the ratio of the total molar amount of the diamine monomer to the total molar amount of the dianhydride monomer is 1: 0.99 to 1.
In the preparation method, preferably, the adhesion modifier is selected from one or more of KBM602, KBM603, KBE603, KBM903, KBE9103, KBM573 and KBM6123 in an amount of 0.1-2.0% of the mass of the polyamic acid coating adhesive; preferably 0.5 to 1.0 percent;
the defoaming agent is selected from one or more of PA-600, PA-630, KF-96 and KS-7708 in the Xinyue chemical industry, and the addition amount of the defoaming agent is 0.1-1.0% of the mass of the polyamic acid coating glue; preferably 0.3-0.5%;
the leveling agent is selected from one or more of Dow Corning DC-3, DC-29, ByK-306 and BYK333, and the addition amount is 0.1-1.0% of the mass of the polyamic acid coating adhesive; preferably 0.2 to 0.5%.
Compared with the prior art, the invention has the advantages that:
(1) the polyamic acid coating adhesive is formed by polymerizing alicyclic diamine, aliphatic diamine containing siloxane chain segments, aromatic tetracarboxylic dianhydride containing ketone groups and aromatic tetracarboxylic dianhydride containing hydroxyl groups, wherein the aromatic dianhydride ensures that a film obtained after the polyamic acid is thermally imidized has better mechanical strength, heat resistance and electrical insulation performance; the alicyclic diamine and the aliphatic diamine can reduce the glass transition temperature of the obtained polyamic acid film, realize complete curing at a lower temperature (200-260 ℃) and ensure complete thermal imidization in the electronic packaging process, thereby ensuring the yield and the production efficiency of electronic devices; the polyamic acid coating obtained by random copolymerization of different diamines and dianhydrides contains a large amount of ketone groups, hydroxyl groups and siloxane groups in molecular chains, and the polyamic acid is improved to have good bonding strength with different substrate materials such as nickel, aluminum nitride, silicon carbide and the like on a molecular level.
(2) The polyamic acid coating adhesive provided by the invention has the advantages that various auxiliary agents are introduced into the polyamic acid coating adhesive, so that micro bubbles in the polyamic acid coating adhesive can be eliminated, the coating process flow is simplified, the self-leveling performance and the bonding strength with a base material are further improved, the yield of electric devices is obviously improved, and the production cost is reduced.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of DMF +56.45g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2 hours, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBM603, 0.15g of shin-Etsu chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5h to uniformly disperse all the auxiliary agents in a polyamide acid system to obtain the polyamide acid coating adhesive.
Comparative example 1:
the preparation method of the polyamic acid coating adhesive of the comparative example comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (242.35g of DMF +60.59g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (10.91g) of pyromellitic dianhydride in batches, and uniformly reacting for 2.0h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBM603, 0.15g of shin-Etsu chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5h to uniformly disperse the functional additives in the polyamide acid system to obtain the polyamide acid coating adhesive.
Comparative example 2:
the preparation method of the polyamic acid coating adhesive of the comparative example comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a single solvent (282.26g DMF) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2 hours, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBM603, 0.15g of shin-Etsu chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5h to uniformly disperse all the auxiliary agents in a polyamide acid system to obtain the polyamide acid coating adhesive.
Comparative example 3:
the preparation method of the polyamic acid coating adhesive of the comparative example comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of DMF +56.45g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2 hours, wherein the reaction temperature is controlled at 10 ℃; and after the reaction is finished, continuously stirring and reacting for 0.5h to obtain the polyamic acid coating glue.
Example 2:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (242.35g of DMF +60.59g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride and 0.05mol (16.16g) of 3,3 ' -diphenylmethanoltetracarboxylic dianhydride in batches, and uniformly reacting for 2.0-3.0 h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBM603, 0.15g of shin-Etsu chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse the functional auxiliaries in a polyamide acid system to obtain the polyamide acid coating adhesive.
Example 3:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of DMF +56.45g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 2,2 ', 3, 3' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2.0-3.0 h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBM603, 0.15g of shin-Etsu chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse the functional auxiliaries in a polyamide acid system to obtain the polyamide acid coating adhesive.
Example 4:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (249.38g of DMF +62.34g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (21.31g) of 1, 3-bis (3, 4-dicarboxyphenyl) pyromellitic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2.0-3.0 h;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBM603, 0.15g of shin-Etsu chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse the functional auxiliaries in a polyamide acid system to obtain the polyamide acid coating adhesive.
Example 5:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of NMP +56.45g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2.0-3.0 h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shinyless chemical KBM603, 0.15g of shinyless chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse all the auxiliary agents in a polyamide acid system to obtain the polyamide acid coating adhesive.
Example 6:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of DMF +56.45g of methyl isobutyl ketone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2.0-3.0 h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shinyless chemical KBM603, 0.15g of shinyless chemical PA-630 and 0.15g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse all the auxiliary agents in a polyamide acid system to obtain the polyamide acid coating adhesive.
Example 7:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of DMF +56.45g of cyclohexanone) at a reaction temperature of 10 ℃ under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2.0-3.0 h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.5g of shin-Etsu chemical KBM603, 0.3g of shin-Etsu chemical PA-630 and 0.3g of Dow Corning DC-3 into the reaction system obtained in the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse all the auxiliary agents in a polyamide acid system to obtain the polyamide acid coating adhesive.
Example 8:
the invention relates to a preparation method of polyamic acid coating glue, which comprises the following steps:
(1) 0.095mol (19.95g) of 4, 4' -diaminodicyclohexylmethane and 0.005mol (1.24g) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in a mixed solvent (225.81g of DMF +56.45g of cyclohexanone) under a nitrogen atmosphere;
(2) after the diamine monomer in the step (1) is completely dissolved, sequentially adding 0.05mol (16.11g) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 0.05mol (12.51g) of 3, 6-dihydroxy pyromellitic dianhydride in batches, and uniformly reacting for 2.0-3.0 h, wherein the reaction temperature is controlled at 10 ℃;
(3) and (3) sequentially adding 0.25g of shin-Etsu chemical KBE603, 0.15g of shin-Etsu chemical KF-96 and 0.15g of BYK-306 into the reaction system obtained after the step (2) in batches, and stirring for reacting for 0.5-1.0 h to uniformly disperse all the auxiliary agents in the polyamide acid system to obtain the polyamide acid coating adhesive.
Table 1 shows the viscosity test results of the polyamic acid coating pastes prepared in examples 1 to 8, and it can be seen from table 1 that the polyamic acid coating pastes prepared according to the present invention have low viscosity, are not likely to generate bubbles when coated on a substrate or a product, and have good leveling property.
Table 2 shows the performance data of films with a thickness of 20-25 μm obtained by thermal imidization of the polyamic acid coatings prepared in examples 1-8.
TABLE 1 viscosity of Polyamic acid coating paste Polyamic acid
TABLE 2 film-related Performance data
Viscosity test method of polyamic acid coating paste in table 1: tested according to GB/T2794-.
The film-related property test methods in table 2:
Tg: tested according to HB 7655-1999 standard;
insulating strength: testing according to GB/T1408.1-2016 standard;
tensile strength and elongation: testing according to GB/T1040.3-2006 standard;
tensile shear strength: testing according to GB/T7124 + 2008 standard;
t peel strength: tested according to GB/T2791-.
Claims (6)
1. A preparation method of polyamic acid coating glue is characterized in that the polyamic acid coating glue is mainly formed by polymerizing alicyclic diamine, aliphatic diamine containing siloxane chain segments, aromatic tetracarboxylic dianhydride containing ketone groups and aromatic tetracarboxylic dianhydride containing hydroxyl groups, and specifically comprises the following steps:
(1) dissolving alicyclic diamine and aliphatic diamine containing siloxane chain segment in mixed solvent in inert gas atmosphere; the mixed solvent is a mixed solvent of a polar aprotic solvent and a ketone solvent in a mass ratio of (2.0-8.0): 1.0, wherein the polar aprotic solvent is selected from one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and the ketone solvent is selected from one or more of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone; the addition amount of the mixed solvent accounts for 80.0-90.0% of the mass of the polyamic acid coating glue; the molar ratio of the cycloaliphatic diamine to the siloxane segment-containing aliphatic diamine is 95: 5;
(2) and (2) adding aromatic tetracarboxylic dianhydride containing ketone groups and aromatic tetracarboxylic dianhydride containing hydroxyl groups into the system obtained in the step (1) for reaction, after the reaction is finished, adding an adhesion modifier, a defoaming agent and a leveling agent into the reaction product, and stirring for 0.5-1.0 h to uniformly disperse all the auxiliary agents in the polyamic acid resin to obtain the polyamic acid coating adhesive, wherein the molar ratio of the aromatic tetracarboxylic dianhydride containing ketone groups to the aromatic tetracarboxylic dianhydride containing hydroxyl groups is (0.5-1.2): 1.0.
2. The method of claim 1, wherein the cycloaliphatic diamine is selected from the group consisting of
One or more of the above;
the aliphatic diamine containing the siloxane segment is selected from
One or more of them.
3. The process according to claim 1, wherein the aromatic tetracarboxylic dianhydride containing a ketone group is selected from the group consisting of
One or more of the above;
the aromatic tetracarboxylic dianhydride containing hydroxyl is selected from
One or more of them.
4. The production method according to any one of claims 1 to 3,
the total adding amount of the diamine monomer and the dianhydride monomer accounts for 10.0-20.0% of the mass of the polyamic acid coating glue.
5. The process according to any one of claims 1 to 3, wherein in the step (2), the reaction temperature is 10 to 35 ℃ and the reaction time is 2 to 3 hours.
6. The preparation method according to claim 1, wherein the adhesion modifier is one or more selected from KBM602, KBM603, KBE603, KBM903, KBE9103, KBM573 and KBM6123 in an amount of 0.1-2.0% of the mass of the polyamic acid coating glue;
the defoaming agent is selected from one or more of PA-600, PA-630, KF-96 and KS-7708 in the Xinyue chemical industry, and the addition amount of the defoaming agent is 0.1-1.0% of the mass of the polyamic acid coating glue;
the leveling agent is selected from one or more of Dow Corning DC-3, DC-29, ByK-306 and BYK333, and the addition amount of the leveling agent is 0.1-1.0% of the mass of the polyamic acid coating adhesive.
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