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CN-121991343-A - Block type polyimide resin and preparation method and application thereof

CN121991343ACN 121991343 ACN121991343 ACN 121991343ACN-121991343-A

Abstract

The invention provides a block polyimide resin, a preparation method and application thereof. The molecular main chain of the block polyimide resin comprises hard segment units and soft segment units which are alternately distributed, wherein the soft segment units contain more flexible groups, the glass transition temperature is lower, the hard segment units contain more rigid conjugated groups, and the glass transition temperature is higher. When the temperature is increased and the soft segment unit is changed into a high-elastic state, the hard segment unit is still maintained in a glass state, so that the block type polyimide resin can still maintain certain mechanical strength and enhance the processing performance when the block type polyimide resin has better fusion bonding capability. And the block polyimide resin has better thermal stability, mechanical property and dimensional stability, and has good application prospect.

Inventors

  • ZHOU HUI
  • TAO RUOYUAN
  • YANG JIMING
  • Guo Jiacong
  • LI ZEQIU
  • TONG HUA

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241104

Claims (12)

  1. 1. A block polyimide resin, wherein the molecular main chain of the block polyimide resin comprises hard segment units and soft segment units which are alternately distributed, the hard segment units have a structure shown in a formula I, and the soft segment units comprise a structure shown in a formula II: in the formula I, the compound (I), x is more than or equal to 5 and less than or equal to 25, ar 1 is selected from Ar 2 is selected from Wherein R 1 is selected from H, C-C3 alkyl or trifluoromethyl, L 1 is selected from single bond, ether bond or-C (O) NH-; in the formula II, the compound of the formula I, y is more than or equal to 5 and less than or equal to 25, and B is selected from Wherein R 2 is selected from H, C C3 alkyl or trifluoromethyl, R 3 and R 4 are each independently selected from H or methyl, L 2 is selected from ether linkage, -C (R 5 R 6 ) -, -C (O) -, and, R 5 and R 6 are each independently selected from H, C C3 alkyl or trifluoromethyl; A is selected from One or more of 1, 6-hexamethylene, z is 32-34, L 3 、L 4 and L 5 are each independently selected from ether bond, methylene, -C (O) -, -S (O 2 ) -, and, R 7 and R 8 are each independently selected from H, methyl or trifluoromethyl.
  2. 2. The block polyimide resin according to claim 1, wherein the polymerization degree of the molecular main chain is not less than 50.
  3. 3. The block polyimide resin according to claim 2, wherein the polymerization degree of the molecular main chain is 100 to 200.
  4. 4. The block polyimide resin according to claim 1, wherein the number of the polymerized units of the soft segment unit is 30 to 70% of the total number of the polymerized units on the molecular main chain.
  5. 5. The block polyimide resin according to any one of claims 1 to 4, wherein the glass transition temperature of the block polyimide resin is 200 to 300 ℃ and/or the thermal decomposition temperature of the block polyimide resin is not less than 450 ℃.
  6. 6. A process for producing a block polyimide resin according to any one of claims 1 to 5, comprising the steps of: 1) Preparation of polyimide resin solution of hard segment unit or soft segment unit Dissolving a diamine compound N1 in a solvent under an inert atmosphere, adding a dianhydride compound G1 into the solvent, and reacting for 4-48 hours at 5-45 ℃ to obtain a hard segment unit or soft segment unit polyamic acid solution; adding an azeotropic water-carrying agent into the polyamic acid solution, and reacting for 12-24 hours at 150-180 ℃ to carry out water generated in the reaction by the azeotropic water-carrying agent; 2) Preparation of block polyimide resin Adding diamine compound N2 into the polyimide resin solution of the amino-terminated hard segment unit or soft segment unit prepared in the step 1) in an inert atmosphere, dissolving the polyimide resin solution, adding dianhydride compound G2 into the polyimide resin solution, reacting for 4-48 hours at 5-45 ℃ to obtain a block type polyamide acid solution, adding an azeotropic water carrying agent into the polyamide acid solution, reacting for 12-24 hours at 150-180 ℃ to carry out water generated in the reaction with the azeotropic water carrying agent, and removing the azeotropic water carrying agent from the solution at 180 ℃ to obtain the block type polyimide resin solution, or performing heat treatment on the block type polyamide acid solution at 300-400 ℃ to obtain the block type polyimide resin; The diamine compound N1 and the diamine compound N2 are different and have structures of formula 1 and formula 2, respectively: H 2 N-Ar 2 -NH 2 formula 1;H 2 N-A-NH 2 formula 2; The dianhydride compound G1 and the dianhydride compound G2 are different and have structures of formula 3 and formula 4, respectively: when the diamine compound N1 has a structure shown in formula 1, the dianhydride compound G1 has a structure shown in formula 3, and when the diamine compound N2 has a structure shown in formula 2, the dianhydride compound G2 has a structure shown in formula 4.
  7. 7. The process according to claim 6, wherein the dianhydride compound G1 and/or the dianhydride compound G2 are added to the reaction system three times in an amount of 60wt%, 30wt% and 10wt%, respectively.
  8. 8. The preparation method according to claim 6 or 7, wherein in step 1), the solid content of the hard segment unit or soft segment unit polyamic acid solution is 5% -15%; And/or in the step 2), the solid content of the block type polyamide acid solution is 10% -25%.
  9. 9. A block polyimide film comprising the block polyimide resin according to any one of claims 1 to 5.
  10. 10. The block polyimide film according to claim 9, wherein the film has a tensile strength of not less than 150MPa, an elongation at break of not less than 20%, a linear thermal expansion coefficient of 15 to 40ppm/K, and an absolute value of dimensional stability of not more than 0.15%.
  11. 11. A flexible copper clad laminate comprising the block type polyimide film of claim 9 or 10 and copper foil compounded on one side or both side surfaces of the block type polyimide film.
  12. 12. An application of the flexible copper-clad plate of claim 11 in the field of circuit boards.

Description

Block type polyimide resin and preparation method and application thereof Technical Field The invention belongs to the field of polymers, and relates to a block polyimide resin, a preparation method and application thereof. Background The flexible copper-clad plate is a substrate of a circuit board and is an indispensable basic material in the electronic circuit industry. According to the type and structure of the material, the flexible copper-clad plate can be divided into a glue-type flexible copper-clad plate and a glue-free flexible copper-clad plate, wherein the glue-free flexible copper-clad plate has more excellent performance. There are three main methods of producing the flexible copper-clad plate without glue, namely coating method, pressing method and sputtering plating method. Among them, the lamination method and the coating method are used for producing the non-adhesive double-sided board products, which require thermoplastic polyimide, and more flexible groups exist on the molecular main chain, so that the molecular chain segments have higher activity capability and lower glass transition temperature, but the flexible groups also cause the reduction of mechanical properties. In the application process, the thermoplastic polyimide resin is coated on two sides of the conventional polyimide film, and the conventional polyimide film has excellent mechanical properties and dimensional stability, can neutralize the negative influence of the reduction of the mechanical properties caused by the thermoplastic polyimide resin, but also has more severe requirements on the properties of the conventional polyimide film and the thickness and the precision of the thermoplastic polyimide. CN114989605A discloses a polyimide resin with low thermal expansion coefficient, which is prepared by mixing thermoplastic polyimide resin and conventional polyimide resin according to a certain proportion, and the prepared mixed resin has low thermal expansion coefficient and can give consideration to better optical performance while maintaining excellent melt processability. Although the resin is improved in terms of processability, expansion coefficient and optical properties, it is not concerned about mechanical properties, heat resistance and dimensional stability of the resin. Therefore, it is important to develop a polyimide resin having excellent melt processability, mechanical properties, heat resistance and dimensional stability. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides a block type polyimide resin, a preparation method and application thereof, wherein a molecular main chain of the block type polyimide resin comprises hard segment units and soft segment units which are alternately distributed, wherein the soft segment units contain more flexible groups, the glass transition temperature is lower, the hard segment units contain more rigid conjugated groups and have higher glass transition temperature, the hard segment units and the soft segment units are alternately distributed, so that the block type polyimide resin has proper glass transition temperature, when the temperature is increased, the soft segment units become a high-elastic state, and the hard segment units are still maintained in a glass state, wherein the high-elastic state is favorable for keeping the resin with better fusion bonding capability, and the glass state is favorable for keeping the resin with better mechanical property, heat resistance and dimensional stability. The invention provides a block type polyimide resin, wherein a molecular main chain of the block type polyimide resin comprises hard segment units and soft segment units which are alternately distributed, the hard segment units have a structure shown in a formula I, and the soft segment units comprise a structure shown in a formula II: in the formula I, the compound (I), x is more than or equal to 5 and less than or equal to 25, ar 1 is selected from And/orAr 2 is selected fromWherein R 1 is selected from H, C-C3 alkyl or trifluoromethyl, L 1 is selected from single bond, ether bond or-C (O) NH-; in the formula II, the compound of the formula I, y is more than or equal to 5 and less than or equal to 25, and B is selected from Wherein R 2 is selected from H, C C3 alkyl or trifluoromethyl, R 3 and R 4 are each independently selected from H or methyl, L 2 is selected from ether linkage, -C (R 5R6) -, -C (O) -, and,R 5 and R 6 are each independently selected from H, C C3 alkyl or trifluoromethyl; A is selected from One or more of 1, 6-hexamethylene, z is 32-34, L 3、L4 and L 5 are each independently selected from ether bond, methylene, -C (O) -, -S (O 2) -, and,R 7 and R 8 are each independently selected from H, methyl or trifluoromethyl. In an alternative embodiment, the molecular backbone has a degree of polymerization of 50 or greater. In an alternative embodiment, the polymerization degree of the molecular main chain is 100-200.