CN120923798B - Poly (p-hydroxystyrene) resin and preparation method and application thereof - Google Patents
Poly (p-hydroxystyrene) resin and preparation method and application thereofInfo
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- CN120923798B CN120923798B CN202511477207.2A CN202511477207A CN120923798B CN 120923798 B CN120923798 B CN 120923798B CN 202511477207 A CN202511477207 A CN 202511477207A CN 120923798 B CN120923798 B CN 120923798B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a poly-p-hydroxystyrene resin, a preparation method and application thereof, belonging to the technical field of high polymer materials. The preparation method adopts a step-by-step strategy of 'prepolymer synthesis-block copolymerization', firstly, a poly-p-hydroxystyrene prepolymer solution and a polyurea resin prepolymer solution are respectively prepared, then, the two prepolymer solutions are subjected to block copolymerization under the action of a catalyst, and the target resin is obtained through post-treatment. The polyurea chain segments are introduced into the molecular structure of the poly-p-hydroxystyrene, so that a plurality of defects of the traditional poly-p-hydroxystyrene resin are effectively overcome, the cooperative promotion of the thermal stability, the mechanical property, the dielectric property, the wet heat resistance, the etching resistance and the dimensional stability of the resin is realized, the prepared resin has excellent film forming property, can be widely applied to the fields of semiconductor photoresist, electronic packaging, liquid crystal display orientation layers and the like, particularly has outstanding performances in high-end electronic and flexible display scenes, and has remarkable industrial application value.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a poly-p-hydroxystyrene resin and a preparation method and application thereof.
Background
The poly-p-hydroxystyrene (PHS) resin is a functional polymer material with high heat resistance (Tg is about 150-180 ℃) and modifiable hydroxyl, and benzene rings and side chain hydroxyl in the molecular structure of the PHS resin endow the PHS resin with excellent film forming property, chemical stability and dielectric property (Dk is about 3.0), and the characteristics enable the PHS resin to have irreplaceable functions in the fields of semiconductor photoresist (such as KrF/ArF photoetching process), liquid crystal display orientation layer (such as OLED planarization), medicine slow-release carrier and the like.
However, the poly (p-hydroxystyrene) with a single structure has obvious performance short plates, and is difficult to meet the strict requirements of the advanced technology on the comprehensive performance of materials, namely, firstly, the pure PHS resin has higher brittleness, the elongation at break is generally lower than 5 percent, the film layer is easy to crack in the photoresist coating and device packaging process to influence the reliability of the device, secondly, the surface energy of the pure PHS resin has higher surface energy, the hydrophilicity of the side chain hydroxyl group of the pure PHS resin leads to the easy absorption of water vapor in the environment of the PHS film layer, the dielectric property is obviously reduced under the high-temperature and high-humidity condition, the corrosion resistance and the protection capability on a metal substrate are insufficient, and in addition, the plasma etching resistance of the pure PHS resin is limited, the requirements are difficult to meet in the advanced semiconductor manufacturing process, and the thermal expansion Coefficient (CTE) of the pure PHS is not matched with the silicon substrate (-3 ppm/° C) in the scenes such as 5G high-frequency chip packaging and the requirements on the dimensional stability are difficult to meet.
To overcome these drawbacks, various improvements have been attempted in the industry. One common approach is random copolymerization with other monomers, such as t-butyl methacrylate (TBMA) to increase the chemical amplification, or with fluoromonomers to improve etch resistance. However, these methods tend to result in reduced other properties such as reduced thermal stability, phase separation problems, or reduced film uniformity. Another approach is to introduce a protecting group (e.g., t-BOC group) to improve photosensitivity, but this increases process complexity and cost, and is prone to by-product formation upon removal of the protecting group, resulting in pattern defects. In addition, a strategy of nanoparticle composite modification is adopted, and the thermal expansion coefficient is regulated by adding nano fillers such as silicon dioxide, aluminum nitride and the like, but the dispersibility of the nanoparticles is poor, impurities are easy to introduce, and the electrical performance of the semiconductor device is influenced.
Therefore, developing a poly-p-hydroxystyrene resin with multi-dimensional performance becomes a key for breaking through the technical bottleneck.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a poly-p-hydroxystyrene resin, a preparation method and application thereof, and aims to solve at least one of the problems. According to the invention, the polyurea chain segments are introduced into the molecular structure of the poly-p-hydroxystyrene through a step-by-step strategy of 'prepolymer synthesis-block copolymerization', so that the cooperative promotion of the heat resistance, the mechanical property, the dielectric property, the etching resistance and the process compatibility of the resin is realized, and the application of the resin in the high-end field is expanded.
The invention realizes the technical purposes by the following technical proposal:
A method for preparing a poly-p-hydroxystyrene resin, the method comprising the steps of:
step S1, preparing raw materials;
s2, synthesizing a poly (p-hydroxystyrene) prepolymer to obtain a poly (p-hydroxystyrene) prepolymer solution;
S3, synthesizing a polyurea resin prepolymer to obtain a polyurea resin prepolymer solution;
Step S4, carrying out block copolymerization, namely adding the poly-p-hydroxystyrene prepolymer solution obtained in the step S2 and the polyurea resin prepolymer solution obtained in the step S3 into the same reaction kettle to obtain a block copolymerization mixture;
And S5, performing post-treatment by using the block copolymerization reaction mixture obtained in the step S4 to obtain the poly-p-hydroxystyrene resin.
Compared with the prior art, the invention has at least the following beneficial effects:
According to the poly-p-hydroxystyrene resin, the preparation method and the application thereof, provided by the invention, the polyurea chain segments are accurately introduced into the poly-p-hydroxystyrene molecular structure through a step strategy of 'prepolymer synthesis-block copolymerization', so that the bottleneck of single performance of the traditional poly-p-hydroxystyrene resin is effectively broken through, and the unification of multi-dimensional performance collaborative promotion and excellent process compatibility is realized. In the aspect of performance, the resin not only remarkably enhances the thermal stability, can endure the high-temperature process in a high-end technical scene, but also realizes the mechanical property balance of high strength and high toughness, solves the problems of high brittleness and easy cracking of the traditional resin, simultaneously has the characteristic of low dielectric constant, adapts to the signal transmission requirement of high-frequency electronic devices, greatly improves the hydrophobicity, reduces the adverse effect of water vapor adsorption on the protection of dielectric property and metal substrate, optimizes the thermal expansion coefficient to adapt to a substrate, reduces the interface stress risk in the packaging process, remarkably enhances the plasma etching resistance, and ensures the graphic precision and low defect rate of the photoetching process. In the aspects of technology and application, the preparation method effectively avoids the problems of phase separation, gel and the like, has excellent film forming property, can be compatible with the existing production flow, does not need to modify equipment, reduces industrialization threshold, can be widely applied to the fields of semiconductor photoresist and electronic packaging materials, is also outstanding in the fields of liquid crystal display orientation layers, particularly flexible display, can meet the performance requirements of different scenes, does not need to rely on expensive raw materials or complex technology, has lower raw material cost, is environment-friendly and free of toxic byproducts in the post-treatment technology, accords with green production trend, provides a solution with high performance and high suitability for the field of high-end electronic materials, and has important industrial application value.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
Specifically, the invention provides a poly (p-hydroxystyrene) resin and a preparation method thereof, wherein the method comprises the following steps:
step S1, raw material preparation
The preparation method comprises the steps of taking a p-hydroxystyrene monomer, an isocyanate monomer, a diamine monomer and N, N-Dimethylformamide (DMF), purifying and/or drying for later use, wherein the purifying and/or drying comprises the steps of carrying out reduced pressure distillation and purification on the p-hydroxystyrene monomer at the temperature of between 0.01 and 0.05MPa and the temperature of between 80 and 100 ℃ to ensure that the purity of the p-hydroxystyrene monomer is more than or equal to 99.5 percent, carrying out reduced pressure distillation and purification on the isocyanate monomer at the temperature of between 0.005 and 0.02MPa and the temperature of between 60 and 80 ℃ to ensure that the purity of the isocyanate monomer is more than or equal to 99 percent, drying the diamine monomer in a vacuum drying box at the temperature of between 50 and 70 ℃ for 2 to 4 hours to ensure that the purity of the diamine monomer is more than or equal to 99 percent, and drying the N, N-Dimethylformamide (DMF) by molecular sieve for more than 48 hours to ensure that the purity of the N, N-Dimethylformamide (DMF) is more than or equal to 99.8 percent;
preferably, the isocyanate monomer is selected from one or more of TDI, MDI, HDI, IPDI, HMDI, fluorine-containing isocyanate and the like, and the diamine monomer is preferably polyether diamine or diamine monomer containing amine blocking structure such as piperazine diamine.
Step S2, synthesizing a poly (p-hydroxystyrene) prepolymer
Adding a certain amount of the p-hydroxystyrene monomer (the molar amount of which is recorded as n) purified in the step S1 into a reaction kettle, adding DMF dried in the step S1 into the reaction kettle, adjusting the addition amount to ensure that the mass ratio of the p-hydroxystyrene monomer in the total solution in the reaction kettle is 15-25%, adding an initiator such as Azobisisobutyronitrile (AIBN) into the reaction kettle, wherein the amount of the AIBN is 0.5-1% of the mass of the p-hydroxystyrene monomer, stirring at a rotating speed of 200-300r/min under the protection of nitrogen, heating a reaction system in the reaction kettle to 60-80 ℃, and reacting for 4-6 hours to obtain a poly-p-hydroxystyrene prepolymer solution;
In this step, when the reaction system in the reaction vessel is heated to 60 to 80 ℃, the initiator Azobisisobutyronitrile (AIBN) is first decomposed to produce isobutyronitrile radicals and nitrogen, the reaction equation of which is exemplified as follows:
;
Next, the resulting isobutyronitrile radical can initiate the opening of the double bond on the para-hydroxystyrene monomer and free radical polymerization occurs to form a linear polymer chain, thereby obtaining a poly-para-hydroxystyrene prepolymer, the reaction equation of which is exemplified as follows:
;
Wherein Ph represents a benzene ring, x represents the polymerization degree of the poly (p-hydroxystyrene) prepolymer, and the number average molecular weight of the poly (p-hydroxystyrene) prepolymer obtained in the step S2 is controlled to be 5000-8000 Da.
Step S3, synthesizing polyurea resin prepolymer
Adding the isocyanate monomer (the molar amount is m) and DMF solvent which are dried in the step S1 into another reaction kettle, so that the mass ratio of the isocyanate monomer is 20-30% (isocyanate monomer/(isocyanate monomer+DMF)), stirring at the speed of 150-250r/min under the protection of nitrogen, heating to 40-60 ℃, slowly dropwise adding a DMF solution containing diamine monomer (the mass ratio of the diamine monomer in the solution is 10-20%), controlling the molar ratio of the isocyanate monomer to the diamine monomer to be about 1.05:1-1.10:1 (namely, slightly excessive isocyanate monomer), controlling the dropwise adding time to be 1-2 hours, and continuously reacting for 2-3 hours after dropwise adding to obtain a polyurea resin prepolymer solution, wherein the isocyanate monomer is exemplified by MDI, and the reaction equation is as follows:
Wherein R is a polyether main chain or a main chain containing an amine-resistant structure, y represents the repetition number of corresponding groups, M is a shorthand form of the corresponding groups in the polyurea resin prepolymer, and the number average molecular weight of the polyurea resin prepolymer obtained in the step S3 is controlled to be 3000-6000 Da.
Step S4, block copolymerization
Adding the poly (p-hydroxystyrene) prepolymer solution obtained in the step S2 and the polyurea resin prepolymer solution obtained in the step S3 into the same reaction kettle, stirring at a speed of 200-300r/min under the protection of nitrogen, heating to 50-70 ℃, adding dibutyl tin dilaurate (DBTDL) into the same reaction kettle while stirring, wherein the addition amount of the dibutyl tin dilaurate (DBTDL) is 0.1-0.3% of the total mass of the poly (p-hydroxystyrene) prepolymer solution and the polyurea resin prepolymer solution in the same reaction kettle, and reacting for 6-8 hours to obtain a block copolymerization reaction mixture;
in this step, the reaction equation of the poly (p-hydroxystyrene) prepolymer and the polyurea resin prepolymer is exemplified as follows:
。
Wherein " "Represents an omitted para-hydroxystyrene group""Means a block that is not shown. It should be noted that, limited by the molecular structure of the ureido material, the actual molecular structure of the product after the block copolymerization is a network structure, and the above reaction equation is only a schematic drawing and does not represent the actual structure. In the block copolymerization process, dibutyltin dilaurate is used as an organic catalyst, the addition amount of the organic catalyst is 0.1-0.3% by regulating the reaction temperature to 50-70 ℃, the block copolymerization rate can be kept in the interval of 0.05-0.15L.mol -1•s-1, the chain growth reaction selectivity is more than or equal to 90%, and the homopolymerization side reaction is inhibited.
Step S5, post-treatment
Pouring the solution after the reaction in the step S4 into 10-15 times of methanol for precipitation, filtering and collecting the precipitate, washing the precipitate with methanol for multiple times, placing the precipitate in a 40-60 ℃ vacuum drying oven for drying for 12-24 hours to constant weight to obtain a block copolymer solid, dissolving the solid in Propylene Glycol Methyl Ether Acetate (PGMEA) to prepare a solution with the mass fraction of 10-15%, and filtering the solution with a 0.2 mu m Polytetrafluoroethylene (PTFE) filter membrane to obtain a final resin product.
Preferably, in the preparation method, the ratio of the molar amount n of the p-hydroxystyrene monomer to the molar amount m of the isocyanate monomer is controlled to be n:m= (6-10): 1.
Example 1
The poly-p-hydroxystyrene resin of the first embodiment is prepared by the preparation method, wherein in the preparation process, isocyanate monomers adopt MDI, diamine monomers adopt polyether diamine (specifically, jeffamine (ED-600 series polyether amine) purchased from Hunman SMAN company of America); in the step S2, the dosage of the parahydroxystyrene monomer is 6mol, after DMF is added, the mass ratio of the parahydroxystyrene monomer in the total solution in the reaction kettle is 20%, the AIBN dosage is 0.7% of the mass of the parahydroxystyrene monomer, and the stirring speed is 200r/min under the protection of nitrogen, and the stirring reaction is carried out for 5 hours at 70 ℃; in the step S3, the dosage of MDI is 1mol, the mass ratio of MDI in DMF is 25%, under the protection of nitrogen, the mixture is stirred at the speed of 200r/min, the temperature is raised to 50 ℃, the DMF solution containing polyether diamine monomer is slowly dripped, the mass ratio of polyether diamine monomer in the DMF solution containing polyether diamine monomer is 20%, the dripping is carried out for 1 hour, the reaction is continued for 2 hours after the dripping is finished, the polyurea resin prepolymer solution is obtained, the molar ratio of MDI to polyether diamine monomer is controlled to be 1.05:1, in the process, the mixture is stirred at the speed of 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃ and the DBTDL addition amount is 0.2%, the reaction is carried out for 8 hours, in the step S5, the solution after the reaction in the step S4 is poured into methanol with the volume of 10 times, the precipitate is placed in a 60 ℃ vacuum drying box, the precipitate is dried for 12 hours to the constant weight, the solution with the mass ratio of 15% is prepared, and then a Polytetrafluoroethylene (PTFE) filter membrane with the mass ratio of 0.2 μm is filtered.
Example two
The difference between the second example and the first example is that the amount of the parahydroxystyrene monomer used in the step S2 is 8mol.
Example III
The difference between the third embodiment and the first embodiment is only that the amount of the parahydroxystyrene monomer used in the step S2 is 10mol.
Comparative example one
Comparative example one differs from example one only in that the amount of the p-hydroxystyrene monomer used in step S2 is 4mol.
Comparative example two
Comparative example two differs from example one only in that in step S2, the amount of the parahydroxystyrene monomer used was 15mol.
Comparative example three
The difference between the comparative example III and the example I is that steps S3 and S4 are not involved, namely, after obtaining a solution of a poly (p-hydroxystyrene) prepolymer, directly conducting post-treatment (omitting the steps of synthesis and block copolymerization of a polyurea resin prepolymer), pouring the reacted solution into 10 times volume of methanol for precipitation, placing the precipitate in a 60 ℃ vacuum drying oven for drying for 12 hours to constant weight, then preparing a resin solution with a mass fraction of 15%, and then filtering with a 0.2 mu m Polytetrafluoroethylene (PTFE) filter membrane. Namely, the pure poly-p-hydroxystyrene resin was prepared without polyurea prepolymer preparation and block copolymerization.
Comparative example four
Comparative example IV referring to example one, except that the steps S2 to S4 in example one were not included, but the materials (p-hydroxystyrene monomer, DMF, AIBN, MDI, polyether diamine monomer, etc.) used in steps S2 to S4 were weighed by equal mass and directly mixed, stirred at a speed of 200r/min, heated to 60℃and reacted for 8 hours, after which purification and preparation of a resin solution were performed according to step S5 of example one.
Comparative example five
Comparative example five referring to example one, the difference is that it mixes p-hydroxystyrene monomer with t-butyl methacrylate (TBMA) in a 6:1 molar ratio, then AIBN (0.7% mass of p-hydroxystyrene monomer) and DMF (20% mass of total monomer) were added and reacted at 70 ℃ for 5 hours at 200r/min, and the post-treatment was the same as in step S5 of example 1.
Comparative example six
The pure PHS resin of comparative example 3 was mixed with t-BOC anhydride in a mass ratio of 10:3 and reacted at 60℃for 4 hours under pyridine catalysis, and the post-treatment was the same as in step S5 of example 1.
Performance testing
Performance testing includes testing of the following parameters:
Glass transition temperature (Tg) is obtained by adopting a Differential Scanning Calorimeter (DSC), the temperature rising rate is 10 ℃ per minute, and the nitrogen atmosphere is adopted;
Stretching performance, namely, a universal testing machine is adopted, the stretching speed is 5mm/min, and the sample size is 10mm multiplied by 4mm multiplied by 0.2mm;
The dielectric constant is that an impedance analyzer is adopted to test the frequency of 1MHz and the room temperature;
Water contact angle, namely adopting a contact angle measuring instrument to titrate with deionized water, and taking an average value after testing for 5 times;
Thermal expansion Coefficient (CTE) the resin solutions of the examples and the comparative examples and aluminum nitride filler (particle size 50-100 nm) are mixed according to a mass ratio of 70:30 to prepare an electronic packaging adhesive, and then a Thermal Mechanical Analyzer (TMA) is adopted to measure the thermal expansion coefficient, wherein the temperature range is 25-150 ℃ and the temperature rising rate is 5 ℃ per minute;
film forming property and phase separation, namely observing the uniformity (100 times of magnification) of the surface of the film layer by adopting an optical microscope;
Photoetching defect rate the resin solutions of the examples and the comparative examples are mixed with 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine (photoinitiator) and 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylformate (cross-linking agent) according to the mass ratio of 85:10:5 to prepare photoresist solutions, and then a scanning electron microscope is adopted to observe the defect quantity of 36nm line width patterns;
Plasma etching loss rate, namely preparing a photoresist solution by referring to a photoetching defect rate test, and calculating mass loss per unit time by adopting an inductively coupled plasma etching machine with the power of 300W and the power of being CF 4/O2 =3:1;
The test results were as follows:
As can be seen from the above table, the Tg values (162-174 ℃) of examples one to three were significantly higher than that of the comparative example, wherein example two reached 174 ℃, the pure PHS resin of comparative example three was lifted by 23 ℃ and the ph resin of comparative example six protected by t-BOC was lifted by 14 ℃, which resulted from the rigid network formed by the polyurea hard segments and the PHS benzene rings in the block structure, and the thermal stability was far better than that of the single protecting group modification (comparative example six) or the random copolymerization structure (comparative example five). The tensile strength (21-28 MPa) and elongation at break (84-158%) of the examples are all better than those of the comparative examples, for example, the elongation at break (132%) of the second example is 33 times that of the pure PHS (4%) and 16.5 times that of the PHS resin protected by t-BOC, and the balance of high strength and high toughness may be derived from the synergistic effect that the PHS hard segment provides rigid support and the polyurea soft segment plays an elastic buffering role in the block structure, and the comparative examples generally have the defects of embrittlement or insufficient strength due to the lack of the structure. In terms of improvement of thermal expansion performance, after the aluminum nitride filler is compounded, the CTE value (14-19 ppm/° C) of the embodiment is obviously lower than that of the comparative example (24-37 ppm/° C), the CTE (14 ppm/° C) of the embodiment II is lowest, the matching performance with the silicon substrate (3 ppm/° C) is better, the characteristic is important for electronic packaging, and interface stress and cracking risks caused by expansion mismatch during thermal cycling can be reduced. In addition, the dielectric constant of the embodiment is lower than that of the comparative example, and the dielectric constant of the embodiment II is the lowest, so that the requirement of the high-frequency electronic device on the low-dielectric material is met. The water contact angle test shows that the hydrophobicity of the embodiment is obviously better than that of pure PHS, because the nonpolar polyether structure of the polyurea chain segment reduces the adsorption of water molecules, dielectric loss in high-frequency signal transmission is avoided, and the method is particularly suitable for 5G radio frequency devices and high-density packaging. For film forming quality, the examples all show excellent, no gel or phase separation, the comparative example I (n: m=4:1) causes gel due to excessive polyurea, the comparative example IV (direct mixing) generates serious phase separation due to disordered reaction, and the step-by-step block copolymerization is proved to be the key for guaranteeing film forming property. In addition, when the resin material of the present invention is prepared as a photoresist, the photolithography defect rate (0.01-0.03 pieces/μm2) of the examples is significantly lower than that of the comparative examples, and the plasma etching loss rate (0.28-0.33%/min) is only about 1/9 of that of pure PHS (2.9%/min), and the photolithography performance is excellent.
It should be noted that the poly-p-hydroxystyrene resin of the present invention not only can be applied to the fields of electronic packaging materials and semiconductor photoresists, but also has significant application potential in the fields of liquid crystal display alignment layers, etc. The high Tg (162-174 ℃) can resist the high temperature process (such as annealing process) of the liquid crystal display device, the excellent film forming uniformity (no phase separation) can ensure the smooth surface of an alignment layer, the defect of liquid crystal molecule arrangement is reduced, the pretilt angle of the liquid crystal molecules can be regulated and controlled by proper hydrophobicity (96-109 ℃) to optimize the display contrast, and the low dielectric constant characteristic is beneficial to reducing the driving voltage of a display panel and improving the energy consumption efficiency. Compared with the traditional polyimide orientation material, the resin has both wet heat resistance and process compatibility, and in the bending durability test of the flexible display field, the sample of the second embodiment still maintains more than 85% of initial performance after 10 ten thousand times of bending, which is far superior to the polyimide material (50-60%), and shows technical advantages of cross-field application.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for preparing a poly-p-hydroxystyrene resin, comprising the steps of:
step S1, preparing raw materials;
S2, synthesizing a poly (p-hydroxystyrene) prepolymer to obtain a poly (p-hydroxystyrene) prepolymer solution;
S3, synthesizing a polyurea resin prepolymer to obtain a polyurea resin prepolymer solution;
Step S4, carrying out block copolymerization, namely adding the poly-p-hydroxystyrene prepolymer solution obtained in the step S2 and the polyurea resin prepolymer solution obtained in the step S3 into the same reaction kettle to obtain a block copolymerization mixture;
And S5, performing post-treatment by using the block copolymerization reaction mixture obtained in the step S4 to obtain the poly-p-hydroxystyrene resin.
2. The method for preparing a poly-p-hydroxystyrene resin as set forth in claim 1, wherein in the step S2, the molecular formula of the poly-p-hydroxystyrene prepolymer is:
,
Wherein Ph represents a benzene ring, and x represents the degree of polymerization of the poly-p-hydroxystyrene prepolymer.
3. The method for preparing a poly (p-hydroxystyrene) resin as claimed in claim 1, wherein the step S2 comprises adding the purified p-hydroxystyrene monomer of the step S1 into a reaction kettle, adding DMF dried in the step S1 into the reaction kettle, adjusting the addition amount to ensure that the mass ratio of the p-hydroxystyrene monomer in the total solution in the reaction kettle is 15-25%, adding azobisisobutyronitrile, wherein the amount of azobisisobutyronitrile is 0.5-1% of the mass of the p-hydroxystyrene monomer, stirring at a rotation speed of 200-300r/min under nitrogen protection, heating the reaction system in the reaction kettle to 60-80 ℃, and reacting for 4-6 hours to obtain the poly (p-hydroxystyrene) prepolymer solution.
4. A process for producing a poly-p-hydroxystyrene resin as set forth in claim 3, wherein step S3 comprises,
Adding the isocyanate monomer and DMF solvent dried in the step S1 into another reaction kettle to ensure that the mass ratio of the isocyanate monomer is 20-30%, stirring at the speed of 150-250r/min under the protection of nitrogen, heating to 40-60 ℃, slowly dropwise adding the DMF solution containing diamine monomer, wherein the mass ratio of the diamine monomer in the solution is 10-20%, controlling the molar ratio of the isocyanate monomer to the diamine monomer to be 1.05:1-1.10:1, controlling the dropwise adding time to be 1-2 hours, and continuing to react for 2-3 hours after dropwise adding to obtain the polyurea resin prepolymer solution.
5. The method for producing a poly-p-hydroxystyrene resin as set forth in claim 4, wherein said isocyanate-based monomer is one or more selected from the group consisting of TDI, MDI, HDI, IPDI, HMDI and a fluorine-containing isocyanate.
6. The method for preparing a poly-p-hydroxystyrene resin as set forth in claim 4, wherein the diamine monomer is a polyether diamine monomer or a diamine monomer containing a hindered amine structure.
7. The method for preparing a poly (p-hydroxystyrene) resin as set forth in claim 1, wherein the step S4 comprises adding the poly (p-hydroxystyrene) prepolymer solution obtained in the step S2 and the polyurea resin prepolymer solution obtained in the step S3 to the same reaction vessel, stirring at a speed of 200-300r/min under the protection of nitrogen, heating to 50-70 ℃, adding dibutyl tin dilaurate into the same reaction vessel while stirring, wherein the addition amount is 0.1-0.3% of the total mass of the poly (p-hydroxystyrene) prepolymer solution and the polyurea resin prepolymer solution in the same reaction vessel, and reacting for 6-8 hours to obtain a block copolymerization reaction mixture.
8. The method for producing a poly-p-hydroxystyrene resin as claimed in any one of claims 1 to 7, wherein the ratio of the molar amount n of the p-hydroxystyrene monomer to the molar amount m of the isocyanate monomer is controlled to be n.m= (6 to 10): 1.
9. A parylene resin material produced by the production method according to any one of claims 1 to 8.
10. Use of the poly-p-hydroxystyrene resin material of claim 9 in photoresists, electronic packages, and/or liquid crystal display alignment layers.
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| CN103059313A (en) * | 2012-12-17 | 2013-04-24 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| TW201740199A (en) * | 2016-04-14 | 2017-11-16 | Asahi Chemical Ind | Photosensitive resin composition, method for producing cured embossed pattern and semiconductor device capable of suppressing the occurrence of voids at an interface between a Cu layer and a cured photosensitive resin layer |
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| CN103059313A (en) * | 2012-12-17 | 2013-04-24 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| TW201740199A (en) * | 2016-04-14 | 2017-11-16 | Asahi Chemical Ind | Photosensitive resin composition, method for producing cured embossed pattern and semiconductor device capable of suppressing the occurrence of voids at an interface between a Cu layer and a cured photosensitive resin layer |
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