Poly (p-hydroxystyrene) resin as well as preparation method and application thereof

Abstract

The invention provides poly (p-hydroxystyrene) resin as well as a preparation method and application thereof. The preparation method comprises the following steps: carrying out active anionic polymerization reaction on a compound monomer shown in a formula I under the action of a ligand to obtain a prepolymer; the prepolymer is hydrolyzed; the ligand is potassium tert-butoxide; the reaction temperature of the active anionic polymerization reaction is 20-25 DEG C. The molecular weight MW of the poly (p-hydroxystyrene) resin obtained by the preparation method is 29000-30000, the molecular weight is controllable, and the poly (p-hydroxystyrene) resin has lower molecular weight distribution index, metal impurity content, organic impurity content and water content; moreover, the monomer conversion rate is stabilized to be greater than or equal to 95%, the same molecular weight and molecular weight distribution index of the poly-p-hydroxystyrene resin produced in each batch can be ensured, and the use requirements of KrF photoresist resin are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer synthesis, in particular to a poly-p-hydroxystyrene resin and a preparation method and application thereof. BACKGROUND

[0002] Polyhydroxystyrene system occupies a dominant position in photoresist film-forming resin. The synthesis of high-end semiconductor photoresist resin (KrF and ArF) faces the following main problems: first, from the microscopic point of view, the more fine process requires high-quality polymer structure sequence composition distribution, molecular weight and very narrow PDI, so that the photoresist can better achieve the photoetching effect on finer size, and the development rate and LWR technical indexes are better; second, from the engineering point of view, it is necessary to ensure the batch stability and consistency of all polymer products, and the technical parameter indexes such as molecular weight and molecular weight distribution are required to be very close in each batch, and the more high-end the resin is, the more consistent the quality is.

[0003] In the preparation method of the existing poly-p-hydroxystyrene resin, CN115260348A discloses a controllable and easy-to-produce high molecular weight and narrow distribution poly-p-hydroxystyrene resin and its preparation method and application. The preparation method comprises the following steps: adding a compound monomer represented by formula (I) to a reaction system to perform an active anion polymerization reaction, and then performing a deprotection reaction to obtain a poly-p-hydroxystyrene resin. Although the poly-p-hydroxystyrene resin prepared by the method has a relatively narrow molecular weight distribution, the preparation adopts a low temperature of-80 to-70℃, and the reaction condition is harsh, which is not conducive to industrial production. SUMMARY

[0004] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a poly-p-hydroxystyrene resin and a preparation method and application thereof, which are used to solve the problems in the prior art.

[0005] To achieve the above-mentioned purposes and other related purposes, the present application is obtained by the following technical solutions.

[0006] The present application provides a preparation method of a poly-p-hydroxystyrene resin, comprising the following steps:

[0007] The compound monomer of formula I is subjected to an active anion polymerization reaction under the action of a ligand to obtain a prepolymer;

[0008] The prepolymer is hydrolyzed;

[0009] The ligand is potassium tert-butoxide, and the reaction temperature of the active anion polymerization reaction is 20 to 25℃.

[0010] Preferably, the structural formula of the compound monomer of formula I is

[0011]

[0012] wherein R1 is selected from one of C1-C7 alkyl, C4-C7 cycloalkyl, C1-C7 alkoxy and C1-C7 silyl.

[0013] More preferably, the compound monomer of formula I is p-tert-butoxystyrene.

[0014] If the amount of the ligand is too little, the conversion rate of the monomer is low, and the molecular weight distribution index PDI of the poly-p-hydroxystyrene resin prepared is large; if the amount of the ligand is too much, the conversion rate of the monomer and the molecular weight distribution index of the poly-p-hydroxystyrene resin prepared therefrom will not be greatly improved. Preferably, the molar ratio of the ligand to the compound monomer of formula I is (10-20):1. It can be 10-15:1, 15-20:1. Within a certain range, the more the amount of the ligand, the higher the conversion rate of the monomer, and the smaller the molecular weight distribution index of the poly-p-hydroxystyrene resin prepared.

[0015] Preferably, the active anionic polymerization reaction uses an initiator, and the initiator is sec-butyllithium.

[0016] More preferably, the molar ratio of the initiator to the compound monomer of formula I is (0.004-0.006):1.

[0017] Preferably, the active anionic polymerization reaction uses a first solvent, and the first solvent is toluene.

[0018] Preferably, the active anionic polymerization reaction uses a terminator, and the terminator is methanol. More preferably, the terminator is degassed methanol. The terminator functions to terminate the active anionic polymerization reaction.

[0019] Preferably, the reaction time of the active anionic polymerization reaction is 3-4 h.

[0020] Preferably, the hydrolysis uses a catalyst, and the catalyst is hydrochloric acid. More preferably, the concentration of the hydrochloric acid is 36-38%.

[0021] More preferably, the molar ratio of the catalyst to the prepolymer is (10-15):1.

[0022] Preferably, the hydrolysis uses a second solvent, and the second solvent is acetone.

[0023] Preferably, the hydrolysis temperature is 55-70°C. It can be 55-60°C, 60-70°C.

[0024] Preferably, the hydrolysis time is 12-24 h.

[0025] Preferably, the active anion polymerization reaction further comprises a post-treatment step, which comprises separation, drying. More preferably, the separation comprises precipitation, filtration. Further preferably, the precipitation is precipitation by adding the solution into 10-20 times volume of methanol. Further preferably, the filtration is obtaining filtrate by solid-liquid separation, and adjusting the filtrate to neutral with 10% sodium hydroxide aqueous solution. More preferably, the drying is drying the precipitate in a vacuum oven at 55-65°C.

[0026] Preferably, the hydrolysis reaction further comprises a post-treatment step, which comprises separation, drying. More preferably, the separation comprises precipitation, filtration. Further preferably, the precipitation is precipitation by adding the solution into 10-20 times volume of n-hexane / water (v / v: 10:1). Further preferably, the filtration is obtaining filtrate by solid-liquid separation, and adjusting the filtrate to neutral with 10% sodium hydroxide aqueous solution. More preferably, the drying is drying the precipitate in a vacuum oven at 55-65°C.

[0027] The application also discloses a poly-p-hydroxystyrene resin prepared by the preparation method.

[0028] Preferably, the weight average molecular weight of the poly-p-hydroxystyrene resin is 29000-30000.

[0029] Preferably, the molecular weight distribution index of the poly-p-hydroxystyrene resin is <1.1.

[0030] Preferably, the metal impurity content of the poly-p-hydroxystyrene resin is <100 ppb.

[0031] Preferably, the organic impurity content of the poly-p-hydroxystyrene resin is <100 ppm.

[0032] Preferably, the water content of the poly-p-hydroxystyrene resin is <0.5%.

[0033] The application also discloses a use of the poly-p-hydroxystyrene resin prepared by the preparation method as a KrF photoresist resin.

[0034] The application discloses a poly-p-hydroxystyrene resin, a preparation method and a use thereof, and has the following beneficial effects:

[0035] (1) The molecular weight M Wthe molecular weight is controllable, and has a low molecular weight distribution index, metal impurity content, organic impurity content, and water content; and the monomer conversion rate is stable at ≥ 95%, which ensures that the molecular weight and molecular weight distribution index of the poly-p-hydroxystyrene resin produced in each batch are the same, and meet the use requirements of the KrF photoresist resin;

[0036] (2) The preparation method has good stability not only for the poly-p-hydroxystyrene resin prepared in a small test, but also for the poly-p-hydroxystyrene resin prepared in a pilot test and an enlarged test, and has industrial operability;

[0037] (3) The preparation method is simple, and the poly-p-hydroxystyrene resin can be prepared at room temperature without the need of low-temperature conditions, which can greatly reduce the production cost and production difficulty, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The figure shows the nuclear magnetic spectrum of the poly-p-hydroxystyrene resin prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0039] The embodiments of the present application are described below through specific concrete examples, and those skilled in the art can easily understand other advantages and effects of the present application from the disclosure of the present specification. The present application can also be implemented or applied through other different concrete embodiments, and each detail in the present specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present application.

[0040] It should be understood that the process equipment or device not specifically mentioned in the following examples is the conventional equipment or device in the art.

[0041] In addition, it should be understood that the one or more method steps mentioned in the present application do not exclude that there can be other method steps before and after the combination steps or other method steps can be inserted between the explicitly mentioned steps, unless otherwise specified; it should also be understood that the combination connection relationship between the one or more devices / apparatuses mentioned in the present application does not exclude that there can be other devices / apparatuses before and after the combination devices / apparatuses or other devices / apparatuses can be inserted between the two explicitly mentioned devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not a limitation on the arrangement order of each method step or a limitation on the range of implementation of the present application. The change or adjustment of the relative relationship, without substantial change of the technical content, is also regarded as the implementation range of the present application.

[0042] Example 1

[0043] The embodiment provides a specific preparation method of a poly-p-hydroxystyrene resin, and the specific steps are as follows.

[0044] (1) Preparation of a prepolymer

[0045] In a vacuum atmosphere and at 25 DEG C, 160g of dried toluene is added to a reaction container, and then sec-butyllithium (1.3mmol), potassium tert-butoxide (2.3mol) and p-tert-butoxystyrene (40.7g, 0.23mol) are sequentially added, the reaction is terminated after 3h by adding degassed methanol (0.5mL).

[0046] After the reaction is completed, the reaction solution is added to 20 times the volume of methanol for precipitation, and the filtrate is obtained by filtration, 10% sodium hydroxide solution is added to the filtrate to adjust the pH to 7, and then the mixture is added to 20 times the volume of methanol for precipitation, and the precipitate is obtained by filtration and dried.

[0047] (2) Preparation of a poly-p-hydroxystyrene resin

[0048] Under an inert atmosphere, the prepolymer is dissolved in acetone at 60 DEG C, 37% hydrochloric acid is added, and the mixture is stirred overnight after being sealed, and the molar ratio of hydrochloric acid to the prepolymer is 10:1.

[0049] After the hydrolysis reaction is completed, the reaction solution is added to n-hexane / water (v / v: volume ratio is 10:1) for precipitation, and the filtrate is obtained by filtration, 10% sodium hydroxide solution is added to the filtrate to adjust the pH to 7, and then the mixture is added to 20 times the volume of methanol for precipitation, and the precipitate is obtained by filtration and dried.

[0050] The poly-p-hydroxystyrene resin prepared in Example 1 is subjected to 1 HNMR detection, and the detection spectrum is as shown in Figure 1 .

[0051] Example 2

[0052] The embodiment provides a specific preparation method of a poly-p-hydroxystyrene resin, and the specific preparation method is basically the same as that in Example 1, and the difference is that the amount of potassium tert-butoxide used in step (1) is 3.45mol.

[0053] Example 3

[0054] The embodiment provides a specific preparation method of a poly-p-hydroxystyrene resin, and the specific preparation method is basically the same as that in Example 1, and the difference is that the amount of potassium tert-butoxide used in step (1) is 4.6mol.

[0055] Comparative Example 1

[0056] This comparative example is a comparative example of Example 1, and differs from Example 1 only in that in step (1), the amount of potassium tert-butoxide used is 1.15 mol.

[0057] Comparative Example 2

[0058] This comparative example is a comparative example of Example 1, and differs from Example 1 only in that in step (1), no potassium tert-butoxide is added.

[0059] Comparative Example 3

[0060] This comparative example is a comparative example of Example 1, and differs from Example 1 only in that in step (1), benzene is used instead of toluene.

[0061] Comparative Example 4

[0062] This comparative example is a comparative example of Example 1, and differs from Example 1 only in that in step (1), dioxane is used instead of toluene.

[0063] The poly-p-hydroxystyrene resins prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to GPC analysis, and the results are shown in Table 1.

[0064] The poly-p-hydroxystyrene resins prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to ICP-MS detection of metal impurity content, and the results are shown in Table 1, under the following detection conditions:

[0065] Inductively coupled plasma mass spectrometer (instrument model NEXION 5000G)

[0066] Plasma power is 1500 W;

[0067] Plasma gas flow is 16 L / min;

[0068] Auxiliary gas flow is 1.2 L / min;

[0069] Atomizer temperature is -5°C;

[0070] Oxygen flow: 0.035 L / min;

[0071] Injection speed: 100 uL / min.

[0072] The poly-p-hydroxystyrene resins prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to GC-MS detection of organic impurity content, and the results are shown in Table 1, under the following detection conditions:

[0073] Instrument model: Agilent 8890-5977; Gas chromatography conditions: GC column model: HP-5ms, length: 30 m, inner diameter: 0.25 mm; injection port temperature: 280℃; injection volume: 1 μL; split ratio: 20:1; column flow rate: 1.00 mL / min; solvent delay: 2.3 min; column oven temperature program: initial temperature 50℃ for 1 min, then increased to 320℃ at 30℃ / min for 3 min.

[0074] Mass spectrometry conditions: Transfer line temperature: 250℃; MS ion source temperature: 230℃; Quadrupole temperature: 150℃; Scan range m / z: 29-550; Scan mode: Dual scan SCAN & SIM.

[0075] The poly-p-hydroxystyrene resins prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to moisture detection using a moisture detector, and the detection results are shown in Table 1.

[0076] Table 1

[0077]

[0078] The above examples are only illustrative of the principles and effects of the present application, and are not intended to limit the present application. Any person skilled in the art can modify or change the above examples without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical thought disclosed in the present application should be covered by the claims of the present application.

Claims

1. A process for the preparation of a poly-p-hydroxystyrene resin, characterized in that, The method comprises the following steps: a pre-polymer is obtained by subjecting a monomer of the compound of formula I to an active anion polymerization reaction in the presence of a ligand; the pre-polymer is hydrolyzed; the ligand is potassium tert-butoxide; the active anion polymerization reaction is carried out at a temperature of 20-25℃.

2. The production method according to claim 1, characterized by, The monomer of the compound of formula I has the following structural formula R1 is selected from C1-C7 alkyl, C4-C7 cycloalkyl, C1-C7 alkoxy and C1-C7 silane.

3. The preparation method according to claim 1, characterized in that The molar ratio of the ligand to the monomer of the compound of formula I is (10-20):1; and / or, the active anion polymerization reaction uses an initiator, and the initiator is sec-butyllithium.

4. The production method according to claim 3, characterized by, The molar ratio of the initiator to the monomer of the compound of formula I is (0.004-0.006):

1.

5. The preparation method according to claim 1, characterized in that The active anion polymerization reaction uses a first solvent, and the first solvent is toluene; and / or, the active anion polymerization reaction uses a terminating agent, and the terminating agent is methanol.

6. The method of claim 1, wherein, The hydrolysis uses a catalyst, and the catalyst is hydrochloric acid; and / or, the hydrolysis system comprises a second solvent, and the second solvent is acetone; and / or, the hydrolysis temperature is 55-70℃.

7. The preparation method according to claim 1, characterized in that The active anion polymerization reaction further comprises a post-treatment step, and the post-treatment step comprises separation and drying; and / or, the hydrolysis reaction further comprises a post-treatment step, and the post-treatment step comprises separation and drying.

8. A poly-p-hydroxystyrene resin prepared by the method of any one of claims 1-7.

9. The poly-p-hydroxystyrene resin of claim 8, wherein, The poly-p-hydroxystyrene resin has a weight average molecular weight of 29,000-30,000; and / or, the poly-p-hydroxystyrene resin has a molecular weight distribution index <1.1; and / or, the poly-p-hydroxystyrene resin has a metal impurity content <100 ppb; and / or, the poly-p-hydroxystyrene resin has an organic impurity content <100 ppm; and / or, the poly-p-hydroxystyrene resin has a water content <0.5%.

10. Use of a poly-p-hydroxystyrene resin prepared by the method of any one of claims 1-7 as a KrF photoresist resin.

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