Method for acrylate polymerization reaction under synergistic regulation of hydrogen bonds and Lewis acids and without synergistic regulation of hydrogen bonds and Lewis acids

Abstract

The present invention belongs to the field of polymer polymerization and relates to a method for acrylate polymerization under the synergistic regulation of hydrogen bonds and Lewis acids and without the synergistic regulation of hydrogen bonds and Lewis acids, comprising the following steps: using an acrylate compound as a monomer raw material, carrying out a polymerization reaction by a (thio)urea anion in an organic solvent or without the participation of an organic solvent under the condition of the participation of a Lewis acid, wherein the polymerization reaction temperature is -20°C to 90°C and the reaction time is 0.02 min to 3600 min; wherein, the Lewis acid is a boron-containing compound. The present invention uses a boron-containing compound as the Lewis acid, and the initiator after adding the boron reagent makes up for the defects of the polymerization system initiated by a single (thio)urea anion, such as low conversion rate and wide molecular weight distribution under the condition of high-equivalent monomer feeding. The prepared polymer has a narrow molecular weight distribution and a molecular weight closer to the theoretical molecular weight.

Description

Technical Field

[0001] The present invention belongs to the field of polymer polymerization, relates to polyacrylate polymers and their polymerization processes, and particularly relates to a method for acrylate polymerization based on the synergistic regulation of hydrogen bonds and Lewis acids and without the synergistic regulation of hydrogen bonds and Lewis acids. Background Art

[0002] Developing sustainable catalysis or efficient, living / controlled polymerization methods is a long-standing scientific challenge in the field of polymer chemistry. The currently used catalytic systems generally contain metals, resulting in certain metal residues in the finally obtained polymers, which in turn affects the product performance and limits the application of polymers in the biomedical and microelectronics fields. Therefore, the development of non-metal catalytic / initiating systems has broad application value and industrial prospects in the field of polymer materials.

[0003] In the prior art, the Hong research group (Macromolecules 2021, 54, 8495 - 8502) reported that triisobutylphosphine was used as a Lewis base, and by reacting with boron compounds with different acidities and steric hindrances such as [tris(pentafluorophenyl)borane, tris(2,6-difluorophenyl)borane], tris(2,4-difluorophenyl)borane was finally determined as an excellent Lewis acid, which could achieve efficient polymerization under industrial conditions such as room temperature or even 60 - 80 °C. This borane has good thermal stability and considerable air / moisture tolerance, and polymers with molecular weights in the range of 5000 - 200000 g / mol and a narrow molecular weight distribution (Mw / Mn < 1.14) were prepared by the polymerization reaction. However, the monomer material methyl methacrylate was not involved in this research report.

[0004] So far, it has been difficult to obtain poly(methyl methacrylate) using non-metal catalytic methods. The range of non-metal Lewis acids available for screening is limited and the polymerization effect is generally average. For example, some literature reports that B(C 6 F 5 ) 3 is used as a Lewis acid to participate in the polymerization reaction, and its controllability and polymerization results are worse than those of the polymerization reaction participated by organoaluminum Lewis acids. Moreover, the preparation of this borane is difficult, and its water-sensitive property also limits the subsequent application transformation. Summary of the Invention

[0005] The object of the present invention is to solve the above problems existing in the prior art, and a method for acrylate polymerization based on the synergistic regulation of hydrogen bonds and Lewis acids and without the synergistic regulation of hydrogen bonds and Lewis acids is proposed. A boron-containing compound is used as the Lewis acid, and the initiator after adding the boron reagent makes up for the defects of the polymerization system initiated by a single (thio)urea anion, such as low conversion rate and wide molecular weight distribution under the condition of high equivalent monomer feeding. The prepared polymer has a narrow molecular weight distribution and a molecular weight closer to the theoretical molecular weight.

[0006] The technical solution of the present invention is as follows:

[0007] A method for acrylate polymerization based on the synergistic regulation of hydrogen bonds and Lewis acids and without the synergistic regulation of hydrogen bonds and Lewis acids, comprising the following steps:

[0008] Using an acrylate compound as a monomer raw material, under the participation of a Lewis acid, a (thio)urea anion is used to carry out a polymerization reaction in an organic solvent or without the participation of an organic solvent. The polymerization reaction temperature is -20°C to 90°C, and the reaction time is 0.02 min to 3600 min;

[0009] Further, in the above steps, the acrylate compound monomer raw material and the Lewis acid are first mixed evenly, and then the (thio)urea anion is added, and the polymerization reaction is carried out in an organic solvent or without the participation of an organic solvent. The polymerization reaction temperature is -20°C to 90°C, and the reaction time is 0.02 min to 3600 min;

[0010] Wherein, the molar ratio of the acrylate compound, the Lewis acid and the (thio)urea anion is (1 to 400):(0.01 to 0.70):(0.10 to 0.25); the molar ratio of the three can be any ratio within the range of (1 to 400):(0.01 to 0.70):(0.01 to 0.25), for example, it can be 200:0.28:0.1, 200:0.42:0.15, 200:0.36:0.13, 400:0.42:0.15, 400:0.28:0.10, 400:0.36:0.13, 100:0.05:0.10, 100:0.15:0.25 or 100:0.35:0.13, etc., and it can also be any other ratio not listed in the above range.

[0011] The Lewis acid is selected from boron-containing compounds, and the boron-containing compounds include but are not limited to 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (PinBH), substituted pinacol borane (PinBR), 9-borabicyclo[3.3.1]nonane (9-BBN), 9-substituted-9-borabicyclo[3.3.1]nonane (9-R-9-BBN), 5-chloro-5H-dibenz[b,d]borole, bis(pinacolato)diboron (Pin 2 B 2 ), triethylborane (BEt 3 ), borate ester, aminoborane (including monoaminoborane, diaminoborane or triaminoborane), or any one or more of them; their structural formulas are respectively:

[0012] (PinBH), (PinBR), (9-BBN), (9-R-9-BBN), (5-chloro-5H-dibenz[b,d]borole), (Pin 2 B 2 ), (BEt 3 ), (borate ester), (monoaminoborane), (diaminoborane), (triaminoborane);

[0013] Among them, the R group is a group such as alkyl, aryl, alkenyl, alkynyl, silyl, etc.; the R' and R" groups are groups such as alkyl, aryl, silyl, etc.

[0014] Furthermore, the acrylate compound has the following structure:

[0015]

[0016] Among them, R 5 is H or a C1-C4 alkyl group, and R 6 is selected from a C1-C23 alkyl group, a C1-C5 alkenyl group, a heterocyclic methyl group, an aryl group, a substituted silyl group, and the substituting group of the substituted silyl group is a C1-C8 alkyl group or a C1-C5 alkenyl group.

[0017] In some embodiments, the acrylate monomers include, but are not limited to, one or more of methyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, furfuryl methacrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate, and stearyl acrylate.

[0018] Furthermore, the molar ratio of the acrylate compound, Lewis acid, and (thio)urea anion is (20 - 200):(0.10 - 0.40):(0.10 - 0.20).

[0019] Furthermore, when the polymerization reaction is carried out in an organic solvent, the organic solvent is one or more of toluene, tetrahydrofuran, n-hexane, and dichloromethane, and the concentration of the acrylate compound in the organic solvent is 0.16 - 16 mol / L. The specific concentration value is any value within the range of 0.16 - 16 mol / L. For example, it can be 0.16 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2.5 mol / L, 3 mol / L, 6.5 mol / L, 9 mol / L, 10 mol / L, 12 mol / L, 14 mol / L, or 16 mol / L, etc.

[0020] Furthermore, the (thio)urea is prepared by the reaction of (thio) isocyanate and primary amine or secondary amine.

[0021] The (thio)urea anion is directly prepared by the reaction of a strong base and the prepared (thio)urea. The strong base is tetrabutylammonium hydroxide, and the reaction general formula is as follows:

[0022]

[0023] The R group is one of alkyl, cycloalkyl, substituted alkyl, aryl, or substituted aryl. The R' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl, or substituted phenyl. The R'' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl, or substituted phenyl.

[0024] The synthesis steps for directly preparing the (thio)urea anion by the above method are as follows:

[0025] Take a certain amount of (thio)isocyanate, add a certain amount of dichloromethane to dilute or dissolve the reaction raw material, and add secondary amine or primary amine under stirring at room temperature according to the molar ratio of (thio)isocyanate: primary amine (or secondary amine) of 1:1 - 2; stir the reaction raw material solution at room temperature overnight (12 - 24 hours), drain the reaction solution, wash the obtained solid twice with hexane and then filter and drain to obtain the corresponding (thio)urea. Weigh a certain amount of the obtained (thio)urea and dissolve it in anhydrous methanol, add a methanol solution of 1.01 equivalents of tetrabutylammonium hydroxide at 0 °C, and stir the reaction solution at room temperature overnight (12 - 24 hours) after the addition is complete, and then drain it under vacuum to obtain the target (thio)urea anion.

[0026] Alternatively, other strong bases such as alkyllithium, sodium alkoxide, potassium alkoxide, lithium diisopropylamide (LDA), potassium bis(trimethylsilyl)amide (KHMDS), etc. are first used to remove protons to obtain the (thio)urea metal salt, and then the metal ion-free (thio)urea salt is prepared by reacting with ammonium halide, phosphonium halide, etc. The specific steps are as follows:

[0027] Indirectly prepared by reacting another type of strong base with (thio)urea and then reacting with ammonium halide or phosphonium halide. The general reaction formula is as follows:

[0028]

[0029] Among them, another type of strong base includes but is not limited to nBuLi, EtONa, CH 3 OLi, tBuOK, lithium diisopropylamide (LDA), potassium bis(trimethylsilyl)amide (KHMDS), etc.; Z = S, O; the R group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, and the R 1 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, and the R 2 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, and the R 3 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, and the R 4 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl; the R' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl, and the R'' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl;

[0030] The ammonium halide and phosphonium halide have the following structures:

[0031]

[0032] Among them, A = N or P; the R 1 group is any one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, and the R2 The base is any one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, R 3 The base is any one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, R 4 The base is any one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl; X is bromide ion, chloride ion or iodide ion.

[0033] The preparation of (thio)urea anion by the above indirect method is as follows:

[0034] The corresponding (thio)urea is prepared by the same method as the direct preparation method. A certain amount of (thio)urea is dissolved in hexane, and 1-1.2 equivalents of strong base (including LDA or KHMDS or sodium alkoxide or potassium alkoxide, etc.) are added dropwise at 0 °C. After the addition is completed, the mixture is stirred at room temperature for 5 hours, then filtered. The remaining solid is washed twice with hexane and then dried by suction to obtain the corresponding (thio)urea metal salt; A certain amount of this (thio)urea metal salt is taken, dissolved in tetrahydrofuran, and an equivalent amount of ammonium halide or phosphonium halide is added under stirring at 0 °C. After the addition is completed, the reaction solution is stirred at room temperature overnight; Then it is dried by suction under vacuum conditions, and the residue is extracted with toluene. The toluene solutions are combined and then dried by suction to obtain the target product (thio)urea anion.

[0035] Furthermore, the structural formula of the (thio)urea is as follows:

[0036]

[0037] Among them, the R group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, the R' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl, and the R'' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl;

[0038] Among them, n is an integer greater than or equal to 1.

[0039] Furthermore, the structural formula of the (thio)urea is as follows:

[0040] Urea:

[0041]

[0042]

[0043] Thiourea:

[0044]

[0045] Among them, R = (cyclo)alkyl, aryl, allyl, silyl, 4-morpholinylalkyl, aminoalkyl or alkoxyalkyl;

[0046] R’ is any one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl;

[0047] R” is any one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl.

[0048] Furthermore, the general formula of the (thio)urea anion is as follows:

[0049]

[0050] wherein, Z = O or S, A = N or P; R 1 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, R 2 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, R 3 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, R 4 group is one of alkyl, cycloalkyl, substituted alkyl, aryl or substituted aryl, R' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl, and R'' group is one of methyl, ethyl, isopropyl, phenyl, trimethylsilyl, tert-butyl, cyclohexyl or substituted phenyl.

[0051] Furthermore, the (thio)urea anion includes TUA-1 to TUA-8, wherein TUA-1 is a (thio)urea anion with hydrogen bond regulation function, and its structural formula is as follows:

[0052]

[0053] TUA-2 to TUA-8 are (thio)urea anions without hydrogen bond regulation function, and their structural formulas are as follows:

[0054]

[0055] The polymerization reaction temperature can be any temperature within the range of -20°C to 90°C. For example, the polymerization temperature can be -20°C, -10°C, 0°C, 10°C, 20°C, 25°C, 30°C, 40°C, 60°C, 80°C, 85°C or 90°C, etc., and can also be any other temperature within this range. Furthermore, the polymerization reaction temperature is 0°C to 60°C; preferably, the polymerization reaction temperature can also be 30°C to 50°C.

[0056] The time of the polymerization reaction can be any value within the range of 0.02 min to 3600 min. For example, it can be 0.02 min, 10 min, 20 min, 38 min, 60 min, 80 min, 90 min, 120 min, 240 min, 300 min, 500 min, 800 min, 1200 min, 1400 min, 1500 min, 1600 min, 1800 min, 1920 min, 2200 min, 2500 min, 3000 min, 3200 min, 3600 min, etc., or any other time not listed within this range; further, preferably, the polymerization reaction time is 38 min to 1660 min; more preferably, the polymerization reaction time is 90 min to 300 min.

[0057] In the method for polymerizing acrylate based on the synergistic regulation of hydrogen bond and Lewis acid, using TUA-1 as the (thio)urea anion and the compound in-situ generated from the boron-containing compound and the (thio)urea anion as the initiator, the initiator after adding the boron reagent remedies the defects of low conversion rate and wide molecular weight distribution in the polymerization system initiated by the (thio)urea anion alone under the condition of high-equivalent monomer feeding. At the same time, it also improves the problem that the molecular weight of the polymer obtained in the prior art using organoaluminum as the Lewis acid in the TUA-1 system regulated by hydrogen bond is much larger than the theoretical molecular weight.

[0058] The following takes the example of polymerizing methyl methacrylate (MMA) with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (PinBH) and TUA-1 for illustration. The reaction mechanism is as follows:

[0059]

[0060] In the above reaction, when the (thio)urea anion is mixed into the mixed solution of the monomer and the boron reagent, one molecule of the boron reagent acts with the (thio)urea anion, and the other molecule of the boron reagent and the N-H group on the (thio)urea anion act on the carbonyl group together to activate the monomer. At the same time, it also plays a protective role on the active species generated in the reaction, greatly avoiding the occurrence of side reactions, making the system more controllable, the molecular weight of the obtained polymer close to the theoretical molecular weight, and the molecular weight distribution becoming narrower. The controllability of the reaction is improved, and high-equivalent monomers can be converted in an equimolar amount.

[0061] When a (thio)urea anion without hydrogen bonding is used to polymerize acrylate compounds in cooperation with a boron compound, there will be no hydrogen bonding during the reaction process, and only the boron reagent will participate in activating the monomer alone. In comparison, when a (thio)urea anion with hydrogen bonding cooperates with a boron reagent to participate in the reaction, the molecular weight distribution of the resulting polymer is narrower (1.01 - 1.50), but the reaction time is longer; while when a (thio)urea anion without hydrogen bonding cooperates with a boron reagent to participate in the reaction, the molecular weight distribution of the resulting polymer is wider (1.6 - 3.1), but the polymerization rate is higher and the required time is shorter.

[0062] Advantages of the present invention:

[0063] (1) The present invention utilizes the synergistic effect of a Lewis acid and a (thio)urea anion with or without hydrogen bonding regulation to initiate the polymerization reaction of acrylates, and PinBH shows the best catalytic effect; the molecular weight of the resulting polyacrylate polymer is in the range of 5000 - 200000 g / mol, and the molecular weight distribution The monomer conversion rate is as high as 100%, and the syndiotacticity is greater than 50%. The raw materials of this initiation system are cheap and easily available, the catalyst has high stability, the reaction has good controllability, and it can realize low-cost and large-scale industrial production.

[0064] (2) The present invention conducts the polymerization reaction under the co-regulation of hydrogen bonding and boron Lewis acid, which can effectively reduce the occurrence of side reactions such as backbiting; after adding Lewis acid to participate in the co-regulation, the induction period of the polymerization reaction is appropriately shortened, which improves the disadvantages under the condition of no Lewis acid participation in regulation to a certain extent and the result that only high molecular weight polymers can be obtained when metal Lewis acid participates in the reaction, prepares a polymer with a molecular weight closer to the theoretical molecular weight, and at the same time solves the problem of metal residue in the polymer.

[0065] (3) The (thio)urea anion with hydrogen bonding combined with boron Lewis acid can achieve anionic polymerization under solvent-free conditions. This system can effectively reduce the post-treatment steps and reaction costs, providing feasibility for industrial application. Description of the drawings

[0066] Figure 1 It is the Malditof-MS test spectrum of low molecular weight poly(methyl methacrylate) of the TUA-1 / Pin / BH system;

[0067] Figure 2 It is Figure 1 The enlarged view of the boxed part in the figure;

[0068] Figure 3 It is the Malditof-MS data analysis chart of low molecular weight poly(methyl methacrylate) of the TUA-1 / Pin / BH system;

[0069] Figure 4 It is a linear graph of the molecular weight and conversion rate - reaction time for the TUA-1 / Pin / BH system;

[0070] Figure 5 It is a linear graph of different equivalent monomer feed - polymer molecular weight - PDI for the TUA-2 / PinBH system. Detailed implementation manners

[0071] To further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0072] Example 1

[0073] The (thio)urea anion is prepared by the direct preparation method, and the steps are as follows:

[0074] Put a certain amount of thioisocyanate (or isocyanate) into a reaction flask, add a certain amount of dichloromethane to dilute the thioisocyanate (or isocyanate), and then add secondary amine or primary amine according to the molar ratio of thioisocyanate (or isocyanate): primary amine (secondary amine) = 1:1 under stirring at room temperature; stir overnight at room temperature, drain the reaction solution, wash the obtained solid twice with hexane and then filter and drain, and the corresponding (thio)urea can be obtained; weigh a certain amount of the obtained (thio)urea and dissolve it in anhydrous methanol, add a methanol solution of 1.01 equivalents of tetrabutylammonium hydroxide at 0 °C, stir the reaction solution overnight at room temperature after dropping, and then drain it under vacuum to obtain the target (thio)urea anion.

[0075] Example 2

[0076] The (thio)urea anion is prepared by the indirect method, and the steps are as follows:

[0077] The corresponding (thio)urea is prepared by the same method as the direct preparation method. Take a certain amount of (thio)urea and dissolve it in hexane, dropwise add 1 equivalent of sodium alkoxide at 0 °C, stir at room temperature for 5 hours after dropping, then filter, wash the remaining solid twice with hexane and then drain to obtain the corresponding (thio)urea metal salt; take a certain amount of the (thio)urea metal salt, add tetrahydrofuran to dissolve it, add an equivalent amount of ammonium chloride or phosphonium chloride under stirring at 0 °C, stir the reaction solution overnight at room temperature after dropping, then drain it under vacuum conditions, extract the residue with toluene, combine the toluene solutions and then drain to obtain the (thio)urea anion.

[0078] Example 3

[0079] TUA-1 is used as an anion with hydrogen bond regulation effect, and different Lewis acids are used to polymerize acrylate monomers. The different Lewis acids selected in this specific example are PinBH, 9-BBN or Pin 2 B 2 , and the selected polyacrylates are MMA or MA.

[0080] During the feeding process of the polymerization reaction, after mixing the Lewis acid and the monomer, TUA-1 is added; the specific operation is as follows:

[0081] The polymerization reaction is carried out in a glove box. MMA is taken and mixed with PinBH or 9-BBN respectively, or MA is taken and mixed with Pin2B2, then a certain amount of toluene is added or no solvent is added, and then TUA-1 is added to maintain [M] 0 = 4.8 M or 10 M or 0.16 M or 16 M; the polymerization reaction time is set according to the time in Table 1, and the polymerization temperature is room temperature (the temperature under non-room temperature is separately marked and explained in Table 1);

[0082] After the reaction is completed; take 0.1 mL of the reaction solution and perform 1 1H NMR test to obtain the conversion rate and the stereoregularity of the polymer. Outside the glove box, add methanol containing 5% HCl to the reaction solution to terminate the reaction, then wash the polymer with a large amount of methanol, and put it in an oven to dry to a constant weight at 40 °C. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography.

[0083] As shown in Table 1 below, when TUA-1 is used as an anion with the effect of hydrogen bond regulation, different Lewis acids and different reaction conditions are used, and different catalytic results are obtained.

[0084] Table 1 Summary of the results of the polymerization of MMA and MA catalyzed by TUA-1 with different Lewis acids and different reaction conditions

[0085]

[0086] Note: a, b, c, d indicate that the reaction temperatures are 40, 50, 80, 80 °C respectively.

[0087] Example 4

[0088] TUA-2 is used as an anion without hydrogen bond regulation effect, and different Lewis acids are used to polymerize acrylate monomers to compare the polymerization initiation effect of TUA-1 with hydrogen bond regulation effect. The different Lewis acids selected in this specific example are PinBH, 9-BBN or Pin 2 B 2 , and the selected polyacrylate is MMA.

[0089] In the charging process of the polymerization reaction, Lewis acid (PinBH, 9-BBN or Pin 2 B 2 ) is mixed and stirred with MMA and TUA-8. The specific operation is as follows:

[0090] The polymerization reaction is carried out in a glove box. MMA is taken and mixed with PinBH, 9-BBN or Pin 2 B 2 respectively, and then a certain amount of toluene is added or no solvent is added. Subsequently, TUA-8 is added, and [M] 0 is maintained at 4.8 M or 10 M or 0.16 M or 16 M; the polymerization reaction time is set according to the time in Table 2, and the polymerization temperature is room temperature (the temperature under non-room temperature is separately marked and explained in Table 1);

[0091] After the reaction is completed; 0.1 mL of the reaction solution is taken, and 1 HNMR test is carried out with deuterated chloroform to obtain the conversion rate and the stereoregularity of the polymer. Outside the glove box, methanol containing 5% HCl is added to the reaction solution to terminate the reaction, and then the polymer is washed with a large amount of methanol and placed in an oven to be dried to a constant weight at 40 °C. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography.

[0092] As shown in Table 2 below, as a comparison, TUA-1 with hydrogen bond regulation effect, in this example, TUA-8 without N-H group is used as the anion without hydrogen bond regulation effect. When different Lewis acids and different reaction conditions are used in combination, different catalytic results are obtained.

[0093] Table 2 Summary of the results of catalyzing MMA polymerization under different Lewis acids and different reaction conditions

[0094]

[0095] Note: a indicates that the reaction temperature is -20 °C respectively.

[0096] Example 5

[0097] TUA-1 is used as the anion with hydrogen bond regulation effect, and PinBH is used as the Lewis acid to carry out the experiment and calculation of the initiation efficiency of bulk polymerization of methyl methacrylate (MMA). This example is to verify the reaction rate or the time required to complete 100% conversion, and at the same time judge whether the polymerization reaction is a linear controlled polymerization according to the data.

[0098] The polymerization reaction was carried out in a glove box. MMA monomer, PinBH and TUA-1 were pipetted and mixed. After all the reaction raw materials were mixed, the timing started. Samples were taken at the same time intervals until the reaction ended. Methanol containing 5% HCl was added to the reaction solution to terminate the reaction. Subsequently, the polymer was washed with a large amount of methanol and placed in an oven to dry to a constant weight at 40 °C. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography.

[0099] The obtained polymer was tested by time-of-flight mass spectrometry Malditof-Ms, as Figure 1 and Figure 2 shown. The analysis results are as Figure 3 shown, indicating that a linear polymer was obtained in this polymerization reaction.

[0100] The results obtained by sampling at intervals using TUA-1 as the anion with hydrogen bond regulation and PinBH as the Lewis acid for the catalysis of methyl methacrylate are summarized in Table 3 (LA:LB = 2.8:1).

[0101] Table 3 Results of polymerizing methyl methacrylate using PinBH as the Lewis acid

[0102]

[0103] In this example, it was detected whether the polymerization changed linearly with time. According to the obtained data for analysis, a linear graph as Figure 4 shown was obtained. A conversion rate of 5.39% appeared at 161 min, indicating that the initiation efficiency was not high. At this time, only 5.39% of the monomers polymerized. As the reaction time increased, the conversion rate continuously increased.

[0104] Example 6

[0105] TUA-2 was used as the anion without hydrogen bond regulation, and PinBH was used as the Lewis acid for the gradient homopolymerization of methyl methacrylate to detect the controllability of the polymerization system.

[0106] The polymerization reaction was carried out in a glove box. The molar ratio of TUA-2 to PinBH was maintained at 1:2.8, and the homopolymerization reactions of 100 equivalents, 200 equivalents, 300 equivalents, and 400 equivalents of methyl methacrylate were carried out in parallel. The polymerization reaction was carried out in toluene solution at room temperature. The obtained polymerization results are summarized in Table 4:

[0107] Table 4 Results of polymerizing different equivalents of methyl methacrylate using PinBH as the Lewis acid in combination with TUA-2

[0108]

[0109] This example is to detect whether the polymerization controllability increases linearly with the monomer feed amount, and analyze the obtained data to obtain a linear graph as shown in Figure 5 shown below.

[0110] Example 7

[0111] TUA-2 was used as an anion without hydrogen bond regulation, and PinBH was used as a Lewis acid for the synthesis and characterization of low-equivalent poly(methyl methacrylate). The polymerization reaction was carried out in a glove box. The molar ratio of methyl methacrylate, TUA-2 and PinBH was 20:2:5.6. The polymerization reaction was carried out in toluene solution at room temperature until the reaction ended. Methanol containing 5% HCl was added to the reaction solution to terminate the reaction. Subsequently, the polymer was washed with a large amount of methanol and dried in an oven at 40 °C to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The molecular weight was 1210 g / mol, and the molecular weight distribution The obtained polymer will be used for NMR and Malditof-Ms tests for the study of the polymerization mechanism.

[0112] Example 8

[0113] Under solvent-free conditions, TUA-1 was used as an anion with hydrogen bond regulation, and PinBH was used as a Lewis acid for the homopolymerization of methyl methacrylate.

[0114] The polymerization reaction was carried out in a glove box. Under the condition of no organic solvent participation, methyl methacrylate, PinBH and TUA-1 were taken. Among them, the molar ratio of methyl methacrylate, TUA-1 and PinBH was 20:0.13:0.36. The reaction was carried out at a polymerization temperature of 25 °C for 1320 min to obtain poly(methyl methacrylate). After the reaction ended, methanol containing 5% HCl was added to the reaction solution to terminate the reaction. Subsequently, the polymer was washed with a large amount of methanol and dried in an oven at 40 °C to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The molecular weight was 45200 g / mol, and the molecular weight distribution

[0115] Example 9

[0116] Under the condition of toluene as a solvent, TUA-3 was used as an anion without hydrogen bond regulation, and diamino borane was used as a Lewis acid for the homopolymerization of butyl acrylate.

[0117] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, butyl acrylate, diborane diamine and TUA-3 were taken. Among them, the molar ratio of butyl acrylate to TUA-3 and diborane diamine was 200:0.10:0.26; The reaction was carried out at a polymerization temperature of 80 °C for 30 min to obtain high molecular weight polybutyl acrylate; After the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction. Subsequently, the polymer was washed with a large amount of methanol and placed in an oven at 40 °C to dry to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography, and the molecular weight was 1752000 g / mol, and the molecular weight distribution

[0118] Example 10

[0119] Under the condition that dichloromethane was used as a solvent, TUA-4 was used as an anion without hydrogen bond regulation effect, and borate ester was used as a Lewis acid for the homopolymerization of methyl acrylate.

[0120] The polymerization reaction was carried out in a glove box. Under the condition that dichloromethane was used as a solvent, methyl acrylate, borate ester and TUA-4 were taken. Among them, the molar ratio of methyl methacrylate to TUA-4 and borate ester was 20:0.06:0.168; The reaction was carried out at room temperature for 5 min to obtain polymethyl acrylate; After the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction. Subsequently, the polymer was washed with a large amount of methanol and placed in an oven at 40 °C to dry to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography, and the molecular weight was 61230 g / mol, and the molecular weight distribution

[0121] Example 11

[0122] TUA-5 was used as an anion without hydrogen bond regulation effect, and triaminoborane was used as a Lewis acid for the homopolymerization of lauryl methacrylate.

[0123] The polymerization reaction was carried out in a glove box. TUA-5 and toluene were pre-configured into a solution in advance, and the concentration of TUA-5 in toluene was 0.048 mol / L. The required toluene solution of TUA-5, triaminoborane and lauryl methacrylate were taken and mixed. Among them, the molar ratio of lauryl methacrylate to TUA-5 and triaminoborane was 20:0.06:0.168; The reaction was carried out at a polymerization temperature of 25 °C for 90 min to obtain poly lauryl methacrylate; After the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction. Subsequently, the polymer was washed with a large amount of methanol and placed in an oven at 40 °C to dry to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography, and the molecular weight was 71200 g / mol, and the molecular weight distribution

[0124] Example 12

[0125] Using TUA-6 as the anion without hydrogen bond regulation effect, and paired with BEt 3 as the Lewis acid for the homopolymerization of dodecyl acrylate.

[0126] The polymerization reaction was carried out in a glove box. TUA-6 and toluene were pre-prepared into a solution. The concentration of TUA-6 in toluene was 0.048 mol / L. The toluene solution of TUA-6, BEt 3 and dodecyl acrylate were pipetted and mixed. Among them, the molar ratio of dodecyl acrylate to TUA-6 and BEt 3 was 20:0.06:0.168; the reaction was carried out at a polymerization temperature of -20 °C for 90 min to obtain poly(dodecyl acrylate); after the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction, and then the polymer was washed with a large amount of methanol and placed in an oven at 40 °C to dry to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The molecular weight was 54960 g / mol, and the molecular weight distribution

[0127] Example 13

[0128] Using TUA-7 as the anion without hydrogen bond regulation effect, and paired with Pin2B2 as the Lewis acid, the homopolymerization of octadecyl acrylate was carried out in toluene.

[0129] The polymerization reaction was carried out in a glove box. Octadecyl acrylate, Pin2B2 and TUA-7 were pipetted and mixed. Among them, the molar ratio of octadecyl acrylate to TUA-7 and Pin2B2 was 20:0.06:0.06; the reaction was carried out at a polymerization temperature of room temperature for 60 min to obtain high-molecular-weight poly(octadecyl acrylate); after the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction, and then the polymer was washed with a large amount of methanol and placed in an oven at 40 °C to dry to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The molecular weight was 85200 g / mol, and the molecular weight distribution

[0130] Example 14

[0131] Under the condition of using toluene as the solvent, using TUA-2 as the anion without hydrogen bond regulation effect, and paired with PinBH as the Lewis acid for the homopolymerization of stearyl methacrylate.

[0132] The polymerization reaction was carried out in a glove box. Stearyl methacrylate, PinBH and TUA-2 were pipetted and mixed. Among them, the molar ratio of stearyl methacrylate to TUA-2 and PinBH was 10:0.03:0.06; the reaction was carried out at room temperature for 60 min to obtain a polymer; after the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction, and then the polymer was washed with a large amount of methanol and placed in an oven to be dried to a constant weight at 40 °C. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography, and the molecular weight was 85120 g / mol, and the molecular weight distribution

[0133] Example 15

[0134] Under the condition of using toluene as a solvent, TUA-8 was used as an anion without hydrogen bond regulation effect, and PinBH was used as a Lewis acid for the copolymerization of lauryl methacrylate and methyl methacrylate.

[0135] The polymerization reaction was carried out in a glove box. Lauryl methacrylate, methyl methacrylate, PinBH and TUA-8 were pipetted and mixed. Among them, the molar ratio of methyl methacrylate, lauryl methacrylate to TUA-8 and PinBH was 15:5:0.03:0.06; the reaction was carried out at room temperature for 90 min to obtain a copolymer; after the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction, and then the copolymer was washed with a large amount of methanol and placed in an oven to be dried to a constant weight at 40 °C. The molecular weight and molecular weight distribution of the obtained copolymer were measured by gel permeation chromatography, and the molecular weight was 102100 g / mol, and the molecular weight distribution

[0136] Example 16

[0137] Under the condition of using toluene as a solvent, TUA-8 was used as an anion without hydrogen bond regulation effect, and PinBH was used as a Lewis acid for the copolymerization of butyl acrylate and methyl methacrylate.

[0138] The polymerization reaction was carried out in a glove box. Methyl methacrylate, butyl acrylate, PinBH and TUA-8 were pipetted and mixed. Among them, the molar ratio of methyl methacrylate, butyl acrylate to TUA-8 and PinBH was 5:20:0.03:0.06; the reaction was carried out at room temperature for 180 min to obtain a copolymer; after the reaction was completed, methanol containing 5% HCl was added to the reaction solution to terminate the reaction, and then the copolymer was washed with a large amount of methanol and placed in an oven to be dried to a constant weight at 40 °C. The molecular weight and molecular weight distribution of the obtained copolymer were measured by gel permeation chromatography, and the molecular weight was 146300 g / mol, and the molecular weight distribution

[0139] The above description is only a preferred embodiment of the present invention and is not a limitation of the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, modifications, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for acrylate polymerization reaction based on the synergistic regulation of hydrogen bonds and Lewis acids and without the synergistic regulation of hydrogen bonds and Lewis acids, characterized in that, it comprises the following steps: Using acrylate compounds as monomer raw materials, under the participation of Lewis acid, the polymerization reaction is carried out by thiourea anions in an organic solvent or without the participation of an organic solvent. The polymerization reaction temperature is -20°C to 90°C, and the reaction time is 0.02 min to 3600 min; wherein, the molar ratio of the acrylate compound, Lewis acid and thiourea anion is (1 - 400):(0.01 - 0.70):(0.10 - 0.25); the Lewis acid is a boron-containing compound, and the boron-containing compound includes any one or several of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 9-borabicyclo[3.3.1]nonane, 5-chloro-5H-dibenz[b,d]borole, triethylborane, borate ester, aminoborane; The thiourea anions include TUA-1 to TUA-8, wherein, TUA-1 is a thiourea anion with hydrogen bond regulation function, and its structural formula is as follows: TUA-2 to TUA-8 are thiourea anions without hydrogen bond regulation function, and their structural formulas are as follows:

2. The method according to claim 1, characterized in that, First, the acrylate compound and the Lewis acid are mixed evenly, and then the thiourea anion is added, and the polymerization reaction is carried out in an organic solvent or without the participation of an organic solvent.

3. The method according to claim 1, characterized in that, The molar ratio of the acrylate compound, Lewis acid and thiourea anion is (20 - 200):(0.10 - 0.40):(0.10 - 0.20).

4. The method according to claim 1, characterized in that, When carrying out the polymerization reaction in an organic solvent, the organic solvent is one or several of toluene, tetrahydrofuran, n-hexane, dichloromethane, and the concentration of the acrylate compound in the organic solvent is 0.16 - 16 mol / L.

5. The method according to claim 1, characterized in that, The polymerization reaction temperature is 0°C to 60°C.

6. The method according to claim 1, characterized in that, The polymerization reaction time is 38 min to 1660 min.

7. The method according to claim 1, characterized in that, The boron-containing compound includes bis(pinacolato)diboron.

Images