Method for (non) biomass-sourced (methyl) acrylate (co) polymerization reaction based on hydrogen bond participation-free S negative nucleophilic center-containing thiourea anion and Lewis acid synergistic regulation

Abstract

The invention relates to a (non) biomass-sourced (methyl) acrylate (co) polymerization reaction method under the synergistic regulation of a hydrogen bond-free S negative nucleophilic center-containing thiourea anion initiator and organic aluminum lewis acid, and belongs to the technical field of polymer synthesis. Biomass-sourced and non-biomass-sourced (methyl) acrylate monomers are used as raw materials, and conjugated addition polymerization is carried out under the action of a bimolecular concerted catalysis system in which organic aluminum lewis acid participates in monomer activation, the molar ratio of the biomass-sourced or non-biomass-sourced (methyl) acrylate compound to the organic aluminum lewis acid to the thiourea anion is (1-800): (0.20-0.50): (0.10-0.25), the reaction is performed for 0.05-1440 minutes under the condition that the polymerization temperature is-60-90 DEG C, and the poly (methyl) acrylate homopolymer or copolymer is obtained. Syndiotactic copolymerization among monomers and block copolymerization among monomers with different polarities can be realized. The polymerization process provided by the invention can realize the polymerization of biomass-sourced and non-biomass-sourced (methyl) acrylics, the raw materials are cheap, the operation is convenient, and the reaction time is short, so that the low-cost and large-scale industrial production is realized; moreover, polymers with different properties can be prepared by virtue of rich monomer adaptability, and a research basis is provided for subsequent recovery and cyclic utilization of the polymers.

Description

Technical Field

[0001] The present invention belongs to the field of polymer polymerization, and relates to (meth)acrylate polymers derived from biomass and non-biomass sources and their polymerization processes. Specifically, it relates to a method for polymerizing (meth)acrylate monomers derived from biomass and non-biomass sources under the synergistic regulation of a thiourea anion containing an S nucleophilic center without hydrogen bond participation and a Lewis acid. Background Art

[0002] In many branches of the polymer industry, monomers based on (meth)acrylates derived from biomass and non-biomass sources play a crucial role as materials for polymer films, paints, sealants, coatings, and various adhesives used in modern technological processes. Anionic polymerization is an efficient living / controlled polymerization method widely used in the polymerization of (meth)acrylate monomers, with great potential and value in industrial applications.

[0003] In 1995, Haddleton et al. reported the preparation of homopolymers and various block copolymers of lauryl methacrylate (LMA) derived from biomass using a triisobutylaluminum / tert-butyllithium initiating system. By anionic polymerization in a triisobutylaluminum / tert-butyllithium system, a narrow molecular weight distribution PLMA-b-PMMA block copolymer (M n = 14.3 kg / mol, D = 1.20, I * = 113%) was synthesized in toluene as a solvent at near ambient temperature. In 1996, the H.E. Müller research group polymerized MMA at room temperature using a tert-butyllithium / 2,6-di-tert-butyl-4-methylphenoxy-bis(diisobutyl)aluminum (tBuLi / iBu2Al(BHT)) catalytic system. The monomer conversion reached 93.4%, and the resulting polymer had a relatively wide molecular weight distribution with a molecular weight of 8.50 kg / mol higher than the theoretical molecular weight (5.02 kg / mol), and the stereoregularity of the polymer was syndiotactic. In 2004, Inoue et al. initiated the anionic polymerization of tert-butyl acrylate (tBA) using a combination of a potassium tert-butoxide / triisobutylaluminum (tBuOK / iBu3Al) system and controlled the polymerization in terms of molecular weight and molecular weight distribution. The resulting polymer had a molecular weight of 20.0 - 80.0 kg / mol, much larger than the theoretical molecular weight (6.4 - 19.2 kg / mol), and the polymer had a narrow molecular weight distribution In the study of anionic polymerization, the initiator mainly undergoes a Michael addition reaction between the C anion as the nucleophilic center and the polar double bond of the monomer, thereby initiating the polymerization reaction. In 2020, we invented a method to polymerize methyl methacrylate (MMA) to prepare poly(methyl methacrylate) (PMMA) using a thiourea anion with a hydrogen bond as the initiator alone (Patent No. ZL2020115928009). However, due to the too low activation degree of the monomer by the single hydrogen bond interaction, the reaction has a long induction period, resulting in poor controllability and conversion rate for the polymerization of MMA with a dosage higher than 200 equivalents. Subsequently, in 2022, based on the previous work, we introduced an organoaluminum Lewis acid as a co-catalyst to participate in the polymerization reaction of MMA, and obtained PMMA with a relatively high molecular weight (Patent No. ZL2022110155840). Although this system can prepare PMMA with a narrow molecular weight distribution under the premise of a high monomer feed amount, the actual molecular weight of the obtained polymer deviates far from the theoretical molecular weight, resulting in too low initiation efficiency. Subsequently, in 2023, we changed the organoaluminum Lewis acid to an organoboron Lewis acid, which improved the polymerization initiation efficiency of the system (Patent Application No. 2023105523156). In this work, we found that eliminating the N-H structure in the thiourea anion, that is, eliminating the hydrogen bond interaction between the anion and the monomer, has a positive effect on the polymerization reaction. Therefore, in this work, we used a thiourea anion without a hydrogen bond as the initiator and paired it with an organoaluminum Lewis acid for polymerization research. This system is a further improvement and expansion of the previous invention. Compared with the previous system, the current system has the following advantages: 1. By eliminating the hydrogen bond interaction between the N-H group of the initiator and the monomer, the activation mode of the monomer is unified and improved, that is, only the organoaluminum Lewis acid is used to activate the monomer, greatly improving the controllability of the polymerization; 2. Realized the living / controlled preparation of homopolymers, eliminated side reactions, and further enabled high-equivalent homopolymerization and copolymerization reactions; 3. The monomer range was expanded to monomers from biomass sources, realizing the controlled homopolymerization and copolymerization of such compounds, laying a foundation for the research on the production of high molecular materials with different properties.

[0004] Specific comparison data are shown in the following table. Under the same conditions, taking 200 equivalents of MMA as an example:

[0005]

[0006] Summary of the Invention

[0007] The object of the present invention is to solve the above problems existing in the prior art, and a method for polymerizing biomass-derived and non-biomass-derived (meth)acrylates under the synergistic regulation of a thiourea anion containing an S negative nucleophilic center without hydrogen bond participation and a Lewis acid is proposed. An organoaluminum compound is used as the Lewis acid, and when combined with the thiourea anion, a polymerization system can be obtained that has a narrow molecular weight distribution of the polymer, a molecular weight closer to the theoretical molecular weight, and can well achieve copolymerization initiation / catalysis.

[0008] The technical solution of the present invention is as follows:

[0009] A method for polymerizing biomass-derived and non-biomass-derived (meth)acrylates under the synergistic regulation of a thiourea anion containing an S negative nucleophilic center without hydrogen bond participation and an organoaluminum Lewis acid, comprising the following steps:

[0010] Using biomass-derived and non-biomass-derived (meth)acrylate compounds as monomer raw materials, under the condition of the participation of an organoaluminum Lewis acid, the thiourea 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 -60 to 90 °C, and the reaction time is 0.05 min to 1440 min;

[0011] Further, in the above steps, first, the biomass-derived and non-biomass-derived (meth)acrylate compound monomer raw materials are mixed evenly with the organoaluminum Lewis acid, 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. The polymerization reaction temperature is -60 to 90 °C, and the reaction time is 0.05 min to 1440 min;

[0012] Further, in the above steps, when carrying out a copolymerization reaction, the monomers can be used to prepare a copolymer by a one-pot one-step method, that is, a plurality of monomers are mixed and then subjected to a polymerization reaction; or a sequential addition method can be used to prepare a copolymer, that is, different monomers are added sequentially, and the latter monomer is added after the conversion of the previous monomer is completed;

[0013] Among them, the molar ratio of the (meth)acrylate compounds from biomass sources and non-biomass sources, the organoaluminum Lewis acid, and the thiourea anion is (1 - 800):(0.20 - 0.50):(0.10 - 0.25); the molar ratio of the three can be any ratio within the range of (1 - 800):(0.20 - 0.50):(0.10 - 0.25), for example, it can be 200:0.2:0.1, 200:0.4:0.1, 200:0.25:0.125, 400:0.2:0.1, 400:0.4:0.10, 400:0.25:0.125, 800:0.2:0.10, 800:0.4:0.1 or 800:0.25:0.125, etc., and it can also be any other ratio not listed in the above range.

[0014] The Lewis acid is selected from alkyl / phenoxy aluminum, and the alkyl / phenoxy aluminum includes but is not limited to bis(2,6 - di - tert - butyl - 4 - methylphenoxy)(methyl)aluminum (MeAl(BHT)2), (2,6 - di - tert - butyl - 4 - methylphenoxy)(diisobutyl)aluminum ( i Bu2AlBHT), bis(2,6 - di - tert - butyl - 4 - methylphenoxy)(isobutyl)aluminum ( i BuAl(BHT)2), bis(diphenylamino)(methyl)aluminum, bis(diphenylamino)(isobutyl)aluminum, bis(diphenylamino)(ethyl)aluminum, bis(diisopropylamino)(methyl)aluminum, bis(diisopropylamino)(isobutyl)aluminum, bis(diisopropylamino)(ethyl)aluminum, bis(morpholino)(methyl)aluminum, bis(morpholino)(isobutyl)aluminum, bis(morpholino)(ethyl)aluminum, bis(pyrrolyl)(methyl)aluminum, bis(pyrrolyl)(isobutyl)aluminum, bis(pyrrolyl)(ethyl)aluminum, bis(pyrrolidinyl)(methyl)aluminum, bis(pyrrolidinyl)(isobutyl)aluminum, bis(pyrrolidinyl)(ethyl)aluminum, (diphenylamino)(dimethyl)aluminum, (diphenylamino)(diisobutyl)aluminum, (diphenylamino)(diethyl)aluminum, (diisopropylamino)(dimethyl)aluminum, (diisopropylamino)(diisobutyl)aluminum, (diisopropylamino)(diethyl)aluminum, (morpholino)(dimethyl)aluminum, (morpholino)(diisobutyl)aluminum, (morpholino)(diethyl)aluminum, (pyrrolyl)(dimethyl)aluminum, (pyrrolyl)(diisobutyl)aluminum, (pyrrolyl)(diethyl)aluminum, (pyrrolidinyl)(dimethyl)aluminum, (pyrrolidinyl)(diisobutyl)aluminum, (pyrrolidinyl)(diethyl)aluminum, triphenylaluminum, tris(4 - fluorophenyl)aluminum, tris(pentafluorophenyl)aluminum, triisobutylaluminum ( i Bu3Al), trimethylaluminum, and triethylaluminum, any one or several of them; their structural formulas are respectively:

[0015]

[0016] Furthermore, the (meth)acrylate compounds from biomass sources and non-biomass sources have the following structure:

[0017]

[0018] Among them, R5 is H or an alkyl group with 1 - 4 carbon atoms, and R6 is selected from an alkyl group with 1 - C 23 alkyl group, an alkenyl group with 1 - 5 carbon atoms, a heterocyclic methyl group, an aryl group, a substituted silyl group, and the substituent group of the substituted silyl group is an alkyl group with 1 - 8 carbon atoms or an alkenyl group with 1 - 5 carbon atoms.

[0019] In some embodiments, the (meth)acrylate monomers from biomass sources and non-biomass sources include, but are not limited to, thymyl methacrylate (T-MA), carvyl methacrylate (C-MA), paeonol methacrylate (P-MA), sesamyl methacrylate (S-MA), sesamyl acrylate (S-A), menthyl methacrylate (M-MA), α-methylene-γ-butyrolactone (MBL), α-methylene-γ-valerolactone, and methyl methacrylate (MMBL), n-butyl acrylate (nBA), methyl methacrylate (MMA), 2-ethylhexyl methacrylate (EHMA), isooctyl acrylate (EHA), lauryl methacrylate (LMA), dodecyl acrylate (nDA), dicyclopentyl methacrylate (HDCPMA) from biomass sources, or one or more of them.

[0020]

[0021] Furthermore, the molar ratio of the (meth)acrylate compounds from biomass sources and non-biomass sources, the organoaluminum Lewis acid, and the thiourea anion is (1 - 800):(0.20 - 0.50):(0.10 - 0.25).

[0022] Furthermore, when the polymerization reaction is carried out in an organic solvent, the organic solvent is one or more of toluene, tetrahydrofuran, n-hexane, dichloromethane, N,N-dimethylformamide, and the concentration of the (meth)acrylate compounds from biomass sources and non-biomass sources in the organic solvent is 0.1 - 4.8 mol / L.

[0023] Furthermore, the structural formula of the thiourea anion is as follows:

[0024]

[0025]

[0026] Among them, Z = S; the R1 group is one of an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, the R2 group is one of an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, the R3 group is one of an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, the R4 group is one of an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, the R group is one of a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, a tert-butyl group, a cyclohexyl group or a substituted phenyl group, the R' group is one of a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, a tert-butyl group, a cyclohexyl group or a substituted phenyl group, and the R'' group is one of a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, a tert-butyl group, a cyclohexyl group or a substituted phenyl group.

[0027] Further, the thiourea anions include TUA'-1 to TUA'-28, and their structural formulas are as follows:

[0028]

[0029]

[0030]

[0031] The polymerization reaction temperature can be any temperature within the range of -60 to 90 °C. For example, the polymerization temperature can be -60 °C, -40 °C, -20 °C, 0 °C, 30 °C, 60 °C, 90 °C, etc., and can also be any other temperature within this range. Further, preferably, the polymerization reaction temperature can also be 15 °C to 30 °C.

[0032] The time of this polymerization reaction can be any value within the range of 0.05 min to 1440 min. For example, it can be 0.05 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, etc., and can also be any other time not listed within this range; further, preferably, the polymerization reaction time is 60 min to 240 min;

[0033] Further, in the method for copolymerizing biomass-derived and non-biomass-derived (meth)acrylates synergistically regulated by a thiourea anion containing an S negative nucleophilic center without hydrogen bond participation and a Lewis acid, TUA'-2 is used as the thiourea anion, and an organoaluminum compound is used as the Lewis acid to study the polymerization mechanism. The reaction is studied by adding two moles of organoaluminum Lewis acid. One mole of it plays the role of activating the monomer, and the other mole forms an "ate" complex with the thiourea anion as the initiator. The polymer prepared by the thiourea anion / organoaluminum Lewis acid system has a narrow molecular weight distribution, and the molecular weight is closer to the theoretical molecular weight.

[0034] The following is bis(2,6-di-tert-butyl-4-methylphenoxy)(isobutyl)aluminum ( i The example of using Bu(BHT)2Al) as Lewis acid and TUA′-2 to polymerize methyl methacrylate (MMA) is explained as follows:

[0035]

[0036] The aggregation mechanism is i Bimolecular catalytic activation mode involving BuAl(BHT)2. i BuAl(BHT)2 generates two complexes: 1 mol i BuAl(BHT)2 and 1 mol TUA′-2 form an “ate” complex, and another 1 mol i BuAl(BHT)2 activates MMA through complexation, making the activated monomer more susceptible to TUA′-2 / i The nucleophilic attack of the "ate" complex of BuAl(BHT)2(1:1). And after a monomer is inserted, i A new "ate" complex is formed between the BuAl(BHT)2 molecule and the growing chain end. i The BuAl(BHT)2 molecule is released and can reactivate a new MMA monomer. The molecular weight (18.6-56.3 kg / mol) of the polymer obtained by this polymerization system is close to the theoretical molecular weight (10.2-40.3 kg / mol), and the molecular weight distribution is narrow (1.10-1.14).

[0037] Beneficial effects of the present invention:

[0038] (1) The present invention utilizes the synergistic effect of Lewis acid and thiourea anion containing S negative nucleophilic center without hydrogen bond regulation to initiate biomass-derived and non-biomass-derived (meth)acrylate (co)polymerization reaction, and the molecular weight of the obtained biomass-derived or non-biomass-derived poly (meth)acrylate polymer is in the range of 3200 to 260000 g / mol, the molecular weight distribution D is 1.10 to 1.27, and the monomer conversion rate is as high as 100%. The raw materials of the initiation system are cheap and easy to obtain, the catalyst is highly stable and easy to store, and the reaction controllability is good, so that low-cost and large-scale industrial production can be achieved.

[0039] (2) After eliminating the N-H structure on the thiourea anion in the present invention, that is, after eliminating the hydrogen bond interaction between the anion N-H structure and the monomer, the induction period of the polymerization reaction is significantly shortened in the presence of organoaluminum Lewis acid, and there is no occurrence of side reactions such as "backbiting" at the active chain end of the obtained polymer; the catalytic system can prepare polymers with molecular weights closer to the theoretical molecular weights, and the reaction conditions are mild with high conversion rates;

[0040] (3) The present invention is a living controllable polymerization with high initiation efficiency, which can provide (co)polymers with controllable molecular weights. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 For the TUA'-2 / i Relationship curve diagrams of (a) MMA conversion rate, molecular weight and molecular weight distribution, and (b) GPC curve diagrams at different MMA conversion rates under the BuAl(BHT)2 system;

[0042] Figure 2 For the TUA'-2 / i Correlation diagram of molecular weight and molecular weight distribution with the ratio of [MMA]0 / [TUA'-2]0 under the BuAl(BHT)2 system.

[0043] Figure 3 For the TUA'-2 / i GPC curve diagrams of PMMA obtained at different ratios of [MMA]0 / [TUA'-2]0 under the BuAl(BHT)2 system.

[0044] Figure 4 For the TUA'-2 / i Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) of low molecular weight poly-MMA under the BuAl(BHT)2 system.

[0045] Figure 5 For Figure 4 Partial enlarged view.

[0046] Figure 6 For the TUA'-2 / i Infrared spectrum diagram of low molecular weight poly-MMA under the BuAl(BHT)2 system

[0047] Figure 7 For the TUA'-2 / i Low molecular weight poly-MMA under the BuAl(BHT)2 system 13 13C NMR

[0048] Figure 8 For the TUA'-2 / iUnder the BuAl(BHT)2 system, (a) GPC curve of the diblock copolymerization of LMA and MMA; (b) DSC curves of PMMA, PLMA homopolymers and copolymers Detailed implementation manners

[0049] To further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 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.

[0050] Example 1

[0051] Using TUA'-2 as an anion without hydrogen bond regulation effect, different Lewis acids are used to polymerize (meth)acrylate monomers from biomass sources or non-biomass sources. The different Lewis acids selected in this specific embodiment are i BuAl(BHT)2, i Bu2AlBHT, i Bu3Al, MeAl(BHT)2, and the selected (meth)acrylate is MMA.

[0052] During the feeding process of the polymerization reaction, the Lewis acid ( i BuAl(BHT)2, i Bu2AlBHT, i Bu3Al, MeAl(BHT)2), MMA and TUA'-2 are mixed and stirred. The specific operations are as follows:

[0053] The polymerization reaction is carried out in a glove box. MMA is taken and mixed with i BuAl(BHT)2, i Bu2AlBHT, i Bu3Al, MeAl(BHT)2 respectively, and a certain amount of toluene is added, and then TUA'-2 is added. Maintain [M]0 = 3.2 M or 4.8 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);

[0054] After the reaction is completed; take 0.1 mL of the reaction solution, and use deuterated chloroform for 1 1H NMR test to obtain the conversion rate. 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 at 40 °C to dry to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography.

[0055] As shown in Table 1 below, different catalytic results are obtained when using TUA′-2 as the anion without hydrogen bond regulation effect and different Lewis acids.

[0056] Table 1 Summary of the results of the catalytic polymerization of MMA with different Lewis acids in combination with TUA′-2

[0057] Number Monomer / Lewis acid Solvent Time (min) Conversion rate (%) <![CDATA[M n GPC (g / mol)]]> D 1 <![CDATA[200eq MMA:2 i BuAl(BHT)2]]> Toluene 60 >99 26900 1.12 2 <![CDATA[200eq MMA:2 i Bu2AlBHT]]> Toluene 60 >99 114200 1.22 3 <![CDATA[200eq MMA:2 i Triethylaluminum]]> Toluene 60 >99 558200 1.55 4 <![CDATA[200eq MMA:2MeAl(BHT)2]]> Toluene 60 >99 69300 1.33

[0058] Example 2

[0059] TUA′-2 was used as the anion without hydrogen bond regulation effect and was combined with i BuAl(BHT)2 as the Lewis acid to conduct experiments and calculations on the initiation efficiency of bulk polymerization of methyl methacrylate (MMA). This example was to verify the reaction rate or the time required to complete 100% conversion, and at the same time, judge whether the polymerization reaction was a linear controlled polymerization based on the data.

[0060] The polymerization reaction was carried out in a glove box. MMA monomer, i BuAl(BHT)2 and TUA′-2 were pipetted and mixed; after all the reaction raw materials were mixed, timing started, and samples were taken at regular intervals until the reaction ended. 5% HCl-containing methanol 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 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.

[0061] Using TUA′-2 as the anion without hydrogen bond regulation effect and using i BuAl(BHT)2 as the Lewis acid, the results obtained by sampling at intervals during the catalysis of MMA are summarized in Table 2.

[0062] Table 2 Data of the conversion of MMA polymerization in the TUA′-2 / i BuAl(BHT)2 system

[0063]

[0064]

[0065] This example was to detect whether the polymerization increased linearly with time. Based on the obtained data for analysis, a linear graph as shown in Figure 1 (a) was obtained. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography, and a GPC curve graph as shown in Figure 1 (b) was obtained. A conversion rate of 28.54% at 6 min indicated a relatively high initiation efficiency, and at this time, 28.54% of the monomers had polymerized; as the reaction time increased, the conversion rate continuously increased.

[0066] Example 3

[0067] Using TUA′-2 as the anion without hydrogen bond regulation effect, paired with i BuAl(BHT)2 as the Lewis acid for gradient homopolymerization of MMA, and detecting the controllability of the polymerization system.

[0068] The polymerization reaction was carried out in a glove box, maintaining the molar ratio of TUA′-2 and i BuAl(BHT)2 at 1:2. Homopolymerization reactions of 100 equivalents, 200 equivalents, 300 equivalents, and 400 equivalents of MMA were carried out in parallel. The polymerization reaction was carried out at room temperature in a toluene solution. The obtained polymerization results are summarized in Table 3:

[0069] Table 3 Data of polymerizing different equivalents of MMA in the TUA′-2 / i BuAl(BHT)2 system

[0070]

[0071] In this example, it was detected whether the polymerization controllability increased linearly with the change of the monomer feed amount. According to the obtained data for analysis, the linear graph as shown in Figure 2 was obtained. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography, and the GPC curve graph as shown in Figure 3 was obtained.

[0072] Example 4

[0073] Using TUA′-2 as the anion without hydrogen bond regulation effect, paired with i BuAl(BHT)2 as the Lewis acid for the synthesis and characterization of low-equivalent polymers of MMA. The polymerization reaction was carried out in a glove box. The molar ratio of MMA, TUA′-2, and i BuAl(BHT)2 was 30:1:2. The polymerization reaction was carried out at 25 °C in a toluene solution until the reaction ended. 5% HCl-containing methanol 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 3500 g / mol, and the molecular weight distribution D = 1.12. The obtained low-molecular-weight polymer was tested by MALDI-TOF-MS. As shown in Figure 4 and the analysis results are as shown in Figure 5 , indicating that the polymerization reaction obtained a linear polymer. The obtained low-molecular-weight polymer was also tested by infrared spectroscopy and 13 13C NMR. The results are as shown in Figure 6 and Figure 7, indicating that a sulfur atom serves as the nucleophilic central atom to initiate polymerization.

[0074] Example 5

[0075] Under the condition of toluene as the solvent, TUA′-2 is used as the anion without hydrogen bond regulation, and i BuAl(BHT)2 is used for the copolymerization of MMA and lauryl methacrylate (LMA).

[0076] The polymerization reaction is carried out in a glove box. Under the condition of toluene as the solvent, MMA, LMA, i BuAl(BHT)2 and TUA′-2 are transferred. Among them, the molar ratio of TUA′-2, i BuAl(BHT)2, MMA, and LMA is 1:2:100:100; the reaction is carried out for 120 min at a polymerization temperature of 25 °C. After the reaction, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is washed with a large amount of methanol and dried in an oven at 40 °C to constant weight. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography (as Figure 8 (a)), the molecular weight is 55600 g / mol, and the molecular weight distribution D = 1.17. The DSC analysis of the copolymer (as Figure 8 (b)) shows two glass transition temperatures (T g 1 =-51.08 °C; T g 2 =118 °C), which are close to the glass transition temperatures of PLMA (T g =-59.91 °C) and PMMA (T g =123 °C) respectively. These results indicate that the obtained copolymer is a block copolymer with a well-defined structure, rather than a random copolymer or a mixture of PMMA and PLMA.

[0077] Example 6

[0078] Under the condition of toluene as the solvent, TUA′-1 is used as the anion without hydrogen bond regulation, and bis(diphenylamino)(methyl)aluminum is used for the homopolymerization of methyl acrylate ( n BA).

[0079] The polymerization reaction is carried out in a glove box. Under the condition of toluene as the solvent, n BA, bis(diphenylamino)(methyl)aluminum, and TUA′-1 are transferred. Among them, TUA′-1, bis(diphenylamino)(methyl)aluminum, and nThe molar ratio of BA is 1:2:100; the reaction is carried out at a polymerization temperature of -60 °C for 120 min. After the reaction, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography, with a molecular weight of 30000 g / mol and a molecular weight distribution D = 1.35.

[0080] Example 7

[0081] Under the condition that toluene is used as a solvent, TUA'-3 is used as an anion without hydrogen bond regulation, and bis(diisopropylamino)(methyl)aluminum is used to carry out the homopolymerization of dicyclopentyl methacrylate (HDCPMA).

[0082] The polymerization reaction is carried out in a glove box. Under the condition that toluene is used as a solvent, HDCPMA, bis(diisopropylamino)(methyl)aluminum and TUA'-3 are pipetted. Among them, the molar ratio of TUA'-3, bis(diisopropylamino)(methyl)aluminum and HDCPMA is 1:2:100; the reaction is carried out at a polymerization temperature of 25 °C for 120 min. After the reaction, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography, with a molecular weight of 30100 g / mol and a molecular weight distribution D = 1.16.

[0083] Example 8

[0084] Under the condition that N,N-dimethylformamide is used as a solvent, TUA'-4 is used as an anion without hydrogen bond regulation, and i Bu2AlBHT is used to carry out the homopolymerization of isooctyl acrylate (EHA).

[0085] The polymerization reaction is carried out in a glove box. Under the condition that N,N-dimethylformamide is used as a solvent, EHA, i Bu2AlBHT and TUA'-4 are pipetted. Among them, the molar ratio of TUA'-4, i Bu2AlBHT and EHA is 1:2:100; the reaction is carried out at a polymerization temperature of 90 °C for 120 min. After the reaction, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography, with a molecular weight of 33600 g / mol and a molecular weight distribution D = 1.36.

[0086] Example 9

[0087] Under the condition that n-hexane is used as the solvent, TUA′-5 is used as the anion without hydrogen bond regulation, and MeAl(BHT)2 is used for the homopolymerization of S-MA.

[0088] The polymerization reaction was carried out in a glove box. Under the condition that n-hexane was used as the solvent, S-MA, MeAl(BHT)2 and TUA′-5 were taken. Among them, the molar ratio of TUA′-5, MeAl(BHT)2 and S-MA was 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 60 min. 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 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. The molecular weight was 15400 g / mol, and the molecular weight distribution D = 1.19.

[0089] Example 10

[0090] Under the condition that dichloromethane is used as the solvent, TUA′-6 is used as the anion without hydrogen bond regulation, and bis(pyrrolyl)(ethyl)aluminum is used for the copolymerization of T-MA and MMA.

[0091] The polymerization reaction was carried out in a glove box. Under the condition that dichloromethane was used as the solvent, T-MA, MMA, bis(pyrrolyl)(ethyl)aluminum and TUA′-6 were taken. Among them, the molar ratio of TUA′-6, bis(pyrrolyl)(ethyl)aluminum and T-MA, MMA was 1:2:100:100; the reaction was carried out at a polymerization temperature of 25 °C for 60 min. 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 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. The molecular weight was 49100 g / mol, and the molecular weight distribution D = 1.46.

[0092] Example 11

[0093] Under the condition that toluene is used as the solvent, TUA′-7 is used as the anion without hydrogen bond regulation, and (morpholinyl)(diisobutyl)aluminum is used for the homopolymerization of M-MA.

[0094] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, M-MA, (morpholino)(diisobutyl)aluminum and TUA'-7 were taken. Among them, the molar ratio of TUA'-7, (morpholino)(diisobutyl)aluminum and M-MA was 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 30 min. 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 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. The molecular weight was 19600 g / mol and the molecular weight distribution D = 1.50.

[0095] Example 12

[0096] Under the condition that n-hexane was used as a solvent, TUA'-8 was used as an anion without hydrogen bond regulation, and (diisopropylamino)(diisobutyl)aluminum was used for the homopolymerization of C-MA.

[0097] The polymerization reaction was carried out in a glove box. Under the condition that n-hexane was used as a solvent, C-MA, (diisopropylamino)(diisobutyl)aluminum and TUA'-8 were taken. Among them, the molar ratio of TUA'-8, (diisopropylamino)(diisobutyl)aluminum and C-MA was 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 30 min. 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 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. The molecular weight was 15700 g / mol and the molecular weight distribution D = 1.28.

[0098] Example 13

[0099] Under the condition that toluene was used as a solvent, TUA'-9 was used as an anion without hydrogen bond regulation, and i Bu3Al was used for the homopolymerization of P-MA.

[0100] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, P-MA, MeAl(BHT)2 and TUA'-9 were taken. Among them, TUA'-9, i Bu3Al and P-MA had a molar ratio of 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 30 min. 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 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. The molecular weight was 13200 g / mol and the molecular weight distribution D = 1.16.

[0101] Example 14

[0102] Under the condition that toluene is used as a solvent, TUA′-10 is used as an anion without hydrogen bond regulation, and (pyrrolidinyl)(dimethyl)aluminum is used to carry out the homopolymerization of P-MA.

[0103] The polymerization reaction is carried out in a glove box. Under the condition that toluene is used as a solvent, P-MA, (pyrrolidinyl)(dimethyl)aluminum and TUA′-10 are pipetted. Among them, the molar ratio of TUA′-10, (pyrrolidinyl)(dimethyl)aluminum and P-MA is 1:2:100; the reaction is carried out at a polymerization temperature of 25 °C for 60 min. After the reaction is completed, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography. The molecular weight is 16300 g / mol, and the molecular weight distribution D = 1.45.

[0104] Example 15

[0105] Under the condition that tetrahydrofuran is used as a solvent, TUA′-11 is used as an anion without hydrogen bond regulation, and MeAl(BHT)2 is used to carry out the homopolymerization of MMA.

[0106] The polymerization reaction is carried out in a glove box. Under the condition that toluene is used as a solvent, MMA, MeAl(BHT)2 and TUA′-11 are pipetted. Among them, the molar ratio of TUA′-11, MeAl(BHT)2 and MMA is 1:4:100; the reaction is carried out at a polymerization temperature of 25 °C for 90 min. After the reaction is completed, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography. The molecular weight is 18200 g / mol, and the molecular weight distribution D = 1.31.

[0107] Example 16

[0108] Under the condition that tetrahydrofuran is used as a solvent, TUA′-11 is used as an anion without hydrogen bond regulation, and MeAl(BHT)2 is used to carry out the copolymerization of MMA and n BA.

[0109] The polymerization reaction is carried out in a glove box. Under the condition that toluene is used as a solvent, MMA, n BA, MeAl(BHT)2 and TUA′-11 are pipetted. Among them, the molar ratio of TUA′-11, MeAl(BHT)2 and MMA, nThe molar ratio of BA is 1:4:100:100; the reaction is carried out at a polymerization temperature of -20°C for 90 minutes. After the reaction is completed, 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 at 40°C to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography, and the molecular weight is 24600 g / mol, and the molecular weight distribution D=1.31.

[0110] Embodiment 17

[0111] In tetrahydrofuran as solvent, TUA′-12 was used as an anion without hydrogen bond regulation, and (pyrrolyl)(diisobutyl)aluminum was used to n BA homopolymer.

[0112] The polymerization reaction was carried out in a glove box with toluene as solvent. n BA, (pyrrolyl) (diisobutyl) aluminum and TUA'-12, wherein TUA'-12, (pyrrolyl) (diisobutyl) aluminum and n The molar ratio of BA is 1:4:100; the reaction is carried out at a polymerization temperature of -60°C for 90 minutes. After the reaction is completed, 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 at 40°C to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography, and the molecular weight is 24600 g / mol, and the molecular weight distribution D=1.58.

[0113] Embodiment 18

[0114] In tetrahydrofuran as solvent, SA and MMA were copolymerized with triphenylaluminum using TUA′-13 as an anion without hydrogen bond regulation.

[0115] The polymerization reaction was carried out in a glove box. SA, MMA, triphenylaluminum and TUA′-13 were pipetted in tetrahydrofuran as a solvent, wherein the molar ratio of TUA′-13, triphenylaluminum and SA to MMA was 1:4:100:100; the reaction was carried out at a polymerization temperature of 25°C for 90 minutes. 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 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 31200 g / mol, and the molecular weight distribution D=1.42.

[0116] Embodiment 19

[0117] Under the condition that toluene is used as the solvent, TUA′-14 is used as the anion without hydrogen bond regulation, and bis(pyrrolidinyl)(methyl)aluminum is used for the homopolymerization of nDA.

[0118] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as the solvent, nDA, bis(pyrrolidinyl)(methyl)aluminum and TUA′-14 were transferred. Among them, the molar ratio of TUA′-14, bis(pyrrolidinyl)(methyl)aluminum and nDA was 1:4:100; the reaction was carried out at a polymerization temperature of 25 °C for 90 min. 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. The molecular weight was 13600 g / mol, and the molecular weight distribution D = 1.22.

[0119] Example 20

[0120] Under the condition that dichloromethane is used as the solvent, TUA′-15 is used as the anion without hydrogen bond regulation, and (pyrrolidinyl)(diisobutyl)aluminum is used for the homopolymerization of EHMA.

[0121] The polymerization reaction was carried out in a glove box. Under the condition that dichloromethane was used as the solvent, EHMA, (pyrrolidinyl)(diisobutyl)aluminum and TUA′-15 were transferred. Among them, the molar ratio of TUA′-15, (pyrrolidinyl)(diisobutyl)aluminum and EHMA was 1:4:100; the reaction was carried out at a polymerization temperature of 25 °C for 90 min. 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. The molecular weight was 15200 g / mol, and the molecular weight distribution D = 1.19.

[0122] Example 21

[0123] Under the condition that tetrahydrofuran is used as the solvent, TUA′-16 is used as the anion without hydrogen bond regulation, and bis(diphenylamino)(ethyl)aluminum is used for the homopolymerization of EHA.

[0124] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, EHA, bis(diphenylamino)(ethyl)aluminum and TUA'-16 were transferred. Among them, the molar ratio of TUA'-16, bis(diphenylamino)(ethyl)aluminum and EHA was 1:4:100; the reaction was carried out at a polymerization temperature of 25 °C for 90 min. 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 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, with the molecular weight being 12400 g / mol and the molecular weight distribution D = 1.18.

[0125] Example 22

[0126] Under the condition that toluene was used as a solvent, TUA'-17 was used as an anion without hydrogen bond regulation, and tris(4-fluorophenyl)aluminum was used for the homopolymerization of MA.

[0127] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, MA, tris(4-fluorophenyl)aluminum and TUA'-17 were transferred. Among them, the molar ratio of TUA'-17, tris(4-fluorophenyl)aluminum and MA was 1:4:100; the reaction was carried out at a polymerization temperature of 25 °C for 90 min. 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 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, with the molecular weight being 12900 g / mol and the molecular weight distribution D = 1.15.

[0128] Example 23

[0129] Under the condition that toluene was used as a solvent, TUA'-18 was used as an anion without hydrogen bond regulation, and (pyrrolidinyl)(diisobutyl)aluminum was used for the homopolymerization of MBL.

[0130] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, MBL, (pyrrolidinyl)(diisobutyl)aluminum and TUA'-18 were transferred. Among them, the molar ratio of TUA'-18, (pyrrolidinyl)(diisobutyl)aluminum and MBL was 1:4:100; the reaction was carried out at a polymerization temperature of 25 °C for 120 min. 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 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, with the molecular weight being 12300 g / mol and the molecular weight distribution D = 1.56.

[0131] Example 24

[0132] Under the condition that toluene is used as a solvent, TUA′-19 is used as an anion without hydrogen bond regulation, and (pyrrolyl)(diethyl)aluminum is used to carry out the homopolymerization of MMBL.

[0133] The polymerization reaction is carried out in a glove box. Under the condition that toluene is used as a solvent, MMBL, (pyrrolyl)(diethyl)aluminum and TUA′-19 are pipetted. Among them, the molar ratio of TUA′-19, (pyrrolyl)(diethyl)aluminum and MMBL is 1:4:100; the reaction is carried out at a polymerization temperature of 25 °C for 180 min. After the reaction is completed, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography. The molecular weight is 15900 g / mol, and the molecular weight distribution D = 1.35.

[0134] Example 25

[0135] Under the condition that dichloromethane is used as a solvent, TUA′-20 is used as an anion without hydrogen bond regulation, and (morpholinyl)(diethyl)aluminum is used to carry out the homopolymerization of MMA.

[0136] The polymerization reaction is carried out in a glove box. Under the condition that dichloromethane is used as a solvent, MMA, (morpholinyl)(diethyl)aluminum and TUA′-20 are pipetted. Among them, the molar ratio of TUA′-20, (morpholinyl)(diethyl)aluminum and MMA is 1:4:100; the reaction is carried out at a polymerization temperature of 25 °C for 300 min. After the reaction is completed, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is 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 are measured by gel permeation chromatography. The molecular weight is 18700 g / mol, and the molecular weight distribution D = 1.63.

[0137] Example 26

[0138] Under the condition that toluene is used as a solvent, TUA′-21 is used as an anion without hydrogen bond regulation, and MeAl(BHT)2 is used to carry out the homopolymerization of MMA.

[0139] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, MMA, MeAl(BHT)2 and TUA′-21 were taken. Among them, the molar ratio of TUA′-21, MeAl(BHT)2 and MMA was 1:2:100; the reaction was carried out for 120 min at a polymerization temperature of 25 °C. 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 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, with the molecular weight being 16700 g / mol and the molecular weight distribution D = 1.43.

[0140] Example 27

[0141] Under the condition that toluene was used as a solvent, TUA′-22 was used as an anion without hydrogen bond regulation, and bis(pyrrolidinyl)(methyl)aluminum was used for the homopolymerization of MMA.

[0142] The polymerization reaction was carried out in a glove box. Under the condition that toluene was used as a solvent, MMA, bis(pyrrolidinyl)(methyl)aluminum and TUA′-22 were taken. Among them, the molar ratio of TUA′-22, bis(pyrrolidinyl)(methyl)aluminum and MMA was 1:2:100; the reaction was carried out for 60 min at a polymerization temperature of 25 °C. 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 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, with the molecular weight being 28500 g / mol and the molecular weight distribution D = 1.23.

[0143] Example 28

[0144] Under the condition that tetrahydrofuran was used as a solvent, TUA′-23 was used as an anion without hydrogen bond regulation, and i Bu3Al was used for the homopolymerization of MMA.

[0145] The polymerization reaction was carried out in a glove box. Under the condition that tetrahydrofuran was used as a solvent, MMA, i Bu3Al and TUA′-23 were taken. Among them, TUA′-23, i Bu3Al and MMA had a molar ratio of 1:2:100; the reaction was carried out for 180 min at a polymerization temperature of 25 °C. 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 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, with the molecular weight being 12400 g / mol and the molecular weight distribution D = 1.13.

[0146] Example 29

[0147] In the presence of tetrahydrofuran as a solvent, TUA′-24 was used as an anion without hydrogen bond regulation, and i Bu3Al was used for the homopolymerization of MMA.

[0148] The polymerization reaction was carried out in a glove box. In the presence of tetrahydrofuran as a solvent, MMA, i Bu3Al and TUA′-24 were taken. Among them, the molar ratio of TUA′-24, i Bu3Al and MMA was 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 30 min. After the reaction, 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, with the molecular weight being 16400 g / mol and the molecular weight distribution D = 1.33.

[0149] Example 30

[0150] In the presence of tetrahydrofuran as a solvent, TUA′-25 was used as an anion without hydrogen bond regulation, and (diisopropylamino)(diisobutyl)aluminum was used for the copolymerization of MMA and M-MA.

[0151] The polymerization reaction was carried out in a glove box. In the presence of tetrahydrofuran as a solvent, MMA, (diisopropylamino)(diisobutyl)aluminum and TUA′-25 were taken. Among them, the molar ratio of TUA′-25, (diisopropylamino)(diisobutyl)aluminum and MMA was 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 80 min. Subsequently, a tetrahydrofuran solution of M-MA was added. After the reaction, 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, with the molecular weight being 31400 g / mol and the molecular weight distribution D = 1.11.

[0152] Example 31

[0153] In the presence of 1,4-dioxane as a solvent, TUA′-26 was used as an anion without hydrogen bond regulation, and (diisopropylamino)(diisobutyl)aluminum was used for the copolymerization of LMA and MBL.

[0154] The polymerization reaction was carried out in a glove box. Under the condition that 1,4-dioxane was used as a solvent, LMA, (diisopropylamino)(diisobutyl)aluminum and TUA′-26 were taken. Among them, the molar ratio of TUA′-26, (diisopropylamino)(diisobutyl)aluminum and LMA was 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 100 min. Subsequently, a solution of MBL was added. 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 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. The molecular weight was 15400 g / mol, and the molecular weight distribution D = 1.18.

[0155] Example 32

[0156] Under the condition that 1,4-dioxane was used as a solvent, TUA′-27 was used as an anion without hydrogen bond regulation, and i BuAl(BHT)2 was used for the homopolymerization of MMA.

[0157] The polymerization reaction was carried out in a glove box. Under the condition that 1,4-dioxane was used as a solvent, MMA, i BuAl(BHT)2 and TUA′-27 were taken. Among them, TUA′-27, i BuAl(BHT)2 and MMA had a molar ratio of 1:2:100; the reaction was carried out at a polymerization temperature of 25 °C for 60 min. 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 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. The molecular weight was 13400 g / mol, and the molecular weight distribution D = 1.15.

[0158] Example 33

[0159] Under the condition that tetrahydrofuran was used as a solvent, TUA′-28 was used as an anion without hydrogen bond regulation, and i BuAl(BHT)2 was used for the homopolymerization of MMA.

[0160] The polymerization reaction was carried out in a glove box. Under the condition that tetrahydrofuran was used as a solvent, MMA, i BuAl(BHT)2 and TUA′-28 were taken. Among them, TUA′-28, iThe molar ratio of BuAl(BHT)2 to MMA is 1:2:100; the reaction is carried out for 90 min at a polymerization temperature of 25 °C. After the reaction is completed, methanol containing 5% HCl is added to the reaction solution to terminate the reaction. Subsequently, the polymer is washed with a large amount of methanol and dried in an oven at 40 °C to constant weight. The molecular weight and molecular weight distribution of the obtained polymer are measured by gel permeation chromatography, with the molecular weight being 12,700 g / mol and the molecular weight distribution D = 1.09.

[0161] The above description is only the 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 make equivalent substitutions for some of the technical features. Any modification, equivalent substitution, modification, 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 (co)polymerization of (meth)acrylates from biomass and non-biomass sources based on a thiourea anion initiator containing a negative nucleophilic center of S without hydrogen bond participation and an organic aluminum Lewis acid under the coordinated regulation, characterized in that: The following steps are involved: The (meth) acrylic acid ester compounds of biomass and non-biomass sources are used as monomer raw materials, and a polymerization reaction is carried out by thiourea anion in an organic solvent or without the participation of an organic solvent under the condition of participation of an organic aluminum Lewis acid, the polymerization reaction temperature is -60 to 90° C., and the reaction time is 0.05 min to 1440 min; The molar ratio of the biomass-derived or non-biomass-derived (meth)acrylate compound to the organic aluminum Lewis acid and the thiourea anion is (1-800): (0.20-0.50): (0.10-0.25); the organic aluminum Lewis acid is selected from alkyl / phenoloxy / amino aluminum, and the alkyl / phenoloxy / amino aluminum includes bis(2,6-di-tert-butyl-4-methylphenoxy)(methyl)aluminum, (2,6-di-tert-butyl-4-methylphenoxy)(di isobutyl)aluminum, bis(2,6-di-tert-butyl-4-methylphenoxy)(isobutyl)aluminum, bis(diphenylamino)(methyl)aluminum, bis(diphenylamino)(isobutyl)aluminum, bis(diphenylamino)(ethyl)aluminum, bis(diisopropylamino)(methyl)aluminum, bis(diisopropylamino)(isobutyl)aluminum, bis(diisopropylamino)(ethyl)aluminum, bis(morpholino)(methyl)aluminum, bis(morpholino)(isobutyl)aluminum, bis(morpholino)(ethyl)aluminum, bis(pyrrole (diphenylamino)(dimethyl)aluminum, (diphenylamino)(diisobutyl)aluminum, (diphenylamino)(diethyl)aluminum, (diisopropylamino)(dimethyl)aluminum, (diisopropylamino)(diisobutyl)aluminum, (diisopropylamino)(diethyl)aluminum, Any one or more of (morpholinyl)(dimethyl)aluminum, (morpholinyl)(diisobutyl)aluminum, (morpholinyl)(diethyl)aluminum, (pyrrolyl)(dimethyl)aluminum, (pyrrolyl)(diisobutyl)aluminum, (pyrrolyl)(diethyl)aluminum, (pyrrolidyl)(dimethyl)aluminum, (pyrrolidyl)(diisobutyl)aluminum, (pyrrolidyl)(diethyl)aluminum, triphenylaluminum, tris(4-fluorophenyl)aluminum, tris(pentafluorophenyl)aluminum, triisobutylaluminum, trimethylaluminum and triethylaluminum. The (meth)acrylate monomers of biomass origin and non-biomass origin include, but are not limited to, thymol methacrylate (T-MA), carvyl methacrylate (C-MA), paeonyl methacrylate (P-MA), sesame methacrylate (S-MA), sesame acrylate (SA), menthyl methacrylate (M-MA), α-methylene-γ-butyrolactone (MBL), α-methylene-γ-valerolactone, and methyl acrylate (MMBL), n-butyl acrylate (nBA), methyl methacrylate (MMA), 2-ethyl-hexyl methacrylate (EHMA), isooctyl acrylate (EHA), lauryl methacrylate (LMA), dodecyl acrylate (nDA), and dicyclopentyl methacrylate (HDCPMA). One or more.

2. The method according to claim 1, characterized in that Firstly, the (meth)acrylate compounds of biomass origin and non-biomass origin are uniformly mixed with the organic aluminum Lewis acid, and then thiourea anions are added to carry out polymerization reaction in an organic solvent or without the participation of an organic solvent.

3. The general structural formula of the thiourea anion is as follows: in, Z=S; R1 is an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; R2 is an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; R3 is an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; R4 is an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; R is a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, a tert-butyl group, a cyclohexyl group or a substituted phenyl group; R′ is a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, a tert-butyl group, a cyclohexyl group or a substituted phenyl group; and R″ is a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, a tert-butyl group, a cyclohexyl group or a substituted phenyl group.

4. The method according to claim 3, characterized in that The thiourea anion includes TUA'-1 to TUA'-28, and its structural formula is as follows:

5. The method according to claim 1, characterized in that The molar ratio of the (meth) acrylic acid ester compound from biomass and non-biomass to Lewis acid and thiourea anion is (1-800): (0.20-0.50): (0.10-0.25).

6. The method according to claim 1, characterized in that When the polymerization reaction is carried out in an organic solvent, the organic solvent is one or more of toluene, tetrahydrofuran, n-hexane, dichloromethane, and N,N-dimethylformamide, and the concentration of the biomass-derived and non-biomass-derived (meth)acrylate compounds in the organic solvent is 0.1 to 4.8 mol / L.

7. The method according to claim 1, characterized in that The polymerization reaction temperature is -60 to 90°C.

8. The method according to claim 1, characterized in that The polymerization reaction time is 0.05 min to 1440 min.

Images