Application of phosphorus ylides organophosphorus as lewis base in catalysis of polar vinyl monomer polymerization

Abstract

The application provides application of phosphorus ylide organophosphine as Lewis base in catalysis of polar vinyl monomer polymerization, and belongs to the technical field of polymer synthesis. The application utilizes phosphorus ylide organophosphine as Lewis base, and through Lewis base and Lewis acid synergistic catalysis of polar vinyl monomer polymerization under the cooperation of Lewis acid, realizes active controllable polymerization of polar vinyl monomer by changing steric hindrance and electronic effect of Lewis acid and Lewis base, and can realize active controllable homopolymerization and copolymerization (random copolymerization and block copolymerization) of different polar vinyl monomers. The molecular weight of the obtained polymer increases with the increase of the monomer to catalyst ratio, so that the system can realize the molecular weight of the polymer reaching more than 10 6 g / mol, the measured value of the molecular weight of the obtained polymer is basically consistent with the theoretical value, the monomer conversion rate is 100%, and the initiation efficiency is close to 100%.

Description

Technical Field

[0001] This invention relates to the field of polymer synthesis technology, and in particular to the application of phosphorus lepidols as Lewis bases in the catalytic polymerization of polar vinyl monomers. Background Technology

[0002] Organophosphorus compounds are important catalysts and ligands in chemical reactions, and are required in a wide variety of reactions, such as cross-coupling reactions, hydrogenation reactions, and functional group reactions. The reason organophosphorus compounds are so important in chemical reactions is that their electronic and steric effects are highly tunable; by adjusting these effects and steric hindrance, they can be adapted to various reactions. Therefore, the development of novel organophosphorus compounds is of great significance in the field of chemistry.

[0003] Polar vinyl monomers are polar monomers containing vinyl groups that are conjugated with those polar groups. Polar vinyl polymers formed from these monomers are olefin polymers with polar groups as side chains. Polar vinyl polymers have significant advantages over traditional non-polar polyolefin materials in terms of viscosity, toughness, interfacial properties, and compatibility. Taking polymethyl methacrylate (PMMA) as an example, PMMA is characterized by high transparency and strong impact resistance, and is commonly known as plexiglass. PMMA is widely used in all aspects of daily life and production. Therefore, polar vinyl polymers have broad application prospects and enormous development potential.

[0004] However, the following problems exist in the polymerization system of polar vinyl monomers: (1) a narrow molecular weight distribution and a high molecular weight cannot be obtained at the same time; (2) a transition metal catalyst is often required; (3) the reaction conditions are relatively harsh and require high or low temperatures; (4) the polymerization rate decreases as the monomer concentration decreases, and the monomer cannot be completely converted; (5) it is difficult to copolymerize different monomers, and the polymerization structure is not rich enough. Summary of the Invention

[0005] In view of this, the present invention aims to provide the application of phosphorus phosphine ylidene organophosphorus as a Lewis base in the catalytic polymerization of polar vinyl monomers. The present invention uses phosphorus phosphine ylidene organophosphorus as a Lewis base catalyst to achieve efficient and controlled-activity addition polymerization of polar vinyl monomers, as well as copolymerization between different polar vinyl monomers, with high monomer conversion rates.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides the application of phosphorus lydephosphonates as Lewis bases in the catalytic polymerization of polar vinyl monomers;

[0008] The phosphorus ylide organophosphine has the structure shown in Formula I:

[0009]

[0010] In Formula I, A1 is alkyl or aryl; A2 is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl; A3 is alkyl, aryl, alkenyl, guanidinyl, pyridyl, alkylsilyl or alkenylsilyl; A4 is alkyl, aryl, alkenyl, cyano, p-benzenesulfonyl, alkylsilyl or alkenylsilyl.

[0011] Preferably, the polar vinyl monomer comprises one or more of methyl methacrylate, allyl methacrylate, allyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, methyl acrylate, allyl acrylate, allyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, benzyl acrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0012] This invention provides a catalyst system for the polymerization of polar vinyl monomers, comprising a Lewis base and a Lewis acid, wherein the Lewis base comprises a phosphorus ylide organophosphorus having the structure shown in Formula I:

[0013]

[0014] In Formula I, A1 is alkyl or aryl; A2 is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl; A3 is alkyl, aryl, alkenyl, guanidinyl, pyridyl, alkylsilyl or alkenylsilyl; A4 is alkyl, aryl, alkenyl, cyano, p-benzenesulfonyl, alkylsilyl or alkenylsilyl.

[0015] The Lewis acid includes organoboron and / or organaluminum.

[0016] Preferably, the Lewis acid has one of the structures shown in Formula II-1 to Formula II-11:

[0017]

[0018] In formulas II-1 to II-11, R1 is methyl, ethyl, isopropyl, isobutyl, phenyl, pentafluorophenyl, naphthyl, or halogen; R2 is methyl, ethyl, isopropyl, isobutyl, or halogen; and R3 is hydrogen, methyl, ethyl, or halogen.

[0019] Preferably, the molar ratio of the Lewis acid to the Lewis base is 1 to 100:1.

[0020] This invention provides a method for the catalytic, living, and controlled polymerization of polar vinyl monomers, comprising the following steps:

[0021] Using polar vinyl monomers as monomer raw materials, conjugate addition polymerization is carried out under the synergistic catalysis of Lewis acid and Lewis base;

[0022] The Lewis base comprises a phosphorus ylphosphine zylidene organophosphine having the structure shown in Formula I:

[0023]

[0024] In Formula I, A1 is alkyl or aryl; A2 is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl; A3 is alkyl, aryl, alkenyl, guanidinyl, pyridyl, alkylsilyl or alkenylsilyl; A4 is alkyl, aryl, alkenyl, cyano, p-benzenesulfonyl, alkylsilyl or alkenylsilyl.

[0025] The Lewis acid includes organoboron and / or organaluminum.

[0026] Preferably, the molar ratio of the polar vinyl monomer, Lewis acid, and Lewis base is 25–50000:1–100:1.

[0027] Preferably, the conjugated addition polymerization is carried out under conditions of organic solvent or solvent-free conditions.

[0028] Preferably, the organic solvent is one or more of toluene, dichloromethane, 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide.

[0029] Preferably, the conjugate addition polymerization temperature is -78°C to room temperature, and the reaction time is 10 seconds to 72 hours.

[0030] This invention provides the application of phosphorus lyophosphorus foliatol as a Lewis base in the catalytic polymerization of polar vinyl monomers; the phosphorus lyophosphorus foliatol has the structure shown in Formula I. This invention utilizes phosphorus lyophosphorus foliatol as a Lewis base, and in the synergistic effect of Lewis acids, to catalyze the polymerization of polar vinyl monomers through the synergistic catalysis of the Lewis base and Lewis acid. By changing the steric hindrance and electronic effects of the Lewis acid and Lewis base, the living controlled polymerization of polar vinyl monomers can be achieved. Living controlled homopolymerization and copolymerization (random copolymerization and block copolymerization) of different polar vinyl monomers can be realized. The molecular weight of the resulting polymer increases linearly with the increase of the monomer-to-catalyst ratio, thus this system can achieve polymers with molecular weights up to 10. 6 At g / mol or higher levels, the molecular weight of the obtained polymer is basically consistent with the theoretical value, the monomer conversion rate is 100%, and the initiation efficiency is close to 100%.

[0031] This invention provides a method for the catalytically controlled polymerization of polar vinyl monomers, comprising the following steps: using polar vinyl monomers as monomer raw materials, performing conjugate addition polymerization under the synergistic catalysis of Lewis acids and Lewis bases; wherein the Lewis base comprises organophosphorus ylidene phosphine, and the Lewis acid comprises organoboron and / or organoaluminum. The catalyst used in this invention has inexpensive raw materials, is simple to operate, involves few synthesis steps, can be synthesized in large quantities, and does not contain precious metals. The polymerization method provided by this invention has a fast polymerization rate, complete monomer conversion, and the polymerization rate does not decrease with decreasing monomer concentration (the polymerization rate follows a zero-order reaction with the monomer). The polymerization initiation efficiency is close to 100%, the polymer molecular weight can be predicted, and polymers with molecular weights up to 10 can be obtained. 6 The invention produces ultra-high molecular weight polymers at g / mol or higher levels with a narrow molecular weight distribution (PDI < 1.10). Furthermore, the catalytic system of this invention can achieve copolymerization between vinyl monomers of different polarities (random copolymerization, block copolymerization, and sequential block copolymerization), and can synthesize triblock (meth)acrylate thermoplastic elastomers in a one-pot process.

[0032] Furthermore, the polymerization method provided by this invention uses a small amount of catalyst and has a wide range of monomer applicability. Attached Figure Description

[0033] Figure 1 This is the reference synthetic route for organophosphorus ylidene phosphine;

[0034] Figure 2 This is the synthetic route for the organophosphorus ylide YPhos1;

[0035] Figure 3 This is the proton NMR spectrum of organophosphorus ylidene phosphine YPhos1;

[0036] Figure 4 This is the phosphine spectrum of the organophosphine ylide YPhos1;

[0037] Figure 5 This is the carbon spectrum of the organophosphorus ylide YPhos1;

[0038] Figure 6 This is a GPC overlay diagram of the polymer obtained by YPhos1 / (BHT)2AlMe catalyzing MMA in Example 1, Table 1;

[0039] Figure 7 Table 1 of Example 1 shows the linear relationship between the molecular weight of the polymer obtained by MMA catalyzing YPhos1 / (BHT)2AlMe and [MMA]0 / [YPhos1]0.

[0040] Figure 8Table 1 of Example 1 shows the linear relationship between the molecular weight (Mn), conversion (η), and dispersion index (PDI) of the polymer obtained by YPhos1 / (BHT)2AlMe catalysis of 1600 equivalent MMA.

[0041] Figure 9 This is a GPC overlay diagram of the polymer obtained by YPhos1 / (BHT)2AlEt catalyzing MMA in Example 1, Table 1.

[0042] Figure 10 Table 1 of Example 1 uses YPhos1 / (BHT)Al i GPC overlay of polymers obtained from Bu2-catalyzed MMA;

[0043] Figure 11 This is a gel permeation chromatogram of the chain extension experiment in Example 2;

[0044] Figure 12 This is a gel permeation chromatogram of the random copolymerization experiment in Example 3;

[0045] Figure 13 This is a gel permeation chromatogram of the triblock copolymerization experiment in Example 3;

[0046] Figure 14 This is a diagram showing the mechanical properties of the elastomer in Example 4. Detailed Implementation

[0047] This invention provides the application of phosphorus lydephosphonates as Lewis bases in the catalytic polymerization of polar vinyl monomers;

[0048] The phosphorus ylide organophosphine has the structure shown in Formula I:

[0049]

[0050] In Formula I, A1 is alkyl or aryl, specifically, A1 is preferably phenyl, substituted phenyl, cyclohexyl, or substituted cyclohexyl; A2 is alkyl, aryl, alkenyl, alkylsilyl, or alkenylsilyl, specifically, A2 is preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, cyclohexyl, phenyl, substituted phenyl, allyl, vinyl, guanidinyl, pyridyl, or trimethylsilyl; A3 is alkyl, aryl, alkenyl, guanidinyl, pyridyl, alkylsilyl, or alkenylsilyl, specifically... A3 is preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, cyclohexyl, phenyl, substituted phenyl, guanidine, allyl, vinyl, pyridyl, or trimethylsilyl; A4 is alkyl, aryl, alkenyl, cyano, p-phenylsulfonyl, alkylsilyl, or alkenylsilyl. Specifically, A4 is preferably methyl, ethyl, isopropyl, cyano, p-phenylsulfonyl, n-propyl, n-butyl, tert-butyl, cyclohexyl, phenyl, substituted phenyl, allyl, vinyl, pyridyl, or trimethylsilyl.

[0051] In this invention, the phosphorus lepidol organophosphorus source is either commercially available or synthesized by design.

[0052] As a specific embodiment of the present invention, the reference synthetic route for the phosphorus ylide organophosphorus is as follows: Figure 1 As shown.

[0053] In this invention, the phosphorus lecithin organophosphorus preferably has the structure shown in Formula I-1:

[0054]

[0055] In Equation I-1, the selectable ranges of A1 and A4 are the same as those above.

[0056] More preferably, the phosphorus ylide organophosphorus has the following structure:

[0057]

[0058] Taking YPhos1 as an example, the synthetic route of the organophosphorus phosphide ylide of the present invention is as follows: Figure 2 As shown; the proton spectrum of YPhos1 is as follows. Figure 3 As shown, the phosphine spectrum is as follows Figure 4 As shown, the carbon spectrum is as follows Figure 5 As shown.

[0059] In this invention, the polar vinyl monomer preferably includes (meth)acrylate monomers and / or acrylamide monomers, and more preferably one or more of methyl methacrylate, allyl methacrylate, allyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, methyl acrylate, allyl acrylate, allyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, benzyl acrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide, with specific structural formulas as follows:

[0060]

[0061] This invention provides a catalyst system for the polymerization of polar vinyl monomers, comprising a Lewis base and a Lewis acid, wherein the Lewis base comprises a phosphorus ylide organophosphorus having the structure shown in Formula I:

[0062]

[0063] In Formula I, A1 is alkyl or aryl; A2 is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl; A3 is alkyl, aryl, alkenyl, guanidinyl, pyridyl, alkylsilyl or alkenylsilyl; A4 is alkyl, aryl, alkenyl, cyano, p-benzenesulfonyl, alkylsilyl or alkenylsilyl.

[0064] In this invention, the preferred structure of Formula I is the same as described above, and will not be repeated here.

[0065] In this invention, the Lewis acid comprises organoboron and / or organaluminum; the Lewis acid has one of the structures shown in Formula II-1 to Formula II-11:

[0066]

[0067] In formulas II-1 to II-11, R1 is methyl, ethyl, isopropyl, isobutyl, phenyl, pentafluorophenyl, naphthyl, or halogen; R2 is methyl, ethyl, isopropyl, isobutyl, or halogen; and R3 is hydrogen, methyl, ethyl, or halogen.

[0068] As a specific embodiment of the present invention, the preferred structure of the Lewis acid is as follows:

[0069]

[0070] In this invention, the molar ratio of the Lewis acid to the Lewis base is preferably 1 to 100:1, more preferably 2 to 50:1, and even more preferably 10 to 30:1.

[0071] This invention provides a method for the catalytic, living, and controlled polymerization of polar vinyl monomers, comprising the following steps:

[0072] Using polar vinyl monomers as monomer raw materials, conjugate addition polymerization is carried out under the synergistic catalysis of Lewis acid and Lewis base;

[0073] The Lewis base comprises a phosphorus ylphosphine zylidene organophosphine having the structure shown in Formula I:

[0074]

[0075] In Formula I, A1 is alkyl or aryl; A2 is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl; A3 is alkyl, aryl, alkenyl, guanidinyl, pyridyl, alkylsilyl or alkenylsilyl; A4 is alkyl, aryl, alkenyl, cyano, p-benzenesulfonyl, alkylsilyl or alkenylsilyl.

[0076] The Lewis acid includes organoboron and / or organaluminum.

[0077] In this invention, the preferred structures of the Lewis acid and Lewis base are the same as those described above, and will not be repeated here.

[0078] In this invention, the polar vinyl monomer preferably includes one or more of methyl methacrylate, allyl methacrylate, allyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, methyl acrylate, allyl acrylate, allyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, benzyl acrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0079] In this invention, the molar ratio of the polar vinyl monomer, Lewis acid, and Lewis base is preferably 25–50000:1–100:1, more preferably 50–20000:1–100:1, even more preferably 100–10000:2–50:1, and even more preferably 500–5000:10–30:1.

[0080] In this invention, the conjugate addition polymerization has three feeding methods: 1. Lewis acid and Lewis base are premixed for 10 minutes, and then the monomer is added; 2. Lewis acid and monomer are premixed, and then the Lewis base is added; 3. Lewis base and monomer are premixed, and then the Lewis acid is added.

[0081] In this invention, the conjugate addition polymerization is carried out under conditions of organic solvent or solvent-free conditions. That is, the conjugate addition polymerization can be carried out either bulk polymerization or using an organic solvent as the polymerization medium.

[0082] In this invention, when the reaction conditions involve the use of an organic solvent, the organic solvent is one or more selected from toluene, dichloromethane, 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide. In this invention, the amount of the organic solvent used is preferably such that the monomer concentration is 0.1–10 mol / L, more preferably 1–5 mol / L.

[0083] In this invention, the temperature of the conjugate addition polymerization is preferably -78°C to room temperature, and the reaction time is preferably 10 seconds to 72 hours.

[0084] The following examples illustrate the application of the phosphorus lyde organophosphorus provided by the present invention as a Lewis base in the catalytic polymerization of polar vinyl monomers. However, these examples should not be construed as limiting the scope of protection of the present invention.

[0085] In this invention, the structures and numbering of the Lewis bases used in the embodiments are as follows:

[0086]

[0087] Example 1: Lewis acid-base pair polymerization of MMA based on phosphorus ylide organophosphorus bases

[0088] The polymerization reaction was carried out in a glove box. 1 mL of MMA (9.4 mmol) and an appropriate amount of toluene solvent were measured into a 30 mL reaction flask (total solution volume 10 mL). Lewis base and Lewis acid were added separately, and timing was started. After stirring for a period of time until the monomer was completely converted, the reaction flask was removed from the glove box, and the polymerization reaction was terminated by adding 5% HCl / methanol solution. The polymer was filtered, washed thoroughly with methanol, and dried under vacuum at 50 °C to constant weight. The molecular weight and molecular weight distribution of the obtained polymer were determined by gel permeation chromatography.

[0089] The results obtained by catalysis under different Lewis acids and bases and different reaction conditions are summarized in Tables 1 and 2. In Tables 1 and 2, the molar ratio of Lewis acid to Lewis base is 2:1. The GPC overlay diagram of the polymer obtained by YPhos1 / (BHT)2AlMe catalysis is shown below. Figure 6The linear relationship between the molecular weight of the obtained polymer and [MMA]0 / [YPhos1]0 is shown in the figure. Figure 7 The polymer with a molecular weight (M) obtained by catalyzing 1600 equivalent MMA with YPhos1 / (BHT)2AlMe was obtained. n The linear relationship between the conversion rate (η) and the dispersion factor (PDI) is shown in the figure below. Figure 8 The GPC overlay diagram of the polymer obtained by YPhos1 / (BHT)2AlEt catalysis is shown below. Figure 9 YPhos1 / (BHT)Al i The GPC overlay diagram of the polymer obtained by Bu2 catalysis is shown below. Figure 10 .

[0090] Table 1. Dimethylphosphine-substituted triphenylphosphine ylides as Lewis bases (YPhos1)

[0091]

[0092]

[0093] Table 2. Diphenylphosphine-substituted triphenylphosphine ylides as Lewis bases (YPhos4)

[0094]

[0095] Example 2: Chain extension of MMA

[0096] The polymerization reaction was carried out in a glove box. 22.5 mg of (BHT)₂AlMe was weighed into a 30 mL reaction flask, and MMA (1 mL, 9.4 mmol) was added. After the monomer and Lewis acid had fully reacted, an appropriate amount of solvent (total solution volume 10 mL) was added, followed by 8.2 mg of YPhos1. Timing was started, and the mixture was stirred for a period of time until the monomer was completely converted. Then, the same amount of MMA (1 mL, 9.4 mmol) was added again, and this process was repeated several times until all monomers were completely converted. The reaction flask was then removed from the glove box, and the polymerization reaction was terminated by adding 5% HCl / methanol solution. The polymer was filtered out, washed thoroughly with methanol, and dried under vacuum at 60 °C to constant weight. The molecular weight and molecular weight distribution of the obtained polymer were determined by gel permeation chromatography.

[0097] The results of chain extension experiments using the YPhos1 and (BHT)2AlMe system are summarized in Table 3. See the relevant GPC diagrams. Figure 11 This ideal chain extension experiment demonstrates that the catalytic polymerization system can achieve good retention of activity at the polymer chain ends.

[0098] Table 3. Results of chain extension experiments in MMA polymerization.

[0099]

[0100] Example 3: Copolymerization of methyl methacrylate (MMA) and allyl methacrylate (BMA)

[0101] Taking the preparation of poly(PMMA-block-PBMA-block-PMMA) as an example: The polymerization reaction was carried out in a glove box. 21.6 mg of Lewis acid was weighed into a 20 mL reaction flask, and MMA (0.5 mL, 4.7 mmol) was added. After the monomers and Lewis acid had fully reacted, an appropriate amount of solvent (total solution volume 5 mL) was added, followed by 8.2 mg of YPhos1. Timing was started, and the mixture was stirred for a period of time until the monomers were completely converted. Then, BMA (633 μL, 4.68 mmol) was added. After a period of time, once the monomers were completely converted, a certain amount of MMA (0.5 mL, 4.7 mmol) was added. After all monomers were completely converted, the reaction flask was removed from the glove box, and the polymerization reaction was terminated by adding 5% HCl / methanol solution. The polymer was filtered out, washed thoroughly with methanol, and dried under vacuum at 60 °C to constant weight. The molecular weight and molecular weight distribution of the obtained polymer were determined by gel permeation chromatography. See the GPC diagrams for the relevant homopolymers and copolymers. Figure 12 , Figure 13 .

[0102] Table 4. Copolymerization of MMA and BMA

[0103]

[0104]

[0105] a Random copolymerization: Two monomers are added simultaneously.

[0106] Example 4: One-pot synthesis of triblock all-methacrylate thermoplastic elastomer

[0107] Taking the synthesis of triblock (PMMA-block PBA-block PMMA) thermoplastic elastomer as an example: The polymerization reaction was carried out in a glove box. 5.4–21.6 mg of Lewis acid was weighed into a 20 mL reaction flask, and 0.1–0.5 mL of MMA (0.94–4.7 mmol) was added. After the monomers and Lewis acid had fully reacted, an appropriate amount of solvent (total solution volume 5–10 mL) was added, followed by 2.1–8.2 mg of YPhos1. Timing was started, and the mixture was stirred until 50% of the monomers were converted. Then, 600–2200 μL of BA (4.7–23.5 mmol) was added. After a period of time until all monomers were completely converted, the reaction flask was removed from the glove box, and the polymerization reaction was terminated by adding 5% HCl / methanol solution. The polymer was filtered out, washed thoroughly with methanol, and dried under vacuum at 60 °C to constant weight. The resulting polymer was dissolved again in chloroform and passed through a glass slide to form a long membrane. The mechanical properties of the obtained membrane were tested using a tensile testing machine, and the test results are shown in Table 5. The mechanical property diagrams of the obtained elastomer are shown below. Figure 14 .

[0108] Table 5. Triblock copolymers of MMA and BA

[0109]

[0110] Example 5 Polymerization of vinyl monomers with different polarities

[0111] This embodiment investigates the Lewis acid-base pair catalysis of the polymerization of vinyl monomers with different polarities using organophosphorus ylidene phosphate as Lewis base. The polymerization reaction was carried out in a glove box. Appropriate amounts of polar vinyl monomers and 30 mL of toluene were measured into a reaction flask (total solution volume 10 mL). Lewis base and Lewis acid were added separately, and timing was started. After stirring for a period of time until the monomers were completely converted, the reaction flask was removed from the glove box, and the polymerization reaction was terminated by adding 5% HCl / methanol solution. The polymer was filtered, thoroughly washed with methanol, and dried under vacuum at 50 °C to constant weight. The molecular weight and molecular weight distribution of the obtained polymer were determined by gel permeation chromatography. The polymerization results of vinyl monomers with different polarities are shown in Table 6.

[0112] Table 6. Polymerization results of vinyl monomers with different polarities

[0113] Monomer: Lewis acid (molar ratio) Time (min) Conversion rate (%) <![CDATA[M n (10 4 g / mol)]]> PDI 200FMA:2LA-3 180 100 68.5 1.39 400FMA:2LA-3 1440 95 89.5 1.37 200MEMA:2LA-6 4 100 4.6 1.22 400MEMA:2LA-6 10 100 9.6 1.20 200MC:2LA-21 120 75 2.6 1.46 200MS:2LA-25 240 100 4.6 1.25 400HMA:2LA-22 10 100 8.9 1.51 800ES:2LA-25 1440 95 25.6 1.29 400EC:2LA-25 1440 100 9.6 1.19

[0114] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A catalyst system for catalyzing the polymerization of polar vinyl monomers, comprising a Lewis base and a Lewis acid, wherein the Lewis base comprises a phosphorus ylide organophosphorus, and the phosphorus ylide organophosphorus has a structure shown in any one of the formulas YPhos1 to YPhos5: ； The Lewis acid has a structure shown in any one of the formulas LA-1, LA-3 to LA-12: ； The polar vinyl monomers include (meth)acrylate monomers and / or acrylamide monomers; The molar ratio of the polar vinyl monomer, Lewis acid, and Lewis base is 100~10000:2~50:

1.

2. A method for the catalytically controlled polymerization of polar vinyl monomers, comprising the following steps: Using polar vinyl monomers as monomer raw materials, conjugate addition polymerization is carried out under the synergistic catalysis of Lewis acid and Lewis base; The Lewis base includes phosphorus lyophosphorus organophosphorus, which has the structure shown in any one of the formulas YPhos1 to YPhos5 in claim 1. The Lewis acid has the structure shown in any one of the formulas LA-1, LA-3 to LA-12 in claim 1; The molar ratio of the polar vinyl monomer, Lewis acid, and Lewis base is 100~10000:2~50:

1.

3. The method according to claim 2, characterized in that, The conjugate addition polymerization is carried out under conditions of organic solvent or solvent-free conditions.

4. The method according to claim 3, characterized in that, The organic solvent is one or more of toluene, dichloromethane, 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide.

5. The method according to claim 2 or 3, characterized in that, The conjugate addition polymerization is carried out at temperatures ranging from -78°C to room temperature, and the reaction time ranges from 10 seconds to 72 hours.

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