Hindered Lewis Acid-Base Pair--flp Catalyzed Living Polymerization of Vinyl Polar Monomers

One--FLP, polar monomer technology, applied in the field of active controllable polymerization system, can solve the problems of low initiation efficiency, limited degree of polymerization, monomer adaptability, etc., achieve mild reaction conditions, narrow molecular weight distribution, monomeric The effect of wide applicability

Active Publication Date: 2020-08-04
JILIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Bernhard Rieger et al. broadened the adaptability of the substrate by carefully selecting the appropriate Lewis acid-base pair (J.Am.Chem.Soc., 2016, 138, 7776-7781), and obtained a polymer with a narrow molecular weight distribution. However, the monomer Low ratio to catalyst, limited degree of polymerization
More critically, the side reaction of chain termination has not been effectively solved, so the block polymerization of different monomers cannot be carried out, which greatly restricts the application of this method.
[0004] At present, the main problem facing the catalytic polymerization of polar vinyl monomers is that the same catalytic system cannot solve the following problems at the same time: 1) the adaptability of monomers, the monomers cannot be completely converted; 2) the narrow molecular weight distribution and high molecular weight polymers cannot Both; 3) transition metal catalysis is often required; 3) the reaction is slow, the reaction is uncontrollable, and the theoretical molecular weight and the actual molecular weight are greatly different; 4) the initiation efficiency is low, and the catalyst consumption is large; 5) the copolymerization between different monomers cannot be carried out ( random copolymerization and block copolymerization)

Method used

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  • Hindered Lewis Acid-Base Pair--flp Catalyzed Living Polymerization of Vinyl Polar Monomers
  • Hindered Lewis Acid-Base Pair--flp Catalyzed Living Polymerization of Vinyl Polar Monomers
  • Hindered Lewis Acid-Base Pair--flp Catalyzed Living Polymerization of Vinyl Polar Monomers

Examples

Experimental program
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Effect test

Embodiment 1

[0044] The conjugate addition polymerization of embodiment 1 methyl methacrylate (MMA)

[0045] There are two feeding methods in the polymerization process: 1. Lewis acid and Lewis base are pre-mixed for 5 minutes, and then monomer is added; 2. Lewis acid and monomer are pre-mixed, and then Lewis base is added. Regardless of the feeding method, the conjugated addition polymerization of the vinyl polar monomer can be well realized.

[0046] The polymerization reaction was carried out in a glove box, and methyl methacrylate (0.5mL, 4.68mmol) was measured, and an appropriate amount (making the total solution volume 5mL) toluene was added to a 20 ml reaction bottle, Lewis base and Lewis acid were added respectively, and Start timing, stir for a period of time until the monomer is completely converted, take the reaction bottle out of the glove box, and add 5% HCl / methanol solution to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methan...

Embodiment 2

[0054] Example 2 Conjugate addition polymerization of allyl methacrylate (AMA) and N,N-dimethylacrylamide (DMAA)

[0055] The polymerization reaction was carried out in a glove box, and an appropriate amount of toluene was weighed (to keep the total volume of the solution at 5 mL) in a 20 mL reaction bottle, and Lewis base and Lewis acid were added (in molar ratio, Lewis acid: Lewis base=2:1), Stir for 10 minutes, then add allyl methacrylate (633 μL, 4.68 mmol) or N,N-dimethylacrylamide (482 μL, 4.68 mmol), and start timing, stir for a period of time until the monomer is completely converted, and then add The reaction bottle was taken out from the glove box, and 5% HCl / methanol solution was added to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methanol, and dried under vacuum at 50°C to constant weight. The resulting polymer was 1 H identification (see attached Figure 8 ), indicating that the reaction selectively occurs at the...

Embodiment 3

[0059] The chain extension of embodiment 3MMA

[0060] The polymerization reaction was carried out in the glove box, and MeAl(BHT) was weighed 2 (22.5mg, 4.68×10 -2 mmol) in a 20 ml reaction flask, add MMA (0.5mL, 4.68mmol), add an appropriate amount of toluene (the total volume of the solution is 5mL), after the monomer and Lewis acid fully react, add the NHO1 (3.6 mg, 2.34×10 -2 mmol), and start timing, after stirring for a period of time, after the complete conversion of the monomers, add the same amount of MMA (0.5mL, 4.68mmol) as the first addition, and repeat this several times. After all the monomers are completely converted, add The reaction bottle was taken out from the glove box, and 5% HCl / methanol solution was added to terminate the polymerization reaction. The polymer was filtered off, washed thoroughly with methanol, and dried under vacuum at 50°C to constant weight. The molecular weight and molecular weight distribution of the resulting polymers were determi...

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Abstract

Belonging to the technical field of polymer synthesis, the invention relates to a frustrated Lewis pair FLP catalyzed vinyl polar monomer living polymerization method. A vinyl polar monomer is adoptedas the monomer raw material for conjugate addition polymerization under the synergic catalysis of a frustrated Lewis pair, in terms of mole, Lewis acid is greater than Lewis base and smaller than themonomer, and the ratio of the monomer to the Lewis base is 20-3200:1, the reaction temperature is room temperature, and the reaction time is 30sec-24h. The method provided by the invention has the characteristics of easily available raw materials, convenient operation, mild reaction conditions, rapidity, high conversion rate, wide monomer adaptability and the like, also the catalyst dosage is small, and the initiation efficiency is close to 100%, therefore the method is living controlled polymerization, and can realize random copolymerization and block copolymerization between different polarmonomers.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, and in particular relates to an activity controllable polymerization system based on the synergistic catalysis of hindered Lewis acid-base pair (FLP) of azacyclic olefin (NHO), which can be applied to vinyl polar monomers The living controllable conjugate addition polymerization, as well as the random and block copolymerization between different vinyl polar monomers. Background technique [0002] Polar vinyl monomer polymers have excellent weather resistance, decorative properties, adhesive properties, and are easily converted into water-soluble polymers. Polymethyl methacrylate (PMMA) is a typical representative of this type of polymer, commonly known as plexiglass. PMMA has many excellent properties. Compared with inorganic glass, it has high transparency, better impact resistance, 200 times that of inorganic glass products, almost no risk of fracture, stable chemical properties, re...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F120/14C08F4/54C08F120/40C08F120/54C08F293/00
CPCC08F4/54C08F120/14C08F120/40C08F120/54C08F293/005
Inventor 张越涛何江华王前义
Owner JILIN UNIV
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