Method for preparing acrylate cross-linked copolymer by one-step method

Abstract

The invention relates to the field of preparation of cross-linked polymers, and aims to provide a method for preparing an acrylate cross-linked copolymer by a one-step method. The method comprises thefollowing steps: adding a free radical polyfunctionality initiator PFI, an acrylate monomer, a comonomer and a polyamine ligand into a reactor, and adding a proper amount of a solvent; after deoxidation, adding copper powder under the protection of nitrogen; then reacting for 12 to 630 minutes at the temperature of 40 to 110 DEG C; and after the reaction is finished, extracting with a solvent toremove unreacted monomers and small molecular components, thereby obtaining the acrylate cross-linked copolymer. According to the invention, the acrylate cross-linked copolymer can be prepared by theone-step method through free radical copolymerization of a monovinyl monomer (without a divinyl monomer); the synthesis conditions are simple, for example, PFI synthesis is convenient, and the structure and the functionality are variable; the monomer is a commercial reagent; the functionality of a branching point of the prepared product is variable, the product has a breakable branching point, thebreakable cross-linkable copolymer can be converted into a linear chain segment after being broken, and the average molecular weight and molecular weight distribution of the chain segment can be measured.

Description

technical field

[0001] The present invention relates to the field of preparation of cross-linked polymers, in particular to a method for preparing acrylate-based cross-linked copolymers by one-step method. Background technique

[0002] Compared with linear polymers, cross-linked polymers have a more complex three-dimensional network structure, and their mechanical properties, thermal stability, abrasion resistance, solvent resistance and creep resistance are significantly different. , adhesives, drug controlled release and other fields have important applications.

[0003] Crosslinked polymers can be prepared by condensation polymerization of polyfunctional monomers or by copolymerization of vinyl monomers with a small amount of divinyl monomers. Polycondensation of polyfunctional monomers can be used to prepare well-defined cross-linked polymers. The monomers involved can be either small-molecule multifunctional monomers or multifunctional macromonomers. For example, by ...

Examples

Embodiment 1

[0050] The synthesis of embodiment 1 polyamine ligand TPEN

[0051] Dissolve 13.12 g (0.08 mol) of 2-chloromethylpyridine hydrochloride in 30 mL of deionized water, cool in an ice bath, slowly add 15 mL of an aqueous solution containing 0.08 mol of sodium hydroxide, and the solution turns pink. After adding 60 mL of a DCM solution containing 1.2 g (0.02 mol) of ethylenediamine, it was warmed to room temperature. Within 50 hours, 15 mL of an aqueous solution in which 0.08 mol of sodium hydroxide was dissolved was added. The reaction was stopped, the organic phase was washed with 3×10 mL of 15% aqueous NaOH solution, and the organic phase was dried over anhydrous magnesium sulfate. The filtrate obtained after filtration was concentrated in vacuo and extracted with boiling ether to obtain the crude product. The crude product was crystallized three times from ether to give pale yellow needles. Vacuum dried to constant weight, weighed and yield calculated (37%). 1 H NMR (400MHz...

Embodiment 2

[0052] Example 2 Synthesis of Small Molecular Polybrominated Compound 3a

[0053] 2.7g (2×10 -2 mol) 1,1,1-trimethylol-propane, 8mL (6×10 -2 mol) triethylamine and 50 mL of DCM were mixed, placed in a 250 mL three-necked flask, and cooled in an ice bath. will contain 8.2 mL (6.6 x 10 -2 mol) 2-bromo-2-methylpropionyl bromide in DCM (50 mL) was dropped into the three-necked flask dropwise, and a white precipitate appeared during the dropwise addition. After the dropwise addition, the temperature was raised to room temperature (25° C.), and the reaction was continued for 18 hours. The filtrate obtained by filtration was washed three times with 50 mL of 1mol / L HCl solution, saturated NaHCO 3 washed three times with aqueous solution, three times with 50 mL of deionized water, once with 50 mL of saturated NaCl, and then washed with anhydrous MgSO 4 Dry overnight. The filtrate obtained after filtration was concentrated to obtain a yellow viscous liquid. The crude product was ...

Embodiment 3

[0054] Example 3 Synthesis of Small Molecule Polybrominated Compound 3b

[0055] The 2-bromo-2-methylpropionyl bromide in Example 2 was replaced with 7 mL (6.6×10 -2 mol) 2-bromopropionyl bromide, and all the other operation steps are the same as in Example 2. White crystals were obtained (73% yield). 1 H NMR (400MHz, CDCl 3 )δ(ppm): 4.68-4.73(3H,q,O=C-CH-),3.94(6H,s,CH 2 -O-C=O),1.91-1.97(9H,d,O=C-CH(CH 3 )-), 1.63-1.73(2H,q,CH 3 -CH 2 -),0.84-0.95(3H,t,CH 3 -CH 2 -). Elemental analysis: measured value (theoretical value): C, 33.29 (33.42); H, 4.31 (4.30).

technical field

[0001] The present invention relates to the field of preparation of cross-linked polymers, in particular to a method for preparing acrylate-based cross-linked copolymers by one-step method. Background technique

[0002] Compared with linear polymers, cross-linked polymers have a more complex three-dimensional network structure, and their mechanical properties, thermal stability, abrasion resistance, solvent resistance and creep resistance are significantly different. , adhesives, drug controlled release and other fields have important applications.

[0003] Crosslinked polymers can be prepared by condensation polymerization of polyfunctional monomers or by copolymerization of vinyl monomers with a small amount of divinyl monomers. Polycondensation of polyfunctional monomers can be used to prepare well-defined cross-linked polymers. The monomers involved can be either small-molecule multifunctional monomers or multifunctional macromonomers. For example, by ...

Examples

Embodiment 1

[0050] The synthesis of embodiment 1 polyamine ligand TPEN

[0051] Dissolve 13.12 g (0.08 mol) of 2-chloromethylpyridine hydrochloride in 30 mL of deionized water, cool in an ice bath, slowly add 15 mL of an aqueous solution containing 0.08 mol of sodium hydroxide, and the solution turns pink. After adding 60 mL of a DCM solution containing 1.2 g (0.02 mol) of ethylenediamine, it was warmed to room temperature. Within 50 hours, 15 mL of an aqueous solution in which 0.08 mol of sodium hydroxide was dissolved was added. The reaction was stopped, the organic phase was washed with 3×10 mL of 15% aqueous NaOH solution, and the organic phase was dried over anhydrous magnesium sulfate. The filtrate obtained after filtration was concentrated in vacuo and extracted with boiling ether to obtain the crude product. The crude product was crystallized three times from ether to give pale yellow needles. Vacuum dried to constant weight, weighed and yield calculated (37%). 1 H NMR (400MHz...

Embodiment 2

[0052] Example 2 Synthesis of Small Molecular Polybrominated Compound 3a

[0053] 2.7g (2×10 -2 mol) 1,1,1-trimethylol-propane, 8mL (6×10 -2 mol) triethylamine and 50 mL of DCM were mixed, placed in a 250 mL three-necked flask, and cooled in an ice bath. will contain 8.2 mL (6.6 x 10 -2 mol) 2-bromo-2-methylpropionyl bromide in DCM (50 mL) was dropped into the three-necked flask dropwise, and a white precipitate appeared during the dropwise addition. After the dropwise addition, the temperature was raised to room temperature (25° C.), and the reaction was continued for 18 hours. The filtrate obtained by filtration was washed three times with 50 mL of 1mol / L HCl solution, saturated NaHCO 3 washed three times with aqueous solution, three times with 50 mL of deionized water, once with 50 mL of saturated NaCl, and then washed with anhydrous MgSO 4 Dry overnight. The filtrate obtained after filtration was concentrated to obtain a yellow viscous liquid. The crude product was ...

Embodiment 3

[0054] Example 3 Synthesis of Small Molecule Polybrominated Compound 3b

[0055] The 2-bromo-2-methylpropionyl bromide in Example 2 was replaced with 7 mL (6.6×10 -2 mol) 2-bromopropionyl bromide, and all the other operation steps are the same as in Example 2. White crystals were obtained (73% yield). 1 H NMR (400MHz, CDCl 3 )δ(ppm): 4.68-4.73(3H,q,O=C-CH-),3.94(6H,s,CH 2 -O-C=O),1.91-1.97(9H,d,O=C-CH(CH 3 )-), 1.63-1.73(2H,q,CH 3 -CH 2 -),0.84-0.95(3H,t,CH 3 -CH 2 -). Elemental analysis: measured value (theoretical value): C, 33.29 (33.42); H, 4.31 (4.30).

Images