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CN110483707B - Vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability - Google Patents

Vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability Download PDF

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CN110483707B
CN110483707B CN201910716174.0A CN201910716174A CN110483707B CN 110483707 B CN110483707 B CN 110483707B CN 201910716174 A CN201910716174 A CN 201910716174A CN 110483707 B CN110483707 B CN 110483707B
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李坚
刘佳
任强
汪称意
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Changzhou University
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Abstract

本发明公开了一种具有良好可控性的乙烯基单体RAFT阳离子无皂乳液聚合方法，包括如下步骤：首先在四口烧瓶中加入含氟两亲性大分子RAFT试剂、酸及水，然后搅拌溶解，再加入乙烯基单体Ⅱ和引发剂，室温搅拌，抽真空通氩气，引发温度下反应，间隔取样，测定转化率，转化率达90％以上时，停止反应，制得所述乙烯基单体RAFT阳离子无皂乳液；所述含氟两亲性大分子RAFT试剂为含氨基聚丙烯酸酯含氟嵌段共聚物，其结构式为：

Figure DDA0002155493870000011
其中，M1为含氟丙烯酸酯结构单元，x＝2～100；M2为含氨基丙烯酸酯结构单元，y＝2～100；M3为乙烯基单体的结构单元，z＝0～100。该方法简单，所得聚合物可控性好。

Figure 201910716174

The invention discloses a cationic soap-free emulsion polymerization method of vinyl monomer RAFT with good controllability. Stir and dissolve, then add vinyl monomer II and initiator, stir at room temperature, vacuumize and pass argon, initiate the reaction at the temperature, take samples at intervals, measure the conversion rate, stop the reaction when the conversion rate reaches more than 90%, and obtain the Vinyl monomer RAFT cationic soap-free emulsion; the fluorine-containing amphiphilic macromolecular RAFT reagent is an amino-containing polyacrylate fluorine-containing block copolymer, and its structural formula is:

Figure DDA0002155493870000011
Wherein, M1 is a fluorine-containing acrylate structural unit, x=2-100; M2 is an amino-containing acrylate structural unit, y=2-100; M3 is a vinyl monomer structural unit, z=0-100. The method is simple, and the obtained polymer has good controllability.

Figure 201910716174

Description

Vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability
Technical Field
The invention relates to the field of emulsion polymerization, in particular to a fluorine-containing amphiphilic macromolecular RAFT reagent, a preparation method thereof and application thereof in RAFT cation soap-free emulsion polymerization of vinyl monomers.
Background
Reversible addition fragmentation chain transfer (RAFT) is an important controllable living radical polymerization method, and RAFT emulsion polymerization is a new development of the RAFT method in recent years, and is characterized in that the polymerization reaction speed is high, the polymer structure and molecular weight can be designed and controlled, and polymers with various structures can be synthesized; the product is polymer emulsion, can be used as water-based paint and water-based ink, and is environment-friendly. The development of RAFT aqueous emulsion polymerisation is therefore of great importance in both academic and industrial fields. The RAFT soap-free emulsion polymerization is characterized in that an amphiphilic macromolecular emulsifier with RAFT active groups is synthesized in advance or formed in the polymerization process, then self-emulsification is carried out to form micelles, and soap-free emulsion polymerization is carried out, so that the method has the advantage of no influence of a surfactant on the performance of a product. At present, most of amphiphilic macromolecular emulsifiers adopted in RAFT soap-free emulsion polymerization are anionic macromolecular RAFT reagents, namely hydrophilic groups in molecules are carboxyl groups, sulfonic groups and the like, and patent CN103497272A discloses soap-free emulsion polymerization by using amphiphilic macromolecular RAFT reagents containing carboxylic groups or sulfonic groups. Patent CN104558453A discloses the synthesis of a cationic fluorine-containing amphiphilic block copolymer, but does not give a method for the emulsion polymerization of common vinyl monomer cationic RAFT. The cationic emulsion has unique advantages and is widely applied to various fields such as chemical additives, cell separation, adhesives and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the problems in the prior art, the invention adopts the amino-containing polyacrylate fluorine-containing block copolymer as the cationic fluorine-containing amphiphilic macromolecular RAFT reagent, and provides the RAFT cationic soap-free emulsion polymerization method of the vinyl monomer with good controllability.
The technical scheme adopted by the invention for solving the technical problems is as follows: a vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability comprises the following steps:
firstly, adding a fluorine-containing amphiphilic macromolecular RAFT reagent, acid and water into a four-neck flask, stirring for dissolving, then adding a vinyl monomer II and an initiator, stirring at room temperature, vacuumizing and introducing argon, reacting at the initiation temperature, sampling at intervals, measuring the conversion rate, and stopping the reaction when the conversion rate reaches over 90 percent to prepare the vinyl monomer RAFT cation soap-free emulsion;
the adopted fluorine-containing amphiphilic macromolecular RAFT reagent is an amino-containing polyacrylate fluorine-containing block copolymer, and the structure of the fluorine-containing amphiphilic macromolecular RAFT reagent is as follows:
Figure BDA0002155493850000021
wherein:
m1 is a fluorine-containing acrylate structural unit, and X is 2-100. Preferably from the homopolymerization or copolymerization of trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl methacrylate.
M2 is an amino acrylate-containing structural unit, and Y is 2-100. Preferably obtained by homopolymerization or copolymerization of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate and N-hydroxymethyl acrylamide.
M3 is a structural unit of a vinyl monomer, and Z is 0-100. Preferably methyl methacrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, isooctyl acrylate, ethyl methacrylate, isobutyl methacrylate, styrene homopolymerization or copolymerization.
Further, the acid is one or more of acetic acid, hydrochloric acid, phosphoric acid and p-toluenesulfonic acid; the vinyl monomer II is one or more of styrene, butyl acrylate, ethyl acrylate, methyl acrylate, isooctyl acrylate, methyl methacrylate, butyl methacrylate and vinyl acetate; the initiator is 2, 2-azobis (2-methylpropionamidine) dihydrochloride.
Further, the molar ratio of the vinyl monomer II to the fluorine-containing amphiphilic macromolecular RAFT reagent is 10: 1-1000: 1, the molar ratio of the acid to the amino group in the fluorine-containing amphiphilic macromolecular RAFT reagent is 0.1: 1-50: 1, the dosage of the initiator is 10-0.1% of the weight of the vinyl monomer II, the dosage of the water is 0.5-10 times of the total weight of the vinyl monomer II and the fluorine-containing amphiphilic macromolecular RAFT reagent, the reaction temperature is room temperature-80 ℃, and the reaction time is 0.5-8 hours.
Further, the amino-containing polyacrylate fluorine-containing block copolymer is prepared by the following steps:
step 1, adding the amino acrylate-containing monomer, the vinyl monomer I, a solvent, an initiator and an RAFT reagent S-n-dodecyl-S' - (2-isobutyric acid group) trithiocarbonate into a three-neck flask, uniformly mixing, vacuumizing a system, introducing argon, circulating for 3 times, reacting at a certain initiation temperature, sampling at intervals to determine the conversion rate, and stopping the reaction when the conversion rate reaches more than 80% to obtain the amino polyacrylate macromolecule RAFT reagent;
and 2, adding the fluorine-containing acrylate monomer, the solvent and the initiator into the amino-containing polyacrylate macromolecular RAFT reagent prepared in the step 1, uniformly mixing, vacuumizing the system, introducing argon, circulating for 3 times, reacting at the initiation temperature, sampling at intervals, determining the conversion rate, and finishing the reaction after the conversion rate is more than 80% to prepare the amino-containing polyacrylate fluorine-containing block copolymer amphiphilic macromolecular RAFT reagent.
Furthermore, the fluorine-containing acrylate monomer is any one or a mixture of two or more of trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl methacrylate;
the amino acrylate monomer is any one or a mixture of two or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate and N-hydroxymethyl acrylamide;
the vinyl monomer I is any one or a mixture of two or more of methyl methacrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, isooctyl acrylate, ethyl methacrylate, isobutyl methacrylate and styrene.
Furthermore, the solvent in the step 1 and the step 2 is any one or more of ethanol, propylene glycol monomethyl ether, propylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol methyl ether, propylene glycol monobutyl ether, propylene glycol butyl ether, ethylene glycol monobutyl ether, ethylene glycol butyl ether and tetrahydrofuran; the initiator in the step 1 and the step 2 is azobisisobutyronitrile or azobisisoheptonitrile.
Furthermore, in the step 1, the molar ratio of the amino acrylate-containing monomer to the vinyl monomer I is 20: 1-1: 10, and the amount of the initiator is 10-0.1% of the total weight of the amino acrylate-containing monomer and the vinyl monomer I; the dosage of the RAFT reagent is 10 to 0.01 percent of the total molar weight of the amino-containing acrylate monomer and the vinyl monomer I; the dosage of the solvent is 0.1-10 times of the total weight of the amino-containing acrylate monomer and the vinyl monomer I;
and/or the molar ratio of the fluorine-containing acrylate monomer in the step 2 to the amino-containing polyacrylate macromolecule RAFT reagent prepared in the step 1 is 10: 1-1000: 1, and the using amount of the solvent is 10-80% of the total weight of the fluorine-containing acrylate monomer and the amino-containing polyacrylate macromolecule RAFT reagent prepared in the step 1; the dosage of the initiator is 10 to 0.1 percent of the weight of the fluorine-containing acrylate monomer.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a RAFT cation soap-free emulsion polymerization method of a vinyl monomer with good controllability. The method is simple, and the obtained polymer has good controllability.
Drawings
FIG. 1 in example 1, the polystyrene molecular weight is plotted as a function of conversion.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
Example 1
The styrene RAFT cation soap-free emulsion polymerization method with good controllability comprises the following steps:
step 1, synthesizing an amino-containing polyacrylate macromolecular RAFT reagent:
12.5g (0.0875mol) of dimethylaminoethyl acrylate (DMAEA) monomer, 49.9g (0.48mol) of styrene (St) monomer, 41.9g of propylene glycol monomethyl ether as a solvent, and 1.14X 10 times As Initiator (AIBN) were weighed out-3mol, RAFT reagent (S-n-twelve)alkyl-S' - (2-isobutyric acid group) trithiocarbonate) 1.82g (0.005mol) of the mixed solution was charged into a 250mL three-necked flask. After uniform mixing, vacuumizing the system, introducing argon, circulating for 3 times, reacting for 560min under 70 ℃ oil bath, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. And stopping the reaction when the conversion rate reaches more than 80 percent to prepare a mixed solution containing the amino-containing polyacrylate macromolecule RAFT reagent P (DMAEA-co-St), wherein the number average molecular weight of the amino-containing polyacrylate macromolecule RAFT reagent is 7800 measured by GPC.
Step 2, synthesizing amphiphilic macromolecule RAFT reagent containing amino polyacrylate fluorine-containing block copolymer
23.6g (0.1mol) of hexafluorobutyl acrylate (HFBA) monomer was weighed and added to the mixed solution containing amino polyacrylate-containing macroRAFT agent P (DMAEA-co-St) prepared in step 1 (the specific mass or molar amount of P (DMAEA-co-St) was determined by measuring the solid content and molecular weight thereof), and then 15.75g of propylene glycol methyl ether and 1.14X 10 initiator (AIBN) were added-3And mol, after uniform mixing, vacuumizing the system, introducing argon, circulating for 3 times, reacting for 365min under 70 ℃ oil bath, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. After the conversion rate reaches 80 percent, the reaction is finished to obtain the amphiphilic macromolecular RAFT reagent P (DMAEA-co-St) -b-PHFBA containing the amino polyacrylate fluorine-containing segmented copolymer, wherein the number average molecular weight is 13600 g/mol. Step 3, styrene RAFT cationic soap-free emulsion polymerization with good controllability
Firstly, 0.08g of acetic acid, 19.10g of deionized water and magnetons are added into a 100mL three-neck flask, and then 1.41g (1.04 x 10) of fluorine-containing amphiphilic macromolecular RAFT reagent prepared in the step 2 is added-4mol) and stirring until complete dissolution. Then 1.04g (0.01mol) of styrene and 0.01g (4.0X 10 mol) of initiator (AIBA) were added-5mol), stirring at room temperature, vacuumizing, introducing argon, carrying out oil bath reaction at 70 ℃ for 30min, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. The conversion rate reaches more than 90 percent, the reaction is stopped to obtain the polystyrene emulsion with the designed molecular weight of 23600g/mol and the molecular weight of 24600g/mol measured by GPC and the PDI of 1.40.
Example 2
The butyl acrylate RAFT cationic soap-free emulsion polymerization method with good controllability comprises the following steps:
step 1, synthesis of amino polyacrylate containing macro RAFT agent, same as step 1 in example 1.
Step 2, synthesis of the fluorine-containing amphiphilic macromolecular RAFT reagent, the same as in step 2 of example 1.
Step 3, butyl acrylate RAFT cationic soap-free emulsion polymerization with good controllability
Firstly, 0.08g of acetic acid, 19.10g of deionized water and magnetons are added into a 100mL three-neck flask, and then 1.41g (1.04 x 10) of fluorine-containing amphiphilic macromolecular RAFT reagent prepared in the step 2 is added-4mol) and stirring until complete dissolution. Then 1.29g (0.01mol) of butyl acrylate and 0.01g (4.0X 10) of initiator (AIBA) were added-5mol), stirring at room temperature, vacuumizing, introducing argon, carrying out oil bath reaction at 70 ℃ for 30min, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. The conversion rate reaches more than 90 percent, the reaction is stopped to obtain polybutyl acrylate emulsion with the designed molecular weight of 25600g/mol, the number average molecular weight of 24300g/mol measured by GPC and the PDI of 1.46
Example 3
The vinyl acetate RAFT cation soap-free emulsion polymerization method with good controllability comprises the following steps:
step 1, synthesis of amino polyacrylate containing macro RAFT agent, same as step 1 in example 1.
Step 2, synthesis of the fluorine-containing amphiphilic macromolecular RAFT reagent, the same as in step 2 of example 1.
Step 3, vinyl acetate RAFT cation soap-free emulsion polymerization with good controllability
Firstly, 0.08g of acetic acid, 19.10g of deionized water and magnetons are added into a 100mL three-neck flask, and then 1.41g (1.04 x 10) of fluorine-containing amphiphilic macromolecular RAFT reagent prepared in the step 2 is added-4mol) and stirring until complete dissolution. Then, 0.86g (0.01mol) of vinyl acetate and 0.01g (4.0X 10 mol) of initiator (AIBA) were added-5mol), stirring at room temperature, vacuumizing, introducing argon, carrying out oil bath reaction at 70 ℃ for 30min, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. Transformation ofStopping the reaction when the rate reaches more than 90 percent to obtain polyvinyl acetate emulsion with the designed molecular weight of 22000g/mol and the conversion rate of 50 percent. The number average molecular weight by GPC was 16200g/mol, PDI: 1.21.
Example 4
Step 1, synthesis of amino-containing polyacrylate macromolecular RAFT reagent
13.7g (0.0875mol) of dimethylaminoethyl methacrylate (DMAEMA) monomer, 48.1g (0.48mol) of Methyl Methacrylate (MMA) monomer, 30g of propylene glycol monomethyl ether as a solvent, and 5.07X 10g of An Initiator (AIBN) are weighed-4mol, a mixed solution of 1.82g (0.005mol) of RAFT reagent (S-n-dodecyl-S' - (2-isobutyric acid group) trithiocarbonate) was charged into a 250mL three-necked flask. After uniform mixing, vacuumizing the system, introducing argon, circulating for 3 times, reacting for 560min under 70 ℃ oil bath, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. The conversion rate reaches more than 80 percent, the reaction is stopped, and the amino-containing polyacrylate macromolecular RAFT reagent P (DMAEMA-co-MMA) is prepared, and the number average molecular weight is 8800 measured by GPC.
Step 2, synthesizing amphiphilic macromolecule RAFT reagent containing amino polyacrylate fluorine-containing block copolymer
23.6g (0.1mol) of hexafluorobutyl acrylate (HFBA) monomer was weighed and added to the mixed solution containing amino group-containing polyacrylate macroRAFT agent P (DMAEA-co-MMA) obtained in step 1, followed by addition of 15.75g of propylene glycol methyl ether and 1.14X 10g of initiator (AIBN)-3And mol, after uniform mixing, vacuumizing the system, introducing argon, circulating for 3 times, reacting for 365min under 70 ℃ oil bath, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. After the conversion rate reaches 80 percent, the reaction is finished to obtain the amino-containing polyacrylate fluorine-containing block copolymer fluorine-containing amphiphilic macromolecule RAFT reagent P (DMAEA-co-MMA) -b-PHFBA, and the number average molecular weight is 10400 g/mol.
Step 3, styrene RAFT cationic soap-free emulsion polymerization with good controllability
Firstly, 0.08g of acetic acid, 19.10g of deionized water and magnetons are added into a 100mL three-neck flask, and then 1.08g (1.04 x 10) of fluorine-containing amphiphilic macromolecular RAFT reagent prepared in the step 2 is added-4mol) is stirred until the solution is completely dissolved. Then 1.04g (0.01mol) of styrene and 0.01g (4.0X 10 mol) of initiator (AIBA) were added-5mol), stirring at room temperature, vacuumizing, introducing argon, carrying out oil bath reaction at 70 ℃ for 30min, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. The conversion rate reaches more than 90 percent, the reaction is stopped to obtain the polystyrene emulsion with the designed molecular weight of 20400g/mol and the molecular weight of 21400g/mol measured by GPC and the PDI of 1.35.
Comparative example 1
A styrene RAFT soap-free emulsion polymerization process comprising the steps of:
step 1, synthesis of amino polyacrylate containing macro RAFT agent, same as step 1 in example 1.
Step 2, synthesis of amphiphilic block copolymer P (DMAEA-co-St) -b-PBA
1.71g of propylene glycol methyl ether was weighed and added to the mixed solution containing amino polyacrylate macro RAFT reagent P (DMAEA-co-St) prepared in step 1, and then 2.56g (0.02mol) of butyl acrylate monomer (BA) and 4.0X 10 AIBN were added-4And (3) mol, vacuumizing, introducing argon, carrying out oil bath reaction at 70 ℃ for 300min, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. After the conversion rate reaches 80%, the reaction is finished, petroleum ether is obtained and precipitated to obtain an amphiphilic block copolymer P (DMAEA-co-St) -b-PBA, the designed molecular weight is 12800, the molecular weight is 11000 measured by GPC, and the molecular weight distribution is 1.34.
And 3, taking the amino-containing polyacrylate segmented copolymer P (DMAEA-co-St) -b-PBA with the actual molecular weight of 11000g/mol and the molecular weight distribution of 1.34 prepared in the step 2 as an amphiphilic macromolecular RAFT reagent, and polymerizing the styrene RAFT soap-free emulsion.
Firstly, 0.08g of acetic acid, 19.10g of deionized water and magnetons are added into a 100mL three-neck flask, and then 1.14g (1.04 x 10) of the amphiphilic macromolecular RAFT reagent is added-4mol) and stirring until complete dissolution. Then 1.04g (0.01mol) of styrene and 0.01g (4.0X 10 mol) of initiator (AIBA) were added-5mol), stirring at room temperature, vacuumizing, introducing argon, carrying out oil bath reaction at 70 ℃ for 30min, sampling at intervals, and measuring the conversion rate by using a gas chromatograph. The conversion rate reaches more than 90 percent, the reaction is stopped to obtain the polystyrene emulsion with the designed molecular weight of 201000g/mol and the GPC measurementThe average molecular weight is 17900g/mol, PDI is 3.00, and controllability is poor.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability is characterized in that: the method comprises the following steps: firstly, adding a fluorine-containing amphiphilic macromolecular RAFT reagent, acid and water into a four-neck flask, stirring for dissolving, then adding a vinyl monomer II and an initiator, stirring at room temperature, vacuumizing and introducing argon, reacting at the initiation temperature, sampling at intervals, measuring the conversion rate, and stopping the reaction when the conversion rate reaches over 90 percent to prepare the vinyl monomer RAFT cation soap-free emulsion;
the fluorine-containing amphiphilic macromolecule RAFT reagent is an amino-containing polyacrylate fluorine-containing block copolymer, and the structural formula of the fluorine-containing amphiphilic macromolecule RAFT reagent is as follows:
Figure DEST_PATH_IMAGE002AA
wherein M1 is a fluorine-containing acrylate structural unit, and x = 2-100;
m2 is an amino-containing acrylate structural unit, and y = 2-100;
m3 is a structural unit of a vinyl monomer, and z = 0-100;
the fluorine-containing amphiphilic macromolecular RAFT reagent is prepared by the following steps:
step 1, adding the amino acrylate-containing monomer, the vinyl monomer I, a solvent, an initiator and an RAFT reagent S-n-dodecyl-S' - (2-isobutyric acid group) trithiocarbonate into a three-neck flask, uniformly mixing, vacuumizing a system, introducing argon, circulating for 3 times, reacting at a certain initiation temperature, sampling at intervals to determine the conversion rate, and stopping the reaction when the conversion rate reaches more than 80% to obtain the amino polyacrylate macromolecule RAFT reagent;
and 2, adding the fluorine-containing acrylate monomer, a solvent and an initiator into the amino-containing polyacrylate macromolecular RAFT reagent prepared in the step 1, uniformly mixing, vacuumizing a system, introducing argon, circulating for 3 times, reacting at an initiation temperature, sampling at intervals, determining the conversion rate, and finishing the reaction after the conversion rate is more than 80% to prepare the fluorine-containing amphiphilic macromolecular RAFT reagent.
2. The well controllable vinyl monomer RAFT cationic soap-free emulsion polymerization process of claim 1, wherein: the fluorine-containing acrylate monomer is one or a mixture of two or more of trifluoroethyl methacrylate, trifluoroethyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl methacrylate;
the amino acrylate monomer is any one or a mixture of two or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate and N-hydroxymethyl acrylamide;
the vinyl monomer I is any one or a mixture of more than two of methyl methacrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, isooctyl acrylate, ethyl methacrylate, isobutyl methacrylate and styrene.
3. The well controllable vinyl monomer RAFT cationic soap-free emulsion polymerization process of claim 1, wherein: the solvent in the step 1 and the step 2 is any one or more of ethanol, propylene glycol monomethyl ether, propylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol methyl ether, propylene glycol monobutyl ether, propylene glycol butyl ether, ethylene glycol monobutyl ether, ethylene glycol butyl ether and tetrahydrofuran; the initiator in the step 1 and the step 2 is azobisisobutyronitrile or azobisisoheptonitrile.
4. The well controllable vinyl monomer RAFT cationic soap-free emulsion polymerization process of claim 1, wherein:
in the step 1, the mol ratio of the amino acrylate monomer to the vinyl monomer I is 20: 1-1: 10, and the amount of the initiator is 10-0.1% of the total weight of the amino acrylate monomer and the vinyl monomer I; the dosage of the RAFT reagent is 10-0.01 percent of the total molar weight of the amino-containing acrylate monomer and the vinyl monomer I; the dosage of the solvent is 0.1-10 times of the total weight of the amino-containing acrylate monomer and the vinyl monomer I;
and/or the molar ratio of the fluorine-containing acrylate monomer in the step 2 to the amino-containing polyacrylate macromolecule RAFT reagent prepared in the step 1 is 10: 1-1000: 1, and the using amount of the solvent is 10-80% of the total weight of the fluorine-containing acrylate monomer and the amino-containing polyacrylate macromolecule RAFT reagent prepared in the step 1; the dosage of the initiator is 10 to 0.1 percent of the weight of the fluorine-containing acrylate monomer.
5. The well controllable vinyl monomer RAFT cationic soap-free emulsion polymerization process of claim 1, wherein: the acid is one or more of acetic acid, hydrochloric acid, phosphoric acid and p-toluenesulfonic acid; the vinyl monomer II is one or more of styrene, butyl acrylate, ethyl acrylate, methyl acrylate, isooctyl acrylate, methyl methacrylate, butyl methacrylate and vinyl acetate; the initiator is 2, 2-azobis (2-methylpropionamidine) dihydrochloride.
6. The well controllable vinyl monomer RAFT cationic soap-free emulsion polymerization process of claim 1, wherein: the molar ratio of the vinyl monomer II to the fluorine-containing amphiphilic macromolecular RAFT reagent is 10: 1-1000: 1, the molar ratio of the acid to the amino group in the fluorine-containing amphiphilic macromolecular RAFT reagent is 0.1: 1-50: 1, the dosage of the initiator is 10-0.1% of the weight of the vinyl monomer II, the dosage of the water is 0.5-10 times of the total weight of the vinyl monomer II and the fluorine-containing amphiphilic macromolecular RAFT reagent, the reaction temperature is room temperature-80 ℃, and the reaction time is 0.5-8 hours.
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