CN103232567B - A kind of method preparing fluorinated acrylate or acrylate copolymer - Google Patents
A kind of method preparing fluorinated acrylate or acrylate copolymer Download PDFInfo
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Abstract
The present invention relates to a kind of method preparing fluorinated acrylate or acrylate copolymer, its concrete steps are as follows: in the reactor filling solvent, successively add fluoro-acrylate monomer or acrylic monomer, vinyl monomer dissolves, add linking agent and initiator subsequently, stirred solution, thus obtain uniform monomer solution; Open the switch of laser reactive device, regulate electric current and cause Distance geometry and cause the time, excite monomer polymerization; Powered-down, utilizing liberated heat in polyreaction to make front end continue to advance, is polymkeric substance unreacted complete monomer conversion; Again polymkeric substance is carried out drying, obtain fluorinated acrylate or acrylate copolymer.More simple in preparation technology of the present invention, the reaction times shortens greatly; Adopt the method for induced with laser, realize the reaction of remote induced polymerization.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of intelligent macromolecule material technical field, more specifically to a kind of method adopting induced with laser to prepare fluorinated acrylate or acrylate copolymer fast.
Background technology
Fluoropolymer has the excellent over-all properties such as good unreactiveness, surface property and optical property, extremely strong high and low temperature resistance, abnormal oilness, excellent electrical insulating property, ageing resistance, radioresistance and minimum water-absorbent, is widely used in the numerous areas such as Aeronautics and Astronautics, military project, petrochemical industry and building materials.In acrylic monomer polymerization process, a certain amount of fluoro-acrylate monomer of copolymerization, significantly can reduce surface energy polymer, it is better than polyacrylic ester that it refuses oily effect, and this is lower than methacrylic acid fluorinated ester relevant with the fluorine ester contained critical surface tension of vinylformic acid; In fluorinated copolymer, introducing suitable second comonomer is the important means regulating finishing composition performance, reduce costs.
Acrylic acid esters co-polymer passes through polymerization or the acrylic ester grafted high molecular polymer formed to polymer molecule by acrylate or methacrylic ester with other vinyl monomers.Product has that excellent thermostability and optical stability, resistance of oxidation are strong, weathering resistance, not easily oxidized, for this reason, enjoy the concern of Chinese scholars.Research shows, functional monomer is introduced: Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, acrylamide, N hydroxymethyl acrylamide, NIPA, N-caprolactam, vinyl pyrrolidone, urethane, tetrafluoroethylene etc. in polymeric chain, under repolymerization condition, original linear macromolecule is made to generate cross-linked network, improve the cohesive strength of multipolymer on the one hand, the introducing of functional group enhances the performance of polymkeric substance on the other hand.
Frontal Polymerization is a kind of rapid polymerization means that a kind of chemical energy utilizing chemical reaction self to release is polymkeric substance conversion of monomer.And Frontal Polymerization has been used to prepare optical material, packing material, interpenetrating(polymer)networks, intelligent dyestuff etc.But large-scale industrialization still has many problems not yet to solve at present.The preparation process of Laboratory Function material is all generally carry out in beaker or test tube, and using electric iron as heating installation, whole process is long for heat-up time, operates more complicated.
Summary of the invention
The technical problem to be solved in the present invention overcomes the reaction of traditional tank polymerization to prepare fluorinated acrylate and acrylate copolymer materials cost is high, complex process, long reaction time, have the shortcomings such as waste discharge, thus provide a kind of a kind of method preparing fluorinated acrylate or acrylate copolymer of more cost-saving, affected simple induced with laser Frontal Polymerization.For industry, prepare functional materials on a large scale opens new way to the polymerization process of long distance laser induction fast.
Technical scheme of the present invention is: a kind of method preparing fluorinated acrylate or acrylate copolymer, it is characterized in that adopting laser reactive device induction initiated polymerization to complete; Its concrete steps are as follows:
A ﹑, in the reactor filling solvent, successively adds fluoro-acrylate monomer or acrylic monomer, vinyl monomer dissolves to obtain uniform mixture, add linking agent and initiator subsequently, stirred solution, thus obtain uniform monomer solution;
B, mix after, open the switch of laser reactive device, regulate electric current and cause Distance geometry cause the time, excite monomer polymerization; Close the power supply of laser reactive device, utilizing liberated heat in polyreaction to make front end continue to advance, is polymkeric substance unreacted complete monomer conversion;
The polymkeric substance of C, taking-up step B gained carries out drying, finally obtains fluorinated acrylate or acrylate copolymer.
The add-on of the solvent described in preferred steps A, fluoro-acrylate monomer or acrylic monomer, vinyl monomer, linking agent and initiator accounts for 20% ~ 40%, 10% ~ 40%, 20% ~ 45%, 0.8% ~ 2% and 0.8% ~ 2% of monomer solution total mass respectively.
Preferably described laser reactive device is the one in infrared solid laser reactive device, carbon dioxide laser reactor or Ultra-Violet Laser reactor.The working current of preferred laser reactive device is 4 ~ 50mA; Laser initiation distance is 1.5 ~ 20m; The laser initiation time is 10 ~ 100 seconds.
Preferably described fluoro-acrylate monomer is the one in perfluoroethyl butyl ester, methacrylic acid fluorine alkane esters, Perfluoroalkyl acrylate, perfluoroalkylethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or trifluoromethyl acrylate; Described acrylic monomer is the one in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, tert-butyl acrylate or butyl methacrylate.
Preferably with the one that the vinyl monomer of fluoro-acrylate monomer copolymerization is in Propylene glycol monoacrylate, Hydroxyethyl acrylate, methyl methacrylate, zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, NIPA, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or tetrafluoroethylene; Be one or more in zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, NIPA, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or tetrafluoroethylene with the vinyl monomer of acrylic monomer copolymerization.
Preferably described solvent is the one in glycerine, toluene, methyl-sulphoxide, 1-Methyl-2-Pyrrolidone or DMF.Preferably described initiator is the one in benzoyl peroxide, tertbutyl peroxide, hydrogen peroxide, ammonium persulphate, Potassium Persulphate, 1-hydroxy cyclohexyl phenylketone (184) or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907); Described linking agent is the one in methylene-bisacrylamide (MBAA), Vinylstyrene or TEGDMA.
Preferably described reactor is cylindrical reactor; Reactor diameter is between 15 ~ 100mm, and height is between 150 ~ 1000mm.
Reaction process as shown in Figure 1.Pour in reactor after fluorinated acrylate or acrylic monomer, vinyl monomer, initiator, linking agent and solvent mix according to above-mentioned weight percent, open the switch of laser apparatus, regulate electric current (4 ~ 50mA) and cause distance (1.5 ~ 20m), exciting monomer polymerization.The initiation time of laser is about 10 ~ 100 seconds, closes the power supply of laser apparatus, and utilizing liberated heat in polyreaction to make front end continue to advance, is polymkeric substance unreacted complete monomer conversion.
Beneficial effect:
1. the method for induced with laser Frontal Polymerization is compared traditional polymerization process, and more simple in preparation technology, the required reaction times shortens greatly, and traditional polymerization needs 2 ~ 6 hours, as long as and the present invention 1 ~ 3 minute, be a kind of reaction pattern efficiently.
2. the present invention adopts the method for induced with laser, and laser apparatus can realize the reaction of remote induced polymerization, by regulating the scale of the area control reaction volume of radioreaction thing, for the industrialization of Frontal Polymerization has strided forward again solid step forward.
Accompanying drawing explanation
Fig. 1 is that the synthesis of laser polymerization method is containing fluorinated acrylate and acrylate copolymer polymerization process schematic diagram; Wherein A is monomer mixture, and B is polymkeric substance, is 1. laser initiation, 2. closes light source, 3. propagation direction, front end, is 4. front end surface, and be 5. laser apparatus, 6. laser beam, 7. silicon is anti-.
Embodiment
Below by way of specific embodiment, the present invention is described, but the present invention is not merely now due to these embodiments.
Embodiment 1
6g methacrylic acid fluorine alkane esters 18g Propylene glycol monoacrylate is dissolved in the DMF of 15.2g and is made into homogeneous solution, and the methylene-bisacrylamide then adding 0.4g accounts for the benzoyl peroxide with 0.4g, finally adds after stirring.Mixing rear immigration diameter is 25mm, in the cylindrical reactor of high 200mm; And initiation distance is set in 3m place, opens ultraviolet laser switch, regulate laser current to 6mA, trigger monomer is polymerized, and the initiation time of laser is 10 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, by polymkeric substance infrared analysis, and 1200cm
-1place is the infrared signature peak of C-F, 3458cm
-1place is the infrared signature peak of O-H, illustrates that the polymkeric substance obtained is poly-(methacrylic acid fluorine alkane esters-Propylene glycol monoacrylate) multipolymer.
Embodiment 2
8g Perfluoroalkyl acrylate and Propylene glycol monoacrylate 16g are dissolved in the toluene of 15g and are made into homogeneous solution, then add the methylene-bisacrylamide of 0.4g and the benzoyl peroxide of 0.6g, finally add after stirring.Mixing rear immigration diameter is 25mm, in the cylindrical reactor of high 200mm; And initiation distance is set in 5m place, opens infrared solid laser switch, regulate laser current to 8mA, trigger monomer is polymerized, and the initiation time of laser is 10 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, by polymkeric substance infrared analysis, and 1180cm
-1place is the infrared signature peak of C-F, 3444cm
-1place is the infrared signature peak of O-H, illustrates that the polymkeric substance obtained is poly-(Perfluoroalkyl acrylate-Propylene glycol monoacrylate) multipolymer.
Embodiment 3
19.2g vinylformic acid hexafluoro butyl ester and vinyl imidazole 28.8g.Be dissolved in the DMF of 30g and be made into homogeneous solution, then add the TEGDMA of 1.2g and the ammonium persulphate of 0.8g, stir.Mixing rear immigration diameter is 50mm, in the cylindrical reactor of high 200mm; And initiation distance is set in 5m place, opens infrared solid laser switch, regulate laser current to 20mA, trigger monomer is polymerized, and the initiation time of laser is 20 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, by polymkeric substance infrared analysis, and 1185cm
-1place is the infrared signature peak of C-F, 1105cm
-1and 1650cm
-1be respectively the stretching vibration peak of imidazole ring and imidazole ring C=N, illustrate that the polymkeric substance obtained is poly-(vinylformic acid hexafluoro butyl ester-vinyl imidazole) multipolymer.
Embodiment 4
The N hydroxymethyl acrylamide of 72g Hexafluorobutyl mathacrylate and 72g is dissolved in the 1-Methyl-2-Pyrrolidone of 88.5g and is made into homogeneous solution, then adds the methylene-bisacrylamide of 3.75g and the benzoyl peroxide of 3.75g, stirs.Mixing rear immigration diameter is 50mm, in the cylindrical reactor of high 600mm; And initiation distance is set in 10m place, opens carbon dioxide laser switch, regulate laser current to 15mA, regulate bright dipping spot size, just in time radiation is at reaction-ure surface to make hot spot, and trigger monomer is polymerized, and the initiation time of laser is 45 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, by polymkeric substance infrared analysis, and 1165cm
-1place is the infrared signature peak of C-F, 3456cm
-1place is the infrared signature peak of O-H, illustrates that the polymkeric substance obtained is poly-(Hexafluorobutyl mathacrylate-N hydroxymethyl acrylamide) multipolymer.
Embodiment 5
100g methacrylic acid fluorine alkane esters and Hydroxyethyl acrylate 100g are dissolved in the DMF of 43.75g and are made into homogeneous solution, then add the methylene-bisacrylamide of 3.75g and the ammonium persulphate of 2.5g, stir.Mixing rear immigration diameter is 60mm, in the cylindrical reactor of high 500mm; And initiation distance is set in 15m place, opens carbon dioxide laser switch, regulate laser current to 30mA, trigger monomer is polymerized, and the initiation time of laser is 80 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, by polymkeric substance infrared analysis, and 1195cm
-1place is the infrared signature peak of C-F, 3450cm
-1place is the infrared signature peak of O-H, illustrates that the polymkeric substance obtained is poly-(methacrylic acid fluorine alkane esters-Hydroxyethyl acrylate) multipolymer.
Embodiment 6
75g methyl methacrylate and NIPA 75g are dissolved in the methyl-sulphoxide of 83.75g and are made into homogeneous solution, then add the TEGDMA of 2.5g and the Potassium Persulphate of 3.75g, stir.Mixing rear immigration diameter is 100mm, in the cylindrical reactor of high 300mm; And initiation distance is set in 15m place, opens carbon dioxide laser switch, regulate laser current to 40mA, trigger monomer is polymerized, and the initiation time of laser is 80 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, and by polymkeric substance thermogravimetric analysis, the relation of material mass and temperature can illustrate that the polymkeric substance obtained is poly-(methyl methacrylate-NIPA) multipolymer.
Embodiment 7
60g methacrylic acid and zinc acrylate resin 120g are dissolved in the methyl-sulphoxide of 108g and are made into homogeneous solution, then add the methylene-bisacrylamide of 6g and the 1-hydroxy cyclohexyl phenylketone of 6g, stir.Mixing rear immigration diameter is 50mm, in the cylindrical reactor of high 900mm; And initiation distance is set in 18m place, opens carbon dioxide laser switch, regulate laser current to 45mA, trigger monomer is polymerized, and the initiation time of laser is 100 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because reacting continuous heat release, continues initiated polymerization, until be polymkeric substance unreacted complete monomer conversion.Semi-manufactured polymer, obtains polymeric articles after drying, and by polymkeric substance thermogravimetric analysis, the relation of material mass and temperature can illustrate that the polymkeric substance obtained is poly-(methacrylic acid-acrylic acid zinc) multipolymer.
Claims (5)
1. prepare a method for fluoro-acrylate copolymer, its concrete steps are as follows:
A ﹑, in the reactor filling solvent, successively adds fluoro-acrylate monomer, vinyl monomer dissolves to obtain uniform mixture, add linking agent and initiator subsequently, stirred solution, thus obtain uniform monomer solution; Wherein said fluoro-acrylate monomer is the one in perfluoroethyl butyl ester, Perfluoroalkyl acrylate, perfluoroalkylethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate or dodecafluoroheptyl methacrylate; Described vinyl monomer is the one in Propylene glycol monoacrylate, Hydroxyethyl acrylate, methyl methacrylate, zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, NIPA, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or tetrafluoroethylene; Initiator is the one in benzoyl peroxide, tertbutyl peroxide, hydrogen peroxide, ammonium persulphate, Potassium Persulphate, 1-hydroxy cyclohexyl phenylketone or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone; Described linking agent is the one in methylene-bisacrylamide, Vinylstyrene or TEGDMA;
B, mix after, open the switch of laser reactive device, regulate electric current and cause Distance geometry cause the time, excite monomer polymerization; Close the power supply of laser reactive device, utilizing liberated heat in polyreaction to make front end continue to advance, is polymkeric substance unreacted complete monomer conversion; Wherein the working current of laser reactive device is 4 ~ 50mA; Laser initiation distance is 1.5 ~ 20m; The laser initiation time is 10 ~ 100 seconds;
The polymkeric substance of C, taking-up step B gained carries out drying, finally obtains fluoro-acrylate copolymer.
2. method according to claim 1, is characterized in that the add-on of the solvent described in steps A, fluoro-acrylate monomer, vinyl monomer, linking agent and initiator accounts for 20% ~ 40%, 15% ~ 40%, 20% ~ 45%, 0.8% ~ 2% and 0.8% ~ 2% of monomer solution total mass respectively.
3. method according to claim 1, is characterized in that described laser reactive device is the one in infrared solid laser reactive device, carbon dioxide laser reactor or Ultra-Violet Laser reactor.
4. method according to claim 1, is characterized in that: described solvent is the one in glycerine, toluene, methyl-sulphoxide, 1-Methyl-2-Pyrrolidone or DMF.
5. method according to claim 1, is characterized in that: described reactor diameter is between 15 ~ 100mm, and height is between 150 ~ 1000mm.
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| CN104629064B (en) * | 2015-01-27 | 2017-06-09 | 南京工业大学 | A kind of method that continuous Frontal Polymerization of use induced with laser water-oil phase quickly prepares double-deck hydrogel |
| CN105218733A (en) * | 2015-11-03 | 2016-01-06 | 宋介珍 | A kind of preparation method of high-strength polytetrafluoroethyl-ne sheet material of outdoor use |
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| JPWO2019235108A1 (en) * | 2018-06-06 | 2021-04-22 | 富士フイルム株式会社 | Modifiers, compositions, hard coat films, articles with hard coat films, and image display devices |
| CN108840628A (en) * | 2018-07-27 | 2018-11-20 | 余文冰 | A kind of sound-absorbing concrete and preparation method thereof |
| CN109553715B (en) * | 2018-10-30 | 2020-11-13 | 三明学院 | Fluorine-containing acrylate random copolymer, preparation method and application thereof |
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