CN103232567A - Method for preparing fluorinated acrylate or acrylate copolymer - Google Patents
Method for preparing fluorinated acrylate or acrylate copolymer Download PDFInfo
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- CN103232567A CN103232567A CN2013101397038A CN201310139703A CN103232567A CN 103232567 A CN103232567 A CN 103232567A CN 2013101397038 A CN2013101397038 A CN 2013101397038A CN 201310139703 A CN201310139703 A CN 201310139703A CN 103232567 A CN103232567 A CN 103232567A
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- polymerization
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 229920001577 copolymer Polymers 0.000 title claims abstract description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000000977 initiatory effect Effects 0.000 claims abstract description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- -1 methacrylic acid fluorine alkane esters Chemical class 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- ZESXUEKAXSBANL-UHFFFAOYSA-N trifluoromethyl prop-2-enoate Chemical compound FC(F)(F)OC(=O)C=C ZESXUEKAXSBANL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 8
- 239000012456 homogeneous solution Substances 0.000 description 7
- 230000002045 lasting effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for preparing a fluorinated acrylate or acrylate copolymer. The method comprises the following specific steps: sequentially adding fluorinated acrylic acid monomers or acrylic acid type monomers and vinyl monomers into a reactor containing a solvent for dissolution, then adding a cross-linking agent and an initiator, and stirring a solution to get a uniform monomer solution; turning on a switch of a laser reactor, and regulating current, initiation distance and initiation time to initiate the polymerization of the monomers; and turning off a power supply, utilizing heat released from polymerization reaction to continuously propel the front end and completely convert the unreacted monomers to a polymer; and further drying the polymer to get the fluorinated acrylate or acrylate copolymer. The preparation process disclosed by the invention is simpler, and the reaction time is greatly shortened; and a laser induction method is adopted for realizing long-distance induction of polymerization reaction.
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 that adopts induced with laser to prepare fluorinated acrylate or acrylate copolymer fast.
Background technology
Fluoropolymer has good unreactiveness, surface property and optical property, extremely strong high and low temperature resistance, unusual oilness, excellent electrical insulating property, ageing resistance, radioresistance and minimum excellent comprehensive performances such as water-absorbent, is widely used in numerous areas such as Aeronautics and Astronautics, military project, petrochemical industry and building materials.In the acrylic monomer polymerization process, a certain amount of fluoro-acrylate monomer of copolymerization, can significantly reduce surface energy polymer, it is better than polyacrylic ester that it refuses oily effect, and this is low more relevant than methacrylic acid fluorinated ester with the fluorine ester contained critical surface tension of vinylformic acid; In fluorinated copolymer, introducing the second suitable monomer is the important means of regulating the finishing composition performance, reducing cost.
Acrylic acid esters co-polymer is by polymerization or the acrylic ester grafted high molecular polymer that forms to the polymer molecule by acrylate or methacrylic ester and other vinyl monomers.Product has that good thermostability and optical stability, resistance of oxidation are strong, weathering resistance, be difficult for oxidizedly, for this reason, enjoys the concern of Chinese scholars.Studies show that, introduce functional monomer in the polymeric chain: Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, acrylamide, N hydroxymethyl acrylamide, N-N-isopropylacrylamide, N-caprolactam, vinyl pyrrolidone, urethane, tetrafluoroethylene etc., under the repolymerization condition, make original linear macromolecule generate cross-linked network, improved the cohesive strength of multipolymer on the one hand, the introducing of functional group has strengthened polymer properties on the other hand.
The front end polymerization is a kind ofly to utilize chemical energy that chemical reaction self emits a kind of rapid polymerization means of conversion of monomer for polymkeric substance.And the front end polymerization has been used to prepare optical material, packing material, interpenetrating(polymer)networks, intelligent dyestuff etc.But large-scale industrialization still has many problems still unresolved at present.The preparation process of Laboratory Function material generally all is to carry out in beaker or test tube, and with electric iron as heating installation, whole process is long heat-up time, operation is complicated.
Summary of the invention
The technical problem to be solved in the present invention is to overcome traditional still formula polyreaction to prepare fluorinated acrylate and acrylate copolymer material cost height, complex process, long reaction time, shortcomings such as waste discharge are arranged, thereby a kind of a kind of method for preparing fluorinated acrylate or acrylate copolymer of saving cost, the polymerization of affected simple induced with laser front end more is provided.The polymerization process that long distance laser is induced is that industrial rapid large-scale prepares functional materials and opened up new way.
Technical scheme of the present invention is: a kind of method for preparing fluorinated acrylate or acrylate copolymer is characterized in that adopting the laser reactive device to induce initiated polymerization to finish; Its concrete steps are as follows:
A ﹑ successively adds fluoro-acrylate monomer or acrylic monomer, vinyl monomer dissolves to obtain uniform mixture, adds linking agent and initiator subsequently in filling the reactor of solvent, stirred solution, thus obtain uniform monomer solution;
B, mix after, open the switch of laser reactive device, regulate electric current and cause distance and initiation time, excite monomer polymerization; Close the power supply of laser reactive device, utilize in the polyreaction liberated heat to make front end continue to advance, unreacted monomer all is converted into polymkeric substance;
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 the 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.
Preferred described laser reactive device is a kind of in infrared solid laser reactive device, carbon dioxide laser reactor or the Ultra-Violet Laser reactor.The working current of preferred laser reactive device is 4～50mA; It is 1.5～20m that laser causes distance; The laser initiation time is 10～100 seconds.
Preferred described fluoro-acrylate monomer is a kind of in vinylformic acid perfluor butyl ester, methacrylic acid fluorine alkane esters, vinylformic acid perfluoro alkyl ethyl, methacrylic acid perfluor alkyl ethide ester, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, methacrylic acid ten difluoro heptyl esters or the trifluoromethyl acrylate; Described acrylic monomer is a kind of in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, tert-butyl acrylate or the butyl methacrylate.
Be a kind of in Propylene glycol monoacrylate, Hydroxyethyl acrylate, methyl methacrylate, zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, N-N-isopropylacrylamide, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or the tetrafluoroethylene with the vinyl monomer of fluoro-acrylate monomer copolymerization preferably; With the vinyl monomer of acrylic monomer copolymerization be in zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, N-N-isopropylacrylamide, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or the tetrafluoroethylene one or more.
Preferred described solvent is glycerine, toluene, methyl-sulphoxide, 1-Methyl-2-Pyrrolidone or N, a kind of in the dinethylformamide.Preferred described initiator is a kind of 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 a kind of in methylene-bisacrylamide (MBAA), Vinylstyrene or the triethylene glycol dimethacrylate.
Preferred described reactor is cylindrical reactor; Reactor diameter is between 15～100mm, and height is between 150～1000mm.
Reaction process as shown in Figure 1.Fluorinated acrylate or acrylic monomer, vinyl monomer, initiator, linking agent and solvent are poured in the reactor after mixing according to above-mentioned weight percent, open the switch of laser apparatus, regulate electric current (4～50mA) and cause distance (1.5～20m), excite monomer polymerization.The initiation time of laser is about 10～100 seconds, closes the power supply of laser apparatus, utilizes in the polyreaction liberated heat to make front end continue to advance, and unreacted monomer all is converted into polymkeric substance.
Beneficial effect:
1. the method for induced with laser front end polymerization traditional polymerization process of comparing, simpler on preparation technology, the required reaction times shortens greatly, and traditional polymerization needs 2～6 hours, and as long as the present invention was a kind of reaction pattern efficiently 1～3 minute.
2. the present invention adopts the method for induced with laser, and laser apparatus can be realized the reaction of remote induced polymerization, and the scale of the area control reaction volume by regulating the radioreaction thing is for the industrialization of front end polymerization has strided forward solid step forward again.
Description of drawings
Fig. 1 contains fluorinated acrylate and acrylate copolymer polymerization process synoptic diagram for the laser polymerization process is synthetic; Wherein A is monomer mixture, and B is polymkeric substance, 1. causes for laser, 2. closes light source, and 3. 4. the front end propagation direction is the front end end face, 5. is laser apparatus, 6. laser beam, and 7. silicon is anti-.
Embodiment
Below by specific embodiment explanation the present invention, but the present invention is not merely now due to these embodiment.
Embodiment 1
6g methacrylic acid fluorine alkane esters 18g Propylene glycol monoacrylate is dissolved in the N of 15.2g, is made into homogeneous solution in the dinethylformamide, and the methylene-bisacrylamide that adds 0.4g then accounts for the benzoyl peroxide with 0.4g, and the back that stirs is last to add.Mixing back immigration diameter is 25mm, in the cylindrical reactor of high 200mm; And be set in the 3m place causing distance, open the ultraviolet laser switch, regulate laser current to 6mA, the trigger monomer polymerization, the initiation time of laser is 10 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to polymkeric substance infrared analysis, 1200cm
-1The place is the infrared signature peak of C-F, 3458cm
-1The place is the infrared signature peak of O-H, illustrates that the polymkeric substance that obtains is poly-(methacrylic acid fluorine alkane esters-Propylene glycol monoacrylate) multipolymer.
Embodiment 2
8g vinylformic acid perfluoro alkyl ethyl and Propylene glycol monoacrylate 16g are dissolved in the toluene of 15g and are made into homogeneous solution, add the methylene-bisacrylamide of 0.4g and the benzoyl peroxide of 0.6g then, and the back that stirs is last to add.Mixing back immigration diameter is 25mm, in the cylindrical reactor of high 200mm; And be set in the 5m place causing distance, open infrared solid laser apparatus switch, regulate laser current to 8mA, the trigger monomer polymerization, the initiation time of laser is 10 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to polymkeric substance infrared analysis, 1180cm
-1The place is the infrared signature peak of C-F, 3444cm
-1The place is the infrared signature peak of O-H, illustrates that the polymkeric substance that obtains is poly-(vinylformic acid perfluoro alkyl ethyl-Propylene glycol monoacrylate) multipolymer.
Embodiment 3
19.2g vinylformic acid hexafluoro butyl ester and vinyl imidazole 28.8g.Be dissolved in the N of 30g, be made into homogeneous solution in the dinethylformamide, add the triethylene glycol dimethacrylate of 1.2g and the ammonium persulphate of 0.8g then, stir.Mixing back immigration diameter is 50mm, in the cylindrical reactor of high 200mm; And be set in the 5m place causing distance, open infrared solid laser apparatus switch, regulate laser current to 20mA, the trigger monomer polymerization, the initiation time of laser is 20 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to polymkeric substance infrared analysis, 1185cm
-1The place 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 that obtains is poly-(vinylformic acid hexafluoro butyl ester-vinyl imidazole) multipolymer.
Embodiment 4
The N hydroxymethyl acrylamide of 72g methacrylic acid hexafluoro butyl ester and 72g is dissolved in the 1-Methyl-2-Pyrrolidone of 88.5g and is made into homogeneous solution, adds the methylene-bisacrylamide of 3.75g and the benzoyl peroxide of 3.75g then, stirs.Mixing back immigration diameter is 50mm, in the cylindrical reactor of high 600mm; And be set in 10m place causing distance, open the carbon dioxide laser switch, regulate laser current to 15mA, adjusting bright dipping spot size, make hot spot just in time radiation at reaction-ure surface, the trigger monomer polymerization, the initiation time of laser is 45 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to polymkeric substance infrared analysis, 1165cm
-1The place is the infrared signature peak of C-F, 3456cm
-1The place is the infrared signature peak of O-H, illustrates that the polymkeric substance that obtains is poly-(methacrylic acid hexafluoro butyl ester-N hydroxymethyl acrylamide) multipolymer.
Embodiment 5
100g methacrylic acid fluorine alkane esters and Hydroxyethyl acrylate 100g are dissolved in the N of 43.75g, are made into homogeneous solution in the dinethylformamide, add the methylene-bisacrylamide of 3.75g and the ammonium persulphate of 2.5g then, stir.Mixing back immigration diameter is 60mm, in the cylindrical reactor of high 500mm; And be set in the 15m place causing distance, open the carbon dioxide laser switch, regulate laser current to 30mA, the trigger monomer polymerization, the initiation time of laser is 80 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to polymkeric substance infrared analysis, 1195cm
-1The place is the infrared signature peak of C-F, 3450cm
-1The place is the infrared signature peak of O-H, illustrates that the polymkeric substance that obtains is poly-(methacrylic acid fluorine alkane esters-Hydroxyethyl acrylate) multipolymer.
Embodiment 6
75g methyl methacrylate and N-N-isopropylacrylamide 75g are dissolved in the methyl-sulphoxide of 83.75g and are made into homogeneous solution, add the triethylene glycol dimethacrylate of 2.5g and the Potassium Persulphate of 3.75g then, stir.Mixing back immigration diameter is 100mm, in the cylindrical reactor of high 300mm; And be set in the 15m place causing distance, open the carbon dioxide laser switch, regulate laser current to 40mA, the trigger monomer polymerization, the initiation time of laser is 80 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to the polymkeric substance thermogravimetric analysis, the relation of material mass and temperature can illustrate that the polymkeric substance that obtains is poly-(methyl methacrylate-N-N-isopropylacrylamide) 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, add the methylene-bisacrylamide of 6g and the 1-hydroxy cyclohexyl phenylketone of 6g then, stir.Mixing back immigration diameter is 50mm, in the cylindrical reactor of high 900mm; And be set in the 18m place causing distance, open the carbon dioxide laser switch, regulate laser current to 45mA, the trigger monomer polymerization, the initiation time of laser is 100 seconds.Electric current is transferred to 0mA, closes laser switch, end face meeting lasting propelling because react continuous heat release continues initiated polymerization, till unreacted monomer all is converted into polymkeric substance.The work in-process polymkeric substance obtains polymeric articles after the drying, by to the polymkeric substance thermogravimetric analysis, the relation of material mass and temperature can illustrate that the polymkeric substance that obtains is poly-(methacrylic acid-zinc acrylate resin) multipolymer.
Claims (9)
1. a method for preparing fluorinated acrylate or acrylate copolymer is characterized in that adopting the laser reactive device to induce initiated polymerization to finish.
2. method for preparing fluorinated acrylate or acrylate copolymer, its concrete steps are as follows:
A ﹑ successively adds fluoro-acrylate monomer or acrylic monomer, vinyl monomer dissolves to obtain uniform mixture, adds linking agent and initiator subsequently in filling the reactor of solvent, stirred solution, thus obtain uniform monomer solution;
B, mix after, open the switch of laser reactive device, regulate electric current and cause distance and initiation time, excite monomer polymerization; Close the power supply of laser reactive device, utilize in the polyreaction liberated heat to make front end continue to advance, unreacted monomer all is converted into polymkeric substance;
The polymkeric substance of C, taking-up step B gained carries out drying, finally obtains fluorinated acrylate or acrylate copolymer.
3. method according to claim 2 is characterized in that the add-on of the solvent described in the 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.
4. method according to claim 2 is characterized in that described laser reactive device is a kind of in infrared solid laser reactive device, carbon dioxide laser reactor or the Ultra-Violet Laser reactor.
5. method according to claim 2, the working current that it is characterized in that laser reactive device among the step B is 4～50mA; It is 1.5～20m that laser causes distance; The laser initiation time is 10～100 seconds.
6. method according to claim 2 is characterized in that: described fluoro-acrylate monomer is a kind of in vinylformic acid perfluor butyl ester, methacrylic acid fluorine alkane esters, vinylformic acid perfluoro alkyl ethyl, methacrylic acid perfluor alkyl ethide ester, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, methacrylic acid ten difluoro heptyl esters or the trifluoromethyl acrylate; Described acrylic monomer is a kind of in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, tert-butyl acrylate or the butyl methacrylate.
7. method according to claim 2 is characterized in that: with the vinyl monomer of fluoro-acrylate monomer copolymerization be a kind of in Propylene glycol monoacrylate, Hydroxyethyl acrylate, methyl methacrylate, zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, N-N-isopropylacrylamide, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or the tetrafluoroethylene; With the vinyl monomer of acrylic monomer copolymerization be in zinc acrylate resin, acrylamide, N hydroxymethyl acrylamide, N-N-isopropylacrylamide, N-caprolactam, vinyl pyrrolidone, vinyl imidazole or the tetrafluoroethylene one or more.
8. method according to claim 3, it is characterized in that: described solvent is glycerine, toluene, methyl-sulphoxide, 1-Methyl-2-Pyrrolidone or N, a kind of in the dinethylformamide.
9. method according to claim 3 is characterized in that: described initiator is a kind of 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 a kind of in methylene-bisacrylamide (MBAA), Vinylstyrene or the triethylene glycol dimethacrylate.10. method according to claim 3 is characterized in that: described reactor diameter is between 15～100mm, and height is between 150～1000mm.
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