CN115703857B - Polyacrylate/polyacrylamide polymer and polymerization process thereof - Google Patents
Polyacrylate/polyacrylamide polymer and polymerization process thereof Download PDFInfo
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- CN115703857B CN115703857B CN202110931892.7A CN202110931892A CN115703857B CN 115703857 B CN115703857 B CN 115703857B CN 202110931892 A CN202110931892 A CN 202110931892A CN 115703857 B CN115703857 B CN 115703857B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 94
- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 68
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- -1 acrylic ester Chemical class 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 238000009826 distribution Methods 0.000 claims abstract description 31
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 25
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 65
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical class CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims description 3
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 3
- DTIFFPXSSXFQCJ-UHFFFAOYSA-N tetrahexylazanium Chemical class CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC DTIFFPXSSXFQCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 17
- 150000003926 acrylamides Chemical class 0.000 abstract description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 36
- 239000004926 polymethyl methacrylate Substances 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- DWXAVNJYFLGAEF-UHFFFAOYSA-N furan-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CO1 DWXAVNJYFLGAEF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical compound C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 2
- RULHPTADXJPDSN-UHFFFAOYSA-M hydron;tetrahexylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC RULHPTADXJPDSN-UHFFFAOYSA-M 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VMRZYTKLQVKYKQ-UHFFFAOYSA-N lithium;1,9-dihydrofluoren-1-ide Chemical compound [Li+].C1=C[C-]=C2CC3=CC=CC=C3C2=C1 VMRZYTKLQVKYKQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 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 application relates to the field of high molecular polymerization, and in particular discloses a polyacrylate/polyacrylamide polymer and a polymerization process thereof. The polymerization process comprises the following steps: in an organic solvent, acrylic ester/acrylamide compounds are used as monomer raw materials, alkali metal alkoxide is used as an initiator, a regulator tetraalkylammonium salt is added, and the reaction is carried out for more than 5 minutes at the polymerization temperature of 0-60 ℃ to obtain the polyacrylate/polyacrylamide polymers. The molecular weight of the polyacrylate/polyacrylamide polymer obtained by the polymerization process is 5000-300000g/mol, the molecular weight distribution is narrow (1.6-3.4), the monomer conversion rate is up to 99%, the syndiotactic degree is more than 40%, the raw materials are cheap, and the reaction time is short, so that the low-cost and large-scale industrial production is realized.
Description
Technical Field
The application relates to the field of high molecular polymerization, in particular to a polyacrylate/polyacrylamide polymer and a polymerization process thereof.
Background
The traditional polyacrylate polymers and polyacrylamide polymers mainly adopt free radical polymerization, and the termination formula is double-radical disproportionation termination, so that the molecular weight and molecular weight distribution of a polymerization product are difficult to control. And the gel effect can be accompanied with the increase of the viscosity of the system in the polymerization process, so that the molecular weight distribution is more difficult to control. The free radical polymerization generally reduces the viscosity of a polymerization system by regulating and controlling the polymerization process in a low conversion rate regulation, a temperature program regulation or a feeding regulation and the like, thereby reducing the molecular weight distribution coefficient of the polymer. However, the degree of chain transfer in the free radical polymerization process is large, so that the molecular mass, distribution, structural regularity and the like of the produced product are difficult to control. At present, the free radical polymerization is difficult to meet the increasing demands of high-performance polyacrylate polymers and polyacrylamide polymers.
In order to better control the molecular weight distribution and the molecular structure regularity, anionic polymerization is generally adopted, and the anionic polymerization of the compound has the characteristics incomparable with other active polymerization methods: the monomers suitable for anionic polymerization are more and can be divided into four types of nonpolar monomers, polar monomers, cyclic monomers and functional monomers; secondly, the solvent has large choice and wide polymerization temperature range, and is a great characteristic of anionic polymerization; thirdly, the anionic polymerization activity seed core has good stability, high polymerization rate and simple polymerization system.
However, the anionic polymerization of the acrylic acid ester compound and the acrylamide compound is basically carried out at a low temperature. For example, most of anionic polymerization of Methyl Methacrylate (MMA) is carried out at a temperature of-78℃or lower, and the reaction temperature is severe. Although few experiments are carried out at 0 ℃, the experiments are not ideal, and the prepared polymethyl methacrylate (PMMA) has a molecular weight distribution as wide as 4.0, the monomer conversion rate is less than or equal to 50%, and the conversion rate is lower. Therefore, the synthesis of MMA by anionic polymerization is limited by the reaction temperature, which makes it difficult to realize low-cost and large-scale industrial production, as are the remaining acrylic acid ester compounds and acrylamide compounds. In order to make new materials better applicable to actual production and realize low-cost and large-scale industrial production, further improvement is urgently needed.
Disclosure of Invention
In order to synthesize the polyacrylate/polyacrylamide polymer by an anionic polymerization mode so as to realize low-cost and large-scale industrial production, the application provides the polyacrylate/polyacrylamide polymer and a polymerization process thereof.
In a first aspect, the application provides a polymerization process of polyacrylate/polyacrylamide polymer, which adopts the following technical scheme:
the polymerization process of polyacrylate/polyacrylamide polymer includes the steps of taking acrylate/acrylamide compound as monomer material, alkali metal alkoxide as initiator, adding regulator tetraalkylammonium salt, and reacting at polymerization temperature of 0-60 deg.c for over 5min to obtain crude polyacrylate/polyacrylamide polymer, wherein the concentration of the acrylate/acrylamide compound in the organic solvent is 0.3-16mol/L, and the molar ratio of the acrylate/acrylamide compound, tetraalkylammonium salt and alkali metal alkoxide is (100-500): (0.02-0.5): (0.01-0.25).
The application uses alkali metal alkoxide as initiator, and under the action of tetraalkylammonium salt, the alkali metal alkoxide and acrylic ester/acrylamide compound (100-500): (0.02-0.5): (0.01-0.25) so that the acrylic ester/acrylamide compound can undergo anionic polymerization reaction at a mild temperature, namely 0-60 ℃ to generate the polyacrylate/polyacrylamide polymer, and the time from the start of the polymerization reaction to the deactivation of the active species or the completion of monomer conversion is only about 5 minutes. The finally synthesized polyacrylate/polyacrylamide polymer has narrow molecular weight distribution range, high syndiotactic degree and high monomer conversion rate. Compared with the existing anionic polymerization reaction with higher syndiotactic degree, narrow molecular weight distribution range and higher monomer conversion rate at the temperature of minus 78 ℃, the anionic polymerization reaction has the advantages of mild reaction condition, short reaction time, low cost of used raw materials and the like, so that the polymerization process of the polyacrylate/polyacrylamide polymer can realize large-scale and low-cost industrial production, and has profound significance for the processing industry of the polyacrylate/polyacrylamide polymer.
The acrylic acid ester compound comprises H 2 C＝CR 1 COOR 2 And lactone, R 1 Is H or alkyl, R 2 Is alkyl, aryl or five membered heterocycle (furan). For example: allyl methacrylate, n-butyl methacrylate, and methacrylic acidTert-butyl, n-butyl acrylate, benzyl methacrylate, furfuryl methacrylate, and alpha-methylene-gamma-butyrolactone, and the like.
The general formula of the acrylamide compound is H 2 C＝CR 3 CONR 4 R 5 ，R 3 Is hydrogen or alkyl, R 4 、R 5 Is alkyl. For example: n, N '-dimethylacrylamide and N, N' -dimethylacrylamide.
The general formula of the tetraalkylammonium salt isR 6 、R 7 、R 8 And R is 9 Is alkyl, A - Is a counter anion. For example: anaerobic counter anions (halide), oxygenated counter anions (carbonate, bicarbonate, sulfate, bisulfate, nitrate, hypochlorite, permanganate, etc.), and organic counter anions (cyanate, acetate, oxalate, etc.).
The general formula of the alkali metal alkoxide isR 11 Is alkyl, R 10 And R is 12 And is H or alkyl, M is common alkali metal sodium and potassium.
The term "alkyl" is used herein in the sense known to those of ordinary skill in the art to refer to a monovalent residue consisting only of carbon and hydrogen atoms, the alkyl group forming a moiety of the formula C n H 2n+1 Is a similar series of the same kind. Alkyl groups may be straight or branched chain alkyl groups, for example alkyl groups may be, but are not limited to, secondary or tertiary alkyl groups, secondary alkyl groups being branched and having a central carbon atom attached to two carbon residues; tertiary alkyl groups are branched and have a central carbon atom attached to 3 carbon residues. "aryl" means C 6 -C 10 Aromatic hydrocarbon groups such as phenyl.
Preferably, the molar ratio of the acrylic ester/acrylamide compound, the tetraalkylammonium salt and the alkali metal alkoxide is 100: (0.06-0.25): (0.06-0.25).
The molar ratio of polyacrylate/polyacrylamide polymer, tetraalkylammonium salt and alkali metal alkoxide is further selected, so that the polymerization reaction of acrylate/acrylamide compound monomers is more sufficient in the polymerization reaction process. The monomer conversion rate is improved, and the molecular weight distribution range of the polyacrylate/polyacrylamide polymer is further reduced, so that the production efficiency of the polyacrylate/polyacrylamide polymer is improved, the production cost is reduced, and the product quality of the polyacrylate/polyacrylamide polymer is improved.
Preferably, the alkali metal alkoxide is potassium tert-butoxide or sodium tert-butoxide, and potassium tert-butoxide is further selected.
Because the potassium tert-butoxide and the sodium tert-butoxide have three methyl groups, the structure can generate electronic effect and spatial effect to ensure that the potassium tert-butoxide and the sodium tert-butoxide have stronger alkalinity and activity than other alkali metal alkoxides, so that the active species of the polymer are more stable in the process of synthesizing the polyacrylate/polyacrylamide polymer, the occurrence of side reaction is reduced, and the monomer conversion rate of acrylic esters/acrylamide compounds is further improved; the controllability of the polymerization reaction is increased, and the synthesized polymer has higher syndiotactic degree and narrower molecular weight distribution range, thereby providing an improvement direction for improving the production efficiency for realizing industrialization of the polyacrylate/polyacrylamide polymer anion polymerization process.
Preferably, the tetraalkylammonium salt is any one of tetrabutylammonium salt, tetrahexylammonium salt, cetyltrimethylammonium salt and benzyltriethylammonium salt.
Tetrabutylammonium salt, tetrahexylammonium salt, hexadecyl trimethyl ammonium salt and benzyl triethyl ammonium salt are used as phase transfer regulator in the polymerization reaction process, and are used as co-initiation system together with potassium tert-butoxide, and the constructed ion pair initiator has good regulation effect in the polymerization reaction of polyacrylate/polyacrylamide polymers, so that the process of forming high polymer by chain growth of low-molecular reaction monomers is accelerated.
Further, tetrabutylammonium salt is more preferable, and tetrabutylammonium bromide is most preferable. The raw materials are cheap and easy to obtain, so that the polymerization reaction is better promoted, and the low-cost industrial production is further promoted.
Preferably, the organic solvent is formed by mixing one or two of toluene, tetrahydrofuran, N' -dimethylformamide, N-hexane and acetonitrile, and more preferably, the organic solvent is toluene.
Typically, the solvent does not directly participate in the polymerization reaction. However, the solvents are often not absolutely inert and induce decomposition of the initiator. Both of these effects may affect the rate of polymerization and the molecular weight. The solvent has a greater influence in ionic polymerization, and the polarity of the solvent has a significant influence on the form and activity of the active ion pairs, the rate of polymerization, the molecular weight distribution, and the chain microstructure.
In order to match the reaction system of alkali metal alkoxide and tetraalkylammonium salt, one or two of toluene, tetrahydrofuran, N' -dimethylformamide, N-hexane and acetonitrile are selected to be mixed, the activities of the alkali metal alkoxide, tetraalkylammonium salt and acrylic ester/acrylamide compound monomers have smaller influence in the organic solvent, and the polymerization reaction rate is further improved.
The further selected toluene makes the molecular weight distribution range of the synthesized polyacrylate/polyacrylamide polymer narrower, and the synthesized polyacrylate/polyacrylamide polymer has stable quality, thereby being more beneficial to the promotion of the synthesis industrialization of the polyacrylate/polyacrylamide polymer.
Preferably, the polymerization temperature is 25-60 ℃, further selected as room temperature.
When the polymerization temperature is 60 ℃, active groups in the reaction system are more active, so that the anionic polymerization reaction is promoted to rapidly proceed towards the direction of synthesizing the polyacrylate/polyacrylamide polymer, the reaction rate of synthesizing the polyacrylate/polyacrylamide polymer is further improved, and the industrial production efficiency is improved. Of course, the polymer is prepared under the condition of room temperature (25 ℃ plus or minus 2 ℃), and the polyacrylate/polyacrylamide polymer with high monomer conversion rate, high syndiotactic degree and narrow molecular weight distribution range can be obtained without heating or cooling, so that the investment of equipment needing heating or cooling is reduced, the energy source needed in industrial production is greatly saved, and the low-cost and large-scale industrial production can be further promoted.
Preferably, the alkali metal alkoxide is dissolved in the organic solvent to obtain the initiation solution, then the regulator tetraalkylammonium salt is dissolved in the acrylic ester/acrylamide compound and stirred uniformly to obtain the reaction solution, and the reaction solution is added into the initiation solution to perform polymerization reaction.
The initiator is fully dissolved first to fully expose active groups, the regulator is dissolved in the reaction monomer to be fully dispersed, and the active groups can fully initiate the monomer in the polymerization reaction process, so that the conversion rate of the monomer is further improved, and the efficiency of preparing the polyacrylate/polyacrylamide polymer is further improved.
Preferably, the polymerization time is 5 to 60 minutes.
In the industrial production process, the control of the reaction time is critical. The reaction time is short, and the initiation of the monomer is insufficient, so that the monomer conversion rate is low, and the waste of raw materials is caused. The reaction time is too long, and the production period of the product is prolonged. The monomer conversion rate of the acrylate/acrylamide compound can reach a higher level within 5-60min, the processing time is shorter, and the obtained polymer polymerized has higher syndiotacticity and narrower molecular weight distribution range, and the polyacrylate/acrylamide polymer with stable quality and uniform quality is obtained.
Preferably, adding an alcohol solvent containing 0.1-0.3mol/L HCl into the crude polyacrylate/polyacrylamide polymer, terminating polymerization to obtain a quenching mixture, adding the quenching mixture into an alcohol solvent with the volume being more than 10 times to form a precipitate, washing the precipitate part with the alcohol solvent to remove unreacted monomers, filtering, and then drying to constant weight to obtain the refined polyacrylate/polyacrylamide polymer.
The method is used for carrying out post-treatment on the crude product of the polyacrylate/polyacrylamide polymer, the treatment steps are simple, the used post-treatment agent is an alcohol solvent, and the price is low and the method is easy to obtain. The high-purity polyacrylate/polyacrylamide polymer fine product can be obtained by using a low-cost post-treatment process. In addition, the solvent used in the post-treatment can be recycled, so that the cost of the post-treatment is further reduced, the production cost of the polyacrylate/polyacrylamide polymer is reduced, and the resource is saved.
In a second aspect, the application provides a preparation method of polyacrylate/polyacrylamide polymer, which adopts the following technical scheme:
the polyacrylate/polyacrylamide polymer is prepared with the polymerization process and has molecular weight of 5000-300000g/mol and molecular weight distribution1.6-3.4, and the syndiotactic degree is more than 40%.
Molecular weight distributionThe smaller the molecular weight distribution, the narrower the molecular weight distribution range, indicating that the lower molecular weight polymer content of the polymer is less, the more concentrated the molecular weight of the resulting polymer, and the closer the processability. In addition, the narrow molecular weight distribution range reflects a more uniform polymer mass.
The degree of syndiotactic of the polymer reflects the stability of the polymer in forming crystal forms, and the high degree of syndiotactic indicates that the crystal forms formed by the polymer are relatively stable and the melting point of the polymer is high. The application has the advantages of high degree of syndiotacticity up to more than 40%, stable crystal form, high strength, easy processing, chemical resistance and the like.
The stability of the product is vital in the industrial production process, and the polyacrylate/polyacrylamide polymer prepared by the method has uniform quality and good stability, and is more beneficial to realizing large-scale industrial production.
In summary, the application has the following beneficial effects:
1. because the application adopts alkali metal alkoxide as an initiator, and takes part in reaction with acrylic ester/acrylamide compounds in a specific molar ratio under the action of tetraalkylammonium salt, compared with the existing anionic polymerization, the application has the advantages of mild reaction temperature, short reaction time, stable quality of the obtained polyacrylate/polyacrylamide polymer, high monomer conversion rate and the like, thereby realizing low-cost and large-scale industrialized preparation of the polyacrylate/polyacrylamide polymer.
2. In the application, toluene is preferably selected as a solvent, the activities of alkali metal alkoxide, tetraalkylammonium salt and acrylic ester/acrylamide compound monomers have smaller influence in toluene, the polymerization reaction rate is further improved, the molecular mass distribution range of the synthesized polyacrylate/polyacrylamide polymer is narrower, and the molecular weight of the synthesized polyacrylate/polyacrylamide polymer is stable, so that the industrialized promotion of the polyacrylate/polyacrylamide polymer is facilitated.
3. According to the method disclosed by the application, the compound participating in the reaction is fully dissolved first, so that the acrylic ester/acrylamide compound is polymerized and fully reacted at a milder temperature, the rate of the polymerization reaction is improved, and the energy required by the reaction is reduced, so that the industrial production cost can be saved, and the production efficiency is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
In order to facilitate understanding of the existing anionic polymerization process of acrylate/acrylamide compounds, the initiator, reaction temperature and property parameter arrangement used for preparing the polyacrylate/polyacrylamide polymers in the prior art are shown in table 1.
The serial numbers 1-38 are the preparation of polyacrylate polymers: the numbers 1 to 37, 38 and 39 are MMA, an initiator of furfuryl methacrylate, a reaction temperature and a property parameter of the polymer, respectively.
The serial numbers 39-40 are the preparation of the polyacrylamide polymer: respectively N, N '-dimethyl acrylamide, an initiator of N, N' -dimethyl methacrylamide, a reaction temperature and a property parameter of a polymer.
Wherein broad represents a broad peak and bm represents a multiple broad peak.
TABLE 1 anionic polymerization of acrylic acid esters/acrylamides under different conditions
From the above table, scientists have tried anionic polymerization of polyacrylates/polyacrylamides in a variety of different types of initiators, solvents, and experimental environments. However, in any case, the anionic polymerization is carried out at low temperature (most at-78 ℃ C.). Although few experiments were performed at 0 ℃, none of the experiments was very ideal, the monomer conversion was low, the molecular weight distribution was broad, and even more the ideal unimodal distribution due to anionic polymerization did not appear. Therefore, the anionic polymerization for preparing the polyacrylate/polyacrylamide can only be carried out under the condition of a laboratory at present, and low-cost and industrialized production is difficult to realize.
Based on the above, the application researches an anionic polymerization process of polyacrylate/polyacrylamide which can realize low-cost and industrialized production.
Examples
Laboratory research stage
The room temperature in the examples is the temperature at 25+ -2deg.C, without heating or cooling the reaction body.
Examples 1-5 were designed to demonstrate the effect of the selection of alkali metal alkoxides, tetraalkylammonium salts, on the polymerization reaction.
Example 1
The embodiment discloses a PMMA polymerization process, which comprises the following steps:
a flame-dried 25mL Schlenk flask in a glove box was charged with initiator sodium ethoxide (0.048 mmol,3.3 mg), regulator tetrahexylammonium bisulfate (0.096 mmol,43.4mg,4 eq.) and 4mL of dry organic solvent toluene, and stirred at room temperature for 5min. MMA (19.2 mmol,2mL,800 eq) was then added in one portion to a Schlenk flask which was stirred at room temperature for 5min to obtain a PMMA mixture.
To the PMMA mixture was added a methanol solution containing 0.1mol/LHCl to terminate the polymerization, resulting in a quenched mixture. The quenched mixture was then precipitated into 10-fold excess of methanol, filtered, washed with methanol to remove unreacted monomers, and dried to constant weight in a vacuum oven at 40 ℃ to obtain PMMA.
In the above reaction, MMA: tetrahexylammonium bisulfate: the molar ratio of sodium ethoxide is 100:0.5:0.25.
example 2
This example discloses a polymerization process for PMMA, which differs from example 1 in that:
the modifier was hexadecyl trimethyl ammonium hydroxide (0.04 mmol,1.14 mg), sodium tert-butoxide was used equimolar in place of sodium ethoxide, MMA (96.0 mmol,10mL,4000 eq.) and dried toluene was 20mL.
In the above reaction, MMA: cetyl trimethylammonium hydroxide: the molar ratio of the sodium tert-butoxide is 500:0.02:0.25.
example 3
This example discloses a polymerization process for PMMA, which differs from example 1 in that:
the modifier was equimolar tetrabutylammonium chloride (0.096 mmol,26.7mg,4 eq.) and the initiator was potassium tert-butoxide (0.024 mmol,2.7 mg).
In the above reaction, MMA: tetrabutylammonium chloride: the molar ratio of potassium tert-butoxide is 100:0.5:0.125.
example 4
This example discloses a polymerization process for PMMA, which differs from example 3 in that:
the modifier was equimolar tetrabutylammonium bromide (0.096 mmol,30.9mg,4 eq.).
In the above reaction, MMA: tetrabutylammonium bromide: the molar ratio of potassium tert-butoxide is 100:0.5:0.125.
the polymerization formula of example 4 is as follows, n=100-3000.
Example 5
This example discloses a polymerization process for PMMA, which differs from example 3 in that:
the modifier was equimolar benzyltriethylammonium chloride (0.096 mmol,21.8mg,4 eq).
In the above reaction, MMA: benzyl triethyl ammonium chloride: the molar ratio of potassium tert-butoxide is 100:0.5:0.125.
examples 6-9 were used to compare the effect of process parameters during processing on the preparation of PMMA.
Example 6
This example discloses a polymerization process for PMMA, which differs from example 4 in that the polymerization temperature is 40 ℃.
Example 7
This example discloses a polymerization process for PMMA, which differs from example 4 in that: the Schlenk flask was charged with potassium tert-butoxide, tetrabutylammonium bromide and dried toluene, and MMA was added to the Schlenk flask at once, and reacted at 0℃for 60 minutes.
Example 8
This example discloses a polymerization process for PMMA, which differs from example 7 in that:
tetrabutylammonium bromide and 3ml of dry toluene are put into a Schlenk bottle, MMA is added after dissolution and stirred uniformly, then potassium tert-butoxide is dissolved in 1ml of dry toluene and added into the Schlenk bottle at one time, and the polymerization temperature is 60 ℃ and the reaction time is 5min.
Example 9
This example discloses a polymerization process for PMMA, which differs from example 7 in that:
firstly, filling potassium tert-butoxide and dry toluene into a Schlenk bottle, dissolving tetrabutylammonium bromide into MMA after the potassium tert-butoxide is dissolved, stirring uniformly, then dropwise adding the mixture into the Schlenk bottle, and reacting for 5min at room temperature.
Examples 10-12 are presented to demonstrate the effect of the molar ratio of monomer, initiator, modifier on the preparation of PMMA.
Example 10
The embodiment discloses a PMMA polymerization process.
A flame-dried 25ml Schlenk flask in a glove box was charged with potassium tert-butoxide (0.024 mmol,2.7 mg) and 4ml dry toluene, tetrabutylammonium bromide (0.096 mmol,26.7mg,4 equivalents) was dissolved in MMA (38.4 mmol,4mL,1600 equivalents), and after stirring well, added to the Schlenk flask at once, the Schlenk flask was stirred at room temperature for 5min to obtain a PMMA mixture.
To the PMMA mixture, 0.5mL of a methanol solution containing 0.3mol/LHCl was added to terminate the polymerization to obtain a quenched mixture, which was then precipitated into 15-fold excess methanol, filtered, washed with methanol to remove unreacted monomers, and then dried to constant weight in a vacuum oven at 50℃to obtain PMMA.
In the above reaction, MMA: tetrabutylammonium bromide: the molar ratio of potassium tert-butoxide is 100:0.25:0.0625.
example 11
This example discloses a polymerization process for PMMA, which differs from example 10 in that:
in the above reaction, MMA: tetrabutylammonium bromide: the molar ratio of potassium tert-butoxide is 100:0.063:0.125, MMA (19.2 mmol,2mL,800 eq.) tetrabutylammonium bromide (0.048 mmol,15.5mg,2 eq.) and potassium tert-butoxide (0.024 mmol,2.7 mg).
Example 12
This example discloses a polymerization process for PMMA, which differs from example 10 in that:
in the above reaction, MMA: tetrabutylammonium bromide: the molar ratio of potassium tert-butoxide is 100:0.125:0.25, MMA (9.6 mmol,1mL,400 eq.) tetrabutylammonium bromide (0.012 mmol,3.8mg,0.5 eq.) and potassium tert-butoxide (0.024 mmol,2.7 mg).
Examples 13-15 were used to compare the effect of different organic solvents on the synthesis of PMMA.
Example 13
This example discloses a polymerization process for PMMA, which differs from example 11 only in that: an equal volume of tetrahydrofuran was used instead of dry toluene.
Example 14
This example discloses a polymerization process for PMMA, which differs from example 11 only in that: an equal volume of N, N' -dimethylformamide was used instead of dried toluene.
Example 15
This example discloses a polymerization process for PMMA, which differs from example 11 only in that: n-hexane and acetonitrile 1 were used: 1 the equal volume of the mixture replaces the dry toluene.
Example 16
This example discloses a polymerization process of poly (furfuryl methacrylate), which differs from example 9 in that: the monomer is furfuryl methacrylate, and the molar ratio of the furfuryl methacrylate to tetrabutylammonium bromide and potassium tert-butoxide is 100:0.125:0.25, i.e. the monomer is furfuryl methacrylate (19.2 mmol,4mL,800 eq.) tetrabutylammonium bromide (0.012 mmol,3.8mg,0.5 eq.) potassium tert-butoxide (0.024 mmol,2.7 mg).
The polymerization formula of example 16 is as follows, n=100-3000.
Example 17
This example discloses a polymerization process for poly-N, N' -dimethylacrylamide.
The difference from example 16 is that: the monomer was N, N' -dimethylacrylamide (19.2 mmol,4mL,800 eq.).
The polymerization formula of example 17 is as follows, n=100-3000.
Amplified polymerization experiment
Example 18
This example discloses the preparation of 500g PMMA.
To a 5L polymerization reactor under nitrogen atmosphere, dry toluene (1500 mL), potassium t-butoxide (421.9 mg), tetrabutylammonium bromide (4.172 g) were added in this order, stirring was started at a stirring speed of 100r/min, and MMA monomer (625 mL) was added dropwise to the reaction mixture while stirring, and stirring was performed at room temperature for 30min to obtain a PMMA mixture.
1000mL of a methanol solution containing 0.3mol/LHCl was added to terminate and precipitate the polymer. The reaction mixture was filtered, washed with methanol to remove unreacted monomers, and then dried in a vacuum oven at 50℃to constant weight to obtain 500g of PMMA.
Comparative example
Comparative example 1
Existing polymerization processes with florenyithium (fluorenyl lithium) as initiator.
In a 500mL three-necked flask equipped with a mechanical stirrer, thermometer, Y-type gas channel and flame-dried, 260mL of dried toluene was added via syringe. Subsequently, 11mL of diethyl ether and 19mL of LFLOurentithiaum (0.158 eq.) were added to form a mixture, which was cooled to-70℃in an acetone-dry ice bath, and 10mL (0.94 mol) of MMA monomer was rapidly introduced. The reaction solution was stirred at-70℃for 1 hour to obtain a PMMA mixture. The reaction was then quenched by the addition of 5mL of methanol. The reaction solution was poured into 10 volumes of industrial n-hexane under vigorous stirring, and the polymer was separated and dried under vacuum to obtain PMMA.
Performance test
Test 1
Detecting the number average molecular weight and molecular weight distribution of a polymer
The method comprises the following steps: number average molecular weight Mn and molecular weight distribution of the polymers obtained in examples 1 to 18 and comparative example 1 described aboveUnified GPCAnd (3) analyzing and calculating to obtain the number average molecular weight and molecular weight distribution of the polymer.
Instrument: GPC, PL-GPC50, PD2000, agilent technologies (gel permeation chromatograph, agilent technologies Co.).
Test 2
Detection of syndiotactic rr% of polymer
The method comprises the following steps: the polymers obtained in examples 1 to 18 and comparative example 1 were passed through a Bruker Avance III400MHz Nuclear magnetic resonance Bode instrument 1 The H-NMR characterization gives a peak for measurement analysis, giving a percentage of syndiotactic polymer.
Test 3
The monomer conversion of the polymer was measured.
A0.2 mL aliquot was taken from the PMMA mixture of examples 1-18 and comparative example 1, respectively, and used with 0.4mL DCl 3 Dilution followed by injection into an agilent GC7890 gas chromatograph for monomer conversion by gas chromatography analysis and image data processing.
The specific test data for runs 1-3 are detailed in Table 2.
TABLE 2
As a result of comparison of the data of comparative example 1 and examples 1 to 5, PMMA having a degree of syndiotactic property of 40% or more, a high monomer conversion and a narrow molecular weight distribution can be obtained at room temperature by using an alkali metal alkoxide and a tetrabutylammonium salt which are inexpensive and easily available in the present application. The use of the expensive rare fluorenyl lithium catalyst relative to comparative example 1 and at an extremely low temperature of-70 ℃ produced PMMA with close properties. Therefore, the polymerization process can complete the reaction without cooling equipment, has low equipment investment cost and cheap and easily available raw materials, and can realize large-scale and low-cost industrial production of the polyacrylate/polyacrylamide polymers. Solves the technical problem of low polymerization reaction temperature which is always needed to be solved in the field, and has profound significance for the processing industry of polyacrylate/polyacrylamide polymers.
According to examples 6 to 9, which are obtained by comparing the data with example 4, the feeding mode, the reaction temperature and the reaction time have an influence on the polymerization process, and in industrial production, both high monomer conversion and convenience in the preparation process and the reaction environment are considered, in example 9, potassium tert-butoxide and dry toluene are firstly filled in a Schlenk bottle, tetrabutylammonium bromide is dissolved in MMA after the potassium tert-butoxide is dissolved, and the tetrabutylammonium bromide is dropwise added into the mixture after stirring uniformly, the polymerization temperature is room temperature, and the monomer conversion rate of 96%, the syndiotacticity of 55 and the molecular weight distribution are obtained after reacting for 5min1.76 PMMA.
From the comparison of the data of examples 3 and 4 with examples 10-12, the monomer conversion of examples 10-12 was significantly improved relative to examples 3 and 4, indicating that when the molar ratio of acrylate/acrylamide compound, tetraalkylammonium salt and alkali metal alkoxide was 100: (0.06-0.25): (0.06-0.25), the polymerization reaction is more sufficient, the industrial production efficiency of the polyacrylate/polyacrylamide polymer is improved, and the production cost is reduced.
From a comparison of the data of example 11 with examples 13-15, the organic solvent used in example 11 was dry toluene, and tetrahydrofuran, N' -dimethylformamide and N-hexane and acetonitrile 1 were used in examples 13-15, respectively: 1, the monomer conversion of example 11 reaches 98%, while examples 13-15 are only 92% at maximum. The polymerization reaction has a rapid reaction stage and a stabilization stage, and when the monomer conversion is stabilized at a certain value, the further breakthrough is difficult. In order to match the reaction system of alkali metal alkoxide and tetraalkylammonium salt, the dry toluene further improves the polymerization reaction rate, thereby being more beneficial to the promotion of the synthesis industrialization of polyacrylate/polyacrylamide polymers.
As can be seen from the comparison of the data of examples 16-17 and example 9, the polymer prepared in example 16 is poly (furfuryl methacrylate), the polymer prepared in example 17 is poly (N, N' -dimethylacrylamide), and under the same polymerization conditions as in example 9, the monomer conversion rate is higher, the molecular weight distribution range is narrow and the intermolecular regularity is high, which indicates that the anionic polymerization process of the present application can be used for preparing polyacrylate/polyacrylamide polymers, and the application is wide, and the anionic polymerization process has a remarkable contribution to the technical improvement of the industry.
From a comparison of the data obtained in example 18 and example 10, example 18 was an experiment on a larger scale of the polymerization experiment, producing PMMA with a monomer conversion of 99%, a molecular weight distribution range of 1.76 and a degree of syndiotactic of up to 55%. Therefore, the anionic polymerization process is stable, the product quality is stable after the scale is enlarged, and the method is favorable for further promotion in industrial production.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A polymerization process of polyacrylate/polyacrylamide polymer is characterized in that in an organic solvent, acrylic ester/acrylamide compound is used as a monomer raw material, alkali metal alkoxide is used as an initiator, a regulator tetraalkylammonium salt is added, and the reaction is carried out for more than 5 minutes at the polymerization temperature of 0-60 ℃ to obtain a crude product of the polyacrylate/polyacrylamide polymer, wherein the concentration of the acrylic ester/acrylamide compound in the organic solvent is 0.3-16mol/L, and the molar ratio of the acrylic ester/acrylamide compound, the tetraalkylammonium salt and the alkali metal alkoxide is (100-500): (0.02-0.5): (0.01-0.25).
2. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 1, wherein: the molar ratio of the acrylic ester/acrylamide compound, the tetraalkylammonium salt and the alkali metal alkoxide is 100: (0.06-0.25): (0.06-0.25).
3. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 1, wherein: the alkali metal alkoxide is potassium tert-butoxide or sodium tert-butoxide.
4. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 1, wherein: the tetraalkylammonium salt is any one of tetrabutylammonium salt, tetrahexylammonium salt, cetyltrimethylammonium salt and benzyltriethylammonium salt.
5. The polymerization process of polyacrylate/polyacrylamide polymer according to any one of claims 1 to 4, wherein: the organic solvent is formed by mixing one or two of toluene, tetrahydrofuran, N' -dimethylformamide, N-hexane and acetonitrile.
6. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 5, wherein: the polymerization temperature is 25-60 ℃.
7. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 5, wherein: dissolving alkali metal alkoxide in an organic solvent to obtain an initiation solution, dissolving tetraalkylammonium salt in MMA, uniformly stirring to obtain a reaction solution, and adding the reaction solution into the initiation solution to perform polymerization reaction.
8. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 5, wherein: the polymerization reaction time is 5-60min.
9. The polymerization process of polyacrylate/polyacrylamide polymer according to claim 8, wherein: adding an alcohol solvent containing HCl with the molar concentration of 0.1-0.3mol/L into the crude polyacrylate/polyacrylamide polymer, terminating polymerization to obtain a quenching mixture, adding the quenching mixture into the alcohol solvent with the volume being more than 10 times of that of the quenching mixture to form a precipitate, washing, filtering, and drying to constant weight to obtain the refined polyacrylate/polyacrylamide polymer.
10. A polyacrylate/polyacrylamide polymer characterized in that: prepared by the polymerization process of any one of claims 1-9, having a molecular weight of 5000-300000g/mol, a molecular weight distribution Đ 1.6.6-3.4, and a degree of syndiotactic greater than 40%.
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| WO1999001483A1 (en) * | 1997-07-04 | 1999-01-14 | Basf Aktiengesellschaft | Method for producing polyalkyl(meth)acrylates |
| CN1968979A (en) * | 2004-04-29 | 2007-05-23 | 亚什兰许可和知识产权有限公司 | Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods |
| CN110183639A (en) * | 2019-04-27 | 2019-08-30 | 华东理工大学 | A kind of preparation method and applications of the catalyst for polyester synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999001483A1 (en) * | 1997-07-04 | 1999-01-14 | Basf Aktiengesellschaft | Method for producing polyalkyl(meth)acrylates |
| CN1968979A (en) * | 2004-04-29 | 2007-05-23 | 亚什兰许可和知识产权有限公司 | Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods |
| CN110183639A (en) * | 2019-04-27 | 2019-08-30 | 华东理工大学 | A kind of preparation method and applications of the catalyst for polyester synthesis |
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