CN114262414B - Comb-type ultra-high molecular weight polymer and synthesis method thereof - Google Patents
Comb-type ultra-high molecular weight polymer and synthesis method thereof Download PDFInfo
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- 229920006158 high molecular weight polymer Polymers 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title claims description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 109
- 229910052757 nitrogen Inorganic materials 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 15
- 150000004820 halides Chemical class 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- -1 2-bromopropionic acid allyl ester Chemical class 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 8
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 8
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 7
- WIPLNCYPGHUSGF-UHFFFAOYSA-N prop-2-enyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCC=C WIPLNCYPGHUSGF-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- QNBDJTKBKITRJI-UHFFFAOYSA-N prop-2-enyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCC=C QNBDJTKBKITRJI-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- LEGMXARRVFNLQF-UHFFFAOYSA-N OC([Cu])=O Chemical compound OC([Cu])=O LEGMXARRVFNLQF-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 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 description 28
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 26
- 239000004926 polymethyl methacrylate Substances 0.000 description 26
- 238000010992 reflux Methods 0.000 description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000009461 vacuum packaging Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 8
- HAYWJKBZHDIUPU-UHFFFAOYSA-N (2,4,6-tribromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(Br)C=C(Br)C=C1Br HAYWJKBZHDIUPU-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- OLYBZTAQUPVTEK-UHFFFAOYSA-M C(C(=C)C)(=O)[O-].C[Si+](C)C Chemical compound C(C(=C)C)(=O)[O-].C[Si+](C)C OLYBZTAQUPVTEK-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 229920000120 polyethyl acrylate Polymers 0.000 description 3
- PGQNYIRJCLTTOJ-UHFFFAOYSA-N trimethylsilyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[Si](C)(C)C PGQNYIRJCLTTOJ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- FNYLFWGITLMOHA-UHFFFAOYSA-N 4-chloro-6-methoxy-2-methylsulfanylpyrimidine Chemical compound COC1=CC(Cl)=NC(SC)=N1 FNYLFWGITLMOHA-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002351 wastewater 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 comb-type ultra-high molecular weight polymer and its synthetic method, the molecular weight of the polymer synthesized in this invention can be controlled, prepare comb-type halogenate initiator at first, its N side chain ends that have all contain organic halogenate that can initiate the polymerization reaction, then utilize said comb-type halogenate initiator to adopt the solution polymerization method to prepare the polymer seed of high relative molecular weight first, then remove the initiating monomer with this polymer seed, form the polymer seed of ultra-high molecular weight, this comb-type polymer because of containing N side chains, so its molecular weight is N times that of the linear ultra-high molecular weight polymer, because the molecular weight or molecular morphology is too big, more suitable for some preparation of the device that needs intensity and hardness or make the surface modification of some devices; the process of the invention is smooth, and is suitable for large-scale industrial production, and the weight average molecular weight of the comb-type ultra-high molecular weight polymer prepared by the method is higher than 10000 ten thousand.
Description
Technical Field
The invention belongs to the technical field of high polymers, and particularly relates to a comb-type ultra-high molecular weight polymer and a synthesis method thereof.
Background
Comb polymers are a special polymer with a special structure which is started in recent years, and are shaped like a comb and are composed of a main chain and N side chains. Comb polymers with long backbones and short side chains behave much like branched polymers and have poor flowability, but comb polymers are more regular than branched polymers. The comb polymer is more used for some functional auxiliary agents, such as surfactants, adsorbents, adhesives and the like, the comb polymer with short main chain long side chains is more similar to a linear polymer in performance, the fluidity is better, the comb polymer with short main chain long side chains is mainly used for some functional auxiliary agents, and the comb polymer with short main chain long side chains has little application in materials so far.
In view of the structural morphology of comb polymers, the molecules, both in morphology and in molecular weight, are larger than linear molecules due to the N side chains. Comb polymers with short main chain length side chains are prepared by first preparing N side chain halide-containing initiators and then preparing comb-type polyalkyl (meth) acrylates with short main chain length side chains, each side chain having to be a linear (ultra) high molecular weight polyalkyl (meth) acrylate, by an activity-controlled process. Therefore, the molecular weight of such a polymer is at least N times that of a linear polymer. Comb polymers with short main chain length side chains are somewhat weaker in flowability, toughness, impact resistance than linear polymers of equivalent molecular weight, but far stronger than crosslinked polymers. In terms of abrasion resistance, although not as good as crosslinked polymers, it is much better than linear polymers because of the presence of multiple crosslinking points. At present, a comb polymer prepared by an activity controllable polymerization method is reported a lot, but no report of comb type alkyl methacrylate or comb type alkyl acrylate is seen.
The present invention has been made in view of the above-mentioned circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a comb-type ultrahigh molecular weight polymer and a synthesis method thereof, wherein the method firstly prepares a comb-type halogenated material initiator which is provided with N side chain ends and contains organic halogenated materials capable of initiating polymerization reaction, then prepares polymer seeds with high relative molecular weight by using the comb-type halogenated material initiator firstly by adopting a solution polymerization method, and then initiates monomers by using the polymer seeds to form the ultrahigh molecular weight polymer. Since the comb polymer has N side chains, the molecular weight of the comb polymer is N times that of the linear ultra-high molecular weight polymer, and the comb polymer has an ultra-large molecular form. The ultra-high molecular weight comb polymer is more suitable for preparing devices requiring strength and hardness or performing surface modification on certain devices due to overlarge molecular weight or molecular morphology.
The first object of the present invention is to provide a synthesis method of comb-type ultra-high molecular weight polymer, comprising the steps of:
(1) Preparation of comb-type halide initiator: carrying out free radical polymerization on styrene and 2-bromoisobutyric acid allyl ester and isobutyric acid allyl ester, or styrene and 2-bromopropionic acid allyl ester and allyl propionate to obtain a copolymer of styrene and 2-bromoisobutyric acid allyl ester or a copolymer of styrene and 2-bromopropionic acid allyl ester, namely a comb-type halogenated initiator;
(2) Preparation of polymer seeds: placing a monomer in a dropwise adding device for standby, adding a solvent into a reaction kettle, introducing nitrogen to remove oxygen for standby, adding the comb-type halogenated initiator, the catalyst, the ligand and the auxiliary agent into the reaction kettle, dropwise adding a small amount of monomer under the condition of stirring, heating to a first temperature, heating to a second temperature after the system becomes slightly viscous, slowly dropwise adding the residual monomer, carrying out heat preservation reaction, and cooling to obtain polymer seeds;
(3) Synthesis of comb-type ultra-high molecular weight polymer: under the protection of nitrogen, transferring the polymer seeds into a reactor, introducing nitrogen, heating to a second temperature, slowly dropwise adding excessive monomers under the condition of stirring, simultaneously evaporating the solvent, carrying out reaction at constant temperature after dropwise adding, transferring the product into another reactor under the protection of nitrogen, distilling unreacted monomers under reduced pressure, crushing, and carrying out vacuum drying to obtain the comb-type ultrahigh molecular weight polymer.
The process of the present invention first prepares N side chain halogenide-containing initiators, and then prepares comb polymers with short main chain long side chains by an activity-controllable process, each side chain must be linear high molecular weight polyalkylmethacrylate or polyalkylacrylate, and thus the polymer prepared by the present invention has a molecular weight at least N times that of the linear polymer, and the comb polymers with short main chain long side chains are slightly weaker in reflow property, toughness, impact resistance than the linear polymers of the same molecular weight but far stronger than the crosslinked polymers, and are much better in abrasion resistance than the linear polymers because of the presence of a plurality of crosslinking points, although inferior to the crosslinked polymers.
In the synthesis of the ultra-high molecular weight polymer, excessive monomers can be added to replace the solvent, the solvent is removed, and the added monomers play roles in dilution and dissolution, so that the molecular growth, the reaction mixing and the material transfer are facilitated. The monomer in the present invention may be one alkyl ester or a mixture of several alkyl esters.
Further, the comb-type ultra-high molecular weight polymer comprises comb-type ultra-high molecular weight polyalkylmethacrylate or comb-type ultra-high molecular weight polyalkylacrylate, wherein the alkane of the ester group in the polyalkylmethacrylate or the alkyl acrylate further comprises hetero atoms.
Further, the heteroatom includes silicon or halogen.
Further, the monomer is dehydrated, distilled under reduced pressure, and then introduced with nitrogen to remove dissolved oxygen for standby.
The monomers in steps (1) and (2) of the present invention may be the same or different, and the monomers may be one alkyl ester or a mixture of several alkyl esters.
In the invention, if the boiling point of the monomer is relatively close to that of water, dry sodium hydroxide is adopted for dewatering, and if the boiling point difference is large, reduced pressure distillation can be adopted for dewatering or dry sodium hydroxide treatment is adopted, and in addition, the main purpose of reduced pressure distillation is to remove polymerization inhibitor and other impurities.
Further, the average number of halogen-containing side chains in the copolymer molecule in the step (1) is N, and N is an integer of 5 to 50.
Further, the solvent in the step (2) is an organic solvent, preferably, the solvent is one or more of dimethyl carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl butyrate and ethyl butyrate;
The catalyst is metal or metal ions, preferably, the catalyst is one or more of cuprous iodide, cuprous bromide, cuprous chloride and copper powder;
The ligand is 2, 2-dipyridine and/or pentamethyl diethylenetriamine;
the auxiliary agent is one or more of disodium ethylenediamine tetraacetate, tetrahydrofuran, potassium iodide and carboxyl copper.
Further, in the step (2), the mass ratio of the monomer to the solvent is 1:3-5, and the mass ratio of the monomer, the comb-type halogenated initiator, the catalyst, the ligand and the auxiliary agent is 100:0.01-1:0.01-1:0.05-0.5.
Further, the first temperature in step (2) is 20-60 ℃, and the second temperature in steps (2) and (3) is 60-100 ℃.
The monomer coated in the polymer can be automatically reacted by increasing the reaction temperature and prolonging the reaction time.
In the method for synthesizing the ultra-high molecular weight polymer, the molecular weight of the obtained polymer is increased along with the extension of the reaction time or the increase of the reaction temperature and the reaction pressure in the presence of a large amount of excessive monomers.
The invention adopts a novel method combining a solution polymerization method and a bulk polymerization method, which solves the problems of poor heat dissipation effect and limited molecular growth in the bulk polymerization method and the problem that a large amount of solvent is wrapped in the copolymer in the solution polymerization.
Further, in the step (3), the reaction is carried out at constant temperature until the solid content is 35-45%, and the temperature of vacuum drying is 100-140 ℃.
The comb-type ultra-high molecular weight polymer prepared by the invention needs to be vacuum packed, and aims at: (1) The monomer wrapped in the polymer is automatically reacted, so that residual volatilization is reduced; (2) Protecting the active end of the polymer from being deactivated by contact with oxygen or water, and preparing for subsequent parts or surface treatment.
The second object of the invention is to provide a comb-type ultra-high molecular weight polymer synthesized by the synthesis method.
Further, the comb-type ultra-high molecular weight polymer has a weight average molecular weight higher than 10000 ten thousand.
Compared with the prior art, the invention has the beneficial effects that:
(1) The comb-type ultra-high molecular weight polymer is prepared by adopting the method with controllable activity, the molecular weight of the polymer can be controlled, firstly, a comb-type halogenated initiator is prepared, N side chain ends of the comb-type halogenated initiator all contain organic halogenated matters capable of initiating polymerization reaction, then, the comb-type halogenated initiator is used for preparing polymer seeds with high relative molecular weight by adopting a solution polymerization method, then, the polymer seeds are used for initiating monomers again to form ultra-high molecular weight polymer seeds, and the comb-type polymer contains N side chains, so that the molecular weight of the comb-type polymer is N times that of the linear ultra-high molecular weight polymer, and the molecular weight of the comb-type polymer is also in an ultra-large form, so that the ultra-high molecular weight comb-type polymer is more suitable for preparing devices with strength and hardness or performing surface modification on certain devices because of the molecular weight or the molecular form is too large;
(2) The synthesis method adopts a mode of combining solution polymerization and bulk polymerization, and replaces the solvent with the monomer to avoid the solvent from remaining in the polymer; the large excess monomer plays a role in dilution, avoids bursting caused by gel effect, avoids premature solidification, ensures good heat dissipation effect, and ensures that molecular growth is not limited;
(3) According to the invention, the reaction temperature in each period is controlled, so that the molecular weight of the polymer is improved under the condition of ensuring no reaction fault; the whole reaction of the invention is carried out in the atmosphere of nitrogen, so as to avoid contact with water vapor or oxygen; the whole production process of the invention does not increase the water consumption (mainly constant temperature or cooling water), and no waste water is generated; the invention has smooth process, is convenient for intelligent assembly line operation, is suitable for large-scale industrial production, and the weight average molecular weight of the comb-shaped ultra-high molecular weight polymer prepared by the method is higher than 10000 ten thousand.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
The embodiment provides a synthesis method of comb-type ultrahigh molecular weight polymethyl methacrylate, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: according to the styrene: allyl 2-bromoisobutyrate: allyl isobutyrate: azodiisobutylcyanide mass ratio = 100:12:110:0.8, weighing and mixing all the reagents, adding 500g of toluene solvent, introducing nitrogen into a 1000mL reaction bottle, stirring, raising the temperature to 85 ℃, slowly dripping the mixed reagents, reacting for a period of time at constant temperature after dripping, and rotationally steaming out toluene to obtain powdery styrene and 2-bromoisobutyric acid allyl ester copolymer which is a comb-type halogenated initiator, wherein N=10;
(2) Preparation of comb-type high molecular weight polymethyl methacrylate seeds: firstly taking 100g of methyl methacrylate which is subjected to reduced pressure distillation treatment, introducing nitrogen to remove oxygen for standby, adding 500g of ethyl acetate into a 1000mL three-port reaction bottle, introducing nitrogen to stir, sequentially adding 0.2g of copolymer of styrene and allyl 2-bromoisobutyrate, 0.2g of copper powder, 0.1g of cuprous bromide, 0.05g of pentamethyldiethylenetriamine and 0.05g of disodium ethylenediamine tetraacetate, heating to 50 ℃, adding 10g of methyl methacrylate at one time, reacting until the solution is slightly sticky, then adjusting the temperature to 80 ℃, allowing ethyl acetate to reflux in a condenser tube, slowly dropwise adding the rest 90g of methyl methacrylate, reacting for a period of time at a constant 80 ℃ after dropwise adding, cooling to room temperature to obtain comb-type high molecular weight polymethyl methacrylate seed solution for standby;
(3) Synthesis of comb-type ultra-high molecular weight polymethyl methacrylate: 120g of comb-type high molecular weight polymethyl methacrylate seed solution is taken, wherein the content of the comb-type high molecular weight polymethyl methacrylate is 20g, the comb-type high molecular weight polymethyl methacrylate seed solution is transferred into a 2L reaction kettle with a double-planetary stirrer under the protection of nitrogen, the nitrogen is introduced into the reaction kettle for stirring, the temperature is adjusted to 80 ℃, and when reflux occurs in a condensing tube, 1500g of methyl methacrylate monomer is slowly added dropwise, and the dropping speed is proper when the reflux in the condensing tube is stable. In the process of dropwise adding the monomer, the solvent is removed through a condenser tube, and the rest methyl methacrylate monomer is continuously and slowly dropwise added, so that the stirring is ensured to be operated normally. After the solid content reached 45%, the material was transferred to another vessel under nitrogen protection, unreacted methyl methacrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, sending the particles or powder into a drying chamber, vacuum drying at 110 ℃, cooling, and sealing by a vacuum packaging method.
Example 2
The embodiment provides a synthesis method of comb-type ultrahigh molecular weight polymethyl methacrylate, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: according to the styrene: allyl 2-bromopropionate: allyl propionate: azodiisobutylcyanide mass ratio = 100:28:93:0.8, weighing and mixing all the reagents, adding 500g of toluene solvent, introducing nitrogen into a 1000mL reaction bottle, stirring, raising the temperature to 85 ℃, slowly dripping the mixed reagents, reacting for a period of time at constant temperature after dripping, and rotationally steaming out toluene to obtain powdery styrene and 2-bromopropionic acid allyl ester copolymer which is a comb-type halogenated initiator, wherein N=15;
(2) Preparation of comb-type high molecular weight polymethyl methacrylate seeds: firstly taking 100g of methyl methacrylate which is subjected to reduced pressure distillation treatment, introducing nitrogen to remove oxygen for standby, adding 500g of ethyl acetate into a 1000mL three-port reaction bottle, introducing nitrogen to stir, sequentially adding 0.2g of styrene and 2-bromopropionic acid allyl copolymer, 0.2g of copper powder, 0.15g of cuprous bromide, 0.05g of pentamethyldiethylenetriamine and 0.05g of disodium ethylenediamine tetraacetate, heating to 50 ℃, adding 10g of methyl methacrylate at one time, reacting until the solution is slightly sticky, then adjusting the temperature to 80 ℃, allowing ethyl acetate to reflux in a condenser tube, slowly dropwise adding the rest 90g of methyl methacrylate, reacting for a period of time at a constant 80 ℃ after dropwise adding is completed, cooling to room temperature, and obtaining a comb-type high molecular weight polymethyl methacrylate seed solution for standby;
(3) Synthesis of comb-type ultra-high molecular weight polymethyl methacrylate: 120g of comb-type high molecular weight polymethyl methacrylate seed solution is taken, wherein the content of the comb-type high molecular weight polymethyl methacrylate is 20g, the comb-type high molecular weight polymethyl methacrylate seed solution is transferred into a 2L reaction kettle with a double-planetary stirrer under the protection of nitrogen, the nitrogen is introduced into the reaction kettle for stirring, the temperature is adjusted to 80 ℃, and when reflux occurs in a condensing tube, 1500g of methyl methacrylate monomer is slowly added dropwise, and the dropping speed is proper when the reflux in the condensing tube is stable. In the process of dropwise adding the monomer, the solvent is removed through a condenser tube, and the rest methyl methacrylate monomer is continuously and slowly dropwise added, so that the stirring is ensured to be operated normally. After the solid content reached 45%, the material was transferred to another vessel under nitrogen protection, unreacted methyl methacrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, sending the particles or powder into a drying chamber, vacuum drying at 110 ℃, cooling, and sealing by a vacuum packaging method.
Example 3
The embodiment provides a synthesis method of comb-type ultrahigh molecular weight polymethyl methacrylate, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: step (1) is the same as in example 1;
(2) Preparation of comb-type high molecular weight polymethyl methacrylate seeds: step 1 (2) of the same example
(3) Synthesis of comb-type ultra-high molecular weight polymethyl methacrylate: 120g of comb-type high molecular weight polymethyl methacrylate seed solution is taken, wherein the content of the comb-type high molecular weight polymethyl methacrylate is 20g, the comb-type high molecular weight polymethyl methacrylate seed solution is transferred into a 2L reaction kettle with a double-planetary stirrer under the protection of nitrogen, the nitrogen is introduced into the reaction kettle for stirring, the temperature is adjusted to 80 ℃, and when reflux occurs in a condensing tube, 1500g of methyl methacrylate monomer is slowly added dropwise, and the dropping speed is proper when the reflux in the condensing tube is stable. At the same time as the dropwise addition, the solvent was removed through a condenser tube. After the dropwise addition was completed, the material was transferred to another vessel under nitrogen protection, sealed with nitrogen gas, stored at 50 ℃ for three months, and then unreacted methyl methacrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, feeding the particles or powder into a drying chamber, and vacuum drying at 110 ℃. Cooling, and vacuum packaging.
Example 4
The embodiment provides a synthesis method of comb-type ultra-high molecular weight polybutylmethacrylate, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: step (1) is the same as in example 2;
(2) Preparation of comb-type high molecular weight polybutylmethacrylate seeds: firstly taking 100g of butyl methacrylate treated by reduced pressure distillation, and introducing nitrogen to remove oxygen for standby. In a 1000mL three-port reaction bottle, 500g of ethyl acetate is added, nitrogen is introduced and stirred, 0.2g of copolymer of styrene and 2-bromopropionic acid allyl ester, 0.15g of copper powder, 0.4g of cuprous bromide, 0.5g of pentamethylene diethylenetriamine and 0.25g of disodium ethylenediamine tetraacetate are sequentially added, the temperature is regulated to 50 ℃, 10g of butyl methacrylate is added at one time, the mixture is reacted until the solution is slightly sticky, then the temperature is regulated to 80 ℃, the ethyl acetate is refluxed in a condenser tube, the rest 90g of butyl methacrylate is slowly added dropwise, and the dropping speed is regulated to be in a reflux state. After the completion of the dropwise addition, the reaction was carried out at a constant temperature of 85℃for a while. The reaction is carried out until the butyl methacrylate is completely consumed, and the reaction is cooled to room temperature, so as to obtain comb-type high molecular weight polybutyl methacrylate seeds;
(3) Synthesis of comb-type ultra-high molecular weight polybutylmethacrylate: 120g of comb-type high molecular weight polybutylmethacrylate seed solution is taken, wherein the content of the comb-type high molecular weight polybutylmethacrylate is 20g, the comb-type high molecular weight polybutylmethacrylate seed solution is transferred into a 2L reaction kettle with a double planetary mixer under the protection of nitrogen, the nitrogen is introduced into the reaction kettle for stirring, the temperature is regulated to 80 ℃, and when reflux occurs in a condensing tube, 1500g of polybutylmethacrylate monomer is slowly dripped, and the dripping speed is proper when the reflux in the condensing tube is stable. In the monomer dripping process, the solvent is removed through the condensing tube, and the rest monomers are slowly dripped continuously, so that the stirring is ensured to be operated normally. Transferring the material to another container under the protection of nitrogen until the solid content reaches 40%, removing unreacted butyl methacrylate monomer under reduced pressure, collecting, pulverizing the material into particles or powder after the material is not completely hardened, sending into a drying chamber, vacuum drying at 110 ℃, cooling, and sealing by vacuum packaging method.
Example 5
The embodiment provides a method for synthesizing comb-type ultra-high molecular weight polymethyl methacrylate, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: step (1) is the same as in example 1;
(2) Preparation of comb-type high molecular weight poly (trimethylsilyl methacrylate) seeds: firstly taking 100g of trimethyl silicon methacrylate treated by reduced pressure distillation, and introducing nitrogen to remove oxygen for later use. In a 1000mL three-port reaction bottle, 500g of ethyl acetate is added, nitrogen is introduced and stirred, 0.2g of copolymer of styrene and allyl 2-bromoisobutyrate, 0.05g of copper powder, 0.03g of cuprous bromide, 0.05g of pentamethyldiethylenetriamine and 0.05g of disodium ethylenediamine tetraacetate are sequentially added, 5g of trimethyl silicon methacrylate is added at one time at a temperature of 50 ℃ to react until the solution is slightly sticky, then the temperature of 80 ℃ is adjusted, reflux of ethyl acetate occurs in a condenser tube, the rest 95g of trimethyl silicon methacrylate is slowly added dropwise, and the dropping speed is in a reflux state as standard. After the completion of the dropwise addition, the reaction was carried out at a constant temperature of 80℃for a while. The reaction is carried out until the trimethyl silicone methacrylate is completely consumed, and the reaction is cooled to room temperature, so as to obtain comb-type high molecular weight polymethyl silicone acrylate seed solution;
(3) Preparation of comb-type ultra-high molecular weight polymethyl methacrylate: 120g of comb-type high-molecular-weight polymethyl methacrylate seed solution is taken, wherein the content of the comb-type high-molecular-weight polymethyl methacrylate is 20g, the comb-type high-molecular-weight polymethyl methacrylate seed solution is transferred into a 2L reaction kettle with a double-planetary stirrer under the protection of nitrogen, the nitrogen is introduced into the reaction kettle for stirring, the temperature is adjusted to 80 ℃, and when reflux occurs in a condensing tube, 1500g of trimethyl methacrylate monomer is slowly added dropwise, and the dropping speed is proper when the reflux in the condensing tube is stable. In the dropping process, the solvent is removed through a condensing tube, and the rest of the trimethylsilyl methacrylate monomer is continuously and slowly dropped, so that the normal operation of stirring is ensured. After the solid content reached 45%, the material was transferred to another vessel under nitrogen protection, and unreacted trimethylsilyl methacrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, feeding the particles or powder into a drying chamber, and vacuum drying at 110 ℃. Cooling, and vacuum packaging.
Example 6
The embodiment provides a synthesis method of comb-type ultra-high molecular weight poly (trifluoroethyl methacrylate), which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: step (1) is the same as in example 2;
(2) Preparation of comb-type high molecular weight poly (trifluoroethyl methacrylate) seeds: firstly taking 100g of trifluoroethyl methacrylate treated by reduced pressure distillation, and introducing nitrogen to remove oxygen for later use. In a 1000mL three-port reaction bottle, 500g of ethyl acetate is added, nitrogen is introduced and stirred, 0.2g of copolymer of styrene and 2-bromopropionic acid allyl ester, 0.02g of dibromoethane, 0.05g of copper powder, 0.03g of cuprous bromide, 0.05g of pentamethyldiethylenetriamine and 0.05g of disodium ethylenediamine tetraacetate are sequentially added, the temperature is regulated to 50 ℃, 5g of trifluoroethyl methacrylate is added at one time, the reaction is carried out until the solution is slightly viscous, then the temperature is regulated to 80 ℃, the ethyl acetate is refluxed in a condenser tube, the rest 95g of trifluoroethyl methacrylate is slowly dripped, and the dripping speed is regulated to be the standard of the reflux temperature. After the completion of the dropwise addition, the reaction was carried out at a constant temperature of 80℃for a while. The reaction is carried out until the trifluoroethyl methacrylate is completely consumed, and the reaction is cooled to room temperature, so as to obtain comb-type high molecular weight poly (trifluoroethyl methacrylate) seed solution;
(3) Preparing comb-type ultra-high molecular weight poly (trifluoroethyl methacrylate), taking 120g of comb-type high molecular weight poly (trifluoroethyl methacrylate) seed solution, transferring the comb-type high molecular weight poly (trifluoroethyl methacrylate) seed solution to a 2L reaction kettle with a double planetary mixer under the protection of nitrogen, introducing nitrogen, stirring, adjusting the temperature to 80 ℃, slowly dropwise adding 1500g of the trifluoroethyl methacrylate monomer when reflux occurs in a condenser tube, and ensuring that the dropping speed is proper when the reflux in the condenser tube is stable. In the monomer dripping process, the solvent is removed through the condensing tube, and the rest monomers are slowly dripped continuously, so that the stirring is ensured to be operated normally. After the solid content reached 45%, the material was transferred to another vessel under nitrogen protection, and unreacted trifluoroethyl methacrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, feeding the particles or powder into a drying chamber, and vacuum drying at 110 ℃. Cooling, and vacuum packaging.
Example 7
The embodiment provides a synthesis method of a comb-block ultrahigh molecular weight methyl methacrylate-ethyl acrylate copolymer, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: step (1) is the same as in example 1;
(2) Preparation of comb-type high molecular weight poly (ethyl acrylate) seeds: firstly taking 100g of ethyl acrylate treated by reduced pressure distillation, introducing nitrogen to remove oxygen for standby, adding 500g of ethyl acetate into a 1000mL three-port reaction bottle, introducing nitrogen to stir, sequentially adding 0.2g of styrene and 2-bromopropionic acid allyl copolymer, 0.2g of copper powder, 0.15g of cuprous bromide, 0.05g of pentamethyldiethylenetriamine and 0.05g of disodium ethylenediamine tetraacetate, regulating the temperature to 50 ℃, adding 10g of ethyl acrylate at one time, reacting until the solution is slightly viscous, then regulating the temperature to 80 ℃, allowing the ethyl acetate to reflux in a condenser, slowly dropwise adding the rest 90g of ethyl acrylate, and taking the dropwise adding speed as a standard in a reflux state. After the dripping is finished, reacting for a period of time at a constant temperature of 80 ℃ until the ethyl acrylate is completely consumed, and cooling to room temperature for standby to obtain comb-type high molecular weight polyethyl acrylate seed solution;
(3) Preparing comb-type block ultra-high molecular weight ethyl acrylate and methyl methacrylate copolymer, taking 120g of comb-type high molecular weight ethyl acrylate seed solution, transferring the comb-type high molecular weight ethyl acrylate seed solution into a 2L reaction kettle with a double-planetary stirrer under the protection of nitrogen, introducing nitrogen, stirring, adjusting the temperature to 80 ℃, slowly dropwise adding 280g of ethyl acrylate when reflux occurs in a condenser tube, and stabilizing the dropwise adding speed when reflux in the condenser tube is stable. After the ethyl acrylate monomer is added dropwise, the solvent is removed through a condenser tube, and 1200g of methyl methacrylate is continuously and slowly added dropwise, so that the stirring is ensured to be operated normally. Transferring the material to another container under the protection of nitrogen until the solid content reaches 40%, removing unreacted methyl methacrylate monomer under reduced pressure, collecting, pulverizing the material into particles or powder after the material is not completely hardened, sending into a drying chamber, vacuum drying at 110 ℃, cooling, and sealing by vacuum packaging method. The mass ratio of the polyethyl acrylate to the polymethyl methacrylate chain segment in the copolymer is about 1:1 in sample detection.
Example 8
The embodiment provides a synthesis method for copolymerization of comb-block ultra-high molecular weight trifluoroethyl methacrylate and butyl acrylate, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator, step (1) of example 2;
(2) Preparing comb-type high molecular weight poly (trifluoroethyl methacrylate) seeds, and performing the step (2) in the same way as in the example 6;
(3) Preparing comb-type block ultra-high molecular weight trifluoroethyl methacrylate and butyl acrylate copolymer, taking 120g of comb-type high molecular weight trifluoroethyl methacrylate seed solution, transferring the comb-type high molecular weight trifluoroethyl methacrylate with the content of 20g into a 2L reaction kettle with a double planetary mixer under the protection of nitrogen, introducing nitrogen, stirring, adjusting the temperature to 80 ℃, slowly dropwise adding 1500g of butyl acrylate monomer when reflux occurs in a condenser, and stabilizing the dropwise adding speed until reflux in the condenser. In the process of dropwise adding the monomers, the solvent is removed through a condenser tube, and the rest butyl acrylate monomers are slowly dropwise added, so that the stirring is ensured to be operated normally. After the solid content reached 45%, the material was transferred to another vessel under nitrogen protection, and unreacted butyl acrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, feeding the particles or powder into a drying chamber, and vacuum drying at 110 ℃. Cooling, and vacuum packaging. The mass ratio of the poly (trifluoroethyl methacrylate) to the poly (butyl acrylate) chain segment in the copolymer is about 1:35.
Example 9
The embodiment provides a synthesis method of comb-block ultra-high molecular weight trifluoroethyl methacrylate, 2,4,6 tribromophenyl methacrylate and methyl methacrylate copolymer, which comprises the following specific steps:
(1) Preparation of comb-type halide initiator: step (1) is the same as in example 2;
(2) Preparing comb-type high molecular weight poly (trifluoroethyl methacrylate) seeds, and performing the step (2) in the same way as in the example 6;
Preparation of comb-block high molecular weight trifluoroethyl methacrylate and 2,4,6 tribromophenyl methacrylate copolymer seed:
Taking 300g of comb-type high molecular weight poly (trifluoroethyl methacrylate) seed solution, transferring the comb-type high molecular weight poly (trifluoroethyl methacrylate) seed solution to a 1000mL three-port reaction bottle under the protection of nitrogen, introducing nitrogen, stirring, adjusting the temperature to 80 ℃, mixing 250g of ethyl acetate with 50g of 2,4,6 tribromophenyl methacrylate, slowly dropwise adding the mixture into the reaction bottle, taking the dropwise adding speed as a standard, reacting for a period of time at a constant 80 ℃ after the dropwise adding is finished until the 2,4,6 tribromophenyl methacrylate is completely reacted and consumed, and cooling to room temperature to obtain comb-type block high molecular weight copolymer seed solution of the 2,4,6 tribromophenyl methacrylate and the 2,4,6 tribromophenyl methacrylate;
(3) Preparation of comb-block ultra-high molecular weight trifluoroethyl methacrylate, 2,4,6 tribromophenyl methacrylate and methyl methacrylate by copolymerization: taking 240g of comb-block high molecular weight trifluoroethyl methacrylate and 2,4,6 tribromophenyl methacrylate copolymer seed solution, wherein the content of the comb-block high molecular weight trifluoroethyl methacrylate and 2,4,6 tribromophenyl methacrylate copolymer is 40g, transferring the comb-block high molecular weight trifluoroethyl methacrylate and 2,4,6 tribromophenyl methacrylate copolymer into a 2L reaction kettle with a double-planetary stirrer under the protection of nitrogen, introducing nitrogen for stirring, adjusting the temperature to 80 ℃, slowly dropwise adding 1500g of methyl methacrylate monomer when reflux occurs in a condenser tube, and ensuring that the dropwise adding speed is stable when reflux occurs in the condenser tube. In the process of dropwise adding the monomer, the solvent is removed through a condenser tube, and the rest methyl methacrylate monomer is continuously and slowly dropwise added, so that the stirring is ensured to be operated normally. After the solid content reached 45%, the material was transferred to another vessel under nitrogen protection, unreacted methyl methacrylate monomer was removed under reduced pressure and recovered. When the material is not fully hardened, pulverizing the material into particles or powder, feeding the particles or powder into a drying chamber, and vacuum drying at 110 ℃. Cooling, and vacuum packaging. The mass ratio of the trifluoroethyl methacrylate, the 2,4,6 tribromophenyl methacrylate and the methyl methacrylate chain segments in the copolymer is about 1:1:35.
The comb-type ultra-high molecular weight polymers synthesized in examples 1 to 9 were tested for weight average molecular weight and the results are shown in Table 1.
TABLE 1
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The synthesis method of the comb-type ultra-high molecular weight polymer is characterized by comprising the following steps of:
(1) Preparation of comb-type halide initiator: carrying out free radical polymerization on styrene and 2-bromoisobutyric acid allyl ester and isobutyric acid allyl ester, or styrene and 2-bromopropionic acid allyl ester and allyl propionate to obtain a copolymer of styrene and 2-bromoisobutyric acid allyl ester or a copolymer of styrene and 2-bromopropionic acid allyl ester, namely a comb-type halogenated initiator;
(2) Preparation of polymer seeds: placing the monomer into a dripping device for standby, adding an organic solvent into a reaction kettle, introducing nitrogen to remove oxygen for standby, adding the comb-type halogenated initiator, the catalyst, the ligand and the auxiliary agent into the reaction kettle, dripping a small amount of monomer under the condition of stirring, heating to 20-60 ℃, heating to 60-100 ℃ after the system becomes slightly viscous, slowly dripping the residual monomer, carrying out heat preservation reaction, and cooling to obtain polymer seeds;
the monomer is an alkyl ester or a mixture of several alkyl esters;
the catalyst is metal or metal ions;
(3) Synthesis of comb-type ultra-high molecular weight polymer: transferring polymer seeds into a reactor under the protection of nitrogen, introducing nitrogen, heating to 60-100 ℃, slowly dropwise adding excessive monomers under the condition of stirring, simultaneously evaporating the solvent, reacting at constant temperature after dropwise adding, transferring the product into another reactor under the protection of nitrogen, distilling unreacted monomers under reduced pressure, crushing, and vacuum drying to obtain the comb-type ultrahigh molecular weight polymer;
The weight average molecular weight of the comb-type ultra-high molecular weight polymer is higher than 10000 ten thousand.
2. The method for synthesizing the comb-type ultra-high molecular weight polymer according to claim 1, wherein the monomer is prepared by removing water, distilling under reduced pressure, and then introducing nitrogen to remove dissolved oxygen.
3. The method for synthesizing a comb-type ultrahigh-molecular-weight polymer according to any one of claims 1 to 2, wherein the average number of halogen-containing side chains in the copolymer molecule in the step (1) is N, N being an integer of 5 to 50.
4. The method for synthesizing a comb-type ultra-high molecular weight polymer according to any one of claims 1 to 2, wherein the organic solvent is one or more of dimethyl carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate;
The catalyst is one or more of cuprous iodide, cuprous bromide, cuprous chloride and copper powder;
The ligand is 2, 2-dipyridine and/or pentamethyl diethylenetriamine;
the auxiliary agent is one or more of disodium ethylenediamine tetraacetate, tetrahydrofuran, potassium iodide and carboxyl copper.
5. The method for synthesizing a comb-type ultra-high molecular weight polymer according to any one of claims 1 to 2, wherein the mass ratio of the monomer to the organic solvent in the step (2) is 1:3 to 5, and the mass ratio of the monomer, the comb-type halide initiator, the catalyst, the ligand and the auxiliary agent is 100:0.01 to 1:0.01 to 1:0.05 to 0.5.
6. The method for synthesizing a comb-type ultra-high molecular weight polymer according to claim 1, wherein the reaction is carried out at a constant temperature in the step (3) until the solid content is 35-45%, and the temperature of vacuum drying is 100-140 ℃.
7. A comb-type ultra-high molecular weight polymer synthesized by any one of the synthesis methods of claims 1 to 6, characterized in that the weight average molecular weight of said comb-type ultra-high molecular weight polymer is higher than 10000 ten thousand.
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