CN107973882A - A kind of method for preparing ethyl cellulose graft copolymer with the light-initiated ATRP of no metal - Google Patents
A kind of method for preparing ethyl cellulose graft copolymer with the light-initiated ATRP of no metal Download PDFInfo
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- CN107973882A CN107973882A CN201610922494.8A CN201610922494A CN107973882A CN 107973882 A CN107973882 A CN 107973882A CN 201610922494 A CN201610922494 A CN 201610922494A CN 107973882 A CN107973882 A CN 107973882A
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- Prior art keywords
- ethyl cellulose
- light
- metal
- graft copolymer
- photoinitiator
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- 239000001856 Ethyl cellulose Substances 0.000 title claims abstract description 107
- 229920001249 ethyl cellulose Polymers 0.000 title claims abstract description 107
- 235000019325 ethyl cellulose Nutrition 0.000 title claims abstract description 107
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 48
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 42
- 101710141544 Allatotropin-related peptide Proteins 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 150000003384 small molecules Chemical class 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Natural products OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- QXBUYALKJGBACG-UHFFFAOYSA-N 10-methylphenothiazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3SC2=C1 QXBUYALKJGBACG-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 206010034960 Photophobia Diseases 0.000 claims description 2
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 208000013469 light sensitivity Diseases 0.000 claims description 2
- -1 methacrylic acid furfuryl alcohol ester Chemical class 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- 239000003205 fragrance Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 230000001960 triggered effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 16
- 239000002244 precipitate Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229960003750 ethyl chloride Drugs 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000977 initiatory effect Effects 0.000 description 11
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 125000003431 oxalo group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- ZTVIKZXZYLEVOL-DGKWVBSXSA-N 2-hydroxy-2-phenylacetic acid [(1R,5S)-8-methyl-8-azabicyclo[3.2.1]octan-3-yl] ester Chemical group C([C@H]1CC[C@@H](C2)N1C)C2OC(=O)C(O)C1=CC=CC=C1 ZTVIKZXZYLEVOL-DGKWVBSXSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005059 dormancy Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of method for preparing ethyl cellulose graft copolymer based on the light-initiated ATRP of no metal, comprise the following steps：The first step：Make small molecule photoinitiator, oxalyl chloride reacts the photoinitiator that 1~5h prepares chloride at 0~25 DEG C；Second step：The photoinitiator reaction of ethyl cellulose and chloride prepares ethyl cellulose macromolecular photoinitiator；3rd step：Using the light-initiated ATRP method of no metal, make ethyl cellulose macromolecular photoinitiator, catalyst, monomer in good solvent, 1~10h is reacted under 10~60 DEG C of ultraviolet lamps, polymer precipitates in methyl alcohol, and filtration drying obtains product.The toxic action of the metal catalytics such as copper can be used to avoid common ATRP method by this method, is had the advantages that green, easy to operate, efficient.
Description
Technical field
The present invention relates to a kind of method for preparing ethyl cellulose graft copolymer using the light-initiated ATRP method of no metal.
Background technology
With the increasingly consumption of fossil feedstock, great pass is received to prepare high molecular polymer using renewable resource
Note.Cellulose is the biomass resource of yield maximum in the world, and ethyl cellulose is that a kind of commercialized cellulose ethers derives
Thing, can be dissolved in a variety of organic solvents, be commonly used for synthetic plastic, coating, rubber substitute, ink, insulating materials, it is also possible to
Make adhesive, textile finish etc..
Thermoplastic elastomer (TPE) be it is a kind of and meanwhile have thermoplasticity and elasticity material, its be widely used in as medical instrument,
The fields such as auto industry, clothes manufacture.The thermoplastic elastomer (TPE) of graft type structure is the thermoplastic body elasticity body material of a new generation.For
The added value of ethyl cellulose is improved, the thermoplastic elastic material based on ethyl cellulose is prepared, is usually changed using grafting
The method of property.Atom transfer radical polymerization (ATRP) is a kind of method of most common graft modification.Traditional ATRP method needs
To carry out in the absence of oxygen, severe reaction conditions；Copper is needed as catalyst at the same time, and catalyst is difficult after reaction
It is clean to remove, so as to limit the application range of polymeric material.Recent years, there has been proposed the light-initiated ATRP of no metal
Concept, it is to be swapped using ultraviolet light between catalytic activity kind and dormancy kind, so as to achieve the purpose that controllable polymerization.
Ethyl cellulose graft copolymer is prepared using the light-initiated ATRP method of no metal, not only avoid the poison of copper catalyst in product
Property effect, improve the application range of graft copolymer, and of low cost, it is easy to operate, it is environmentally protective, be more in line with the modern times
The requirement of Green Chemistry, just because of these advantages, this method of the no light-initiated ATRP of metal is obtaining more and more people
Concern.
The content of the invention
The object of the present invention is to provide a kind of graft copolymerization that ethyl cellulose is prepared using the light-initiated ATRP method of no metal
The method of thing, the drawbacks of being difficult to remove using metallic catalyst so as to avoid traditional ATRP, makes the more green ring of polymerization process
Protect, and improve the added value of ethyl cellulose, expand its application range.
Technical solution：The technical scheme is that：A kind of ethyl cellulose prepared based on the light-initiated ATRP of no metal
Graft copolymer, structure are as follows：
Main chain is ethyl cellulose, side chain be with random or block structure copolymer, wherein, R2 is the knot of monomer
Structure unit, n and m are side chain copolymer segment monomer polymerization degree；
The ethyl cellulose graft copolymer prepared based on the light-initiated ATRP of no metal is prepared, is concretely comprised the following steps：The
One step：Small molecule photoinitiator α-bromo-acid, oxalyl chloride is set by certain mol proportion example to be [photoinitiator]/[oxalyl chloride]=1:
(0.5~2) reacts the photoinitiator that 1~5h prepares chloride in dichloromethane solvent at 0~25 DEG C；Second step：Ethyl
Cellulose reacts 10~24h with acid binding agent and the photoinitiator of chloride in good solution system and prepares ethyl cellulose at room temperature
Macromolecular photoinitiator；3rd step：Using the light-initiated ATRP method of no metal, make ethyl cellulose macromolecular photoinitiator, catalysis
Agent, monomer 1, monomer 2 in molar ratio example [ethyl cellulose macromolecular photoinitiator]/[monomer 1]/[monomer 2]/[catalyst]=
1: (2~2000): (2~2000): (0.1~1) reacts 1 in good solvent system under 10~60 DEG C of certain luminous intensities of ultraviolet lamp
~10h, polymer precipitate in methyl alcohol, and filtration drying obtains ethyl cellulose graft copolymer.
The viscosity of the ethyl cellulose for 3~7,18~22,45~55,90~110,180~220,270~
Any of 330mPa.s.
The acid binding agent used described in second step is any of triethylamine and 4-dimethylaminopyridine (DMAP).
Good solvent described in second step and the 3rd step is anhydrous tetrahydro furan, n,N-Dimethylformamide, dimethyl second
Any of acid amides.
Ethyl cellulose macromolecular photoinitiator its structure prepared described in second step is：
The initiator has light sensitivity, can trigger monomer under ultra violet lamp
Polymerization.
Catalyst described in 3rd step is 10 methyl phenothiazine, 5,10- dihydros -5,10- dimethylphenazine, 1,10- Féraud
Any of quinoline, 10- phenyl phenthazine, 10- (4- methoxyphenyls)-phenthazine, 10- (1- naphthyls)-phenthazine.
Monomer described in 3rd step for lauryl methacrylate (LMA), methacrylic acid tetrahydro furfuryl ester (THFMA),
Octadecyl methacrylate (SMA), methyl methacrylate (MMA), butyl acrylate (BA), butyl methacrylate
(MBA), any two lists in methacrylic acid furfuryl alcohol ester, dibutyl itaconate, hydroxyethyl methacrylate, hydroxy-ethyl acrylate
The combination of body.
Ultraviolet intensity of light is between 0.01~0.5mW/cm described in 3rd step.
Beneficial effect：
1. the side of the graft copolymer according to the present invention that ethyl cellulose is prepared using the light-initiated ATRP method of no metal
Method, avoid traditional ATRP using metallic catalyst be difficult to remove the drawbacks of, have the characteristics that it is environmentally protective sustainable, so as to open up
The wide application range of graft copolymer.
2. the graft copolymer of the ethyl cellulose according to the present invention prepared using the light-initiated ATRP method of no metal can
Can be carried out effectively by adjusting species and the ratio of monomer as a kind of novel thermoplastic elastomer, its structure and performance
Regulation and control, so as to substantially increase the added value of ethyl cellulose.
Brief description of the drawings
Fig. 1 is the ultraviolet light of ethyl cellulose, α-bromo-acid and ethyl cellulose macromolecular photoinitiator in embodiment 1
Spectrogram.
Fig. 2 is the infrared spectrogram of ethyl cellulose macromolecular photoinitiator in embodiment 1.
Fig. 3 is that the GPC of ethyl cellulose macromole evocating agent and ethyl cellulose graft copolymer schemes in embodiment 1.
Fig. 4 is ethyl cellulose graft copolymer in embodiment 11HNMR schemes.
Fig. 5 is the load-deformation curve of the one way tensile test of ethyl cellulose graft copolymer in embodiment 1.
Embodiment
Since the method for the graft copolymer for preparing ethyl cellulose based on the light-initiated ATRP method of no metal has a significant impact,
With reference to the embodiment content that the present invention is furture elucidated, but these embodiments are not intended to limit protection scope of the present invention.
Embodiment 1：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 500: 0.1 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1：α-bromo-acid 1g (4.65mmol) is added in round-bottomed flask, add methylene chloride dissolving, and oxalyl is added dropwise
Chlorine 0.71g (5.58mmol) reacts 3h at 5 DEG C, and the photoinitiator of chloride, acyl chlorides content 2.86mmol/g is made；
Step 2：Viscosity is the ethyl cellulose 0.30g (hydroxy radical content is about 1.37mmol) and 4- bis- of 45~55mPa.s
Dimethylaminopyridine 0.50g (4.10mmol) is added in flask to be dissolved with tetrahydrofuran, adds the photoinitiator of 1.43g chlorides
(4.10mmol), is stirred at room temperature 24h, and reaction solution is instilled in distilled water, and filtration drying, is prepared into ethyl cellulose macromolecular light and draws
Send out agent, initiation point content 0.8mmol/g；
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.08mmol/g), monomer 1THFMA 6.52ml (40mmol), monomer 2LMA 11.67ml (40mmol), catalyst 10- first
Base phenthazine 0.0017g (0.008mmol) is dissolved in Tetrahydrofuran System, logical nitrogen 20min, 25 DEG C, ultraviolet intensity of light
5h is reacted under 0.05mW/cm, product precipitates in methyl alcohol, and then filtration drying obtains cellulose graft copolymer, product molecule
Measure Mn：54000g/mol.
Embodiment 2：Viscosity be 270~330mPa.s ethyl cellulose, [ethyl cellulose macromolecular photoinitiator]/
[monomer 1]/[monomer 2]/[catalyst]=1: 500: 300: 0.5 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1 such as embodiment 1；
Step 2：Viscosity is the ethyl cellulose 0.30g (hydroxy radical content is about 1.37mmol) and 4- of 270~330mPa.s
Dimethyl aminopyridine 0.50g (4.10mmol) is added in flask to be dissolved with tetrahydrofuran, adds the light-initiated of 1.43g chlorides
Agent (4.10mmol), is stirred at room temperature 24h, and reaction solution is instilled in distilled water, and filtration drying, is prepared into ethyl cellulose macromolecular light
Initiator, initiation point content 0.6mmol/g
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.06mmol/g), monomer 1THFMA4.89ml (30mmol), monomer 2LMA 5.25ml (18mmol), catalyst 10- methyl
Phenthazine 0.0064g (0.03mmol) is dissolved in Tetrahydrofuran System, logical nitrogen 20min, 25 DEG C, ultraviolet intensity of light
5h is reacted under 0.05mW/cm, product precipitates in methyl alcohol, and then filtration drying obtains cellulose graft copolymer, product molecule
Measure Mn：50000g/mol.
Embodiment 3：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 500: 0.1 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1：α-bromo-acid 1g (4.65mmol) is added in round-bottomed flask, add methylene chloride dissolving, and oxalyl is added dropwise
Chlorine 0.59g (4.65mmol) reacts 5h at 5 DEG C, and the photoinitiator of chloride, acyl chlorides content 2.38mmol/g is made；；
Step 2：Viscosity is the ethyl cellulose 0.30g (hydroxy radical content is about 1.37mmol) and 4- bis- of 45~55mPa.s
Dimethylaminopyridine 0.50g (4.10mmol) is added in flask to be dissolved with tetrahydrofuran, adds the photoinitiator of 1.72g chlorides
(4.10mmol), is stirred at room temperature 24h, and reaction solution is instilled in distilled water, and filtration drying, is prepared into ethyl cellulose macromolecular light and draws
Send out agent, initiation point content 0.7mmol/g；；
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.07mmol/g), monomer 1THFMA 5.70ml (35mmol), monomer 2LMA 10.21ml (35mmol), catalyst 10- first
Base phenthazine 0.0015g (0.007mmol) is dissolved in Tetrahydrofuran System, logical nitrogen 20min, 25 DEG C, ultraviolet intensity of light
6h is reacted under 0.05mW/cm, product precipitates in methyl alcohol, and then filtration drying obtains cellulose graft copolymer, product molecule
Measure Mn：56000g/mol.
Embodiment 4：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 500: 0.1 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1 such as embodiment 1；
Step 2：Viscosity is the ethyl cellulose 0.30g (hydroxy radical content is about 1.37mmol) and three second of 45~55mPa.s
Amine 0.41g (4.10mmol) is added in flask to be dissolved with tetrahydrofuran, adds the photoinitiator of 1.43g chlorides
(4.10mmol), is stirred at room temperature 24h, and reaction solution is instilled in distilled water, and filtration drying, is prepared into ethyl cellulose macromolecular light and draws
Send out agent, initiation point content 0.8mmol/g；
Step 3 such as embodiment 1.
Embodiment 5：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 500: 0.3 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1 such as embodiment 1；
Step 2 such as embodiment 1；
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.08mmol/g), monomer 1THFMA6.52ml (40mmol), monomer 2LMA 11.67ml (40mmol), catalyst 5,10- bis-
Hydrogen -5,10- dimethylphenazine 0.0050g (0.024mmol) is dissolved in n,N-Dimethylformamide system, leads to nitrogen 20min,
25 DEG C, 3h is reacted under ultraviolet intensity of light 0.05mW/cm, and product precipitates in methyl alcohol, and then filtration drying obtains cellulose and connects
Graft copolymer, molecular weight of product Mn：47000g/mol.
Embodiment 6：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 700: 0.1 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1 such as embodiment 1；
Step 2 such as embodiment 1；
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.08mmol/g), monomer 1MMA 4.24ml (40mmol), monomer 2BA 8.06ml (56mmol), catalyst 10- methyl fens
Thiazine 0.0017g (0.008mmol) is dissolved in n,N-Dimethylformamide system, logical nitrogen 20min, 25 DEG C, ultraviolet light
3h is reacted under intensity 0.05mW/cm, product precipitates in methyl alcohol, and then filtration drying obtains cellulose graft copolymer, product
Molecular weight Mn：45000g/mol.
Embodiment 7：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 500: 0.5 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1 such as embodiment 1；
Step 2 such as embodiment 1；
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.08mmol/g), monomer 1MMA 4.24ml (40mmol), monomer 2BA 5.75ml (40mmol), catalyst 10- methyl fens
Thiazine 0.0085g (0.04mmol) is dissolved in Tetrahydrofuran System, logical nitrogen 20min, 25 DEG C, ultraviolet intensity of light
5h is reacted under 0.05mW/cm, product precipitates in methyl alcohol, and then filtration drying obtains cellulose graft copolymer, product molecule
Measure Mn：50000g/mol.
Embodiment 8：Viscosity is the ethyl cellulose of 45~55mPa.s, [ethyl cellulose macromolecular photoinitiator]/[single
Body 1]/[monomer 2]/[catalyst]=1: 500: 500: 0.1 (molar ratio) prepares ethyl cellulose graft copolymer
Step 1 such as embodiment 1；
Step 2 such as embodiment 1；
Step 3：Using the light-initiated ATRP method of no metal, by ethyl cellulose macromolecular photoinitiator 0.1g, (initiation point contains
Measure 0.08mmol/g), monomer 1MMA 4.24ml (40mmol), monomer 2BA 5.75ml (40mmol), catalyst 10- methyl fens
Thiazine 0.0085g (0.04mmol) is dissolved in Tetrahydrofuran System, logical nitrogen 20min, 25 DEG C, ultraviolet intensity of light 0.2mW/
5h is reacted under cm, product precipitates in methyl alcohol, and then filtration drying obtains cellulose graft copolymer, molecular weight of product Mn：
62000g/mol。
Spectrum analysis
Fig. 1 is the ultraviolet light of ethyl cellulose, α-bromo-acid and ethyl cellulose macromolecular photoinitiator in embodiment 1
Spectrogram：It can significantly find out after esterification on the ultraviolet spectrogram of ethyl cellulose macromolecular photoinitiator and occur
The characteristic peak of phenyl ring, shows that ethyl cellulose macromolecular photoinitiator is successfully prepared on obvious α-bromo-acid.
Fig. 2 is the infrared spectrum of ethyl cellulose macromolecular photoinitiator in embodiment 1：1740cm in figure-1Locate ester bond to inhale
Receive peak and also illustrate that α-bromo-acid is successfully introduced on the skeleton of ethyl cellulose, ethyl cellulose macromolecular photoinitiator system
Standby success.
Fig. 3 is that the GPC of ethyl cellulose macromolecular photoinitiator and ethyl cellulose graft copolymer schemes in embodiment 1：
Ethyl cellulose macromolecular photoinitiator can be significantly found out after the light-initiated ATRP polymerization reaction of no metal, and molecular weight has
Obvious increase, is mainly shown as that the elution volume of its GPC curve is less and less, this also show ethyl cellulose graft copolymerization
The successful synthesis of thing.
Fig. 4 is ethyl cellulose graft copolymer in embodiment 11H NMR scheme：By the light-initiated ATRP polymerization of no metal
After reaction, occur the corresponding diagnostic protons peak of phenyl ring in initiator at chemical shift 7.0-7.5ppm, show ethyl cellulose
The successful synthesis of plain graft copolymer.
Fig. 5 is the load-deformation curve of the one way tensile test of ethyl cellulose graft copolymer in embodiment 1：From figure
It is upper to can be seen that the ethyl cellulose graft copolymer has typical elastomer properties, can be as the thermoplastic elastomehc of a new generation
Elastomer material.
Claims (11)
- A kind of 1. method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal, it is characterised in that structure It is as followsMain chain is ethyl cellulose, side chain be with random or block structure copolymer, wherein, R2 is the structure list of monomer Member, n and m are side chain copolymer segment monomer polymerization degree.
- 2. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal described in claim 1 is prepared, It is characterized in that, step is：The first step：Making small molecule photoinitiator α-bromo-acid, oxalyl chloride presses certain mol proportion example in dichloromethane solvent, in The photoinitiator that 1~5h prepares chloride is reacted at 0~25 DEG C；Second step：Ethyl cellulose reacts 10 at room temperature in good solution system with acid binding agent and the photoinitiator of chloride~ 24h prepares ethyl cellulose macromolecular photoinitiator；3rd step：Using the light-initiated ATRP method of no metal, make ethyl cellulose macromolecular photoinitiator, catalyst, monomer 1, list Body 2 in good solvent, reacts 1~10h, polymer is in methanol by certain mol proportion example under 10~60 DEG C of certain luminous intensities of ultraviolet lamp Middle precipitation, filtration drying obtain ethyl cellulose graft copolymer.
- 3. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its Be characterized in that the viscosity of the ethyl cellulose for 3~7,18~22,45~55,90~110,180~220,270~ Any of 330mPa.s.
- 4. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, the reactant described in the first step is [photoinitiator]/[oxalyl chloride]=1: (0.5~2) in molar ratio.
- 5. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, the good solvent described in second step and the 3rd step is anhydrous tetrahydro furan, n,N-Dimethylformamide, dimethyl second Any of acid amides.
- 6. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, the use of acid binding agent is any of triethylamine and 4-dimethylaminopyridine (DMAP) in second step.
- 7. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, ethyl cellulose macromolecular photoinitiator its structure prepared in second step is：The initiator has light sensitivity, monomer can be triggered to gather under ultra violet lamp Close.
- 8. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its Be characterized in that, monomer described in the 3rd step for lauryl methacrylate (LMA), methacrylic acid tetrahydro furfuryl ester (THFMA), Octadecyl methacrylate (SMA), methyl methacrylate (MMA), butyl acrylate (BA), butyl methacrylate (MBA), any two lists in methacrylic acid furfuryl alcohol ester, dibutyl itaconate, hydroxyethyl methacrylate, hydroxy-ethyl acrylate The combination of body.
- 9. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, catalyst described in the 3rd step is 10 methyl phenothiazine, 5,10- dihydros -5,10- dimethylphenazine, 1,10- are luxuriant and rich with fragrance Any of sieve quinoline, 10- phenyl phenthazine, 10- (4- methoxyphenyls)-phenthazine, 10- (1- naphthyls)-phenthazine.
- 10. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, [ethyl cellulose macromolecular photoinitiator]/[monomer 1]/[monomer in molar ratio of reactant described in the 3rd step 2]/[catalyst]=1: (2~2000): (2~2000): (0.1~1).
- 11. the method that ethyl cellulose graft copolymer is prepared based on the light-initiated ATRP of no metal as claimed in claim 2, its It is characterized in that, ultraviolet ray intensity is between 0.01~0.5mW/cm described in the 3rd step.
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| CN114957552A (en) * | 2022-06-24 | 2022-08-30 | 中国林业科学研究院林产化学工业研究所 | Modified ethyl cellulose polymer and preparation method thereof |
| CN115537143A (en) * | 2022-10-10 | 2022-12-30 | 江苏斯瑞达材料技术股份有限公司 | Acrylic pressure-sensitive adhesive easy to peel and preparation method thereof |
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