CN106977644A - A kind of simple synthesis of dissaving polymer - Google Patents
A kind of simple synthesis of dissaving polymer Download PDFInfo
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- CN106977644A CN106977644A CN201710247497.0A CN201710247497A CN106977644A CN 106977644 A CN106977644 A CN 106977644A CN 201710247497 A CN201710247497 A CN 201710247497A CN 106977644 A CN106977644 A CN 106977644A
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of simple synthesis of dissaving polymer, belong to Macroscopic single crystal field.The vinyl monomer is styrene, methacrylate-based monomer and acrylic ester compound, the branched monomer is divinylbenzene, dimethacrylate alcohol ester, diacrylate alkoxide compound, the azo-initiator is azodiisobutyronitrile and ABVN, the catalyst is organic amine, alkaline metal salt compound.The present invention is a kind of new method for preparing branched polymer, passes through azo-initiator and I2In-situ preparation iodide, under catalyst action, realize that the reversible complexation copolymerization of vinyl monomer and branched monomer is closed, the branched polymer of HMW and highly -branched degree is prepared, its reaction condition is gentle, raw material economics environmental protection, suitable for industrialized production, with good application prospect.
Description
Technical field
The present invention relates to the simple synthesis of dissaving polymer, belong to polymer synthesis techniques field.
Background technology
Dissaving polymer is the highly branched macromolecular that a class has three-dimensional structure, is helped in coating, pharmaceutical carrier, processing
There is potential application prospect in terms of agent.The method of current synthesis of super branched polymer, which has, much includes conventional radical polymerization,
ATRP, nitroxide-mediated stable free-radical polymerization etc., wherein conventional radical polymerization needs to add chain-transferring agent, former
Sub- transferring free-radical polymerization needs introducing Ni metal to make polymer " poisoning ", and nitroxide-mediated stable free-radical polymerization needs of a relatively high
Reaction temperature and the substantial amounts of initiator of consumption.It is always material neck using a kind of simply and easily method synthesis of super branched polymer
One of the focus in domain.
The content of the invention
The purpose of the present invention is that there is provided a kind of simple synthesis of dissaving polymer in view of the shortcomings of the prior art.
To achieve the above object, adopt the following technical scheme that herein：A kind of simple synthesis of dissaving polymer, is pressed
Carried out according to following step：
Using vinyl monomer as reaction monomers, branched monomer, azo-initiator is initiator, in organic amine or alkali metal
Under salt compounds catalysis, pass through reversible complexing polymerisation step method synthesis of super branched polymer；The polymeric reaction temperature is 50
DEG C to 200 DEG C, polymerization reaction time is 4~48 hours.
Wherein described reaction monomers and the mol ratio of branched monomer are (80~300):1；Catalyst and branched monomer rub
You are than being (0.1~5):1.
Wherein described vinyl monomer is styrene, methacrylate-based monomer, acrylic ester monomer, including benzene second
Alkene, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate etc..
Wherein described branched monomer is the divinylbenzene for having two double bonds, dimethacrylate alcohol ester, diacrylate alcohol
Ester type compound, including divinylbenzene, dimethacrylate BDO ester, ethylene glycol diacrylate etc..
Wherein described azo-initiator is azodiisobutyronitrile, ABVN etc..Wherein described reaction monomers with
The mol ratio of azo-initiator is (80~300):1.
The catalyst is it is characterized in that the catalyst is organic amine (such as triethylamine, tri-n-butylamine, diethyl triamine
Deng), alkali metal iodine class compound (such as sodium iodide, KI, calcium iodide).
Wherein described polymerisation uses polymerisation in bulk or polymerisation in solution；Wherein polymerisation in solution solvent for use be toluene,
Any one in tetrahydrofuran and diethylene glycol dimethyl ether or two or more mixtures.The quality of polymerisation in solution solvent for use
For 0.2~5 times of monomer mass.
The present invention has following advantages compared with prior art：
1) raw material is cheap, wide using scope：, can using the organic amine and alkaline metal salt compound catalyst of non-toxic inexpensive
With styrene catalyzed, methacrylic, acrylic ester monomer polymerization.
2) polymeric reaction condition is gentle：Range of reaction temperature is 50-200 DEG C, used catalyst not metal ion, easily quilt
Remove, do not influence polymer property.
3) polymerization process is simple：Using easy compound as catalyst, raw materials used monomer has been carried out industrialized production,
Without other intermediates, one-step method can synthesis of super branched polymer.
Brief description of the drawings
Fig. 1 a, b are the hydrodynamic volume and characteristic of the gained branched polymer of embodiment 1 and corresponding linear polymer
Viscosity with molecular weight changing trend diagram.Linear polymer (square), [styrene]：[dimethacrylate 1,4- butanediols
Ester]：[azodiisobutyronitrile]：[iodine]：[sodium iodide]=80:1:1:0.4:0.4 (circle), with molecular weight, branched polymer
Hydrodynamic volume and inherent viscosity it is smaller than linear polymer, it is possible thereby to prove synthetic polymer be branched polymeric
Thing.It will become apparent from the increase with molecular weight from figure, the gap of branched polymer and linear polymer is bigger, illustrates that molecular weight is got over
Greatly, the degree of branching is higher.
Fig. 2 a, b are the hydrodynamic volume and characteristic of the gained branched polymer of embodiment 5 and corresponding linear polymer
Viscosity with molecular weight changing trend diagram.Linear polymer (square), [methyl methacrylate]：[dimethacrylate 1,4-
Butanediol ester]：[ABVN]：[iodine]：[sodium iodide]=80:1:1:0.4:0.4 (circle), it is branched with molecular weight
The hydrodynamic volume and inherent viscosity of polymer are smaller than linear polymer, it is possible thereby to prove that synthetic polymer is branched
Polymer.It will become apparent from the increase with molecular weight from figure, the gap of branched polymer and linear polymer is bigger, illustrates molecule
Amount is bigger, and the degree of branching is higher.
Embodiment
With reference to example, the present invention will be further described, but is not limited only to following examples, for not noting especially
Bright technological parameter, can refer to routine techniques progress.
Embodiment 1
Take 1g (10mmol) styrene, 0.023g (0.1mmol) dimethacrylate BDO ester, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.008g (0.05mmol) sodium iodide are placed in and carried
In the 10mL round-bottomed flasks of rotor, then add 1g tetrahydrofurans and diethylene glycol dimethyl ether makees mixed solvent, liquid nitrogen frozen is put
Change argon gas three times, be placed in 60 DEG C of oil bath pans, react 24h.After reaction terminates, existed again with tetrahydrofuran dissolving reaction product
100mL absolute methanols precipitation obtains being dried in vacuo 12h at white product, 30 DEG C, and weight average molecular weight is 1.38 × 105G/mol, point
Son amount is distributed as 13.6, and Fig. 1 hydrodynamics bodies are seen in average branch factor g'=0.583, Mark-Houwink parameter alpha=0.44
Shown in product and inherent viscosity curve, it was demonstrated that resulting polymers have branched structure.
Embodiment 2
Take 3.75g (10mmol) styrene, 0.023g (0.1mmol) dimethacrylate BDO ester, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.008g (0.05mmol) sodium iodide are placed in and carried
In the 25mL round-bottomed flasks of rotor, then add 8g tetrahydrofurans and diethylene glycol dimethyl ether makees mixed solvent, liquid nitrogen frozen is put
Change argon gas three times, be placed in 60 DEG C of oil bath pans, react 24h.After reaction terminates, existed again with tetrahydrofuran dissolving reaction product
200mL absolute methanols precipitation obtains being dried in vacuo 12h at white product, 30 DEG C, and weight average molecular weight is 3.23 × 105G/mol, point
Son amount is distributed as 15.8, average branch factor g'=0.673, Mark-Houwink parameter alpha=0.46, it was demonstrated that resulting polymers have
There is branched structure.
Embodiment 3
Take 1g (10mmol) styrene, 0.013g (0.1mmol) divinylbenzene, 0.013g (0.05mmol) iodine,
0.020g (0.13mmol) azodiisobutyronitriles and 0.005g (0.05mmol) triethylamine are placed in the 10mL round bottoms with rotor and burnt
In bottle, then add 1g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C of oil bath pans, reacts 24h.
After reaction terminates, the reaction product vacuum in the case where 100mL absolute methanols precipitation obtains white product, 30 DEG C again is dissolved with tetrahydrofuran
12h is dried, weight average molecular weight is 1.60 × 105G/mol, molecular weight distribution is 9.3, average branch factor g'=0.501,
Mark-Houwink parameter alpha=0.41, it was demonstrated that resulting polymers have branched structure.
Embodiment 4
Take 3.75g (10mmol) styrene, 0.013g (0.1mmol) divinylbenzene, 0.013g (0.05mmol) simple substance
Iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.005g (0.05mmol) triethylamine are placed in the 10mL round bottoms with rotor
In flask, then add 3.75g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C of oil bath pans, instead
Answer 24h.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtain white product, 30 DEG C in 200mL absolute methanols precipitation again
Lower vacuum drying 12h, weight average molecular weight is 5.20 × 105G/mol, molecular weight distribution is 11.1, average branch factor g'=
0.621, Mark-Houwink parameter alpha=0.44, it was demonstrated that resulting polymers have branched structure.
Embodiment 5
Take 1g (10mmol) methyl methacrylate, 0.023g (0.1mmol) dimethacrylate BDO ester,
0.013g (0.05mmol) iodine, 0.029g (0.13mmol) ABVNs and 0.008g (0.05mmol) sodium iodide are put
In in the 10mL round-bottomed flasks with rotor, then add 1g tetrahydrofurans and diethylene glycol dimethyl ether make solvent, liquid nitrogen frozen,
Replace argon gas three times, be placed in 60 DEG C of oil bath pans, react 24h.After reaction terminates, existed again with tetrahydrofuran dissolving reaction product
100mL absolute methanols precipitation obtains being dried in vacuo 12h at white product, 30 DEG C, and weight average molecular weight is 4.8 × 105G/mol, point
Son amount is distributed as 5.9, and Fig. 2 hydrodynamic volumes are seen in average branch factor g'=0.339, Mark-Houwink parameter alpha=0.40
With shown in inherent viscosity curve, it was demonstrated that resulting polymers have branched structure.
Embodiment 6
Take 3.75g (10mmol) methyl methacrylate, 0.023g (0.1mmol) dimethacrylate BDO
Ester, 0.013g (0.05mmol) iodine, 0.029g (0.13mmol) ABVNs and 0.008g (0.05mmol) iodate
Sodium is placed in the 25mL round-bottomed flasks with rotor, then adds 3.75g tetrahydrofurans and diethylene glycol dimethyl ether makees solvent, liquid
Chilled nitrogen, displacement argon gas three times, is placed in 60 DEG C of oil bath pans, reacts 24h.After reaction terminates, with tetrahydrofuran dissolving reaction production
Thing is dried in vacuo 12h in the case where 200mL absolute methanols precipitation obtains white product, 30 DEG C again, and weight average molecular weight is 7.2 × 105g/
Mol, molecular weight distribution is 10.2, average branch factor g'=0.552, Mark-Houwink parameter alpha=0.44, it was demonstrated that gained gathers
Compound has branched structure.
Embodiment 7
Take 1g (10mmol) methyl methacrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.009g (0.05mmol) tri-n-butylamine are placed in and carried
In the 10mL round-bottomed flasks of rotor, then add 1g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C
In oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtain white in 100mL absolute methanols precipitation again
Color product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 2.9 × 105G/mol, molecular weight distribution is 12.11, average branch
Factor g'=0.475, Mark-Houwink parameter alpha=0.44, it was demonstrated that resulting polymers have branched structure.
Embodiment 8
Take 3.75g (10mmol) methyl methacrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.009g (0.05mmol) tri-n-butylamine are placed in and carried
In the 25mL round-bottomed flasks of rotor, then add 3.75g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60
In DEG C oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtained again in 200mL absolute methanols precipitation
White product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 6.1 × 105G/mol, molecular weight distribution is 15.41, average branch
Change factor g'=0.526, Mark-Houwink parameter alpha=0.46, it was demonstrated that resulting polymers have branched structure
Embodiment 9
Take 1.4g (10mmol) butyl methacrylate, 0.023g (0.1mmol) dimethacrylate BDO ester,
0.013g (0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.008g (0.05mmol) sodium iodide are put
In in the 10mL round-bottomed flasks with rotor, then addition 1g tetrahydrofurans and toluene make mixed solvent, and liquid nitrogen frozen replaces argon
Gas three times, is placed in 60 DEG C of oil bath pans, reacts 24h.Reaction terminate after, with tetrahydrofuran dissolve reaction product again 100mL without
Water methanol precipitation obtains being dried in vacuo 12h at white product, 30 DEG C, and weight average molecular weight is 5.7 × 105G/mol, molecular weight distribution
For 7.11, average branch factor g'=0.351, Mark-Houwink parameter alpha=0.40, it was demonstrated that resulting polymers have branched knot
Structure.
Embodiment 10
Take 5.25g (10mmol) butyl methacrylate, 0.023g (0.1mmol) dimethacrylate BDO
Ester, 0.013g (0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.008g (0.05mmol) iodate
Sodium is placed in the 25mL round-bottomed flasks with rotor, is then added 10g tetrahydrofurans and toluene and is made mixed solvent, liquid nitrogen frozen,
Replace argon gas three times, be placed in 60 DEG C of oil bath pans, react 24h.After reaction terminates, existed again with tetrahydrofuran dissolving reaction product
200mL absolute methanols precipitation obtains being dried in vacuo 12h at white product, 30 DEG C, and weight average molecular weight is 8.1 × 105G/mol, point
Son amount is distributed as 10.30, average branch factor g'=0.502, Mark-Houwink parameter alpha=0.44, it was demonstrated that resulting polymers
With branched structure.
Embodiment 11
Take 1.4g (10mmol) butyl methacrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.005g (0.05mmol) triethylamine are placed in and carried
In the 10mL round-bottomed flasks of rotor, then add 1g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C
In oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtain white in 100mL absolute methanols precipitation again
Color product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 2.6 × 105G/mol, molecular weight distribution is 10.3, average branch
Factor g'=0.534, Mark-Houwink parameter alpha=0.43, it was demonstrated that resulting polymers have branched structure.
Embodiment 12
Take 5.25g (10mmol) butyl methacrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.005g (0.05mmol) triethylamine are placed in and carried
In the 25mL round-bottomed flasks of rotor, then add 8g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C
In oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtain white in 200mL absolute methanols precipitation again
Color product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 7.5 × 105G/mol, molecular weight distribution is 12.8, average branch
Factor g'=0.569, Mark-Houwink parameter alpha=0.46, it was demonstrated that resulting polymers have branched structure.
Embodiment 13
Take 0.9g (10mmol) methyl acrylate, 0.023g (0.1mmol) dimethacrylate BDO ester,
0.013g (0.05mmol) iodine, 0.029g (0.13mmol) ABVNs and 0.009g (0.05mmol) tri-n-butylamine are put
Make solvent in the 10mL round-bottomed flasks with rotor, then adding 1g tetrahydrofurans, liquid nitrogen frozen, displacement argon gas three times is put
In 60 DEG C of oil bath pans, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and precipitated again in 100mL absolute methanols
Obtain being dried in vacuo 12h at white product, 30 DEG C, weight average molecular weight is 1.8 × 105G/mol, molecular weight distribution is 11.5, is put down
Equal branching factor g'=0.581, Mark-Houwink parameter alpha=0.45, it was demonstrated that resulting polymers have branched structure.
Embodiment 14
Take 3.38g (10mmol) methyl acrylate, 0.023g (0.1mmol) dimethacrylate BDO ester,
0.013g (0.05mmol) iodine, 0.029g (0.13mmol) ABVNs and 0.009g (0.05mmol) tri-n-butylamine are put
Make solvent in the 10mL round-bottomed flasks with rotor, then adding 3.5g tetrahydrofurans, liquid nitrogen frozen replaces argon gas three times,
It is placed in 60 DEG C of oil bath pans, reacts 24h.After reaction terminates, reaction product is dissolved with tetrahydrofuran heavy in 200mL absolute methanols again
Shallow lake obtains being dried in vacuo 12h at white product, 30 DEG C, and weight average molecular weight is 3.0 × 105G/mol, molecular weight distribution is 12.4,
Average branch factor g'=0.652, Mark-Houwink parameter alpha=0.48, it was demonstrated that resulting polymers have branched structure.
Embodiment 15
Take 0.9g (10mmol) methyl acrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.0085g (0.05mmol) KI are placed in band
Have in the 10mL round-bottomed flasks of rotor, then add 1g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60
In DEG C oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtained again in 100mL absolute methanols precipitation
White product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 3.5 × 105G/mol, molecular weight distribution is 5.85, average branch
Change factor g'=0.410, Mark-Houwink parameter alpha=0.41, it was demonstrated that resulting polymers have branched structure.
Embodiment 16
Take 3.38g (10mmol) methyl acrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.0085g (0.05mmol) KI are placed in band
Have in the 25mL round-bottomed flasks of rotor, then add 3.5g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in
In 60 DEG C of oil bath pans, 24h is reacted.After reaction terminates, precipitated again in 200mL absolute methanols with tetrahydrofuran dissolving reaction product
To white product, 12h is dried in vacuo at 30 DEG C, weight average molecular weight is 5.1 × 105G/mol, molecular weight distribution is 7.05, average
Branching factor g'=0.499, Mark-Houwink parameter alpha=0.46, it was demonstrated that resulting polymers have branched structure.
Embodiment 17
1.3g (10mmol) butyl acrylate is taken, 0.013g (0.1mmol) divinylbenzene, 0.013g (0.05mmol) is single
Matter iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.0085g (0.05mmol) KI are placed in the 10mL with rotor
In round-bottomed flask, then add 1g toluene and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C of oil bath pans, reacted
24h.After reaction terminates, the reaction product vacuum in the case where 100mL absolute methanols precipitation obtains white product, 30 DEG C again is dissolved with toluene
12h is dried, weight average molecular weight is 1.2 × 105G/mol, molecular weight distribution is 15.85, average branch factor g'=0.624,
Mark-Houwink parameter alpha=0.46, it was demonstrated that resulting polymers have branched structure.
Embodiment 18
Take 4.88g (10mmol) butyl acrylate, 0.013g (0.1mmol) divinylbenzene, 0.013g (0.05mmol)
Iodine, 0.020g (0.13mmol) azodiisobutyronitriles and 0.0085g (0.05mmol) KI are placed in rotor
In 25mL round-bottomed flasks, then add 10g toluene and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C of oil bath pans,
React 24h.After reaction terminates, dissolve reaction product with toluene and obtained again in 200mL absolute methanols precipitation at white product, 30 DEG C
12h is dried in vacuo, weight average molecular weight is 6.2 × 105G/mol, molecular weight distribution is 20.02, average branch factor g'=
0.674, Mark-Houwink parameter alpha=0.48, it was demonstrated that resulting polymers have branched structure.
Embodiment 19
Take 1.3g (10mmol) butyl acrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.029g (0.13mmol) ABVNs and 0.005g (0.05mmol) triethylamine are placed in and carried
In the 10mL round-bottomed flasks of rotor, then add 1g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C
In oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtain white in 100mL absolute methanols precipitation again
Color product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 3.1 × 105G/mol, molecular weight distribution is 7.75, average branch
Factor g'=0.475, Mark-Houwink parameter alpha=0.42, it was demonstrated that resulting polymers have branched structure.
Embodiment 20
Take 4.88g (10mmol) butyl acrylate, 0.017g (0.1mmol) ethylene glycol diacrylate, 0.013g
(0.05mmol) iodine, 0.029g (0.13mmol) ABVNs and 0.005g (0.05mmol) triethylamine are placed in and carried
In the 10mL round-bottomed flasks of rotor, then add 8g tetrahydrofurans and make solvent, liquid nitrogen frozen, displacement argon gas three times is placed in 60 DEG C
In oil bath pan, 24h is reacted.After reaction terminates, dissolve reaction product with tetrahydrofuran and obtain white in 200mL absolute methanols precipitation again
Color product, 12h is dried in vacuo at 30 DEG C, and weight average molecular weight is 7.5 × 105G/mol, molecular weight distribution is 9.88, average branch
Factor g'=0.512, Mark-Houwink parameter alpha=0.44, it was demonstrated that resulting polymers have branched structure.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of simple synthesis of dissaving polymer, it is characterised in that carry out as steps described below：
Using vinyl monomer as reaction monomers, branched monomer, azo-initiator is initiator, in organic amine or alkaline metal salt
Under compound for catalysis, pass through reversible complexing polymerisation step method synthesis of super branched polymer；The polymeric reaction temperature is arrived at 50 DEG C
200 DEG C, polymerization reaction time is 4~48 hours.
2. the simple synthesis of a kind of dissaving polymer according to claim 1, it is characterised in that wherein described anti-
The mol ratio for answering monomer and branched monomer is (80~300):1；The mol ratio of catalyst and branched monomer is (0.1~5):1.
3. a kind of simple synthesis of dissaving polymer according to claim 1, it is characterised in that wherein described second
Alkenyl monomer is styrene, methacrylate-based monomer, acrylic ester monomer, including styrene, methyl methacrylate,
Butyl methacrylate, methyl acrylate, butyl acrylate etc..
4. a kind of simple synthesis of dissaving polymer according to claim 1, it is characterised in that wherein described branch
It is the divinylbenzene for having two double bonds, dimethacrylate alcohol ester, diacrylate alkoxide compound, including diethyl to change monomer
Alkenyl benzene, dimethacrylate BDO ester, ethylene glycol diacrylate etc..
5. a kind of simple synthesis of dissaving polymer according to claim 1, it is characterised in that wherein described idol
Nitrogen class initiator is azodiisobutyronitrile, ABVN etc.；Mole of wherein described reaction monomers and azo-initiator
Than for（80~300):1.
6. a kind of simple synthesis of dissaving polymer according to claim 1, it is characterised in that the catalyst
To be characterized in that the catalyst is organic amine（Such as triethylamine, tri-n-butylamine, diethyl triamine）, alkali metal iodine class compound
（Such as sodium iodide, KI, calcium iodide）.
7. the simple synthesis of a kind of dissaving polymer according to claim 1, it is characterised in that wherein described poly-
Close reaction and use polymerisation in bulk or polymerisation in solution；Wherein polymerisation in solution solvent for use is toluene, tetrahydrofuran and diethylene glycol
Any one in dimethyl ether or two or more mixtures；The quality of polymerisation in solution solvent for use is the 0.2~5 of monomer mass
Times.
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| CN107501465A (en) * | 2017-08-08 | 2017-12-22 | 常州大学 | Self condense the method that reversible complexing prepares dissaving polymer |
| CN107880161A (en) * | 2017-11-27 | 2018-04-06 | 中山大学 | A kind of stabilized hyperbranched free radical polyalcohol of Photocrosslinkable and its preparation method and application |
| CN108276509A (en) * | 2018-03-05 | 2018-07-13 | 常州大学 | A kind of method that in-situ preparation initiator monomer prepares dissaving polymer |
| CN109735915A (en) * | 2019-01-09 | 2019-05-10 | 四川大学 | Super crosslinking organic nano particle and preparation method thereof, modifying polymer film and preparation method thereof and gel polymer electrolyte |
| CN110184040A (en) * | 2019-07-06 | 2019-08-30 | 西南石油大学 | A kind of dissaving polymer wax-proofing agent and preparation method thereof |
| CN116814248A (en) * | 2023-06-30 | 2023-09-29 | 常州大学 | Preparation method and application of hybridization sulfur quantum dot with room temperature afterglow |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107501465A (en) * | 2017-08-08 | 2017-12-22 | 常州大学 | Self condense the method that reversible complexing prepares dissaving polymer |
| CN107880161A (en) * | 2017-11-27 | 2018-04-06 | 中山大学 | A kind of stabilized hyperbranched free radical polyalcohol of Photocrosslinkable and its preparation method and application |
| CN107880161B (en) * | 2017-11-27 | 2020-05-19 | 中山大学 | Photo-crosslinkable and stabilized hyperbranched free radical polymer and preparation method and application thereof |
| CN108276509A (en) * | 2018-03-05 | 2018-07-13 | 常州大学 | A kind of method that in-situ preparation initiator monomer prepares dissaving polymer |
| CN109735915A (en) * | 2019-01-09 | 2019-05-10 | 四川大学 | Super crosslinking organic nano particle and preparation method thereof, modifying polymer film and preparation method thereof and gel polymer electrolyte |
| CN109735915B (en) * | 2019-01-09 | 2021-08-27 | 四川大学 | Hypercrosslinked organic nanoparticles and preparation method thereof, modified polymer membrane and preparation method thereof, and gel polymer electrolyte |
| CN110184040A (en) * | 2019-07-06 | 2019-08-30 | 西南石油大学 | A kind of dissaving polymer wax-proofing agent and preparation method thereof |
| CN116814248A (en) * | 2023-06-30 | 2023-09-29 | 常州大学 | Preparation method and application of hybridization sulfur quantum dot with room temperature afterglow |
| CN116814248B (en) * | 2023-06-30 | 2024-04-02 | 常州大学 | Preparation method and application of hybridization sulfur quantum dot with room temperature afterglow |
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