CN108276509A - A kind of method that in-situ preparation initiator monomer prepares dissaving polymer - Google Patents
A kind of method that in-situ preparation initiator monomer prepares dissaving polymer Download PDFInfo
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- CN108276509A CN108276509A CN201810179902.4A CN201810179902A CN108276509A CN 108276509 A CN108276509 A CN 108276509A CN 201810179902 A CN201810179902 A CN 201810179902A CN 108276509 A CN108276509 A CN 108276509A
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- Prior art keywords
- monomer
- styrene
- dissaving polymer
- sodium iodide
- initiator
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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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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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
- 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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- 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
- 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
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- Chemical Kinetics & Catalysis (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of methods that in-situ preparation self-initiating monomer prepares dissaving polymer, belong to Macroscopic single crystal field.The invention firstly uses sodium iodides rapidly, efficiently by p-chloromethyl styrene converted in-situ to iodomethyl styrene, simultaneously, it is initiator monomer to iodomethyl styrene to generate, its can continue under the catalysis of sodium iodide occur homopolymerization or with phenylethylene or methyl acrylic ester vinyl monomer copolyreaction, prepare dissaving polymer.The present invention compared with the prior art, initiator monomer in-situ preparation in the reaction, without preparing and purifying in advance.Moreover, it is catalyst not use the metals such as Cu, Fe in reaction system, operation is simple, mild condition, has good application prospect.
Description
Technical field
The present invention relates to a kind of methods that in-situ preparation initiator monomer prepares dissaving polymer, belong to Macroscopic single crystal
Technical field.
Background technology
Dissaving polymer is a kind of highly branched macromolecular with three-dimensional structure, is helped in coating, pharmaceutical carrier, processing
Agent etc. has wide practical use.The synthetic method of dissaving polymer mainly has condensation polymerization and activity/controllable at present
Two kinds of polymerization.Condensation polymerization is only applicable to the monomer containing hydroxyl, carboxyl, amino groups, and the molecular weight of synthetic polymer
It is not high.Activity/controllable polymerization is again poly- including group transfer polymerization, atom transfer radical polymerization, Reversible Addition Fragmentation Chain Transfer
The multiple means such as conjunction.Polyfunctional monomer or initiator monomer to be usually added when such methods prepare dissaving polymer.Draw
Enter polyfunctional monomer and be easy to cause system crosslinking, hardly results in soluble dissaving polymer.And initiator monomer usually needs
It to prepare in advance, preparation process is cumbersome.P-chloromethyl styrene is a small number of initiator monomers being commercialized, and can be passed through
The method of atom transferred free radical prepares dissaving polymer.But need to introduce the metals such as Cu, Fe in polymerization process, it limits
The application range of polymer.
The present invention is under sodium iodide effect, and p-chloromethyl styrene is rapid, the efficient pairs of iodomethyl benzene second of converted in-situ
Alkene.Meanwhile generation to iodomethyl styrene be initiator monomer, can continue under the catalysis of sodium iodide occur homopolymerization or with
Phenylethylene or methyl acrylic ester vinyl monomer copolyreaction, prepare dissaving polymer.The present invention and prior art
It compares, initiator monomer in-situ preparation in the reaction, without preparing in advance.Moreover, be catalyst without using metals such as Cu, Fe,
Operation is simple, mild condition, has good application prospect.
Invention content
The purpose of the present invention is be directed to prior art initiator monomer to prepare in advance and need the metallic catalysts such as Cu, Fe
The shortcomings that, the synthetic method that a kind of in-situ preparation initiator monomer prepares dissaving polymer is provided.
To achieve the above object, it adopts the following technical scheme that herein：Within the scope of set temperature, rapidly will by sodium iodide
The pairs of iodomethyl styrene of p-chloromethyl styrene converted in-situ.Meanwhile generation is initiator monomer to iodomethyl styrene,
It can continue that homopolymerization or anti-with phenylethylene or the copolymerization of methyl acrylic ester vinyl monomer occurs under the catalysis of sodium iodide
It answers.After reaction dissaving polymer is obtained after precipitation, suction filtration, drying.
It is rapid, efficient former that the wherein described sodium iodide can be catalyzed p-chloromethyl styrene within the scope of 50 DEG C to 200 DEG C
Position is converted to iodomethyl styrene, and the molar ratio of p-chloromethyl styrene and sodium iodide is (10~200):1.
The wherein described initiator is the azo initiators such as azodiisobutyronitrile, azobisisoheptonitrile, azo amylalcohol, and monomer
Molar ratio with azo-initiator is (20~200):1.
The wherein described comonomer can be styrene monomer, can also be acrylic ester monomer.
The wherein described reaction uses bulk polymerization or polymerisation in solution；Wherein polymerisation in solution solvent for use is toluene, tetrahydrochysene
Any one in furans and diethylene glycol dimethyl ether.The quality of polymerisation in solution solvent for use is 0.2~5 times of monomer mass.
The present invention has following advantages compared with prior art：
1) raw material is cheap, and use scope is wide：The use of cheap iodide is catalyst, easy large-scale production.
2) polymeric reaction condition is mild：Range of reaction temperature is 50-200 DEG C.
3) polymerization process is simple：Initiator monomer can in-situ preparation, be not necessarily to other intermediates, one-step method can synthesize over-expense
Fluidized polymer.
Description of the drawings
The poly- p-chloromethyl styrene of line style and example 1 prepared by Fig. 1 free radical polymerizations prepares hyperbranched poly to chloromethylbenzene
The inherent viscosity curve of ethylene, [p-chloromethyl styrene]/[azodiisobutyronitrile]/[sodium iodide]=200/1/1.
The poly- p-chloromethyl styrene of line style and example 1 prepared by Fig. 2 free radical polymerizations prepares hyperbranched poly to chloromethylbenzene
The hydrodynamic radius curve of ethylene, [p-chloromethyl styrene]/[azodiisobutyronitrile]/[sodium iodide]=200/1/1.
Specific implementation mode
With reference to example, the present invention will be further described, but is not limited only to following embodiment, for not noting especially
Bright technological parameter can refer to routine techniques progress.
Embodiment 1
Take 1.53g (10mmol) p-chloromethyl styrene, 0.008g (0.05mmol) azodiisobutyronitriles and 0.008g
(0.05mmol) sodium iodide is placed in the 5mL round-bottomed flasks with rotor, and 0.3g diethylene glycol dimethyl ethers are then added and make solvent,
Liquid nitrogen frozen, displacement argon gas three times, are placed at 50 DEG C and react for 24 hours.After reaction, existed again with tetrahydrofuran dissolving reaction product
100mL absolute ethyl alcohols precipitate to obtain white product, and 12h is dried in vacuo at 30 DEG C, and p-chloromethyl styrene monomer conversion is
84%, number-average molecular weight is 8.1 × 103G/mol, weight average molecular weight are 3.76 × 104G/mol, molecular weight distribution 2.45 are put down
Equal branching factor g'=0.39, is shown in shown in Fig. 1 hydrodynamic volumes and inherent viscosity curve, it was demonstrated that resulting polymers have branched
Structure.
Embodiment 2
Take 1.53g (10mmol) p-chloromethyl styrene, 0.008g (0.05mmol) azodiisobutyronitriles and 0.160g
(1mmol) sodium iodide is placed in the 5mL round-bottomed flasks with rotor, liquid nitrogen frozen, and displacement argon gas three times, is placed in 200 DEG C of ontologies
Polymerization is for 24 hours.After reaction, precipitate to obtain white product in 200mL absolute ethyl alcohols again with tetrahydrofuran dissolving reaction product, 30
12h is dried in vacuo at DEG C, p-chloromethyl styrene monomer conversion is 82%, and number-average molecular weight is 7.3 × 103G/mol, weight are equal
Molecular weight is 2.7 × 104G/mol, molecular weight distribution 2.84, average branch factor g'=0.55, it was demonstrated that resulting polymers have
There is branched structure.
Embodiment 3
Take 1.53g (10mmol) p-chloromethyl styrene, 0.080g (0.5mmol) azodiisobutyronitriles and 0.008g
(0.05mmol) sodium iodide is placed in the 5mL round-bottomed flasks with rotor, and then addition 1.53g diethylene glycol dimethyl ethers are made molten
Agent, liquid nitrogen frozen, displacement argon gas three times, are placed at 60 DEG C and react for 24 hours.After reaction, reaction product is dissolved with tetrahydrofuran
It precipitates to obtain white product in 100mL absolute ethyl alcohols again, 12h, p-chloromethyl styrene monomer conversion is dried in vacuo at 30 DEG C
It is 84%, number-average molecular weight is 6.4 × 103G/mol, weight average molecular weight are 1.72 × 104G/mol, molecular weight distribution 2.21,
Average branch factor g'=0.36, it was demonstrated that resulting polymers have branched structure..
Embodiment 4
Take 1.53g (10mmol) p-chloromethyl styrene, 0.012g (0.05mmol) azobisisoheptonitrile and 0.008g
(0.05mmol) sodium iodide is placed in the 15mL round-bottomed flasks with rotor, and then addition 7.65g diethylene glycol dimethyl ethers are made molten
Agent, liquid nitrogen frozen, displacement argon gas three times, are placed at 60 DEG C and react for 24 hours.After reaction, reaction product is dissolved with tetrahydrofuran
It precipitates to obtain white product in 150mL absolute ethyl alcohols again, 12h is dried in vacuo at 30 DEG C.P-chloromethyl styrene monomer conversion
It is 88%, number-average molecular weight is 8.9 × 103G/mol, weight average molecular weight are 3.01 × 104G/mol, molecular weight distribution 2.29,
Average branch factor g'=0.49, it was demonstrated that resulting polymers have branched structure.
Embodiment 5
Take 1.53g (10mmol) p-chloromethyl styrene, 0.013g (0.05mmol) azo amylalcohols and 0.008g
(0.05mmol) sodium iodide is placed in the 15mL round-bottomed flasks with rotor, and then addition 7.65g diethylene glycol dimethyl ethers are made molten
Agent, liquid nitrogen frozen, displacement argon gas three times, are placed at 80 DEG C and react for 24 hours.After reaction, reaction product is dissolved with tetrahydrofuran
It precipitates to obtain white product in 150mL absolute methanols again, 12h, p-chloromethyl styrene monomer conversion is dried in vacuo at 30 DEG C
It is 82%, number-average molecular weight is 7.3 × 103G/mol, weight average molecular weight are 2.7 × 104G/mol, molecular weight distribution 2.84 are put down
Equal branching factor g'=0.55, it was demonstrated that resulting polymers have branched structure.
Embodiment 6
Take 1.53g (10mmol) p-chloromethyl styrene, 0.13g (0.5mmol) azo amylalcohols and 0.16g (0.1mmol)
Sodium iodide is placed in the 10mL round-bottomed flasks with rotor, and 1.53g tetrahydrofurans are then added and make solvent, liquid nitrogen frozen, displacement
Argon gas three times, is placed at 100 DEG C and reacts for 24 hours.After reaction, reaction product is dissolved again in the anhydrous second of 200mL with tetrahydrofuran
Alcohol precipitates to obtain white product, and 12h is dried in vacuo at 30 DEG C, and p-chloromethyl styrene monomer conversion is 78%, the equal molecule of number
Amount is 8.1 × 103G/mol, weight average molecular weight are 3.76 × 104G/mol, molecular weight distribution 2.65, average branch factor g'=
0.39, it was demonstrated that resulting polymers have branched structure.
Embodiment 7
Take 1.53g (10mmol) p-chloromethyl styrene, 0.13g (0.5mmol) azo amylalcohols and 0.008g
(0.05mmol) sodium iodide is placed in the 10mL round-bottomed flasks with rotor, and 3.06g toluene is then added and makees solvent, liquid nitrogen is cold
Freeze, displacement argon gas three times, is placed at 60 DEG C and reacts for 24 hours.After reaction, reaction product is dissolved again in 150mL with tetrahydrofuran
Absolute ethyl alcohol precipitates to obtain white product, and 10h is dried in vacuo at 30 DEG C, and p-chloromethyl styrene monomer conversion is 88%, number
Average molecular weight is 7.8 × 103G/mol, weight average molecular weight are 3.46 × 104G/mol, molecular weight distribution 2.35, average branch because
Sub- g'=0.38, it was demonstrated that resulting polymers have branched structure.
Embodiment 8
1.53g (10mmol) p-chloromethyl styrene is taken, 1.04g (10mmol) styrene, 0.008g (0.05mmol) is occasionally
Nitrogen bis-isobutyronitrile and 0.008g (0.05mmol) sodium iodide are placed in the 10mL round-bottomed flasks with rotor, and 2.59g is then added
Toluene makees solvent, liquid nitrogen frozen, and displacement argon gas three times, is placed at 60 DEG C and reacts for 24 hours.After reaction, it is dissolved with tetrahydrofuran
Reaction product precipitates to obtain white product again in 150mL absolute methanols, and 12h, p-chloromethyl styrene list are dried in vacuo at 30 DEG C
Transformation rate is 75%, and number-average molecular weight is 1.42 × 104G/mol, weight average molecular weight are 9.41 × 104G/mol, molecular weight point
Cloth is 3.58, average branch factor g'=0.37, it was demonstrated that resulting polymers have branched structure.
Embodiment 9
Take 1.53g (10mmol) p-chloromethyl styrene, 1.00g (10mmol) methyl methacrylate, 0.008g
(0.05mmol) azodiisobutyronitrile and 0.008g (0.05mmol) sodium iodide are placed in the 10mL round-bottomed flasks with rotor, so
2.53g toluene is added afterwards and makees solvent, liquid nitrogen frozen, displacement argon gas three times, is placed at 60 DEG C and reacts for 24 hours.After reaction, with four
Hydrogen furans dissolving reaction product precipitates to obtain white product again in 100mL absolute methanols, 12h is dried in vacuo at 30 DEG C, to chloromethane
Base styrene monomer conversion rate is 75%, and number-average molecular weight is 8.9 × 104G/mol, weight average molecular weight are 2.71 × 105G/mol,
Molecular weight distribution is 3.45, average branch factor g'=0.46, it was demonstrated that resulting polymers have branched structure.
Claims (5)
1. a kind of method that in-situ preparation self-initiating monomer prepares dissaving polymer, it is characterised in that as steps described below into
Row：Under sodium iodide effect, p-chloromethyl styrene is rapid, the efficient pairs of iodomethyl styrene of converted in-situ, meanwhile, it generates
To iodomethyl styrene be initiator monomer, can continue under the catalysis of sodium iodide occur homopolymerization or with phenylethylene or first
Base esters of acrylic acid vinyl monomer copolyreaction, prepares dissaving polymer.
2. the method for preparing dissaving polymer according to claim 1, it is characterised in that sodium iodide can be at 50 DEG C to 200
It is catalyzed that p-chloromethyl styrene is rapid, the efficient pairs of iodomethyl styrene of converted in-situ within the scope of DEG C.P-chloromethyl styrene
Molar ratio with sodium iodide is (10~200):1.
3. the method for preparing dissaving polymer according to claim 1, it is characterised in that the wherein described initiator is azo
The azo initiators such as bis-isobutyronitrile, azobisisoheptonitrile, azo amylalcohol, and the molar ratio of monomer and azo-initiator is (20
~200):1.
4. the method for preparing dissaving polymer according to claim 1, it is characterised in that the wherein described comonomer can be with
It is styrene monomer, can also be acrylic ester monomer.
5. the method for preparing dissaving polymer according to claim 1, it is characterised in that reaction using bulk polymerization or
Polymerisation in solution；Wherein polymerisation in solution solvent for use is any one in toluene, tetrahydrofuran and diethylene glycol dimethyl ether.Solution
The quality for polymerizeing solvent for use is 0.2~5 times of monomer mass.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011096A (en) * | 2022-06-23 | 2022-09-06 | 万华化学（宁波）有限公司 | High-hardness scratch-resistant polycarbonate composite material and preparation method thereof |
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| CN102675492A (en) * | 2011-10-27 | 2012-09-19 | 常州大学 | Method for preparing branched polymer |
| CN106977644A (en) * | 2017-04-17 | 2017-07-25 | 常州大学 | A kind of simple synthesis of dissaving polymer |
| CN107501465A (en) * | 2017-08-08 | 2017-12-22 | 常州大学 | Self condense the method that reversible complexing prepares dissaving polymer |
-
2018
- 2018-03-05 CN CN201810179902.4A patent/CN108276509A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005061566A1 (en) * | 2003-12-22 | 2005-07-07 | Lion Corporation | Hyperbranched polymer, process for producing the same and resist composition containing the hyperbranched polymer |
| CN101575402A (en) * | 2009-05-31 | 2009-11-11 | 中国科学院化学研究所 | Multi-arm star-type polymer and preparation method thereof |
| CN102675492A (en) * | 2011-10-27 | 2012-09-19 | 常州大学 | Method for preparing branched polymer |
| CN106977644A (en) * | 2017-04-17 | 2017-07-25 | 常州大学 | A kind of simple synthesis of dissaving polymer |
| CN107501465A (en) * | 2017-08-08 | 2017-12-22 | 常州大学 | Self condense the method that reversible complexing prepares dissaving polymer |
Non-Patent Citations (5)
| Title |
|---|
| A. KOWALCZUK-BLEJA ET AL.: "Controlled radical polymerization of p-(iodomethyl)styrene—a route to branched and star-like structures", 《POLYMER》 * |
| HONGJUN YANG ET AL.: "Synthesis of highly branched polymers by reversible complexation-mediated copolymerization of vinyl and divinyl monomers", 《POLYMER CHEMISTRY》 * |
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| 陈珂龙等: "碘代化合物存在下的可逆-失活自由基聚合研究进展", 《高分子通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011096A (en) * | 2022-06-23 | 2022-09-06 | 万华化学（宁波）有限公司 | High-hardness scratch-resistant polycarbonate composite material and preparation method thereof |
| CN115011096B (en) * | 2022-06-23 | 2023-05-30 | 万华化学（宁波）有限公司 | High-hardness scratch-resistant polycarbonate composite material and preparation method thereof |
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Application publication date: 20180713 |