CN102604013A - Preparation method for dendrimer-star cationic polyacrylamide - Google Patents
Preparation method for dendrimer-star cationic polyacrylamide Download PDFInfo
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- CN102604013A CN102604013A CN2012100605359A CN201210060535A CN102604013A CN 102604013 A CN102604013 A CN 102604013A CN 2012100605359 A CN2012100605359 A CN 2012100605359A CN 201210060535 A CN201210060535 A CN 201210060535A CN 102604013 A CN102604013 A CN 102604013A
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Abstract
The invention relates to a preparation method for dendrimer-star cationic polyacrylamide, which includes the steps: utilizing dithiobenzoate-terminated dendritic polyamidoamine as dendritic polyfunctional group chain transfer agent and AIBN (azodiisobutyronitrile) as initiator to initiate acrylamide and quaternary ammonium cationic monomers to go through reversible addition-fragmentation chain transfer free radical polymerization, so that the dendrimer-star cationic polyacrylamide is prepared. The method is capable of effectively controlling the structure, branched arm numbers, molecular weight, molecular weight distribution and positive charge density of the dendrimer-star cationic polyacrylamide, and is easy in development of series products. The prepared dendrimer-star cationic polyacrylamide has good salt tolerance and resistance to high shear force, and is wide in use range.
Description
Technical field
The present invention relates to a kind of preparation method who sets nuclear star shape cationic polyacrylamide, belong to polymer chemistry and papermaking chemical product technical field.
Background technology
SEPIGEL 305 and verivate thereof are the widely used synthetic macromolecules of each industrial circle.But present polyacrylamide amine product both domestic and external is mainly linear structure; Its molecule can be in particle surface generation reconstruct and diffusion phenomena in the use, and especially under the situation that causes system's specific conductivity to raise gradually in the system owing to the continuous accumulation of water-soluble inorganic salt, the polymer molecule of linear structure can shrink and curl; Cause ability to function to reduce; Result of use descends, and high-molecular weight linear polyacrylamide viscosity is high, the dissolving difficulty, is unfavorable for actually operating.Improve the conventional linear SEPIGEL 305 structure, optimize its performance, the synthetic polymer that exploitation has various topological frameworks becomes the research content of current polymer chemistry.
The development of polymer science and polymkeric substance synthetic technology; Especially the appearance of activity/controllable polymerization technology and constantly perfect;, narrow molecular weight distributions controlled for synthetic molecular weight, the special construction polymkeric substance that structure is clear and definite provide new effective way, and the polymkeric substance of various topological framework is synthesized out.It is exactly wherein a kind of being connected to the tree nuclear star shape polymkeric substance that the dendroid core element forms by many linear homopolymerizations or copolymer chain.It has combined some character of dendritic macromole and star polymer, and its intramolecule has cavity, and peripheral molecular chain is star-branched.Internal cavities effectively complexing holds the dissolved small-molecule substance; Peripheral star-branched structure can make its molecular chain take the conformation that more stretches, and is expected to become the chemical of high-efficiency multi-function.
(Reversible Addition Fragmentation Chain Transfer, RAFT) radical polymerization technique is a kind of important activity/controllable polymerization technology of synthetic tree nuclear star shape polymkeric substance in reversible addition-fracture chain transfer that latest developments are got up.Reversible addition-fragmentation chain transfer free radical polymerization is a kind of new living radical polymerization technique that was proposed in 1998 by people such as Rizzardo; Referring to Chiefari J; (Bill) Chong Y K, Ercole F, et al.Living Free-Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer:The RAFT Process [J] .Macromolecules; 1998,31 (16): 5559-5562.Be about to have chain-transfer agent such as two thioester compound of high chain transfer constant and ad hoc structure, join in traditional radical polymerization system, make polyreaction by uncontrollable become controlled, thereby realize regulation and control to polymer architecture and molecular weight and distribution thereof.Its designed capacity to polymer molecule is strong; And reaction conditions is gentle, the suitable monomers scope is wide, it is many to implement the polymeric method; Can synthesize the polymkeric substance of various topological frameworks such as various structures exquisitenesses, block, star, grafting, be considered to have most one of activity/controllable polymerization technology of industrial prospect with controllable molecular weight and narrow molecular weight distributions.
Utilize the reversible addition-synthetic tree of fragmentation chain transfer free radical polymerization technology nuclear star shape polymkeric substance can adopt two kinds of approach: a kind of is through peripheral terminal groups modification with dendritic macromole; Become dendroid polyfunctional group chain-transfer agent; Reversible addition-the fragmentation chain transfer free radical polymerization of initiation vinyl monomer is synthetic to be the star polymer of core with the dendroid unit, i.e. " nuclear postbrachium earlier " approach; Another kind is the linear polymer that contains reactive group in advance through reversible addition-narrow distribution of fragmentation chain transfer free radical polymerization synthetic molecular weight, end; Then with linear polymer as branching arm and the coupling of dendroid polyfunctional group coupling agent, promptly " examine " approach behind the first arm.Employing end groups such as Pan are that the Vestolen PP 7052 imines dendritic macromole of dithio benzene methyl base is a chain-transfer agent; Successfully synthesized tree nuclear star shape and gathered (N-NSC 11448) with temperature sensitive performance; Referring to Zheng Q; Pan C Y.Preparation and characterization of dendrimer-star PNIPAAM using dithiobenzoate-terminated PPI dendrimer via RAFT polymerization [J] .European Polymer Journal; 2006,42 (4): 807-814.Utilizing dendroid polyfunctional group chain-transfer agent is that the tree nuclear star shape SEPIGEL 305 of initial core will have particular structure and molecular chain conformation and good performance more through RAFT polymerization synthetic with dendritic macromole.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of preparation method who sets nuclear star shape cationic polyacrylamide.
Summary of the invention
A kind of preparation method who sets nuclear star shape cationic polyacrylamide; It is characterized in that; Adopting the end capped dendroid polyamide-amide of dithiobenzoic acid ester is dendroid polyfunctional group chain-transfer agent; Diisopropyl azodicarboxylate (AIBN) is an initiator, and acrylamide triggered and quaternary ammonium cation monomer carries out reversible addition-fragmentation chain transfer free radical polymerization, synthetic tree nuclear star shape cationic polyacrylamide.
Detailed Description Of The Invention
A kind of preparation method who sets nuclear star shape cationic polyacrylamide, step is following:
In the reactor drum that nitrogen conduit, reflux condensate device, constant voltage feeding device and whipping appts are housed, add solvent; In stirring and logical nitrogen downhill reaction device, add acrylic amide, quaternary ammonium cation monomer and dendroid polyfunctional group chain-transfer agent successively then; After the question response monomer mixes; With the temperature regulation in the reactor drum is 25～100 ℃, under stirring and nitrogen protection, adds Diisopropyl azodicarboxylate and isothermal reaction 1～72h.Reaction finishes the back underpressure distillation except that desolvating, and in the crude product that obtains, adds deionized water and makes its dissolving, adds acetone then product is precipitated out, through being drying to obtain tree nuclear star shape cationic polyacrylamide.
Said dendroid polyfunctional group chain-transfer agent is meant that dithiobenzoic acid ester terminal number is respectively 12,24,48,96 dendroid polyamide-amide; It is characterized in that, be to adopt the dendroid polyamide-amide macromole of Tutofusin tris, halogen acyl halide, dithiobenzoic acid sodium opposite end ester group to carry out the end group functional modification successively and the end capped dendroid polyamide-amide of dithiobenzoic acid ester that obtains.The dendroid polyamide-amide macromole of said end ester group, be the finger tip number of ester groups be respectively 4,8,16,32 the 0.5th, 1.5,2.5,3.5 generation one of dendroid polyamide-amide; Said halogen acyl halide is meant one of chloroacetyl chloride, 2-chlorpromazine chloride, 2-chlorine isobutyryl chloride, 3-chlorpromazine chloride, 2-bromo propionyl chloro, bromoacetyl bromide, 2 bromo propionyl bromide and 2-bromine isobutyl acylbromide.
Said quaternary ammonium cation monomer is one of acrylyl oxy-ethyl-trimethyl salmiac (DAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DADMAC).
Said solvent is THF, N, one of N N.
The mol ratio of dendroid polyfunctional group chain-transfer agent and Diisopropyl azodicarboxylate is (0.1～5) in the above-mentioned reaction system: 1
Total monomer in the above-mentioned reaction system (acrylic amide and quaternary ammonium cation monomer sum) is (120～9600) with the mol ratio of dendroid polyfunctional group chain-transfer agent: 1
The monomeric mol ratio of acrylic amide and quaternary ammonium cation is (0.1～10) in the above-mentioned reaction system: 1.
Preferably, the temperature of reaction of above-mentioned reaction system is 50～70 ℃, and the reaction times is 12～36h.Most preferred, temperature of reaction is 65 ℃, and the reaction times is 24h.
Further preferred, in the above-mentioned reaction system, the mol ratio of dendroid polyfunctional group chain-transfer agent and Diisopropyl azodicarboxylate is (0.25～1.5): 1; Total monomer (acrylic amide and quaternary ammonium cation monomer sum) is (500～5000) with the mol ratio of dendroid polyfunctional group chain-transfer agent: 1; The monomeric mol ratio of acrylic amide and quaternary ammonium cation is (0.2～5): 1.
The prepared tree nuclear star of above-mentioned reaction system shape cationic polyacrylamide is that branching arm number is 12～96, molecular weight is 10 * 10
3～10 * 10
5, cationic charge density is 0.5～6.0meqg
-1Be that core, cationic polyacrylamide are the tree nuclear star shape polymkeric substance of branching arm with the dendroid polyamide-amide.
Excellent results of the present invention is following:
The method for preparing tree nuclear star shape cationic polyacrylamide according to the invention can be controlled structure, branching arm number, molecular weight and MWD and the positive charge density of setting nuclear star shape cationic polyacrylamide molecule well, and monomer conversion is high.The molecular structure of prepared tree nuclear star shape cationic polyacrylamide is regular, and tree nuclear inside has cavity, and peripheral molecular chain is star-branched, and the molecular chain conformation stretches, and positive charge density is high, is prone to dissolving, and soltion viscosity is low.Its star-branched structure can delay to adsorb the generation of back molecular chain reconstruct and diffusion phenomena, has good saline-alkaline tolerance, and high shear is had good resistivity.Can be widely used in every field such as papermaking, WWT, oil recovery according to its tree nuclear structure, branching arm number, molecular weight and positive charge density.Be easy to develop series product.
Description of drawings
Fig. 1 is the synthetic route synoptic diagram of the tree nuclear star shape cationic polyacrylamide of the embodiment of the invention 1.
Embodiment
Below in conjunction with embodiment a kind of preparation method who sets nuclear star shape cationic polyacrylamide of the present invention is described further, but is not limited thereto.
Embodiment 1: in the 250mL four-hole boiling flask that reflux condensate device, nitrogen conduit, constant voltage feeding device are housed, add the 75mL THF, to add 8.0g acrylic amide, 15.0g methylacryoyloxyethyl trimethyl ammonium chloride and 0.83g dithiobenzoic acid ester terminal number under the nitrogen successively be 12 dendroid polyamide-amide stirring and feed.After mixing, flask is moved in the water bath with thermostatic control, make temperature of reaction rise to 65 ℃, add the 0.11g Diisopropyl azodicarboxylate, isothermal reaction 24h under stirring and logical nitrogen.Reaction finishes the back underpressure distillation and removes and desolvates, and in the crude product that obtains, adds deionized water and makes its dissolving, and then add acetone product is precipitated out, and is 12 through being drying to obtain branching arm number, molecular weight is 7.5 * 10
4, cationic charge density is 2.5meqg
-1Tree nuclear star shape cationic polyacrylamide.
Embodiment 2: in the 250mL four-hole boiling flask that reflux condensate device, nitrogen conduit, constant voltage feeding device are housed, add the 95mL THF, to add 5.15g acrylic amide, 18.0g acrylyl oxy-ethyl-trimethyl salmiac and 0.64g dithiobenzoic acid ester terminal number under the nitrogen successively be 24 dendroid polyamide-amide stirring and feed.After mixing, flask is moved in the water bath with thermostatic control, make temperature of reaction rise to 70 ℃, add the 0.576g Diisopropyl azodicarboxylate, isothermal reaction 30h under stirring and logical nitrogen.Reaction finishes the back underpressure distillation and removes and desolvates, and in the crude product that obtains, adds deionized water and makes its dissolving, and then add acetone product is precipitated out, and is 24 through being drying to obtain branching arm number, molecular weight is 2.0 * 10
5, cationic charge density is 3.4meqg
-1Tree nuclear star shape cationic polyacrylamide.
Embodiment 3: in the 250mL four-hole boiling flask that reflux condensate device, nitrogen conduit, constant voltage feeding device are housed, add the 50mL THF, to add 2.64g acrylic amide, 20.0g dimethyl diallyl ammonium chloride and 0.21g dithiobenzoic acid ester terminal number under the nitrogen successively be 12 dendroid polyamide-amide stirring and feed.After mixing, flask is moved in the water bath with thermostatic control, make temperature of reaction rise to 60 ℃, add the 0.022g Diisopropyl azodicarboxylate, isothermal reaction 28h under stirring and logical nitrogen.Reaction finishes the back underpressure distillation and removes and desolvates, and in the crude product that obtains, adds deionized water and makes its dissolving, and then add acetone product is precipitated out, and is 12 through being drying to obtain branching arm number, molecular weight is 2.1 * 10
5, cationic charge density is 4.8meqg
-1Tree nuclear star shape cationic polyacrylamide.
Embodiment 4: like embodiment 1, different is total monomer (acrylic amide and methylacryoyloxyethyl trimethyl ammonium chloride sum) and dithiobenzoic acid ester terminal number are that the mol ratio of 12 dendroid polyamide-amide is 2500: 1.
Embodiment 5: like embodiment 2, different is, and dithiobenzoic acid ester terminal number is 24 the dendroid polyamide-amide and the mol ratio of Diisopropyl azodicarboxylate are 1: 1.
Embodiment 6: like embodiment 2, and the mol ratio of different is acrylic amide and acrylyl oxy-ethyl-trimethyl salmiac 4: 1.
Embodiment 7: like embodiment 3, and the mol ratio of different is acrylic amide and dimethyl diallyl ammonium chloride 0.25: 1.
Embodiment 8: like embodiment 1, different is that the solvent that adopts is N, the N N.
Claims (5)
1. preparation method who sets nuclear star shape cationic polyacrylamide; It is characterized in that; Adopting the end capped dendroid polyamide-amide of dithiobenzoic acid ester is dendroid polyfunctional group chain-transfer agent; Diisopropyl azodicarboxylate (AIBN) is an initiator, and acrylamide triggered and quaternary ammonium cation monomer carries out reversible addition-fragmentation chain transfer free radical polymerization, synthetic tree nuclear star shape cationic polyacrylamide.Step is following:
In the reactor drum that nitrogen conduit, constant voltage feeding device, reflux condensate device and whipping appts are housed, add solvent; In stirring, logical nitrogen downhill reaction device, add acrylic amide, quaternary ammonium cation monomer and dendroid polyfunctional group chain-transfer agent successively then; After the question response monomer mixes; With the temperature adjusting in the reactor drum is 25～100 ℃, under stirring and nitrogen protection, adds Diisopropyl azodicarboxylate, isothermal reaction 1～72h.Reaction finishes the back underpressure distillation except that desolvating, and in the crude product that obtains, adds deionized water and makes its dissolving, adds acetone then product is precipitated out, through being drying to obtain tree nuclear star shape cationic polyacrylamide.
Said solvent is THF, N, one of N N; Said quaternary ammonium cation monomer is one of acrylyl oxy-ethyl-trimethyl salmiac (DAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC) and dimethyl diallyl ammonium chloride (DADMAC); Prepared tree nuclear star shape cationic polyacrylamide is that branching arm number is 12～96, molecular weight is 10 * 10
3～10 * 10
5, cationic charge density is 0.5～6.0meqg
-1Be that core, cationic polyacrylamide are the tree nuclear star shape polymkeric substance of branching arm with the dendroid polyamide-amide.
2. the preparation method of tree nuclear star shape cationic polyacrylamide as claimed in claim 1; It is characterized in that; Said dendroid polyfunctional group chain-transfer agent is meant that dithiobenzoic acid ester terminal number is respectively 12,24,48,96 dendroid polyamide-amide; It is characterized in that, be to adopt the dendroid polyamide-amide macromole of Tutofusin tris, halogen acyl halide, dithiobenzoic acid sodium opposite end ester group to carry out the end group functional modification successively and the end capped dendroid polyamide-amide of dithiobenzoic acid ester that obtains.The dendroid polyamide-amide macromole of said end ester group, be the finger tip number of ester groups be respectively 4,8,16,32 the 0.5th, 1.5,2.5,3.5 generation one of dendroid polyamide-amide; Said halogen acyl halide is meant one of chloroacetyl chloride, 2-chlorpromazine chloride, 2-chlorine isobutyryl chloride, 3-chlorpromazine chloride, 2-bromo propionyl chloro, bromoacetyl bromide, 2 bromo propionyl bromide and 2-bromine isobutyl acylbromide.
3. the preparation method of tree nuclear star shape cationic polyacrylamide as claimed in claim 1 is characterized in that the mol ratio of dendroid polyfunctional group chain-transfer agent and Diisopropyl azodicarboxylate is (0.1～5) in the reaction system: 1
4. the preparation method of tree nuclear star shape cationic polyacrylamide as claimed in claim 1; It is characterized in that total monomer in the reaction system (acrylic amide and quaternary ammonium cation monomer summation) is (120～9600) with the mol ratio of dendroid polyfunctional group chain-transfer agent: 1
5. the preparation method of tree nuclear star shape cationic polyacrylamide as claimed in claim 1 is characterized in that the monomeric mol ratio of acrylic amide and quaternary ammonium cation is (0.1～10) in the reaction system: 1.
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| CN103736097A (en) * | 2013-12-31 | 2014-04-23 | 天津大学 | PH and temperature supersensitive dendrimer drug carrier (generation 2.5) and preparation method thereof |
| CN103808626A (en) * | 2014-03-11 | 2014-05-21 | 北京城市排水集团有限责任公司 | Method for detecting quality of cationic polyacrylamide sludge treatment agent |
| CN103834040A (en) * | 2013-12-31 | 2014-06-04 | 天津大学 | Dendrimer drug carrier G3.5 with pH and temperature supersensitivity and preparation method thereof |
| CN103865075A (en) * | 2014-03-04 | 2014-06-18 | 康吉诺（北京）科技有限公司 | Preparation method and application of heteroarm star-shaped polyacrylamide |
| CN107261868A (en) * | 2017-06-28 | 2017-10-20 | 安庆师范大学 | A kind of temperature sensitive type amphipathic nature polyalcohol is modified paper substrate filter membrane and preparation method thereof |
| CN111171226A (en) * | 2018-11-12 | 2020-05-19 | 中石化石油工程技术服务有限公司 | Preparation method of water-soluble filtrate reducer for drilling fluid and drilling fluid |
| WO2021037281A1 (en) * | 2019-08-30 | 2021-03-04 | 苏州大学 | Three-dimensional spherical alpha-helix cationic polypeptide having high-efficiency gene delivery capability, and preparation method and application thereof |
| CN112625179A (en) * | 2021-01-25 | 2021-04-09 | 河南省科学院高新技术研究中心 | Narrow-distribution low-molecular-weight cationic polyacrylamide and preparation method thereof |
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| CN103736097A (en) * | 2013-12-31 | 2014-04-23 | 天津大学 | PH and temperature supersensitive dendrimer drug carrier (generation 2.5) and preparation method thereof |
| CN103834040A (en) * | 2013-12-31 | 2014-06-04 | 天津大学 | Dendrimer drug carrier G3.5 with pH and temperature supersensitivity and preparation method thereof |
| CN103736097B (en) * | 2013-12-31 | 2016-04-13 | 天津大学 | A kind of pH and temperature hypersensitivity dendritic macromole medicine 2.5 generation carrier and preparation method thereof |
| CN103834040B (en) * | 2013-12-31 | 2017-02-15 | 天津大学 | Dendrimer drug carrier G3.5 with pH and temperature supersensitivity and preparation method thereof |
| CN103865075A (en) * | 2014-03-04 | 2014-06-18 | 康吉诺（北京）科技有限公司 | Preparation method and application of heteroarm star-shaped polyacrylamide |
| CN103808626A (en) * | 2014-03-11 | 2014-05-21 | 北京城市排水集团有限责任公司 | Method for detecting quality of cationic polyacrylamide sludge treatment agent |
| CN107261868A (en) * | 2017-06-28 | 2017-10-20 | 安庆师范大学 | A kind of temperature sensitive type amphipathic nature polyalcohol is modified paper substrate filter membrane and preparation method thereof |
| CN107261868B (en) * | 2017-06-28 | 2020-12-22 | 安庆师范大学 | Temperature-sensitive amphiphilic polymer modified paper-based filter membrane and preparation method thereof |
| CN111171226A (en) * | 2018-11-12 | 2020-05-19 | 中石化石油工程技术服务有限公司 | Preparation method of water-soluble filtrate reducer for drilling fluid and drilling fluid |
| CN111171226B (en) * | 2018-11-12 | 2022-04-19 | 中石化石油工程技术服务有限公司 | Preparation method of water-soluble filtrate reducer for drilling fluid and drilling fluid |
| WO2021037281A1 (en) * | 2019-08-30 | 2021-03-04 | 苏州大学 | Three-dimensional spherical alpha-helix cationic polypeptide having high-efficiency gene delivery capability, and preparation method and application thereof |
| CN112625179A (en) * | 2021-01-25 | 2021-04-09 | 河南省科学院高新技术研究中心 | Narrow-distribution low-molecular-weight cationic polyacrylamide and preparation method thereof |
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