CN102492092B - Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization - Google Patents
Method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization Download PDFInfo
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Abstract
The invention discloses a method for preparing a hyperbranched ionic amide type polymer by inverse emulsion polymerization. The method comprises the following steps: firstly polymerizing ionic monomers or firstly copolymerizing the ionic monomers with a part of amide type monomers through the inverse emulsion polymerization of reversible addition-fragmentation chain transfer (RAFT) by adopting an operation process of adding a follow-up phase under the action of a surfactant, then adding the rest of amide type monomers for chain extension, as well as diene type monomers and an RAFT chain transfer agent so as to prepare the hyperbranched ionic amide type polymer, wherein the outer tail end of a branched chain is an ionic monomer block or a copolymer block with high ion content. The hyperbranched ionic amide type polymer obtained by the method disclosed by the invention has good flocculation effect and excellent water dissolubility.
Description
Technical field
The present invention relates to a kind of inverse emulsion polymerization synthetic technology of water-soluble ionic-type acylamide polymer, relate in particular to be a kind ofly applicable to disperse, stick, flocculation and rheology control and there is the preparation method of the ionic acylamide polymer of the dissaving structure that the outer end of branched chain is ionic comonomer block or macroion degree copolymerization block.
Background technology
Ionic acylamide polymer is widely used in the fields such as sewage disposal, mine, iron and steel, petrochemical industry, papermaking, printing and dyeing, sugaring, building materials.
Water-soluble ionic-type acylamide polymer can be by solution polymerization or inverse emulsion polymerization.During solution polymerization, when in system, monomer surpasses 8% as acrylamide content, viscosity is just very high, makes polymerization process wayward, and molecular weight is on the low side.And that inverse emulsion polymerization has polymerization efficiency is high, solid content is high, polymericular weight advantages of higher.CN101298488A discloses adding under the condition that sodium formiate is reagent and additive in polymerization, by conversed phase micro emulsion copolymerization, has prepared the cationic-type polyacrylamide of good stability, and polymericular weight is about 10
6.J.R.Ochoa etc. have reported that take acrylamide (AM) and 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) is reaction monomers, adopt the method for reverse micro emulsion to synthesize the cationic high-molecular flocculant of solid content 30%.
Now widely used ionic acylamide polymer, take linear structure as main as cationic acrylamide flocculating agent, and the ionic acylamide polymer of branched structure is very rarely seen in the application of the aspects such as water treatment.CN1834127c discloses employing composite initiation system, with AM and cationic monomer DMC, carries out aqueous solution adiabatic polymerisation, prepares relative molecular weight and is greater than 10
7cationic-type polyacrylamide.CN1865299 discloses under adiabatic condition and has introduced function monomer, synthesizes the super high molecular weight polyacrylamide of different molecular weight ranges by the synergistic effect of three sections of composite initiation series initiators.But, poorly soluble in water of the linear amides base polymer of ultra-high molecular weight, dissolution rate is lower, and the viscosity of the linear polymer of high molecular is also larger, affects processing characteristics, improves production cost.And compare with linear polymer with the hyperbranched polymer of equimolecular quantity, there is lower viscosity, high rheological variation and good solubility, easy to use.
Hyperbranched polymer is the hyperbranched macromole with triaxial ellipsoid shape D structure of a class, containing a large amount of end and main chain functional groups, conventionally uses the special direct one-step polycondensation of ABx type monomer to make.Sherrington etc. (J.Mater.Chem, 2003,2701-2710) to take the mercaptan of suitable proportion be chain-transfer agent to report, obtains the polymethacrylate of branching by the copolymerization with Ethylene glycol dimethacrylate.(the Macromolecules such as Wang, 2010,4062-4069) reported and adopted semi-continuous operating procedure, by reversible addition-fracture chain, shift (RAFT) polymerization, take dienes monomer as branching agent, under the RAFT of low proportioning chain-transfer agent condition, by the method for solution polymerization, prepare hyperbranched polyacrylamide.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method of preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization is provided.
The object of the invention is to be achieved through the following technical solutions: a kind of inverse emulsion polymerization method of preparing hyperbranched ionic acylamide polymer, comprises the following steps:
(1) preparation external phase: at ambient temperature, by oil-soluble emulsifier, polymeric surface active agent, be dissolved in solvent oil, mix; The mass ratio of described oil-soluble emulsifier, polymeric surface active agent, solvent oil is controlled at 0.4-15:0.01-12:8-68;
(2) preparation disperse phase: water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain-transfer agent, initiator are dissolved in water, are mixed with disperse phase; The mass ratio that wherein water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain turn between agent, initiator, water is controlled at 0.4-15:0-45:0.01-45:0.00045-0.45:0.00009-0.45:3-65;
(3) prepare follow-up phase: amides monomer and dienes monomer are mixed with to the follow-up phase of the aqueous solution, follow-up two portions that divide mutually: the mass ratio between the amides monomer of the follow-up phase of first part, dienes monomer, water is controlled at 0.01-45:0-5:1-40; Mass ratio between the amides monomer of the follow-up phase of second section, dienes monomer, water is controlled at 0.01-45:0-5:1-40; First part is follow-up is controlled at 0.1-5:0.1-5 with the mass ratio of the follow-up phase of second section;
(4) 0.5-25:0.5-25:0.01-10 gets external phase, disperse phase and the follow-up phase that step 1-3 prepares in mass ratio, then under room temperature, mechanical stirring condition, disperse phase is joined in external phase gradually, mixes pre-emulsification, letting nitrogen in and deoxidizing 30 minutes; Add the temperature that raises after initiator, under 25-80 ℃ of condition, carry out polyreaction; React after 0.5-5 hour, 0-3 hour follow-up being added in reaction system of Nei Jiang first part; Continue reaction after 1-3 hour, in 0-3 hour, be added in reaction system second section is follow-up, continue reaction 1-3 hour, prepare hyperbranched ionic acylamide polymer.
The invention has the beneficial effects as follows: the inventive method is by RAFT polymerization process, employing adds the operating procedure of follow-up phase, ion monomer is first carried out to homopolymerization or first carries out copolymerization with part amides monomer, add residue amides monomer chain extension thereafter, be combined with dienes monomer and RAFT chain-transfer agent, prepared the outer end of branched chain and be ionic comonomer block or macroion degree copolymerization block hyperbranched ionic acylamide polymer.The hyperbranched ionic acylamide polymer that the present invention obtains has good flocculating effect and good water-soluble.
Embodiment
The method of preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization of the present invention shifts (RAFT) inverse emulsion polymerization method by semicontinuous reversible addition-fracture, because used the special chain transfer agent that chain transfer constant is high in RAFT polymerization process, the regeneration of reversible addition-fracture occurs for this chain-transfer agent and Propagating Radical shifts, keep free radical activity, realize controlled and radical polymerization " activity ", and can regulate and control the structure of polymkeric substance.Simultaneously, employing adds the operating procedure of follow-up phase, can obtain the outer end of branched chain and be ionic comonomer block or macroion degree copolymerization block hyperbranched ionic acylamide polymer, use in conjunction with low proportioning chain-transfer agent, polyreaction is easily controlled, and can highly transform the stabilized latex that ground forms high solids content.
Specifically, the method for preparing hyperbranched ionic amide type polymer by inverse emulsion polymerization of the present invention, comprises the following steps:
One, preparation external phase: at ambient temperature, oil-soluble emulsifier, polymeric surface active agent are dissolved in to solvent oil, mix;
Solvent oil comprises the liquefied hydrocarbon of aromatic series, cycloalkane, aliphatic category and containing substituent compound, comprises isoparaffin, 120# solvent oil, 200# solvent oil, kerosene, whiteruss, white oil a kind of and composition thereof of tetrachloroethylene, tetracol phenixin, toluene, benzene, dimethylbenzene, octane, dodecane, the tetradecane, different carbon chain.The mass ratio of controlling water in solvent oil and disperse phase is 0.5-2:2-0.5.
The mass ratio of oil-soluble emulsifier, polymeric surface active agent, solvent oil is controlled at 0.4-15:0.01-12:8-68; Wherein oil-soluble emulsifier comprises dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, heavy wool acid polyglycerol ester and Zerol etc. and composition thereof.Polymeric surface active agent is a kind of amphipathic nature polyalcohol, in polymkeric substance, there is hydrophilic, lipophilic group simultaneously, comprise oxyethylene-propylene oxide block copolymer, ten dihydroxystearic acids-epoxyethane block copolymer, acrylate-acrylamide copolymer, acrylate-acrylic copolymer, acrylate-Sipacril 2739OF, acrylate-dimethyl diene ammonium chloride copolymer, acrylate-dimethylaminoethyl methacrylate quaternized copolymer and composition thereof.
Two, preparation disperse phase: water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain-transfer agent, initiator are dissolved in water, are mixed with disperse phase; The mass ratio that wherein water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain turn between agent, initiator, water is controlled at 0.4-15:0-45:0.01-45:0.00045-0.45:0.00009-0.45:3-65;
Water soluble emulsifier is nonionic surface active agent, comprise dehydration sorb sugar ester ethylene oxide adduct, alkyl alcohol or alkylphenol ethylene oxide adduct etc., as Polysorbate 80, polyoxyethylene oleic acid base ether, polyoxyethylene stearyl acid amides, polyoxyethylene nonylplenyl ether etc. and composition thereof.
Amides monomer comprises the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, NIPA, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, NVP etc.
Ionic comonomer comprises anionic monomer, cationic monomer and amphipathic water-soluble monomer.Described anionic monomer comprises vinylformic acid, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, to vinylbenzenesulfonic acid (sodium), to vinyl benzoic acid etc.; Described cationic monomer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-dimethyl ethenylphenyl ammonia and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine etc.; Described amphipathic water-soluble monomer comprises N-(3-sulfonic acid propyl group) 2-vinyl pyridine, 2-acrylyl oxy-ethyl phosphorylcholine etc.
RAFT chain-transfer agent is dithio or trithio compound, comprising dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class etc.Described dithioesters class link transfer agent comprises 4-cyanopentanoic acid dithiobenzoic acid ester.The different base dithiobenzoic acid of 2-cyano group third ester, 2-(2-hydroxyethanoic acid dithio carbonylsulfide) propionic acid, 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid, 2-methoxyethyl 2-phenyl-2-(amyl group thio-carbonyl sulfide) acetic ester etc.Described trithiocarbonate comprises (3-benzene first sulfydryl thio-carbonyl sulfide) propionic acid, 2-(second sulfydryl thio-carbonyl sulfide)-2 Methylpropionic acid, 3-((1-carboxyl second sulfydryl) thio-carbonyl sulfide) propionic acid, 2,2 '-thiocarbonyls two (sulfanyl) two (2 Methylpropionic acid) etc., xanthogenic acid 0 ester class is as xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid etc.
Initiator can be the various initiators that are applicable to polar solvent system, as chemical initiator, and photochemical initiators, radiation initiators etc.Chemical initiator when had peroxide initiator, azo-initiator, oxidation-reduction initiator etc.Conventional peroxide initiator comprises ammonium persulphate, Potassium Persulphate etc., and azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl mew quinoline hydrochloride, azo di-isopropyl mew quinoline etc.Described photochemical initiators comprises (2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone) etc.
Three, prepare follow-up phase: amides monomer and dienes monomer are mixed with to the follow-up phase of the aqueous solution, follow-up two portions that divide mutually: the mass ratio between the amides monomer of the follow-up phase of first part, dienes monomer, water is controlled at 0.01-45:0-5:1-40; Mass ratio between the amides monomer of the follow-up phase of second section, dienes monomer, water is controlled at 0.01-45:0-5:1-40; First part is follow-up is controlled at 0.1-5:0.1-5 with the mass ratio of the follow-up phase of second section;
Dienes compound comprises symmetry and asymmetry vinyl compound; Conventional dienes compound comprises N, N '-methylene-bisacrylamide, diacrylate macrogol ester, Ethylene glycol dimethacrylate etc.Described asymmetric dienes compound comprises (methyl) vinylformic acid vinyloxy group macrogol ester etc.
Four, under room temperature, mechanical stirring condition, disperse phase is joined in external phase gradually, mix pre-emulsification, letting nitrogen in and deoxidizing 30 minutes; Add the temperature that raises after initiator, under 25-80 ℃ of condition, carry out polyreaction; React after 0.5-5 hour, 0-3 hour follow-up being added in reaction system of Nei Jiang first part; Continue reaction after 1-3 hour, in 0-3 hour, be added in reaction system second section is follow-up, continue reaction 1-3 hour, prepare hyperbranched ionic acylamide polymer.
Described emulsifying agent in step 1 and step 2 is nonionic surface active agent.In described step 1, described oil-soluble emulsifier comprises dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, heavy wool acid polyglycerol ester and Zerol etc.; In described step 2, water soluble emulsifier comprises Polysorbate 80, polyoxyethylene oleic acid base ether, polyoxyethylene stearyl acid amides and polyoxyethylene nonylplenyl ether etc., and the hydrophile-lipophile balance value of composite rear emulsifying agent (HLB) is worth between 2-7.
Polymerization temperature is controlled between 25 ℃ to 80 ℃, react after 0.5-5 hour, 0-3 hour the follow-up of Nei Jiang first part, be added in reaction system, continue reaction after 1-3 hour, in second section follow-up being added to reaction system in 0-3 hour, continue reaction 1-3 hour, total reaction time was controlled between 5-17 hour.The final hyperbranched ionic acylamide polymer obtaining be emulsion total amount 5% to 60% between.
Below by specific examples, further illustrate the present invention program and result, but can not think that the present invention only limits in these examples.In example, except specified otherwise, all marks and percentage ratio are all weight ratios.
Embodiment 1
In 100ml there-necked flask, add 1.2 parts of ten dihydroxystearic acids-epoxyethane block copolymers, 1.56 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 3.175 parts of acrylamides, 3.3 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0348 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.24 part of Tween80 are dissolved in 6.26 parts of water (PH=7), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0292 part of over cure ammonium, is warming up to 50 ℃, adds 0.0137 part of sodium bisulfite to start reaction.React after 3 hours, 1.9 parts of acrylamides are dissolved in 1.5 parts of water, add reaction system, react again after 3 hours, by 1.27 parts of acrylamides and 0.0197 part of N, N '-methylene-bisacrylamide is dissolved in 1 part of water, and the constant rate of speed with 6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched Polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 96.5%, its weight-average molecular weight is 2.80 * 10
5, molecular weight distribution is 1.61, the parameter g ' of polymkeric substance branching degree can characterize the degree of branching of molecule, g '=1 of linear polymer, and the g ' <1 of branching molecule for 0.712(g '; Degree of branching is higher, and g ' is less), the flocculating property of sample represents with relative turbidity, the relative turbidity Tr=T/To of Tr=0.453(, To is initial TiO
2the turbidity of turbid solution, T is the TiO adding after sample flocculation agent for some time
2the turbidity of turbid solution, adds 1mg polymer samples/g TiO
2, flocculation time is 30min).
Embodiment 2
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.82 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0145 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 0.5 hour, by 1.37 parts of acrylamides and 0.0082 part of N, N '-methylene-bisacrylamide is dissolved in 1.8 parts of water, add reaction system, react after 1 hour, by 1.37 parts of acrylamides and 0.041 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water again, constant rate of speed with 6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched Polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 86.7%, its weight-average molecular weight is 6.43 * 10
5, molecular weight distribution is 1.5, the parameter g ' of polymkeric substance branching degree is 0.722, the flocculating property of sample represents with relative turbidity, Tr=0.157.
Implementation column 3
The solid content of maintenance system is constant, reduces the content of cationic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, and ion degree is reduced to 15% from 25% of example 2.
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 2.36 parts of acrylamides, 3.88 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0103 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0086 part of over cure ammonium, is warming up to 50 ℃, adds 0.0047 part of sodium bisulfite to start reaction.React after 0.5 hour, by 1.77 parts of acrylamides and 0.0082 part of N, N '-methylene-bisacrylamide is dissolved in 1.8 parts of water, adds reaction system.React again after 3 hours, by 1.77 parts of acrylamides and 0.0246 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water, and the constant rate of speed with 6.7ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.The transformation efficiency of polymerization system is 96%, its weight-average molecular weight is 1.22 * 10
6, molecular weight distribution is 1.18, the parameter g ' of polymkeric substance branching degree is 0.675, the flocculating property of sample represents with relative turbidity, Tr=0.339.
Embodiment 4
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.37 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0146 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 1 hour, 1.82 parts of acrylamides are dissolved in 1.8 parts of water, add reaction system, react again after 1.5 hours, by 1.37 parts of acrylamides and 0.0412 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water, and the constant rate of speed with 6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 90.8%, its weight-average molecular weight is 5.93 * 10
5, molecular weight distribution is 1.74, the parameter g ' of polymkeric substance branching degree is 0.628, the flocculating property of sample represents with relative turbidity, Tr=0.325.
Embodiment 5
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.82 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0146 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 1 hour, 0.46 part of acrylamide is dissolved in 1.8 parts of water, add reaction system, react again after 1.5 hours, by 2.28 parts of acrylamides and 0.0412 part of N, N '-methylene-bisacrylamide is dissolved in 1.5 parts of water, and the constant rate of speed with 7.6ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 89.7%, its weight-average molecular weight is 4.53 * 10
5, molecular weight distribution is 1.8, the parameter g ' of polymkeric substance branching degree is 0.780, the flocculating property of sample represents with relative turbidity, Tr=0.163.
Embodiment 6
In 100ml there-necked flask, add 0.9 part of ten dihydroxystearic acids-epoxyethane block copolymer, 2.04 parts of Span80,8.58 parts of isoparaffins, mechanical stirring mixes and letting nitrogen in and deoxidizing, is mixed with external phase.By 1.82 parts of acrylamides, 5.55 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution (80wt%), 0.0146 part of thin base thiocarbonyl propionic acid of 3-benzene first, 0.06 part of Tween80 are dissolved in 4 parts of water (PH=4.4), are mixed with disperse phase.It is 400 revs/min that stirring velocity is set, and at ambient temperature, disperse phase constant speed is added dropwise to external phase in 1 hour, obtains monomer emulsion, adds 0.0122 part of over cure ammonium, is warming up to 50 ℃, adds 0.0066 part of sodium bisulfite to start reaction.React after 0.5 hour, by 2.74 parts of acrylamides and 0.0246 part of N, N '-methylene-bisacrylamide is dissolved in 3.3 parts of water, and the constant rate of speed with 8.5ml/h in 28min is added drop-wise in reaction system, obtains stable hyperbranched cationic-type polyacrylamide latex.
In this embodiment, the transformation efficiency of polymerization system is 85.9%, its weight-average molecular weight is 5.05 * 10
5, molecular weight distribution is 1.18, the parameter g ' of polymkeric substance branching degree is 0.816, the flocculating property of sample represents with relative turbidity, Tr=0.39.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all fall into protection scope of the present invention.
Claims (6)
1. a reversed phase emulsion synthesis method of preparing hyperbranched ionic acylamide polymer, is characterized in that, comprises the following steps:
(1) preparation external phase: at ambient temperature, oil-soluble emulsifier, polymeric surface active agent are dissolved in to solvent oil, mix; The mass ratio of described oil-soluble emulsifier, polymeric surface active agent and solvent oil is controlled at 0.4-15:0.01-12:8-68;
(2) preparation disperse phase: water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain-transfer agent are dissolved in water, are mixed with disperse phase; Wherein, the mass ratio that water soluble emulsifier, amides monomer, ionic comonomer, RAFT chain turn between agent and water is controlled at 0.4-15:0-45:0.01-45:0.00045-0.45:3-65;
(3) prepare follow-up phase: amides monomer and dienes monomer are mixed with to the follow-up phase of the aqueous solution, follow-up two portions that divide mutually: the mass ratio between the amides monomer of the follow-up phase of first part, dienes monomer, water is controlled at 0.01-45:0-5:1-40; Mass ratio between the amides monomer of the follow-up phase of second section, dienes monomer, water is controlled at 0.01-45:0-5:1-40; First part is follow-up is controlled at 0.1-5:0.1-5 with the mass ratio of the follow-up phase of second section;
(4) 0.5-25:0.5-25:0.01-10 gets external phase, disperse phase and the follow-up phase that prepare step (1)-(3) in mass ratio, then under room temperature, mechanical stirring condition, disperse phase is joined in external phase gradually, mix pre-emulsification, letting nitrogen in and deoxidizing 30 minutes; Add the temperature that raises after initiator, under 25-80 ℃ of condition, carry out polyreaction; React after 0.5-5 hour, 0-3 hour follow-up being added in reaction system of Nei Jiang first part; Continue reaction after 1-3 hour, in 0-3 hour, be added in reaction system second section is follow-up, continue reaction 1-3 hour, prepare hyperbranched ionic acylamide polymer;
Described amides monomer comprises: the two substituted acrylamides of acrylamide, Methacrylamide, N-, N methacrylamide, NIPA, N-acryloyl morpholine, N-(2-hydroxypropyl) acrylamide, N-acryloyl tetramethyleneimine, N-vinyl formamide, NVP; Described ionic comonomer comprises anionic monomer, cationic monomer and amphipathic water-soluble monomer; Described anionic monomer comprises vinylformic acid, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, to vinylbenzenesulfonic acid, to vinyl benzoic acid; Described cationic monomer comprises dimethyl diallyl ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-dimethyl ethenylphenyl amine and quaternary ammonium salt thereof, 2-vinyl pyridine, 4-vinylpridine; Described amphipathic water-soluble monomer comprises N-(3-sulfonic acid propyl group) 2-vinyl pyridine and 2-acrylyl oxy-ethyl phosphorylcholine; Described dienes monomer comprises symmetry and asymmetry vinyl compound; Described symmetry dienes compound comprises N, N '-methylene-bisacrylamide, diacrylate macrogol ester and Ethylene glycol dimethacrylate; Described asymmetry dienes compound comprises (methyl) vinylformic acid vinyloxy group macrogol ester.
2. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (1), described oil-soluble emulsifier is nonionic surface active agent, comprises dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, heavy wool acid polyglycerol ester and Zerol; In described step (2), water soluble emulsifier is nonionic surface active agent, comprises Polysorbate 80, polyoxyethylene oleic acid base ether, polyoxyethylene stearyl acid amides and polyoxyethylene nonylplenyl ether; Polymeric surface active agent in step (1) is a kind of amphipathic nature polyalcohol, in polymkeric substance, there is hydrophilic, lipophilic group simultaneously, comprise oxyethylene-propylene oxide block copolymer, ten dihydroxystearic acids-epoxyethane block copolymer, acrylate-acrylamide copolymer, acrylate-acrylic copolymer, acrylate-Sipacril 2739OF, acrylate-dimethyl diallyl ammonium chloride copolymer and acrylate-dimethylaminoethyl methacrylate quaternized copolymer.
3. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (1), described solvent oil comprises: the liquefied hydrocarbon of aromatic series, cycloalkane, aliphatic category and containing substituent compound.
4. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (1), described solvent oil comprises tetrachloroethylene, tetracol phenixin, toluene, benzene, dimethylbenzene, octane, dodecane, the tetradecane, isoparaffin, 120# solvent oil, 200# solvent oil, kerosene, whiteruss and white oil.
5. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (2), described RAFT chain-transfer agent is dithio or trithio compound, comprises dithiobenzoic acid ester class, trithiocarbonic acid salt, dithiocarbamate(s), xanthate class; Described dithiobenzoic acid ester class comprises 4-cyanopentanoic acid dithiobenzoic acid ester, 2-cyano group sec.-propyl dithiobenzoic acid ester; Described dithiocarbamate(s) is 4-cyano group-4-(diethyl thiocarbamyl sulphur) valeric acid; Described trithiocarbonic acid salt comprises (3-benzene first sulfydryl thio-carbonyl sulfide) propionic acid, 2-(second sulfydryl thio-carbonyl sulfide)-2 Methylpropionic acid, 3-((1-carboxyl second sulfydryl) thio-carbonyl sulfide) propionic acid, 2,2 '-thiocarbonyl two (sulfanyl) two (2 Methylpropionic acid); Xanthate class is selected from xanthogenic acid guanidine-acetic acid, (2-(acetoxyl group) methyl) xanthogen phenylformic acid.
6. prepare according to claim 1 the reversed phase emulsion synthesis method of hyperbranched ionic acylamide polymer, it is characterized in that, in described step (4), described initiator is chemical initiator, and described chemical initiator comprises peroxide initiator, azo-initiator, oxidation-reduction initiator and photochemical initiators; Described peroxide initiator comprises ammonium persulphate, Potassium Persulphate; Described azo-initiator comprises 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline; Described photochemical initiators is (2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone).
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| CN103601893B (en) * | 2013-10-23 | 2015-12-09 | 西北工业大学 | There is the preparation method of the hyperbranched NIPA of long-chain of temperature sensitivity |
| CN103788269B (en) * | 2014-01-24 | 2016-01-20 | 绍兴文理学院 | Polyacrylamide and its preparation method and application |
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| CN105669912B (en) * | 2016-03-03 | 2018-03-13 | 江苏中铁奥莱特新材料股份有限公司 | A kind of method for preparing star-like poly carboxylic acid series water reducer |
| CN107383292B (en) * | 2017-07-11 | 2019-11-19 | 四川大学 | A kind of hydrophobic association type three block polyacrylamide and its preparation method and application |
| FR3088067B1 (en) * | 2018-11-06 | 2020-11-06 | S N F Sa | PROCESS FOR SYNTHESIS OF POLYMERS BY CONTROLLED RADICAL POLYMERIZATION IN REVERSE EMULSION |
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