CN1896112A - Random and copolymer cation macromolecular emulsion and its preparation - Google Patents
Random and copolymer cation macromolecular emulsion and its preparation Download PDFInfo
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- CN1896112A CN1896112A CN200610088071.7A CN200610088071A CN1896112A CN 1896112 A CN1896112 A CN 1896112A CN 200610088071 A CN200610088071 A CN 200610088071A CN 1896112 A CN1896112 A CN 1896112A
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Abstract
A random copolymerized cationic macromolecular emulsifier and its production are disclosed. The emulsifier consists of hydrophobic monomer and hydrophilic monomer. The hydrophobic monomer is selected from methyl-propenoic acid lauryl ester or methyl-propenoic acid octadecyl ester; The hydrophilic monomer is selected from methyl-propenoic-2-(dimethy)carbethoxy, acryloyl-oxyethylated trimethyl-ammonia chloride or methyl-acryloy-oxyethylated trimethyl-ammonia chloride in proportion of 1:9-4:6mol. The process is carried out by selecting oil-soluble azo initiating agent or oil-soluble peroxide initiating agent by normal free-radical polymerization and reacting at 60-80degree. It is fast, simple and has high conversion rate. It can be used for paper additive, binder, anti-static agent, textile finishing auxiliary and sewage water treatment.
Description
Technical field
The present invention relates to a kind of multipolymer, be specifically related to a kind of comb type random copolymers, can be used as cationic macromolecules emulsifying agent and use by methacrylic acid-2-(dimethylamino) ethyl ester or cationic (methyl) acrylyl oxy-ethyl-trimethyl salmiac and long-chain alkyl methacrylates formation.
Background technology
Macromole emulsifying agent is a kind of amphipathic polymkeric substance.Amphipathic nature polyalcohol is defined as: have polymkeric substance hydrophobic and hydrophilic segment or group, hydrophilic segment or group can be ionics, also can be non-ionic types.For amphipathic nature polyalcohol, water is the good solvent of hydrophilic segment or group, is again the precipitation agent of hydrophobic segment.The hydrophobic part self-assembly to reduce they and the contacting of water, forms micella or bilayer structure; And hydrophilic segment stretches in the water.The advantage of amphipathic nature polyalcohol is: as the high-molecular weight component, have the micelle-forming concentration lower than small-molecular emulsifier.Therefore, under the very rare condition of concentration, the surfactivity that they are still remained valid.Compared with low-molecular-weight tensio-active agent, amphipathic nature polyalcohol can use in very wide scope.
Some investigators propose, and the polymkeric substance that contains methacrylic acid (alkyl-substituted amino) esters monomer has the pH responsiveness, show amphiphilic character, also can be used as cationic macromolecules emulsifying agent, obtain the positively charged polymer emulsion particle in surface.These polymkeric substance that are in the news mostly are segmented copolymer greatly, usually adopt various controlled/the living polymerisation process preparation, for example: (1) methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) and methacrylic acid-2-(diethylin) ethyl ester (DEAEMA) segmented copolymer and the protonated product of DMAEMA part, (Butun V.; Armes S.P.; Billingham N.C., Macromolecules; 2001,34 (5): 1148; Houillot L.; Nicolas J.; Save M.; Charleux B.; Li Y.T.; Armes S.P., Langmuir, 2005,21:6726.); (2) AB two blocks or the ABA triblock copolymer formed of methacrylic acid-2-(dimethylamino) ethyl ester and methyl methacrylate (MMA), and based on the macromonomer of DMAEMA, (Amalvy J.I.; UnaliG.F.; Li Y.; Granger-Bevan S.; Armes S.P., Langmuir, 2004,20:4345) the ABA type triblock copolymer of (3) methacrylic acid-2-(dimethylamino) ethyl ester and poly(propylene oxide) (PPO) composition, (Ni P.H.; Pan Q.S.; Zha L.S.; Wang C.C;
A.; Fu S.K., Journal of Polymer Science:Part A:Polymer Chemistry, 2002,40:624); Or the like.These controlled/living polymerisation process are for the preparation Amphipathilic block polymer, their special advantages are arranged, but reaction needed is carried out under severe condition, and the purification of reaction product simultaneously also has difficulties, thereby it is actually rare to carry out the product of suitability for industrialized production and practical application at present.
Acrylyl oxy-ethyl-trimethyl salmiac (trade(brand)name MC-80) is the water-soluble cationic monomer, can be used to prepare cationic flocculant, (Gong Guanqun; Yin Jiagui; Zhang Yingjie, Speciality Petrochemicals, 2002,2:16).The methylacryoyloxyethyl trimethyl ammonium chloride can with vinyl acetate between to for plastic copolymerization cation emulsion, (Zhang Shuxiang; Wang Jingang; Zhu Hong; Jiang Runtian; Li Hui, the polymer journal, 2003,6:875-878).But, do not see that so far bibliographical information utilizes long carbochain ester of methacrylic acid and above-mentioned all kinds of cationic monomer reaction, preparation random and copolymer cation type amphipathic nature polyalcohol.
Summary of the invention
The object of the invention provide a kind of reaction conditions requirement low, be easy to cation macromolecular emulsion of industrializing implementation and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: a kind of random and copolymer cation macromolecular emulsion, and it is the random copolymers that is made of hydrophobic monomer and hydrophilic monomer,
Described hydrophobic monomer is selected from lauryl methacrylate or methacrylic acid stearyl;
Described hydrophilic monomer is selected from, methacrylic acid-2-(dimethylamino) ethyl ester, acrylyl oxy-ethyl-trimethyl salmiac or methylacryoyloxyethyl trimethyl ammonium chloride;
The molar ratio of hydrophobic monomer and hydrophilic monomer is 1: 9～4: 6.
For obtaining mentioned emulsifier, the technical solution used in the present invention is:
A kind of preparation method of random and copolymer cation macromolecular emulsion, adopt the conventional free radical copolymerization process, with lauryl methacrylate or methacrylic acid stearyl is hydrophobic monomer, select methacrylic acid-2-(dimethylamino) ethyl ester, acrylyl oxy-ethyl-trimethyl salmiac, or a kind of in the methylacryoyloxyethyl trimethyl ammonium chloride is hydrophilic monomer, the mol ratio of hydrophobic monomer and hydrophilic monomer is 1: 9～4: 6, taking by weighing reaction monomers drops in the solvent, mix, the initiator that adds monomer molar amount 1～10%, described initiator adopts oil soluble azo-initiator or oil soluble peroxide initiator, reacted 2～7 hours, temperature of reaction is 60～80 ℃, obtains thick product; Remove and desolvate, purify, obtain required cation macromolecular emulsion.
In the technique scheme, hydrophobic monomer is the long alkyl chain methacrylates that following formula is expressed,
In the formula, R
1Be selected from C
12H
25, or C
18H
37
Be lauryl methacrylate (LMA); Methacrylic acid stearyl (SMA).
Hydrophilic monomer comprises, methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA), its structural formula be,
To the sour water phase medium, in various degree protonated can take place in (dimethylamino) ethyl in the said structure, becomes positively charged group-CH in neutrality
2CH
2N
+H (CH
3)
2
Perhaps,
In the formula, R
2Be selected from H, or CH
3,
That is: acrylyl oxy-ethyl-trimethyl salmiac (MC 80), or methylacryoyloxyethyl trimethyl ammonium chloride (DMC).
The multipolymer that adopts technique scheme to obtain, the molecular weight distribution broad, thereby according to the needs of control molecular weight, optimized technical scheme is that in described monomer and initiator system, the positive Dodecyl Mercaptan that adds monomer weight 4～8% is as chain-transfer agent.
Thus, technique scheme can be expressed as following formula (1) or (2),
Formula (1):
In the formula, x: y=1: 9～4: 6 (molar ratios), R
1Be selected from C
12H
25, or C
18H
37
Formula (2):
In the formula, x: y=1: 9～4: 6 (molar ratios), R
1Be selected from C
12H
25, or C
18H
37R
2Be selected from H, or CH
3
Optimized technical scheme, described initiator are selected from Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN), benzoyl peroxide (BPO) and dilauroyl peroxide (LPO).
In the technique scheme, the described method desolvate and purify of removing is, steams to remove at 60～70 ℃ of backspins and desolvates, and thick product precipitates in cold normal hexane, with throw out 40～50 ℃ of vacuum-dryings to constant weight.
In the technique scheme, described solvent is selected from dehydrated alcohol or Virahol, and the consumption of solvent selects to make that the solid content before the reaction is 20% by weight.
In the technique scheme, the purpose that adds chain-transfer agent is the molecular weight of controlling polymers.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. because the present invention adopts conventional radical polymerization to obtain cation macromolecular emulsion, consider that from suitability for industrialized production and the angle that reduces production costs conventional radical polymerization is still one of method at present simple and easy to do, the most with low cost;
2. reaction conditions of the present invention requires low, and reaction monomers is easy to get, and has overcome the shortcoming that living polymerization need carry out under severe condition, and speed of response is fast, and the transformation efficiency height is easy to industrializing implementation;
3. hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (being DMAEMA) has the pH responsiveness among the present invention, can use in the pH of broad scope;
4. the prepared comb type unregulated polymer of the present invention obtains easily, and product especially is suitable as the stablizer of emulsion or mini-emulsion polymerization system, need not to eliminate a small amount of homopolymer that exists in the product, and homopolymer can serve as stablizer and co-stabilizer uses;
5. in the product that the present invention obtains, the hydrophobicity carbochain of long alkyl chain methacrylates anchors to polyalcohol emulsion particle inside; Be with cationic group to stretch to water in the hydrophilic structure unit, play the electrostatic stabilization effect; The random copolymers main chain is attracted to the emulsion particle surface, and more matter is close to the covering of emulsion particle, can prevent that especially monomer makes latex particle stable to the migration of water in the mini-emulsion polymerization process, finally obtains the positively charged polyalcohol emulsion particle in surface.This type of polymer emulsion can be widely used in industries such as yarn fabric arrangement, paper additive, tackiness agent, static inhibitor and sewage disposal.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: Poly (SMA-co-DMAEMA) (1: 9, mol ratio) and preparation thereof
(1) uses activatory alkalescence Al before the preparation of reaction monomers, initiator: methacrylic acid-2-(dimethylamino) ethyl ester uses
2O
3Post is handled, and underpressure distillation is standby to treat then; The methacrylic acid stearyl is directly used; AIBN is standby to treat with the dehydrated alcohol recrystallization.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid stearyl (SMA) 3.8g (0.01mol), hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 16.0g (0.09mol); Initiator A IBN 0.2g (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 127mL (measuring), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed, logical N by solid content 20%
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 7h, cooling discharging.
(3) purification of polymkeric substance: with the reaction product in (2) under 60～70 ℃ of conditions, rotary evaporation removes and to desolvate and part unreacted monomer completely, use cold normal hexane precipitated product then, be dried to constant weight for 40～50 ℃ at vacuum drying oven at last, obtain lurid viscous substance.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out proton nmr spectra (
1H NMR) and gel permeation chromatography (GPC) analyze, and measure the surface tension of its aqueous solution.
1H NMR result shows two kinds of monomer success copolymerization; GPC shows that molecular weight of polymer is 3650g/mol, and molecular weight distributing index (PDI) is 1.47; Record the aqueous phase of Poly (SMA-co-DMAEMA) multipolymer at pH=3.0 by the surface tension method, micelle-forming concentration (cmc) is 2.51g/L, and at the aqueous phase of pH=7.0, cmc is 0.40g/L.
Embodiment two: Poly (SMA-co-DMAEMA) (2: 8, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: identical with embodiment one step [1].
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid stearyl (SMA) 7.0g (0.02mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 12.6g (0.08mol); Initiator A IBN 0.2g (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 127ml (measuring), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed, logical N by solid content 20%
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 3h, cooling discharging.
(3) purification of polymkeric substance: with the reaction product in (2) under 60～70 ℃ of conditions, rotary evaporation removes and to desolvate and part unreacted monomer completely, use cold normal hexane precipitated product then, be dried to constant weight for 40～50 ℃ at vacuum drying oven at last, obtain lurid viscous substance.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out proton nmr spectra (
1H NMR) and gel permeation chromatography (GPC) analyze, and measure the surface tension of the different concns aqueous solution.
1H NMR result shows two kinds of monomer success copolymerization; GPC shows that molecular weight of polymer is 4340g/mol, and molecular weight distributing index (PDI) is 1.49.Record the aqueous phase of Poly (SMA-co-DMAEMA) multipolymer at pH=3.0 by the surface tension method, micelle-forming concentration (cmc) is 1.0g/L, and at the aqueous phase of pH=7.0, cmc is 3.16g/L.
Embodiment three: Poly (SMA-co-DMAEMA) (1: 9, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid stearyl (SMA) 0.39g (1.15mmol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 1.63g (10.3mmol); Initiator A IBN 0.19g (taking by weighing) by 10% of whole monomer molar amounts, be dissolved in the dehydrated alcohol of 17mL (measuring) by solid content 13%, after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 6.5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
(4) sign of polymkeric substance: the polymkeric substance after purifying in (3) is carried out gel permeation chromatography (GPC) analysis, and GPC shows that molecular weight of polymer is 6.4 * 10
3G/mol, molecular weight distributing index (PDI) is 1.49.
Embodiment four: Poly (SMA-co-DMAEMA) (2: 8, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid stearyl (SMA) 0.50g (1.5mmol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 1.0g (6.4mmol); Initiator A IBN 0.03g (taking by weighing) by 2.3% of whole monomer molar amounts, measure 1mL and be dissolved with the ethanolic soln (0.060g/L) of positive Dodecyl Mercaptan, be dissolved in the dehydrated alcohol of 14mL (measuring) by solid content 12%, after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 6.5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
(4) sign of polymkeric substance: the polymkeric substance after purifying in (3) is carried out gel permeation chromatography (GPC) analysis, and GPC shows that molecular weight of polymer is 5.3 * 10
3G/mol, molecular weight distributing index (PDI) is 1.55.
Embodiment five: Poly (SMA-co-DMAEMA) (4: 6, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid stearyl (SMA) 0.88g (2.6mmol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 0.62g (3.9mmol); Initiator A IBN 0.11g (taking by weighing) by 10.3% of whole monomer molar amounts, be dissolved in the dehydrated alcohol of 14mL (measuring) by solid content 11%, after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
(4) sign of polymkeric substance: the polymkeric substance after purifying in (3) is carried out gel permeation chromatography (GPC) analysis, and GPC shows that molecular weight of polymer is 6.9 * 10
3G/mol, molecular weight distributing index (PDI) is 1.67.
Embodiment six: Poly (LMA-co-DMAEMA) (1: 9, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer lauryl methacrylate (LMA) 2.55g (0.01mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 14.2g (0.09mol); Initiator A IBN 0.20g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 86mL (measuring), after stirring by solid content 20%, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 65 ℃, and remains on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
Embodiment seven: Poly (LMA-co-DMAEMA) (2: 8, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer lauryl methacrylate (LMA) 5.1g (0.02mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 12.6g (0.08mol); Initiator A IBN 0.20g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 91mL (measuring), after stirring by solid content 20%, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
Embodiment eight: Poly (SMA-co-MC 80) (1: 9, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out; The monomer acrylyl oxy-ethyl-trimethyl salmiac directly uses.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid stearyl (SMA) 1.0g (0.003mol); Hydrophilic monomer acrylyl oxy-ethyl-trimethyl salmiac (MC 80) 5.3g (0.027mol); Initiator A IBN 0.06g (taking by weighing) by 1.2% of monomer molar amount, 0.3mL positive Dodecyl Mercaptan is dissolved in the dehydrated alcohol of 39.7mL (measuring by solid content 20%), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 3h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
Embodiment nine: Poly (LMA-co-DMC) (1: 9, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: lauryl methacrylate (LMA) and methylacryoyloxyethyl trimethyl ammonium chloride (DMC) directly use; 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) is standby to treat with the dehydrated alcohol recrystallization.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer lauryl methacrylate (LMA) 2.55g (0.01mol); Hydrophilic monomer methylacryoyloxyethyl trimethyl ammonium chloride (DMC) 18.6g (0.09mol); Initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) 0.30g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 107mL (measuring) by solid content 20%, after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 65 ℃, and remains on this temperature and stirring velocity, reaction 2h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
Embodiment ten: Poly (LMA-co-DMC) (1: 9, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: monomer is pressed the method for embodiment nine (1) and is used; BPO chloroform give solvent, methyl alcohol is made precipitation agent, and recrystallization is standby to treat.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer lauryl methacrylate (LMA) 2.55g (0.01mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 18.6g (0.09mol); Initiator B PO 0.29g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 107mL (measuring), after stirring by solid content 20%, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 60 ℃, and remains on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
Embodiment 11: Poly (LMA-co-DMC) (1: 9, mol ratio) and preparation thereof
(1) preparation of reaction monomers, initiator: monomer is pressed the method for embodiment nine (1) and is used; Initiator dilauroyl peroxide (LPO) is made solvent with benzene, and methyl alcohol is made precipitation agent, and recrystallization is standby to treat.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer lauryl methacrylate (LMA) 2.55g (0.01mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 18.6g (0.09mol); Initiator dilauroyl peroxide (LPO) 0.48g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 107mL (measuring) by solid content 20%, after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into
2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
Claims (6)
1. random and copolymer cation macromolecular emulsion, it is the random copolymers that is made of hydrophobic monomer and hydrophilic monomer, it is characterized in that:
Described hydrophobic monomer is selected from lauryl methacrylate or methacrylic acid stearyl;
Described hydrophilic monomer is selected from, methacrylic acid-2-(dimethylamino) ethyl ester, acrylyl oxy-ethyl-trimethyl salmiac or methylacryoyloxyethyl trimethyl ammonium chloride;
The molar ratio of hydrophobic monomer and hydrophilic monomer is 1: 9～4: 6.
2. the preparation method of a random and copolymer cation macromolecular emulsion, it is characterized in that: adopt the conventional free radical copolymerization process, with lauryl methacrylate or methacrylic acid stearyl is hydrophobic monomer, select methacrylic acid-2-(dimethylamino) ethyl ester, acrylyl oxy-ethyl-trimethyl salmiac, or a kind of in the methylacryoyloxyethyl trimethyl ammonium chloride is hydrophilic monomer, the mol ratio of hydrophobic monomer and hydrophilic monomer is 1: 9～4: 6, taking by weighing reaction monomers drops in the solvent, mix, the initiator that adds monomer molar amount 1～10%, described initiator adopts oil soluble azo-initiator or oil soluble peroxide initiator, reacted 2～7 hours, temperature of reaction is 60～80 ℃, remove and desolvate, obtain thick product; Purify, obtain required cation macromolecular emulsion.
3. the preparation method of random and copolymer cation macromolecular emulsion according to claim 2 is characterized in that: in described monomer and initiator system, the positive Dodecyl Mercaptan that adds monomer weight 4～8% is as chain-transfer agent.
4. the preparation method of random and copolymer cation macromolecular emulsion according to claim 2, it is characterized in that: described initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or dilauroyl peroxide.
5. the preparation method of random and copolymer cation macromolecular emulsion according to claim 2, it is characterized in that: the described method of desolvating and purifying of removing is, steam except that desolvating at 60～70 ℃ of backspins, thick product precipitates in cold normal hexane, with throw out 40～50 ℃ of vacuum-dryings to constant weight.
6. the preparation method of random and copolymer cation macromolecular emulsion according to claim 2, it is characterized in that: described solvent is selected from dehydrated alcohol or Virahol, and the consumption of solvent selects to make that the solid content before the reaction is 20% by weight.
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| CN102766234B (en) * | 2012-07-20 | 2015-02-25 | 广州市华宇化工有限公司 | Low-foam soap-free organic fluorine emulsion and preparation method thereof |
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| CN106749893B (en) * | 2016-11-24 | 2019-04-02 | 浙江大学 | A method of improving inverse emulsion system stability |
| CN110204634A (en) * | 2019-06-18 | 2019-09-06 | 宁波南大光电材料有限公司 | A kind of azo-initiator and preparation method thereof |
| CN111072826A (en) * | 2019-12-25 | 2020-04-28 | 广州星业科技股份有限公司 | Amphiphilic high-molecular polymer and preparation method thereof |
| CN111072826B (en) * | 2019-12-25 | 2022-04-15 | 广州星业科技股份有限公司 | Amphiphilic high-molecular polymer and preparation method thereof |
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| CN113583192A (en) * | 2021-08-06 | 2021-11-02 | 浙江理工大学桐乡研究院有限公司 | Synthetic method of high-molecular emulsifier and application of high-molecular emulsifier in preparation of hydroxy silicone oil emulsion |
| CN113583192B (en) * | 2021-08-06 | 2023-06-30 | 浙江理工大学桐乡研究院有限公司 | Synthesis method of high molecular emulsifier and application of high molecular emulsifier in preparation of hydroxyl silicone oil emulsion |
| CN113956503A (en) * | 2021-10-18 | 2022-01-21 | 安徽省领拓新材料科技有限责任公司 | Polycation nano antibacterial agent, preparation method and application thereof |
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