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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- 238000002360 preparation method Methods 0.000 title claims description 38
- 150000001768 cations Chemical class 0.000 title claims description 5
- 229920001577 copolymer Polymers 0.000 title description 6
- 239000000839 emulsion Substances 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 125000002091 cationic group Chemical group 0.000 claims abstract description 19
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims abstract description 19
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002978 peroxides Chemical class 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims description 34
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical group C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 12
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000012986 chain transfer agent Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002216 antistatic agent Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000009988 textile finishing Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 2
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 abstract 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- -1 alkyl methacrylate Chemical compound 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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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 invention relates to a copolymer, in particular to a comb-type random copolymer consisting of 2- (dimethylamino) ethyl methacrylate or cationic (methyl) acryloyloxyethyl trimethyl ammonium chloride and long-chain alkyl methacrylate, which can be used as a cationic macromolecular emulsifier.
Background
The macromolecular emulsifier is an amphiphilic polymer. The definition of amphiphilic polymer is: polymers having hydrophobic and hydrophilic segments or groups, the hydrophilic segments or groups may be ionic or non-ionic. For amphiphilic polymers, water is a good solvent for the hydrophilic segment or groups and is a precipitant for the hydrophobic segment. The hydrophobic parts self-assemble to reduce their contact with water, forming micelles or bilayer structures; while the hydrophilic part extends into the water. The advantages of amphiphilic polymers are: as a high molecular weight component, has a lower critical micelle concentration than small molecule emulsifiers. Thus, they remain effectively surface active under very dilute concentrations. The amphiphilic polymers can be used in a wide range of applications compared to low molecular weight surfactants.
Some researchers have proposed that polymers containing methacrylic acid (alkyl substituted amino) ester monomers have pH responsiveness and exhibit amphiphilic characteristics, and can also be used as cationic macromolecular emulsifiers to obtain polymer latex particles with positive charges on the surface. Most of these reported polymers areBlock copolymers, generally prepared by various controlled/living polymerization methods, for example: (1) 2- (dimethylamino) ethyl methacrylate (DMAEMA) and 2- (diethylamino) ethyl methacrylate (DEAEMA) block copolymers and partially protonated DMAEMA, (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 diblock or ABA triblock copolymers of 2- (dimethylamino) ethyl methacrylate and Methyl Methacrylate (MMA), and DMAEMA-based macromonomers, (Amalvy J.I.; UnaliG.F.; Li Y.; Granger-Bevan S.; Armes S.P., Langmuir, 2004, 20: 4345) (3) ABA triblock copolymers of 2- (dimethylamino) ethyl methacrylate and polypropylene oxide (PPO), (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) (ii) a And so on. These controlled/living polymerization methods have their unique advantages for preparing amphiphilic block polymers, but the reaction needs to be carried out under severe conditions, and the purification of the reaction product is difficult, so that products which can be industrially produced and practically used are rare at present.
Acryloxyethyltrimethylammonium chloride (trade name MC-80) is a water-soluble cationic monomer that can be used to prepare cationic flocculants (scleral group; Yi Jia He; Zhang Yingjie, Fine petrochemical 2002, 2: 16). Methacryloyloxyethyl trimethyl ammonium chloride can be copolymerized with vinyl acetate to prepare cationic emulsion, (Zhangshuxiang, Wangmang, Zhuhong, Jiangrutian, Lihui, Proc. Reynaudiana, 2003, 6: 875-. However, no document has been reported so far for preparing a random copolymerization cationic amphiphilic polymer by reacting a long carbon chain methacrylate with the above cationic monomers.
Disclosure of Invention
The invention aims to provide a cationic macromolecular emulsifier which has low requirement on reaction conditions and is easy to implement industrially and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a random copolymerized cationic macromolecular emulsifier is a random copolymer composed of hydrophobic monomers and hydrophilic monomers,
the hydrophobic monomer is selected from lauryl methacrylate or stearyl methacrylate;
the hydrophilic monomer is selected from 2- (dimethylamino) ethyl methacrylate, acryloyloxyethyltrimethyl ammonium chloride or methacryloyloxyethyltrimethylammonium chloride;
the feeding molar ratio of the hydrophobic monomer to the hydrophilic monomer is 1: 9-4: 6.
In order to obtain the emulsifier, the technical scheme adopted by the invention is as follows:
a preparation method of a random copolymerization cation macromolecular emulsifier adopts a conventional free radical copolymerization method, dodecyl methacrylate or octadecyl methacrylate is taken as a hydrophobic monomer, one of 2- (dimethylamino) ethyl methacrylate, acryloyloxyethyl trimethyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride is selected as a hydrophilic monomer, the molar ratio of the hydrophobic monomer to the hydrophilic monomer is 1: 9-4: 6, reaction monomers are weighed and put into a solvent, the reaction monomers are stirred and mixed, an initiator with the monomer molar weight of 1-10% is added, the initiator adopts an oil-soluble azo initiator or an oil-soluble peroxide initiator, the reaction lasts for 2-7 hours, the reaction temperature is 60-80 ℃, and a crude product is obtained; removing the solvent, and purifying to obtain the required cationic macromolecular emulsifier.
In the technical scheme, the hydrophobic monomer is methacrylic acid long-chain ester expressed by the following formula,
in the formula, R1Is selected from C12H25Or C18H37；
Dodecyl methacrylate (LMA); octadecyl methacrylate (SMA).
The hydrophilic monomer comprises 2- (dimethylamino) ethyl methacrylate (DMAEMA) with a structural formula shown in the specification,
in neutral to acidic aqueous media, (dimethylamino) ethyl groups in the above structure can be protonated to varying degrees to form a positively charged group-CH2CH2N+H(CH3)2。
Or,
in the formula, R2Selected from H, or CH3，
Namely: acryloyloxyethyltrimethylammonium chloride (MC 80), or methacryloyloxyethyltrimethylammonium chloride (DMC).
The copolymer obtained by the technical scheme has wider molecular weight distribution, so according to the requirement of controlling the molecular weight, the preferable technical scheme is that n-dodecyl mercaptan accounting for 4-8% of the weight of the monomer is added into the monomer and initiator system to serve as a chain transfer agent.
Thus, the above technical means can be expressed as the following formula (1) or (2),
formula (1):
wherein x and y are 1: 9-4: 6 (feeding mol ratio), and R is1Is selected from C12H25Or C18H37。
Formula (2):
wherein x and y are 1: 9-4: 6 (feeding mol ratio), and R is1Is selected from C12H25Or C18H37；R2Selected from H, or CH3。
In a preferred embodiment, the initiator is selected from the group consisting of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AVBN), Benzoyl Peroxide (BPO), and Lauroyl Peroxide (LPO).
In the technical scheme, the method for removing the solvent and purifying comprises the steps of removing the solvent by rotary evaporation at the temperature of 60-70 ℃, precipitating a crude product in cold n-hexane, and drying the precipitate at the temperature of 40-50 ℃ in vacuum to constant weight.
In the above technical scheme, the solvent is selected from absolute ethyl alcohol or isopropanol, and the amount of the solvent is selected so that the solid content before the reaction is 20% by weight.
In the above technical scheme, the chain transfer agent is added for the purpose of controlling the molecular weight of the polymer.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. because the cationic macromolecular emulsifier is obtained by adopting the conventional free radical polymerization, the conventional free radical polymerization is still one of the most simple, convenient and cheap methods at present from the aspects of industrial production and production cost reduction;
2. the method has the advantages of low requirement on reaction conditions, easy obtainment of reaction monomers, high reaction speed, high conversion rate and easy industrial implementation, and overcomes the defect that the active polymerization reaction needs to be carried out under harsh conditions;
3. in the invention, the hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA) has pH responsiveness and can be used in a wider pH range;
4. the comb-type random polymer prepared by the invention is easy to obtain, and the product is particularly suitable for being used as a stabilizer of an emulsion or miniemulsion polymerization system, a small amount of homopolymer existing in the product is not required to be removed, and the homopolymer can be used as a stabilizer and an auxiliary stabilizer;
5. in the product obtained by the invention, the hydrophobic carbon chain of methacrylic acid long-chain ester is anchored inside the polymer latex particle; the groups with cations in the hydrophilic structural units extend to the water phase to play a role in electrostatic stabilization; the main chain of the random copolymer is adsorbed on the surface of the latex particles, so that the latex particles are covered more densely, and particularly, the migration of monomers to a water phase in the polymerization process of miniemulsion can be prevented, so that the latex particles are stable, and finally the polymer latex particles with positive charges on the surface are obtained. The polymer emulsion can be widely applied to the industries of textile finishing, paper additives, adhesives, antistatic agents, sewage treatment and the like.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows: poly (SMA-co-DMAEMA) (1: 9, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: 2- (dimethylamino) ethyl methacrylate with activated basic Al before use2O3Performing column treatment, and then distilling under reduced pressure for standby; octadecyl methacrylate was used as is; AIBN was recrystallized from absolute ethanol for future use.
(2) Preparation of the polymer: weighing 3.8g (0.01mol) of hydrophobic monomer octadecyl methacrylate (SMA) and 16.0g (0.09mol) of hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA); initiator AIBN 0.2g (weighed as 1.2% of the total monomer molar weight); measuring 1mL of N-dodecyl mercaptan, dissolving the N-dodecyl mercaptan in 127mL of anhydrous ethanol (measured according to the solid content of 20%), uniformly stirring, pouring the mixture into a 250mL four-necked flask with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and introducing N2Stirring at 350r/min, rapidly heating to 70 deg.C, reacting for 7 hr, cooling, and discharging.
(3) Purification of the polymer: and (3) carrying out rotary evaporation on the reaction product in the step (2) at the temperature of 60-70 ℃ to remove the solvent and part of unreacted monomers, then precipitating the product by using cold n-hexane, and finally drying the product in a vacuum oven at the temperature of 40-50 ℃ to constant weight to obtain a light yellow viscous substance.
(4) Characterization of the polymers: subjecting the purified polymer of (3) to nuclear magnetic resonance hydrogen spectroscopy (1H NMR) and Gel Permeation Chromatography (GPC), and the surface tension of the aqueous solution thereof is measured.1H NMR results showed successful copolymerization of the two monomers; GPC showed the polymer to have a relative molecular mass of 3650g/mol, a molecular weight distribution index (PDI) of 1.47; poly (SMA-co-DMAEMA) copolymer had a critical micelle concentration (cmc) of 2.51g/L in the aqueous phase at pH 3.0 and a cmc of 0.40g/L in the aqueous phase at pH 7.0 as determined by the surface tension method.
Example two: poly (SMA-co-DMAEMA) (2: 8, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: same as in step [1] of the example.
(2) Preparation of the polymer: weighing 7.0g (0.02mol) of hydrophobic monomer octadecyl methacrylate (SMA); 12.6g (0.08mol) of hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA); initiator AIBN 0.2g (weighed as 1.2% of the total monomer molar weight); 1mL of n-dodecyl mercaptan is metered in and dissolved in 127mL (20% by weight solids) of anhydrous ethyl acetateStirring in alcohol, pouring into 250mL four-necked flask equipped with stirrer, reflux condenser, thermometer and nitrogen conduit, introducing N2Stirring at 350r/min, rapidly heating to 70 deg.C, maintaining at the temperature and stirring speed, reacting for 3 hr, cooling, and discharging.
(3) Purification of the polymer: and (3) carrying out rotary evaporation on the reaction product in the step (2) at the temperature of 60-70 ℃ to remove the solvent and part of unreacted monomers, then precipitating the product by using cold n-hexane, and finally drying the product in a vacuum oven at the temperature of 40-50 ℃ to constant weight to obtain a light yellow viscous substance.
(4) Characterization of the polymers: subjecting the purified polymer of (3) to nuclear magnetic resonance hydrogen spectroscopy (1H NMR) and Gel Permeation Chromatography (GPC) and determine the surface tension of aqueous solutions of different concentrations.1H NMR results showed successful copolymerization of the two monomers; GPC showed the polymer to have a relative molecular mass of 4340g/mol and a molecular weight distribution index (PDI) of 1.49. Poly (SMA-co-DMAEMA) copolymer had a critical micelle concentration (cmc) of 1.0g/L in the aqueous phase at pH 3.0 and a cmc of 3.16g/L in the aqueous phase at pH 7.0 as determined by the surface tension method.
Example three: poly (SMA-co-DMAEMA) (1: 9, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: the procedure is as in example one (1).
(2) Preparation of the polymer: weighing 0.39g (1.15mmol) of hydrophobic monomer octadecyl methacrylate (SMA); hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA)1.63g (10.3 mmol); 0.19g of initiator AIBN (weighed according to 10 percent of the molar weight of all monomers) is dissolved in 17mL of absolute ethyl alcohol (weighed according to 13 percent of solid content), after uniform stirring, the mixture is poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and N is introduced2Stirring at 350r/min, rapidly heating to 70 deg.C, reacting for 6.5h, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
(4) Characterization of the polymers: subjecting the purified polymer of (3) to Gel Permeation Chromatography (GPC) analysis, GPC showed that the relative molecular mass of the polymer was 6.4X 103g/mol, molecular weight distribution index (PDI) 1.49.
Example four: poly (SMA-co-DMAEMA) (2: 8, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: the procedure is as in example one (1).
(2) Preparation of the polymer: weighing 0.50g (1.5mmol) of hydrophobic monomer octadecyl methacrylate (SMA); hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA)1.0g (6.4 mmol); 0.03g of initiator AIBN (weighed according to 2.3 percent of the molar weight of all monomers), measuring 1mL of ethanol solution (0.060g/L) dissolved with N-dodecyl mercaptan, dissolving the ethanol solution in 14mL of absolute ethanol (measured according to 12 percent of solid content), pouring the mixture into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube after uniformly stirring, and introducing N2Stirring at 350r/min, rapidly heating to 70 deg.C, reacting for 6.5h, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
(4) Characterization of the polymers: subjecting the purified polymer of (3) to Gel Permeation Chromatography (GPC) analysis, GPC showed that the relative molecular mass of the polymer was 5.3X 103g/mol, molecular weight distribution index (PDI) 1.55.
Example five: poly (SMA-co-DMAEMA) (4: 6, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: the procedure is as in example one (1).
(2) Preparation of the polymer: weighing 0.88g (2.6mmol) of hydrophobic monomer octadecyl methacrylate (SMA); hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA)0.62g (3.9 mmol); initiator AIBN 0.11g(weighing 10.3% of the total monomer molar weight), dissolving in 14mL (weighing 11% of solid content) of absolute ethanol, stirring uniformly, pouring into a 250mL four-necked flask with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, introducing N2Stirring at 350r/min, rapidly heating to 70 deg.C, maintaining at the temperature and stirring speed, reacting for 5 hr, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
(4) Characterization of the polymers: subjecting the purified polymer of (3) to Gel Permeation Chromatography (GPC) analysis, GPC showed that the relative molecular mass of the polymer was 6.9X 103g/mol, molecular weight distribution index (PDI) 1.67.
Example six: poly (LMA-co-DMAEMA) (1: 9, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: the procedure is as in example one (1).
(2) Preparation of the polymer: weighing 2.55g (0.01mol) of hydrophobic monomer Lauryl Methacrylate (LMA); 14.2g (0.09mol) of hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA); 0.20g of initiator AIBN (weighed according to 1.2 percent of the molar weight of all monomers), 1mL of N-dodecyl mercaptan is weighed, dissolved in 86mL of absolute ethyl alcohol (weighed according to 20 percent of solid content), stirred uniformly, poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and introduced with N2Stirring at 350r/min, rapidly heating to 65 deg.C, reacting for 4.5h, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
Example seven: poly (LMA-co-DMAEMA) (2: 8, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: the procedure is as in example one (1).
(2) Preparation of the polymer: weighing hydrophobicity5.1g (0.02mol) of monomeric dodecyl methacrylate (LMA); 12.6g (0.08mol) of hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA); 0.20g of initiator AIBN (weighed according to 1.2 percent of the molar weight of all monomers), 1mL of N-dodecyl mercaptan is weighed and dissolved in 91mL of absolute ethanol (weighed according to 20 percent of solid content), after uniform stirring, the mixture is poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and N is introduced2Stirring at 350r/min, rapidly heating to 70 deg.C, reacting for 4.5h, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
Example eight: poly (SMA-co-MC 80) (1: 9, molar ratio) and preparation thereof
(1) Preparation of reaction monomers and initiators: the process is carried out as in example one (1); the monomer acryloyloxyethyltrimethyl ammonium chloride was used as it was.
(2) Preparation of the polymer: weighing 1.0g (0.003mol) of hydrophobic monomer octadecyl methacrylate (SMA); 5.3g (0.027mol) of hydrophilic monomer acryloyloxyethyltrimethyl ammonium chloride (MC 80); 0.06g of AIBN (weighed according to 1.2 percent of the molar weight of the monomers) as an initiator and 0.3mL of N-dodecyl mercaptan are dissolved in 39.7mL of absolute ethanol (weighed according to 20 percent of the solid content), the mixture is evenly stirred and poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and N is introduced into the bottle2Stirring at 350r/min, rapidly heating to 70 deg.C, maintaining at the temperature and stirring speed, reacting for 3 hr, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
Example nine: poly (LMA-co-DMC) (1: 9, molar ratio) and its preparation
(1) Preparation of reaction monomers and initiators: dodecyl methacrylate (LMA) and methacryloyloxyethyltrimethyl ammonium chloride (DMC) were used directly; azobisisoheptonitrile (ABVN) was recrystallized from absolute ethanol for future use.
(2) Preparation of the polymer: weighing 2.55g (0.01mol) of hydrophobic monomer Lauryl Methacrylate (LMA); 18.6g (0.09mol) of hydrophilic monomer methacryloyloxyethyl trimethyl ammonium chloride (DMC); 0.30g of initiator Azobisisoheptonitrile (ABVN) (weighed according to 1.2 percent of the molar weight of all monomers), 1mL of N-dodecyl mercaptan is weighed and dissolved in 107mL of absolute ethyl alcohol (weighed according to 20 percent of solid content), after uniform stirring, the mixture is poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen conduit, and N is introduced2Stirring at 350r/min, rapidly heating to 65 deg.C, reacting for 2 hr, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
Example ten: poly (LMA-co-DMC) (1: 9, molar ratio) and its preparation
(1) Preparation of reaction monomers and initiators: the monomer was used in the same manner as in example nine (1); BPO is recrystallized for standby use using chloroform as solvent and methanol as precipitant.
(2) Preparation of the polymer: weighing 2.55g (0.01mol) of hydrophobic monomer Lauryl Methacrylate (LMA); 18.6g (0.09mol) of hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA); 0.29g of initiator BPO (weighed according to 1.2 percent of the molar weight of all monomers), 1mL of N-dodecyl mercaptan is weighed and dissolved in 107mL of absolute ethanol (weighed according to 20 percent of solid content), after uniform stirring, the mixture is poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and N is introduced2Stirring at 350r/min, rapidly heating to 60 deg.C, reacting for 4.5h, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
Example eleven: poly (LMA-co-DMC) (1: 9, molar ratio) and its preparation
(1) Preparation of reaction monomers and initiators: the monomer was used in the same manner as in example nine (1); the initiator Lauroyl Peroxide (LPO) is recrystallized for future use using benzene as solvent and methanol as precipitant.
(2) Preparation of the polymer: weighing 2.55g (0.01mol) of hydrophobic monomer Lauryl Methacrylate (LMA); 18.6g (0.09mol) of hydrophilic monomer 2- (dimethylamino) ethyl methacrylate (DMAEMA); 0.48g of initiator Lauroyl Peroxide (LPO) (weighed according to 1.2 percent of the molar weight of all monomers), 1mL of N-dodecyl mercaptan is weighed and dissolved in 107mL of absolute ethyl alcohol (weighed according to 20 percent of solid content), after uniform stirring, the mixture is poured into a 250mL four-necked bottle provided with a stirrer, a reflux condenser tube, a thermometer and a nitrogen guide tube, and N is introduced into the bottle2Stirring at 350r/min, rapidly heating to 70 deg.C, reacting for 4.5h, cooling, and discharging.
(3) Purification of the polymer: the procedure is as in example one (3).
Claims (6)
1. A random copolymerization cation macromolecular emulsifier is a random copolymer composed of hydrophobic monomers and hydrophilic monomers, and is characterized in that:
the hydrophobic monomer is selected from lauryl methacrylate or stearyl methacrylate;
the hydrophilic monomer is selected from 2- (dimethylamino) ethyl methacrylate, acryloyloxyethyltrimethyl ammonium chloride or methacryloyloxyethyltrimethylammonium chloride;
the feeding molar ratio of the hydrophobic monomer to the hydrophilic monomer is 1: 9-4: 6.
2. A preparation method of a random copolymerization cationic macromolecular emulsifier is characterized by comprising the following steps: adopting a conventional free radical copolymerization method, taking dodecyl methacrylate or octadecyl methacrylate as a hydrophobic monomer, selecting one of 2- (dimethylamino) ethyl methacrylate, acryloyloxyethyl trimethyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride as a hydrophilic monomer, weighing a reaction monomer, adding the reaction monomer into a solvent, stirring and mixing, adding an initiator with the monomer molar weight of 1-10%, reacting for 2-7 hours at the reaction temperature of 60-80 ℃ by adopting an oil-soluble azo initiator or an oil-soluble peroxide initiator, and removing the solvent to obtain a crude product, wherein the hydrophobic monomer is one of 2- (dimethylamino) ethyl methacrylate, acryloyloxyethyl trimethyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride, and the molar ratio of the hydrophobic monomer to the hydrophilic monomer is 1: 9-4: 6; purifying to obtain the required cationic macromolecular emulsifier.
3. The method for preparing a random copolymerized cationic macromolecular emulsifier according to claim 2, characterized in that: and adding n-dodecyl mercaptan accounting for 4-8% of the weight of the monomer into the monomer and initiator system to serve as a chain transfer agent.
4. The method for preparing a random copolymerized cationic macromolecular emulsifier according to claim 2, characterized in that: the initiator is selected from azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide or lauroyl peroxide.
5. The method for preparing a random copolymerized cationic macromolecular emulsifier according to claim 2, characterized in that: the solvent removal and purification method comprises the steps of removing the solvent by rotary evaporation at the temperature of 60-70 ℃, precipitating a crude product in cold n-hexane, and drying the precipitate at the temperature of 40-50 ℃ in vacuum to constant weight.
6. The method for preparing a random copolymerized cationic macromolecular emulsifier according to claim 2, characterized in that: the solvent is selected from absolute ethyl alcohol or isopropyl alcohol, and the amount of the solvent is selected so that the solid content before the reaction is 20% by weight.
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