CN102091564A - Acrylic ester polymer surfactant and preparation method thereof - Google Patents
Acrylic ester polymer surfactant and preparation method thereof Download PDFInfo
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- CN102091564A CN102091564A CN2010105761034A CN201010576103A CN102091564A CN 102091564 A CN102091564 A CN 102091564A CN 2010105761034 A CN2010105761034 A CN 2010105761034A CN 201010576103 A CN201010576103 A CN 201010576103A CN 102091564 A CN102091564 A CN 102091564A
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Abstract
The invention discloses an acrylic ester polymer surfactant and a preparation method thereof. The acrylic ester polymer surfactant is characterized in that: solution polymerization is initiated by using free radicals; benzoyl peroxide is used as an initiator; anion hydrophilic methacrylic acid (MAA), lipophilic stearyl methacrylate (SMA) and nonionic hydrophilic poly(ethylene glycol) dimethacrylate (PEGMA) are used as polymerization monomers respectively; and thus, the amphipathic polymer surfactant is synthesized. In the invention, the drawback that the demanding reaction conditions during graft copolymerization and block copolymerization increases cost and limits yield is overcome, the method is simple and convenient to implement, ensures large monomer selection and component variation range, and contributes to promotion and use.
Description
Technical field
The present invention relates to a kind of high molecular surfactant, be specifically related to a kind of methacrylic acid by anionic hydrophilic (MAA), oil loving methacrylic acid stearyl (SMA), the hydrophilic polyethylene glycol methacrylate-styrene polymer of nonionic (PEGMA) by traditional free-radical polymerized synthetic amphipathic random copolymer Poly (MAA-co-SMA-co-PEGMA), the present invention also relates to the preparation method of described acrylic ester high molecular type surfactant simultaneously.
Background technology
High molecular surfactant, it is amphipathic nature polyalcohol, be meant that generally relative molecular mass is more than thousands of, macromolecular compound with surface active function, not only contain hydrophilic group but also contain lipophilic group, its molecule is helical form closely in the aqueous solution, but diameter is than little many of the common polyelectrolyte of identical relative molecular mass.The particular structure characteristics make it that microphase-separated take place in selective solvent, thereby it does not generally form micella, and it is relatively poor to reduce capillary ability, foaming characteristic and wettability; But it has its special advantages at aspects such as protecting colloid, dispersion and flocculations.
In recent years, the research of high molecular surfactant has become one of research focus of domestic and international expert, and everybody developing the synthetic amphipathic nature polyalcohol that has high surface and HMW concurrently as goal in research, makes great efforts developing new product variety and new synthetic method.At present, high molecular surfactant one of the most noticeable application study be stabilization and the application in emulsion polymerisation and dispersin polymerization to dispersion.But rarely seenly carry out the research report that compound self assembly prepares the nuclear shell structure nano microballoon about random amphipathic copolymer and homopolymers.
It is not obvious that the random high molecular surfactant reduces surface-active effect, but the effect of dispersion, thickening, flocculation is very outstanding, during as emulsifying agent or dispersant use, both overcome the shortcoming of small-molecular emulsifier, avoid issuable ill effect when composite use again, possessed a lot of other emulsifying agents or the not available advantage of emulsifying agent compound system.Though have goodish effect when using the clear and definite amphipathic polymer of structure such as graft copolymer and block copolymer, and research is convenient, but, when the emulsifying agent of synthetic these types, nearly all be that ionic polymerization or ring-opening polymerisation even both have concurrently, requirement to reaction condition is very harsh, under common experiment condition, be difficult to the condition that reaches such, and, though utilize grafting and block copolymer bigger value to be arranged in theory research as the emulsifying agent of emulsion polymerisation, yet on using, also do not embody tangible advantage at present, an important reasons is exactly that its reaction condition is very high, thereby increased cost, limited output, and be unfavorable for industrial popularization and utilization.And utilize the amphipathic nature polyalcohol of the synthetic random type of radical polymerization quite different, and method is simple for this kind, and monomeric species selection and the range of forming are wide, help promotion and application.
Summary of the invention
The purpose of this invention is to provide a kind of acrylic ester high molecular type surfactant that can replace small-molecular emulsifier or emulsifying agent compound system, the preparation method of this high molecular surfactant is provided simultaneously.
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of acrylic ester high molecular type surfactant, express by following formula:
In the formula, x is 12～30, and y is 6～20, and z is 10～34.
A kind of preparation method of acrylic ester high molecular type surfactant adopts free radical to cause polymerisation in solution, may further comprise the steps:
(1) is solvent with load weighted three kinds of monomers with the isopropyl alcohol, mixes;
(2) get mixed solution in 1/2 step (1), with benzoyl peroxide (BPO) is initator, stir, in the time of 82 ℃, react under the nitrogen protection condition, behind 1～2.5h, remaining mixture solution is splashed in 1.5～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3.5h;
(3) with gains decompression distillation 2.5～3.5h, it is vacuumized be dried to constant weight again, promptly obtain acrylic ester high molecular type surfactant.
In the technique scheme, in the structural formula of described the 3rd monomer polyethylene glycol methacrylate-styrene polymer (PEGMA), the span of n is 5～10.
In the technique scheme, the mol ratio of described isopropanol solvent and three kinds of monomers is 2: 1.
In the technique scheme, the mol ratio of described initiator amount and three kinds of polymerization single polymerization monomers is 1: 100.
When actual fabrication,, must make with extra care raw material (purification) for guaranteeing degree of purity of production.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
(1) utilize radical polymerization to synthesize the amphipathic nature polyalcohol of random type, method is simple for this kind, and monomeric species selection and the range of forming are wide, help promotion and application.
(2) there is the polyethylene glycol segment simultaneously in the amphipathic nature polyalcohol molecule, chain alkyl and carboxyl, therefore promptly having hydrophobic grouping has hydrophilic radical again, have the characteristics of ionic surfactant and non-ionic surface active agent concurrently, can replace small-molecular emulsifier or emulsifying agent compound system, emulsion is played stabilization, be applied in emulsion polymerisation and the dispersin polymerization.
The specific embodiment
Below in conjunction with embodiment the present invention is further described, following examples only are that the present invention will be described but not it are limited.
Embodiment 1:
By 1: 1: 1: 6 mole proportioning; take by weighing methacrylic acid (MAA) respectively; methacrylic acid stearyl (SMA); polyethylene glycol methacrylate-styrene polymer (PEGMA) and solvent isopropyl alcohol; mix and stir; wherein 1/2nd mixture solution is poured in the three-neck flask; the initiator B PO that adds three kinds of monomer summations 1/100; stir; under 82 ℃ of constant temperature oil baths and nitrogen protection condition, react; 1.5 behind～the 2h; remaining mixture solution is splashed in 2～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3h.With gains decompression distillation 3h, again it is dried to constant weight for 40～60 ℃ as for vacuum drying chamber.Obtain required product, record productive rate＞90%.Product detects the structure of its molecular weight, molecular weight distribution and polymer through gel permeation chromatography and proton nmr spectra, proves to obtain target product.
Embodiment 2:
By 2: 1: 1: 8 mole proportioning; take by weighing methacrylic acid (MAA) respectively; methacrylic acid stearyl (SMA); polyethylene glycol methacrylate-styrene polymer (PEGMA) and solvent isopropyl alcohol; mix and stir; wherein 1/2nd mixture solution is poured in the three-neck flask; the initiator B PO that adds three kinds of monomer summations 1/100; stir; under 82 ℃ of constant temperature oil baths and nitrogen protection condition, react; 1.5 behind～the 2h; remaining mixture solution is splashed in 2～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3h.With gains decompression distillation 3h, again it is dried to constant weight for 40～60 ℃ as for vacuum drying chamber.Obtain required product, record productive rate＞90%.Product detects the structure of its molecular weight, molecular weight distribution and polymer through gel permeation chromatography and proton nmr spectra, proves to obtain target product.
Embodiment 3:
By 3: 1: 1: 10 mole proportioning; take by weighing methacrylic acid (MAA) respectively; methacrylic acid stearyl (SMA); polyethylene glycol methacrylate-styrene polymer (PEGMA) and solvent isopropyl alcohol; mix and stir; wherein 1/2nd mixture solution is poured in the three-neck flask; the initiator B PO that adds three kinds of monomer summations 1/100; stir; under 82 ℃ of constant temperature oil baths and nitrogen protection condition, react; 1.5 behind～the 2h; remaining mixture solution is splashed in 2～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3h.With gains decompression distillation 3h, again it is dried to constant weight for 40～60 ℃ as for vacuum drying chamber.Obtain required product, record productive rate＞90%.Product detects the structure of its molecular weight, molecular weight distribution and polymer through gel permeation chromatography and proton nmr spectra, proves to obtain target product.
Embodiment 4:
By 3: 1: 2: 12 mole proportioning; take by weighing methacrylic acid (MAA) respectively; methacrylic acid stearyl (SMA); polyethylene glycol methacrylate-styrene polymer (PEGMA) and solvent isopropyl alcohol; mix and stir; wherein 1/2nd mixture solution is poured in the three-neck flask; the initiator B PO that adds three kinds of monomer summations 1/100; stir; under 82 ℃ of constant temperature oil baths and nitrogen protection condition, react; 1.5 behind～the 2h; remaining mixture solution is splashed in 2～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3h.With gains decompression distillation 3h, again it is dried to constant weight for 40～60 ℃ as for vacuum drying chamber.Obtain required product, record productive rate＞90%.Product detects the structure of its molecular weight, molecular weight distribution and polymer through gel permeation chromatography and proton nmr spectra, proves to obtain target product.
Embodiment 5:
By 3: 1: 3: 14 mole proportioning; take by weighing methacrylic acid (MAA) respectively; methacrylic acid stearyl (SMA); polyethylene glycol methacrylate-styrene polymer (PEGMA) and solvent isopropyl alcohol; mix and stir; wherein 1/2nd mixture solution is poured in the three-neck flask; the initiator B PO that adds three kinds of monomer summations 1/100; stir; under 82 ℃ of constant temperature oil baths and nitrogen protection condition, react; 1.5 behind～the 2h; remaining mixture solution is splashed in 2～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3h.With gains decompression distillation 3h, again it is dried to constant weight for 40～60 ℃ as for vacuum drying chamber.Obtain required product, record productive rate＞90%.Product detects the structure of its molecular weight, molecular weight distribution and polymer through gel permeation chromatography and proton nmr spectra, proves to obtain target product.
These embodiment only are used to the present invention is described and should not limit the scope of this invention.In addition, after having read content of the present invention, those skilled in the art make the change or the modification of the various equivalent form of values to the present invention, and these equivalent form of values belong to claims institute restricted portion of the application equally.
Claims (5)
1. acrylic ester high molecular type surfactant, express by following formula:
2. acrylic ester high molecular type surfactant, it is characterized in that: the molar ratio of first monomer and second monomer is 1: 1～4: 1, the molar ratio of second monomer and the 3rd monomer is 1: 1～1: 4.
3. acrylic ester high molecular type surfactant, it is characterized in that: causing polymerisation in solution by free radical, is first monomer, second monomer and the 3rd monomer with methacrylic acid (MAA), oil loving methacrylic acid stearyl (SMA), the hydrophilic polyethylene glycol methacrylate-styrene polymer of nonionic (PEGMA) with anionic hydrophilic respectively.
4. acrylic ester high molecular type surfactant, it is characterized in that: in the structural formula of described polyethylene glycol methacrylate-styrene polymer (PEGMA), the span of n is 5～10.
5. the preparation method of an acrylic ester high molecular type surfactant is characterized in that: may further comprise the steps:
(1) is solvent with load weighted three kinds of monomers with the isopropyl alcohol, mixes;
(2) get mixed solution in 1/2 step (1), with benzoyl peroxide (BPO) is initator, stir, in the time of 82 ℃, react under the nitrogen protection condition, behind 1～2.5h, remaining mixture solution is splashed in 1.5～2.5h in the reactor by dropping funel, continue again to stop agitating heating behind reaction 2.5～3.5h;
(3) with gains decompression distillation 2.5～3.5h, it is vacuumized be dried to constant weight again, promptly obtain acrylic ester high molecular type surfactant.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012663A (en) * | 2012-12-05 | 2013-04-03 | 陕西科技大学 | Preparation method for anionic acrylate polymer surfactant |
| CN103897117A (en) * | 2014-04-09 | 2014-07-02 | 中国海洋石油总公司 | Amphipathic quaternary ammonium inner salt as well as preparation method and application thereof |
| CN106008848A (en) * | 2016-05-24 | 2016-10-12 | 中国日用化学工业研究院 | Comb type macromolecular dispersant and preparation method thereof |
| CN106810639A (en) * | 2017-02-15 | 2017-06-09 | 山东鲁岳化工有限公司 | A kind of oil-soluble high molecular surfactant and preparation method thereof |
| CN107057001A (en) * | 2017-03-22 | 2017-08-18 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl Comblike polymers surfactant and its production and use |
| CN110318298A (en) * | 2019-06-26 | 2019-10-11 | 深圳市铭诚生活科技有限公司 | A kind of multilayer paper for kitchen containing compound glue application solution |
| CN111165477A (en) * | 2020-01-23 | 2020-05-19 | 中化化工科学技术研究总院有限公司 | Acetochlor emulsion in water and preparation method thereof |
| CN111269349A (en) * | 2020-01-23 | 2020-06-12 | 中化化工科学技术研究总院有限公司 | Polycarboxylic acid polymer emulsifier and preparation method thereof |
| CN112545764A (en) * | 2020-12-19 | 2021-03-26 | 福建中润纸业有限公司 | Paper diaper and production process thereof |
| CN113307918A (en) * | 2021-06-07 | 2021-08-27 | 东莞长联新材料科技股份有限公司 | Vegetable oil-based polyacrylate nonionic emulsion and preparation method and application thereof |
-
2010
- 2010-12-07 CN CN2010105761034A patent/CN102091564A/en active Pending
Non-Patent Citations (1)
| Title |
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| 吴晓丽等: "甲基丙烯酸酯类两亲性聚合物的合成及其浊点测定", 《苏州大学学报（自然科学版）》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012663A (en) * | 2012-12-05 | 2013-04-03 | 陕西科技大学 | Preparation method for anionic acrylate polymer surfactant |
| CN103897117A (en) * | 2014-04-09 | 2014-07-02 | 中国海洋石油总公司 | Amphipathic quaternary ammonium inner salt as well as preparation method and application thereof |
| CN106008848A (en) * | 2016-05-24 | 2016-10-12 | 中国日用化学工业研究院 | Comb type macromolecular dispersant and preparation method thereof |
| CN106810639A (en) * | 2017-02-15 | 2017-06-09 | 山东鲁岳化工有限公司 | A kind of oil-soluble high molecular surfactant and preparation method thereof |
| CN107057001B (en) * | 2017-03-22 | 2020-04-21 | 中国林业科学研究院林产化学工业研究所 | Rosin-based comb-shaped high-molecular surfactant and preparation method and application thereof |
| CN107057001A (en) * | 2017-03-22 | 2017-08-18 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl Comblike polymers surfactant and its production and use |
| CN110318298A (en) * | 2019-06-26 | 2019-10-11 | 深圳市铭诚生活科技有限公司 | A kind of multilayer paper for kitchen containing compound glue application solution |
| CN110318298B (en) * | 2019-06-26 | 2020-04-21 | 深圳市铭诚生活科技有限公司 | Multilayer kitchen paper containing composite sizing liquid |
| CN111165477A (en) * | 2020-01-23 | 2020-05-19 | 中化化工科学技术研究总院有限公司 | Acetochlor emulsion in water and preparation method thereof |
| CN111269349A (en) * | 2020-01-23 | 2020-06-12 | 中化化工科学技术研究总院有限公司 | Polycarboxylic acid polymer emulsifier and preparation method thereof |
| CN111269349B (en) * | 2020-01-23 | 2022-04-05 | 中化化工科学技术研究总院有限公司 | Polycarboxylic acid polymer emulsifier and preparation method thereof |
| CN112545764A (en) * | 2020-12-19 | 2021-03-26 | 福建中润纸业有限公司 | Paper diaper and production process thereof |
| CN113307918A (en) * | 2021-06-07 | 2021-08-27 | 东莞长联新材料科技股份有限公司 | Vegetable oil-based polyacrylate nonionic emulsion and preparation method and application thereof |
| CN113307918B (en) * | 2021-06-07 | 2022-04-15 | 东莞长联新材料科技股份有限公司 | Vegetable oil-based polyacrylate nonionic emulsion and preparation method and application thereof |
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