CN101485965B - Surface active agent and preparation method thereof - Google Patents
Surface active agent and preparation method thereof Download PDFInfo
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- CN101485965B CN101485965B CN2008102192848A CN200810219284A CN101485965B CN 101485965 B CN101485965 B CN 101485965B CN 2008102192848 A CN2008102192848 A CN 2008102192848A CN 200810219284 A CN200810219284 A CN 200810219284A CN 101485965 B CN101485965 B CN 101485965B
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- maleic anhydride
- pinene
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Abstract
The invention provides a surfactant. The method for preparing the surfactant comprises the following steps: (1) according to the weight ratio of 100:85.4-427, beta-pinene/maleic anhydride copolymers and mono hydroxide radical poly-alkylene oxides are mixed, heated up until the mixture flows and stirred; and (2) when the temperature rises to between 90 and 180 DEG C, a catalyst is added; and (3) the mixture is kept warm and stirred for 3 to 8 hours, the reaction stops, and the mixture is cooled down to obtain the surfactant product. The surfactant prepared by the method is a comb type macromolecule, a main chain comprises a terpene chain segment, and a branched chain is a water soluble alkylene oxide chain segment. During the preparation of the surfactant, the poly-alkylene oxide with mono hydroxide radical is adopted, thereby adjusting the material charging ratio in the reaction between the beta-pinene/maleic anhydride copolymers and the mono hydroxide radical poly-alkylene oxide in the greater range, and obtaining the comb type surfactant with more flexible and changeable structure and unique performance.
Description
Technical field
The present invention relates to a kind of surfactant and preparation method thereof, belong to the preparation field of surfactant.
Background technology
Along with the development of modern technologies, people develop emulsion type products pollution-free, nuisanceless, low-cost and safe and convenient to use in succession to the attention of environmental protection in industrial circles such as adhesive, coating, i.e. " environmental protection " product.After the last century the eighties, emulsion adhesive and coating are occupied an leading position in adhesive and coatings industry.Rosin ester is a tackifier resins, and it is disperseed to become emulsion by emulsification, can well be scattered in the water-based system, and as tackifier, the film forming agent in the emulsion adhesive, the film forming modifier in the water paint, the internal sizing agent of paper pulp etc. in the paper industry.What is particularly worth mentioning is that rosin ester tackifier resins emulsion can significantly improve the performance of emulsion adhesive and coating, and can reduce adhesive and coating cost, be subjected to people's generally attention.
Because rosin ester has three special condensed ring shape structures, sterically hindered very big, be difficult to emulsification, and the polarity of molecule is bigger, even the emulsified aggregation that forms easily again, the rosin ester that poor stability, especially softening point are high, thus emulsifying agent be selected to a key that successfully prepares rosin ester emulsion.
The emulsifying agent of rosin ester tackifier resins emulsion selection the earliest is the emulsifying agent with reference to rosin milk in the glue used in paper-making, uses complete commercial emulsifying agent.Reported in the U.S. Pat 5236624 that adopting the APES sulfuric acid is main anion, cooperated a spot of APES non-ionic surface active agent to form compound emulsifying agent, the preparation rosin ester emulsion.But American-European in recent years to the induced by alkyl hydroxybenzene surfactant restriction use, make will be eliminated out the application of rosin ester emulsion of traditional general purpose table surface-active agent.Reported among the patent WO03068885 of Arizona company in 2003 that employing rosin ester self-emulsifying technology prepares rosin ester emulsion, the rosin ester of its earlier synthetic high acid value with the triethanolamine neutralization, adds the water high speed dispersion and becomes rosin ester emulsion again.The characteristics of this method are cheap, simple, preparations easily, and its weak point is that this rosin ester emulsion is anionic, can only PH greater than the scope of 7 (particularly greater than 9) in use.
The inventor discloses the pectination non-ionic surface active agent of a kind of beta-pinene/maleic anhydride copolymer and polyalkylene oxide grafting at Chinese invention patent (publication number CN101239292) before, this surfactant main chain has the terpenes segment, and side chain is water miscible alkylene oxide segment.When using this surfactant and preparing rosin ester tackifier resins emulsion, the terpenes segment and the rosin ester compatibility performance of main chain are good, can wrap and be attached to the rosin ester particle surface, water miscible alkylene oxide segment is a tree shape and extends in aqueous phase, emulsifying effectiveness is fine, good emulsion stability, and this surfactant is nonionic, can be widely applied in the various systems.But the polyalkylene oxide that this surfactant preparation is used is the polyalkylene oxide of hydroxy terminal or the polyalkylene oxide of amino terminal, it is the polyalkylene oxide of two hydroxyls or two amino, gel when preventing to react with beta-pinene/maleic anhydride copolymer, polyalkylene oxide needs a large amount of the use, obtain the surfactant of following structure, wherein a, b are natural number.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect that prior art exists, a kind of surfactant is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned surfactant.
Purpose of the present invention is achieved through the following technical solutions: a kind of surfactant provided by the invention has the structure as shown in the formula (I):
Wherein o, p, q, m, n are 0 or natural number, and R is alkyl or pi-allyl.Described alkyl is methyl or ethyl.
Described surfactant is the pectination macromolecule, and main chain has the terpenes segment, and side chain is water miscible alkylene oxide segment.
The preparation method of above-mentioned surfactant comprises the steps:
(1) being the beta-pinene/maleic anhydride copolymer of 100:85.4～427 and monohydroxy polyalkylene oxide heat fused with mass ratio begins to stir when flowing;
(2) when temperature reaches 90～180 ℃, add catalyst;
(3) keep stirring 3～8h under 90～180 ℃ of temperature after, stop reaction, cooling, product.
The described monohydroxy polyalkylene oxide of step (1) is that molecular weight is 400～2000 polyalkylene glycol monoalkyl ether or allyl polyether.Described polyalkylene glycol monoalkyl ether is poly glycol monomethyl ether or polyethyleneglycol ether; Described allyl polyether is a kind of in pi-allyl PEO, pi-allyl PPOX, the pi-allyl SYNPERONIC PE/F68.
The quality of the described catalyst of step (2) is 0～0.5% of beta-pinene/maleic anhydride copolymer and a monohydroxy polyalkylene oxide gross mass.Described catalyst is sulfuric acid, phosphoric acid or p-methyl benzenesulfonic acid.
The present invention is with respect to prior art, have following advantage and beneficial effect: polyalkylene oxide is a monohydroxy, can in a big way, regulate the reaction ingredient proportion of beta-pinene/maleic anhydride copolymer and monohydroxy polyalkylene oxide, obtain the structure pectination surfactant of flexibility and changeability, unique properties more.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but the working of an invention mode is not limited thereto.
Embodiment 1
(list of references: Qiu Zhenming, Shen Minmin breathe out brave for a, preparation beta-pinene/maleic anhydride copolymer; The reaction of nopinene and maleic anhydride and product characterize, chemistry circular, 2007,8 (70): 617～620)
B, preparation surfactant
(1) pack in the 250ml four-hole round-bottomed flask of mechanical agitation, nitrogen inlet and thermometer the is housed beta-pinene/maleic anhydride copolymers of 23.4 gram step a preparations and 80 gram mean molecule quantities are 400 poly glycol monomethyl ether, and heating is melted to it to begin when flowing to stir under nitrogen purge;
(2) when temperature reaches 180 ℃, add 0.517 gram phosphoric acid;
(3) keep under temperature and the nitrogen atmosphere, stirring reaction 6 hours drops to 2 to the sample of reaction mass acid number, stops reaction, cooling, surfactant.
The prepared surfactant structure formula that obtains is as figure I, o=p=n=0 wherein, and R is a methyl.
Embodiment 2
(list of references: Qiu Zhenming, Shen Minmin breathe out brave for a, preparation beta-pinene/maleic anhydride copolymer; The reaction of nopinene and maleic anhydride and product characterize, chemistry circular, 2007,8 (70): 617～620)
B, preparation surfactant
(1) pack in the 250ml four-hole round-bottomed flask of mechanical agitation, nitrogen inlet and thermometer the is housed beta-pinene/maleic anhydride copolymers of 23.4 gram step a preparations and 100 gram mean molecule quantities are 2000 polyethyleneglycol ether, and heating is melted to it to begin when flowing to stir under nitrogen purge;
(2) when temperature reaches 90 ℃, do not add catalyst;
(3) under this temperature and nitrogen atmosphere, stirring reaction 3 hours stops reaction, and cooling gets surfactant.
The prepared surfactant structure formula that obtains is as figure I, o=p wherein, and q=n=0, R are ethyls.
Embodiment 3
(list of references: Qiu Zhenming, Shen Minmin breathe out brave for a, preparation beta-pinene/maleic anhydride copolymer; The reaction of nopinene and maleic anhydride and product characterize, chemistry circular, 2007,8 (70): 617～620)
B, preparation surfactant
(1) pack in the 250ml four-hole round-bottomed flask of mechanical agitation, nitrogen inlet and thermometer the is housed beta-pinene/maleic anhydride copolymers of 23.4 gram step a preparations and 75 gram mean molecule quantities are that (the oxirane number of repeat unit is 6 for 500 pi-allyl SYNPERONIC PE/F68, the expoxy propane number of repeat unit is 3, both m=6, n=3), heating is melted to it to begin when flowing to stir;
(2) when temperature reaches 150 ℃, add 0.2 gram p-methyl benzenesulfonic acid;
(3) keep under temperature and the nitrogen atmosphere, stirring reaction 8 hours stops reaction, and cooling gets surfactant.
The prepared surfactant structure formula that obtains is as figure I, o=0 wherein, and p=q, m=6, n=3, R are pi-allyls.
Embodiment 4
(list of references: Qiu Zhenming, Shen Minmin breathe out brave for a, preparation beta-pinene/maleic anhydride copolymer; The reaction of nopinene and maleic anhydride and product characterize, chemistry circular, 2007,8 (70): 617～620)
B, preparation surfactant
(1) pack in the 250ml four-hole round-bottomed flask of mechanical agitation, nitrogen inlet and thermometer the is housed beta-pinene/maleic anhydride copolymers of 23.4 gram step a preparations and 20 gram mean molecule quantities are 400 pi-allyl PEO, and heating is melted to it to begin when flowing to stir under nitrogen purge;
(2) when temperature reaches 120 ℃, add 0.04 gram toluene sulfonic acide;
(3) keep under temperature and the nitrogen atmosphere, stirring reaction 3 hours stops reaction, and cooling gets surfactant.
The prepared surfactant structure formula that obtains is as figure I, o=p wherein, and q=n=0, R are pi-allyls.
Embodiment 5
(list of references: Qiu Zhenming, Shen Minmin breathe out brave for a, preparation beta-pinene/maleic anhydride copolymer; The reaction of nopinene and maleic anhydride and product characterize, chemistry circular, 2007,8 (70): 617～620)
B, preparation surfactant
(1) pack in the 250ml four-hole round-bottomed flask of mechanical agitation, nitrogen inlet and thermometer the is housed beta-pinene/maleic anhydride copolymers of 23.4 gram step a preparations and 20 gram mean molecule quantities are 400 pi-allyl PPOX, and heating is melted to it to begin when flowing to stir under nitrogen purge;
(2) when temperature reaches 120 ℃, add 0.04 gram phosphoric acid;
(3) keep under temperature and the nitrogen atmosphere, stirring reaction 3 hours stops reaction, and cooling gets surfactant.
The prepared surfactant structure formula that obtains is as figure I, o=p wherein, and q=n=0, R are pi-allyls.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. surfactant is characterized in that: have the structure as shown in the formula (I):
Wherein o, p, q, m, n are 0 or natural number, and R is alkyl or pi-allyl;
Described surfactant is the pectination macromolecule, and main chain has the terpenes segment, and side chain is water miscible alkylene oxide segment.
2. a kind of surfactant according to claim 1 is characterized in that: described alkyl is methyl or ethyl.
3. the preparation method of a kind of surfactant according to claim 1 comprises the steps:
(1) being 100: 85.4～427 beta-pinene/maleic anhydride copolymer and monohydroxy polyalkylene oxide heat fused with mass ratio begins to stir when flowing;
(2) when temperature reaches 90～180 ℃, add catalyst;
(3) keep stirring 3～8h under 90～180 ℃ of temperature after, stop reaction, cooling, surfactant.
4. the preparation method of a kind of surfactant according to claim 3, it is characterized in that: the molecular weight of the described monohydroxy polyalkylene oxide of step (1) is between 400～2000.
5. according to the preparation method of claim 3 or 4 described a kind of surfactants, it is characterized in that: the described monohydroxy polyalkylene oxide of step (1) is polyalkylene glycol monoalkyl ether or allyl polyether.
6. the preparation method of a kind of surfactant according to claim 5, it is characterized in that: described polyalkylene glycol monoalkyl ether is poly glycol monomethyl ether or polyethyleneglycol ether; Described allyl polyether is a kind of in pi-allyl PEO, pi-allyl PPOX, the pi-allyl SYNPERONIC PE/F68.
7. the preparation method of a kind of surfactant according to claim 3, it is characterized in that: the quality of the described catalyst of step (2) is 0～0.5% of beta-pinene/maleic anhydride copolymer and a monohydroxy polyalkylene oxide gross mass.
8. according to the preparation method of claim 3 or 7 described a kind of surfactants, it is characterized in that: described catalyst is sulfuric acid, phosphoric acid or p-methyl benzenesulfonic acid.
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| CN2008102192848A CN101485965B (en) | 2008-11-21 | 2008-11-21 | Surface active agent and preparation method thereof |
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| CN2008102192848A CN101485965B (en) | 2008-11-21 | 2008-11-21 | Surface active agent and preparation method thereof |
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| CN101485965A CN101485965A (en) | 2009-07-22 |
| CN101485965B true CN101485965B (en) | 2011-03-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239292A (en) * | 2008-03-14 | 2008-08-13 | 中国科学院广州化学研究所 | Surfactant and preparation and application thereof |
| CN101274241A (en) * | 2003-02-06 | 2008-10-01 | 阿利桑那化学公司 | Terpene resin and hydrocarbon resin-based surfactants and aqueous disperson of tackifier resins |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274241A (en) * | 2003-02-06 | 2008-10-01 | 阿利桑那化学公司 | Terpene resin and hydrocarbon resin-based surfactants and aqueous disperson of tackifier resins |
| CN101239292A (en) * | 2008-03-14 | 2008-08-13 | 中国科学院广州化学研究所 | Surfactant and preparation and application thereof |
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