CN106040087A - Poly terpene-maleic anhydride polyethylene glycol ester surfactant and preparation method thereof - Google Patents
Poly terpene-maleic anhydride polyethylene glycol ester surfactant and preparation method thereof Download PDFInfo
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- CN106040087A CN106040087A CN201610400436.9A CN201610400436A CN106040087A CN 106040087 A CN106040087 A CN 106040087A CN 201610400436 A CN201610400436 A CN 201610400436A CN 106040087 A CN106040087 A CN 106040087A
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- maleic anhydride
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3328—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof heterocyclic
Abstract
The invention discloses a poly terpene-maleic anhydride polyethylene glycol ester macromolecular surfactant. The surfactant has the general structural formula shown in the specification, wherein R is shown in the specification, and the molecular weight of polyethylene glycol is any one of 400, 600, 1,000, 2,000 and 4,000. The invention further discloses a preparation method of the surfactant. According to the method, a one-pot method is adopted for preparation, firstly, industrial dipentene and maleic anhydride are subjected to a D-A addition reaction under the action of a catalyst to form a terpene-maleic anhydride addition product, then the product and polyethylene glycol are subjected to an esterification reaction, and the poly terpene-maleic anhydride polyethylene glycol ester macromolecular surfactant is obtained and has the molecular weight ranging from 1,643 to 5,267. The prepared surfactant has the critical micelle concentration ranging from 3.3 g/L to 6.5 g/L and the surface tension ranging from 33.7 mN/m to 42.1 mN/m and is a novel functional green macromolecular surfactant.
Description
Technical field
The present invention relates to a kind of green functional surfactant and preparation method thereof, particularly relate to a kind of polyterpene Malaysia
Anhydride Polyethylene Glycol ester surfactant and preparation method thereof.Polyterpene maleic anhydride Polyethylene Glycol ester surfactant is double
Introduce bridged ring and ester bond on the basis of amylene structure, make this surfactant not only have emulsifying, foam, high surface etc.
Outside multiple performance, also there is the features such as preferable viscosity.
Background technology
High molecular surfactant refers to that those molecular weight and have the producing high-molecular of surface active function more than thousands of
Compound, it has high molecular tackifying and low molecular surface activity concurrently, aqueous phase and oil phase is all had affinity.There is resistance to height
Temperature, emulsifying capacity is strong, and dispersibility and flocculability are excellent.The character of this uniqueness of high molecular surfactant so that it is be widely used as
Gel, thickening agent, flocculant, dispersant, emulsifying agent, solubilizing agent etc..Being applied to cosmetics, detergent, emulsion is polymerized, medical height
The fields such as molecular material.The requirement of Surfactant is more and more higher at present, does not require nothing more than surfactant and has the property of uniqueness
Matter, also to have the prominent feature of environmental protection.The surfactant of single type is often difficult to meet the needs of productive life, in application often
Different types of surfactant is needed to compound.Therefore, functional surfactant increasingly comes into one's own, same
Molecule introduces different functional groups prepare functional surfactant there is prominent effect.The poly-second of polyterpene maleic anhydride two
Alcohol ester high molecular surfactant is to introduce bridged ring and ester bond on the basis of original dipentene structure, makes this surface activity
Agent not only has outside the multiple performances such as emulsifying, foam, high surface, also has the features such as preferable viscosity.
The by-product that industrial dipentene obtains when being with Oleum Terebinthinae for Material synthesis Camphora or terpineol, is by monocyclic terpene
The liquid mixture formed with bicyclic terpene etc..Dipentene is widely used in spice, organic intermediate, and synthetic resin etc. becomes more meticulous
Production in product.Nowadays the demand of Surfactant raw material is huge, and price rises steadily, and the requirement to environmental conservation
Under conditions of the most day by day improving, expand industrial dipentene utilization in fine chemicals, not only can effectively alleviate domestic
Oil, the shortage of the natural resourcess such as coal but also good economic benefit and social benefit can be produced.Domestic industry at present
Dipentene is cheap, for terebinthine half.So developing this type of surfactant, there is huge resource undoubtedly excellent
Gesture.
Summary of the invention
It is an object of the invention to provide a kind of polyterpene maleic anhydride macrogol ester high molecular surfactant and
Preparation method.This surfactant is with industrial dipentene as raw material, and the surfactant of preparation has preferable surface activity
Can, containing bridged ring and ester bond in product, raw material is cheap and easy to get, and product is biodegradable.
The present invention adopts the following technical scheme that a kind of polyterpene maleic anhydride Polyethylene Glycol ester surfactant.
Its general structure is as follows:
In formula, R represents, the molecular weight 400 of Polyethylene Glycol, 600,
1000, any one in 2000,4000.
The preparation method of polyterpene maleic anhydride macrogol ester high molecular surfactant, it is characterised in that employing
Being one pot reaction: the first step, industrial dipentene and maleic anhydride occur D-A additive reaction to generate terpinene maleic anhydride addition
Thing, second step, terpinene maleic anhydride addition product generates polyterpene maleic anhydride Polyethylene Glycol with Polyethylene Glycol generation esterification
Ester high molecular surfactant.
Wherein industrial dipentene is (1-1.5) with the ratio of maleic anhydride: 1, and such as ratio chooses 1:1,1.1:1,1.2:1,
1.3:1,1.4:1,1.5:1, catalyst is the one in phosphoric acid, phosphorous acid and p-methyl benzenesulfonic acid, and consumption is reactant gross mass
0.2-0.5%, such as choose 0.2%, 0.3%, 0.4%, 0.5%, reaction temperature is 150-200 DEG C, such as, choose 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, response time 1-5h, such as 1h, 2h, 3h, 4h, 5h, obtain terpinene maleic anhydride and add
Become thing.
Terpinene maleic anhydride addition product is 1:(1-1.5 with the ratio of the amount of Polyethylene Glycol material), such as ratio chooses 1:
1.1,1:1.2,1:1.3,1:1.4,1:1.5, catalyst is phosphoric acid, p-methyl benzenesulfonic acid, the one in zinc oxide, and consumption is reaction
The 0.2-0.5% of thing gross mass, such as, choose 0.2%, 0.3%, 0.4%, 0.5%, and reaction temperature is 250-280 DEG C, such as, choose
250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, response time 7-10h, can be 7h, 8h, 9h, 10h, obtains polyterpene maleic anhydride and gathers
Glycol ester high molecular surfactant.
Polyterpene maleic anhydride macrogol ester high molecular surfactant, critical micelle concentration is 3.3-6.5g/L；Table
Surface tension is 33.7-42.1mN/m
Containing caged scaffold in polyterpene maleic anhydride macrogol ester high molecular surfactant, tackifying can be effectively improved,
Containing ester group in molecule, easily biological-degradable, there is functional and environment friendly.
The present invention obtains following technique effect:
1. the present invention uses one kettle way to prepare, and through method synthesis such as addition, esterifications, synthesis technique is easy, containing bridge in molecule
Ring structure and ester bond.
2. this polyterpene maleic anhydride polyethylene glycol type high molecular surfactant has stronger surface activity, and it is critical
Micellar concentration is 3.3-6.5g/L；Surface tension is 33.7-42.1mN/m；
3. present invention process uses biomass resource to be raw material, uses active group splicing principle, by conjugated double bond in dipentene
Structure introduces in surfactant structure, is simultaneously from natural product Oleum Terebinthinae, containing ester group in this surfactant, easily biological
Degraded, has environment friendly, and raw material is cheap to be easy to get, and product toxicity is little.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of polyterpene maleic anhydride Macrogol 600 ester of the present invention.
Detailed description of the invention
Embodiment 1
A kind of polyterpene maleic anhydride macrogol ester high molecular surfactant.
In formula, R represents, the molecular weight of Polyethylene Glycol is 400,
600, any one in 1000,2000,4000.
Embodiment 2
A kind of method of polyterpene maleic anhydride macrogol ester high molecular surfactant, it is characterised in that use one
Pot method reaction: the first step, industrial dipentene and maleic anhydride react generation terpinene maleic anhydride addition product, second step, terpenes horse
Carry out acid anhydride adduct and generate polyterpene maleic anhydride macrogol ester high-molecular surface active with Polyethylene Glycol generation esterification
Agent.Synthesis comprises the following steps:
Weigh 68g industrial dipentene respectively to pour in 500mL four-hole boiling flask with 39.2g maleic anhydride, then be added thereto to appropriate
Phosphorous acid (amount of phosphorous acid accounts for the 0.2% of reactant gross mass), as catalyst, is heated to 180 DEG C, and stirring makes it abundant
Reaction, reaction 1h is basically completed, and obtains terpinene maleic anhydride addition product.
Adding 360g Macrogol 600 to it again, (amount of zinc oxide accounts for reactant gross mass to add appropriate zinc oxide
0.2%) as catalyst, it is warming up to 260 DEG C, stirring reaction 8h, it is cooled to room temperature, obtains product.
Embodiment 3
Synthesis technique is similar to Example 2, and Macrogol 600 can use PEG400,1000,2000,4000 replacements, terpene
Alkene maleic anhydride adduct is 1:(1.1-1.5 with PEG400, the mol ratio of 1000,2000,4000).
Embodiment 4
Product and intermediate carry out IR spectroscopic identification:
3386cm-1It is the stretching vibration characteristic peak of two rings=C-H, 951.33cm-1,847.02cm-1,Bending vibration for C=H
Characteristic peak, 2871.3cm-1For methylene-CH2-absworption peak, 1731.89m-1The characteristic absorption peak of ester group, 1641.93cm-1
For carboxyl peak, 1350.34cm-1Characteristic absorption peak for ring.1110.38 cm-1For the absworption peak of alcohol ehter bond-C-O-C-,
1775.94cm-1And 1847.9cm-1Anhydride both shoulders characteristic peak disappears, and illustrates to have obtained polyterpene maleic anhydride Macrogol 600
Ester, product structure is correct.
Embodiment 5
The some surface active property of surfactant measures, and surface tension is the important parameter of surfactant properties, and this research is adopted
Measure surface tension and the CMC of surfactant by film pull-up method, measuring temperature is 25 DEG C, by measuring series of products not
With the surface tension of aqueous solution during concentration.
Emulsifiability (EP) measures: take product water solution that 40mL mass fraction is 0.1% and 40mL liquid paraffin is poured into
In the tool plug graduated cylinder of 100mL, standing after the most acutely shaking 50 times, record separates the time needed for 10mL water.
Foaming properties (FP) measures: configuration quality mark is the product water solution of 0.5%, takes 20mL product water solution and pours into
In the tool plug graduated cylinder of 100mL, after the most acutely shaking 25 times, record foam height now, after standing 5min, again record bubble
Foam height.
The some surface active property of the surfactant of polyterpene maleic anhydride Macrogol 600 ester is: critical micelle concentration
For 2.1g/L；Emulsifiability 730s；Frothing capacity is 63mm, and stability is 17mm.
Claims (5)
1. a polyterpene maleic anhydride macrogol ester high molecular surfactant, its general structure is as follows:
In formula, R represents Polyethylene Glycol. the molecular weight of Polyethylene Glycol is
400, any one in 600,1000,2000,4000.
2. the method preparing polyterpene maleic anhydride macrogol ester high molecular surfactant described in claim 1,
It is characterized in that, use one pot reaction: the first step, industrial dipentene and maleic anhydride react generation terpinene maleic anhydride
Addition product, second step, terpinene maleic anhydride addition product generates the poly-second of polyterpene maleic anhydride with Polyethylene Glycol generation esterification
Diol ester high molecular surfactant, molecular weight ranges is 1643-5267.
The preparation method of polyterpene maleic anhydride macrogol ester high molecular surfactant the most according to claim 2,
It is characterized in that, industrial dipentene is (1-1.5) with the ratio of maleic anhydride: 1, and catalyst is phosphoric acid, phosphorous acid, p-methyl benzenesulfonic acid
In one, consumption is the 0.2-0.5% of reactant gross mass, and reaction temperature is 150-200 DEG C, react 1-5h, obtain terpenes horse
Carry out acid anhydride adduct.
The preparation method of polyterpene maleic anhydride macrogol ester high molecular surfactant the most according to claim 2,
It is characterized in that, terpinene maleic anhydride addition product is 1:(1-1.5 with the ratio of the amount of Polyethylene Glycol material), catalyst is phosphoric acid,
P-methyl benzenesulfonic acid, the one in zinc oxide, consumption is the 0.2-0.5% of reactant gross mass, and reaction temperature is 250-280 DEG C, instead
7-10h between Ying Shi, obtains polyterpene maleic anhydride Polyethylene Glycol ester surfactant.
Polyterpene maleic anhydride macrogol ester high molecular surfactant the most according to claim 1, critical micell is dense
Degree is 3.3-6.5g/L；Surface tension is 33.7-42.1mN/m.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478258A (en) * | 2022-01-17 | 2022-05-13 | 艾茵化学(深圳)有限公司 | Fatty alcohol ether alpha-pinene-maleic anhydride addition acid surfactant and preparation method thereof |
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| JP2005171022A (en) * | 2003-12-09 | 2005-06-30 | Idemitsu Kosan Co Ltd | Polyethylene glycol ether derivative, nonionic surfactant, and manufacturing method of polyethylene glycol ether derivative |
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| CN101054437A (en) * | 2007-04-29 | 2007-10-17 | 中国林业科学研究院林产化学工业研究所 | Method of preparing hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin |
| CN101698703A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Maleic acid isoalcohol diester and prepration method thereof |
| CN104844763A (en) * | 2015-05-19 | 2015-08-19 | 广西民族大学 | Terpenyl ester hyperdispersant and preparation method for same |
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Patent Citations (5)
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| CN1748013A (en) * | 2003-02-06 | 2006-03-15 | 阿利桑那化学公司 | Terpene resin- and hydrocarbon resin-based surfactants and acqueous disperson of tacifier resins |
| JP2005171022A (en) * | 2003-12-09 | 2005-06-30 | Idemitsu Kosan Co Ltd | Polyethylene glycol ether derivative, nonionic surfactant, and manufacturing method of polyethylene glycol ether derivative |
| CN101054437A (en) * | 2007-04-29 | 2007-10-17 | 中国林业科学研究院林产化学工业研究所 | Method of preparing hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin |
| CN101698703A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Maleic acid isoalcohol diester and prepration method thereof |
| CN104844763A (en) * | 2015-05-19 | 2015-08-19 | 广西民族大学 | Terpenyl ester hyperdispersant and preparation method for same |
Cited By (2)
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| CN114478258A (en) * | 2022-01-17 | 2022-05-13 | 艾茵化学(深圳)有限公司 | Fatty alcohol ether alpha-pinene-maleic anhydride addition acid surfactant and preparation method thereof |
| CN114478258B (en) * | 2022-01-17 | 2024-04-16 | 艾茵化学(深圳)有限公司 | Fatty alcohol ether alpha-pinene-maleic anhydride acid-added surfactant and preparation method thereof |
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