CN106040087B - A kind of polyterpene maleic anhydride polyethylene glycol ester surfactant and preparation method thereof - Google Patents
A kind of polyterpene maleic anhydride polyethylene glycol ester surfactant and preparation method thereof Download PDFInfo
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- CN106040087B CN106040087B CN201610400436.9A CN201610400436A CN106040087B CN 106040087 B CN106040087 B CN 106040087B CN 201610400436 A CN201610400436 A CN 201610400436A CN 106040087 B CN106040087 B CN 106040087B
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- maleic anhydride
- surfactant
- polyterpene
- polyethylene glycol
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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 present invention discloses a kind of polyterpene maleic anhydride macrogol ester high molecular surfactant, and its general structure is as follows：R is represented in formula
Description
Technical field
The present invention relates to a kind of green functional surfactant and preparation method thereof, more particularly to a kind of polyterpene Malaysia
Acid anhydrides polyethylene glycol ester surfactant and preparation method thereof.Polyterpene maleic anhydride polyethylene glycol ester surfactant is double
Bridged ring and ester bond are introduced on the basis of amylene structure, makes the surfactant that not only there is emulsification, foam, high surface etc.
Outside multiple performance, also have the characteristics that preferably sticky.
Background technology
High molecular surfactant refers to those molecular weight more than thousands of and the producing high-molecular with surface active function
Compound, it has high molecular tackifying and low molecular surface-active concurrently, all has affinity to aqueous phase and oil phase.With resistance to height
Temperature, emulsifying capacity is strong, and dispersiveness and flocculability are excellent.This unique property of high molecular surfactant, is widely used as it
Gel, thickener, flocculant, dispersant, emulsifying agent, solubilizer etc..Applied to cosmetics, detergent, emulsion polymerization, medical height
The fields such as molecular material.The requirement more and more higher of Surfactant at present, not requiring nothing more than surfactant has unique property
Matter, also there is the prominent feature of environmental protection.The surfactant of single type is difficult often the needs for meeting production and living, in often
Different types of surfactant is needed to be compounded.Therefore, functional surfactant is increasingly taken seriously, same
Different functional groups is introduced in molecule and prepares functional surfactant with prominent effect.The poly- second two of polyterpene maleic anhydride
Alcohol ester high molecular surfactant is that bridged ring and ester bond are introduced on the basis of original dipentene structure, makes the surface-active
Agent not only has outside the multiple performances such as emulsification, foam, high surface, also has the characteristics that preferably sticky.
The accessory substance that industrial dipentene obtains when being using turpentine oil as Material synthesis camphor or terpinol, it is by monocyclic terpenes
With the liquid mixture of the composition such as bicyclic terpene.Dipentene is widely used in spices, 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 to the requirement of environmental protection
Increasingly improve again under conditions of, expand the utilization in fine chemicals to industrial dipentene, not only can effectively alleviate the country
The shortage of the natural resources such as oil, coal but also it can produce good economic benefit and social benefit.Domestic industry at present
Dipentene is cheap, is terebinthine half.So such surfactant is developed, it is undoubtedly excellent with huge resource
Gesture.
The content of the invention
It is an object of the invention to provide a kind of polyterpene maleic anhydride macrogol ester high molecular surfactant and its
Preparation method.For the surfactant using industrial dipentene as raw material, the surfactant of preparation has preferable surface-active
Can, contain 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：
R is represented in formula, the molecular weight 400 of polyethylene glycol, 600,
1000th, any one in 2000,4000.
The preparation method of polyterpene maleic anhydride macrogol ester high molecular surfactant, it is characterised in that use
It is one pot reaction：With maleic anhydride D-A addition reactions generation terpinene maleic anhydride addition occurs for the first step, industrial dipentene
With polyethylene glycol esterification generation polyterpene maleic anhydride polyethylene glycol occurs for thing, second step, terpinene maleic anhydride addition product
Ester high molecular surfactant.
Wherein the ratio between industrial dipentene and maleic anhydride are（1-1.5）:1, such as ratio selection 1:1,1.1:1,1.2:1,
1.3:1,1.4:1,1.5:1, catalyst is phosphoric acid, and one kind in phosphorous acid and p-methyl benzenesulfonic acid, dosage 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 chooses 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, reaction time 1-5h, such as 1h, 2h, 3h, 4h, 5h, obtain terpinene maleic anhydride and add
Into thing.
The ratio between amount of terpinene maleic anhydride addition product and polyethylene glycol material is 1:（1-1.5）, such as ratio selection 1:
1.1,1:1.2,1:1.3,1:1.4,1:1.5, catalyst is phosphoric acid, p-methyl benzenesulfonic acid, one kind in zinc oxide, and dosage is reaction
The 0.2-0.5% of thing gross mass, such as 0.2% is chosen, 0.3%, 0.4%, 0.5%, reaction temperature is 250-280 DEG C, such as is chosen
250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, reaction time 7-10h, it can be 7h, 8h, 9h, 10h, obtain polyterpene maleic anhydride and gather
Glycol ester high molecular surfactant.
Polyterpene maleic anhydride macrogol ester high molecular surfactant, critical micelle concentration 3.3-6.5g/L；Table
Face tension force is 33.7-42.1mN/m
Contain caged scaffold in polyterpene maleic anhydride macrogol ester high molecular surfactant, thickening can be effectively improved
Property, contain ester group in molecule, easily biological-degradable, there is feature and environment friendly.
The present invention obtains following technique effect：
1. the present invention is prepared using one kettle way, synthesized by addition, the methods of esterification, synthesis technique is easy, contains in molecule
There are caged scaffold and ester bond.
2. the polyterpene maleic anhydride polyethylene glycol type high molecular surfactant has stronger surface-active, its 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 as raw material, principle is spliced using active group, will be conjugated in dipentene
Double bond structure is introduced into surfactant structure, is simultaneously from natural products turpentine oil, ester group is contained in the surfactant, easily
Biodegradation, there is environment friendly, raw material is cheap to be easy to get, and product toxicity is small.
Brief description of the drawings
Fig. 1 is the infrared spectrum of polyterpene maleic anhydride Macrogol 600 ester of the present invention.
Embodiment
Embodiment 1
A kind of polyterpene maleic anhydride macrogol ester high molecular surfactant.
R is represented in formula, the molecular weight of polyethylene glycol is 400,600,
1000th, any one in 2000,4000.
Embodiment 2
A kind of method of polyterpene maleic anhydride macrogol ester high molecular surfactant, it is characterised in that use
It is one pot reaction：The first step, industrial dipentene and maleic anhydride reaction generation terpinene maleic anhydride addition product, second step, terpene
With polyethylene glycol esterification generation polyterpene maleic anhydride macrogol ester macromolecule surface occurs for alkene maleic anhydride adduct
Activating agent.Synthesis comprises the following steps：
68g industrial dipentenes are weighed respectively to pour into 500mL four-hole boiling flasks with 39.2g maleic anhydrides, then are added thereto
Appropriate phosphorous acid（The amount of phosphorous acid accounts for the 0.2% of reactant gross mass）As catalyst, 180 DEG C are heated to, stirring makes it
Fully reaction, reaction 1h are basically completed, and obtain terpinene maleic anhydride addition product.
360g Macrogol 600s are added to it again, add appropriate zinc oxide（The amount of zinc oxide accounts for reactant gross mass
0.2%）As catalyst, 260 DEG C are warming up to, stirring reaction 8h, room temperature is cooled to, obtains product.
Embodiment 3
Synthesis technique is similar to Example 2, and Macrogol 600 can use polyethylene glycol 400,1000,2000,4000 generations
Replace, terpinene maleic anhydride addition product is 1 with polyethylene glycol 400,1000,2000,4000 mol ratio:（1.1-1.5）.
Embodiment 4
Product and intermediate carry out IR Spectral Identifications：
3386cm-1For two yuan of rings=C-H stretching vibration characteristic peak, 951.33cm-1,847.02cm- 1,For C=H bending
Vibration performance 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-1For the characteristic absorption peak of ring.1110.38 cm-1For alcohol ehter bond-C-O-C-'s
Absworption peak, 1775.94cm-1And 1847.9cm-1Acid anhydrides both shoulders characteristic peak disappears, and illustrates to have obtained the poly- second of polyterpene maleic anhydride
The ester of glycol 600, product structure are correct.
Embodiment 5
The some surface active property measure of surfactant, surface tension is the important parameter of surfactant properties, is originally ground
Study carefully using film pull-up method to determine the surface tension of surfactant and CMC, measurement temperature is 25 DEG C, by determining series of products
Various concentrations when the aqueous solution surface tension.
Emulsifiability（EP）Measure：40mL mass fractions are taken to be poured into for the 0.1% product aqueous solution and 40mL atoleines
In 100mL tool plug graduated cylinder, stood after acutely shaking 50 times up and down, record separates the time needed for 10mL water.
Foaming properties (FP) determine：Configuration quality fraction is the 0.5% product aqueous solution, takes the 20mL product aqueous solution to pour into
In 100mL tool plug graduated cylinder, after acutely shaking 25 times up and down, foam height now is recorded, after standing 5min, record steeps again
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, stability 17mm.
Claims (2)
1. a kind of polyterpene maleic anhydride macrogol ester high molecular surfactant, its general structure are as follows：
R is represented in formulaThe molecular weight of polyethylene glycol be 400,600,1000,2000,4000 in any one, poly- terpene
Alkene maleic anhydride macrogol ester high molecular surfactant molecular weight ranges are 1643-5267.
2. a kind of method of the polyterpene maleic anhydride macrogol ester high molecular surfactant prepared described in claim 1,
Characterized in that, using one pot reaction：The first step, industrial dipentene and maleic anhydride reaction generation terpinene maleic anhydride
With polyethylene glycol the esterification generation poly- second of polyterpene maleic anhydride occurs for addition product, second step, terpinene maleic anhydride addition product
Diol ester high molecular surfactant；The ratio between industrial dipentene and maleic anhydride are (1-1.5):1, catalyst is phosphoric acid, phosphorous
Acid, one kind in p-methyl benzenesulfonic acid, dosage are the 0.2-0.5% of reactant gross mass, and reaction temperature is 150-200 DEG C, reaction
1-5h, obtain terpinene maleic anhydride addition product；The ratio between amount of terpinene maleic anhydride addition product and polyethylene glycol material is 1:(1-
1.5), catalyst is phosphoric acid, p-methyl benzenesulfonic acid, one kind in zinc oxide, and dosage is the 0.2-0.5% of reactant gross mass, instead
It is 250-280 DEG C, reaction time 7-10h to answer temperature, obtains polyterpene maleic anhydride polyethylene glycol ester surfactant.
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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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