CN106046233A - Macromolecular thickener and preparation method and application thereof - Google Patents
Macromolecular thickener and preparation method and application thereof Download PDFInfo
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- CN106046233A CN106046233A CN201610383925.8A CN201610383925A CN106046233A CN 106046233 A CN106046233 A CN 106046233A CN 201610383925 A CN201610383925 A CN 201610383925A CN 106046233 A CN106046233 A CN 106046233A
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- ether
- maleic anhydride
- thickener
- copolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Abstract
The invention discloses a salt-resistant and acid-resistant macromolecular thickener. The macromolecular thickener is a derivative or salt of methyl vinyl ether/maleic anhydride copolymer (PVM/MA). The thickener is obtained through a reaction of a long carbon chain oxygen-rich hydroxy compound and the methyl vinyl ether/maleic anhydride copolymer. The long carbon chain oxygen-rich hydroxy compound is selected from fatty alcohol-polyoxyethylene ether or fatty alcohol polyoxy propylene ether or fatty acid polyglycerol ether or a mixture thereof. The derivative has excellent thickening performance at the esterification rate of 20-45% and the number of EO, PO and glycerinum groups being 2-10. According to the derivative of the methyl vinyl ether/maleic anhydride copolymer, viscosity equivalent to that of carbopol can be provided, but salt resistance and acid resistance are greatly improved; the thickener is mild and low in irritation, and can be used for personal care articles, washing agents or other industrial fields to serve as a rheological modifier to achieve the thickening effect.
Description
Technical field
The present invention relates to a kind of macromolecule thickener, be spreading out of Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA)
Biology, further relates to the preparation method and application of described macromolecule thickener.
Background technology
Thickening agent is a kind of polymer builder, also known as rheology control agent, because it can improve system viscosity rapidly and change
It is apt to system rheological characteristic and is widely used in the fields such as personal care articles, furniture nursing product, printing in textiles, food, building.Will
A small amount of thickening agent is added in the system needed, and the viscosity of system can be greatly improved and reach wanting of technique and rheological characteristic
Ask.
Currently used thickening agent mostly is waterborne polymeric, mainly includes natural macromolecular compound, chemical modification
Natural product and synthetic thickening agent.Natural macromolecular compound is mainly polysaccharide polymer, such as sodium alginate, natural
Glue, starch and denatured products thereof etc., its paste producing is convenient, convenient use, but price comparison is expensive, and stability is poor.Change
Learn modified natural product and have carboxy methylation or hydroxyethylated starch or cellulose derivative etc., the effect of this series products have into
One step is improved, but how to be limited by the place of production, and price, performance gap are very big, use limited.Synthetic thickening agent occupies current major part
Thickening agent market, and be widely used in a lot of fields, compare with natural thickener, synthetic thickening agent have natural thickener without
Analogous superiority, such as: synthetic thickening agent does not have seasonality, the not impact of the factor such as climate, region；Synthetic thickening agent
There is stronger armful aqueous；Synthetic thickening agent stores and need not add preservative etc..The most traditional and widely used synthesis
Macromolecule thickener is polyacrylic polymer, such as carbopol.It is not much needing the occasion of thickening, the existence of electrolyte
Evitable, as prepared detergent, cosmetics etc., but polymer carbopol class thickening agent electrolyte res is tance is relatively poor,
The salt tolerance the most how improving product becomes the main bugbear of synthetic thickening agent.Lead in detergent, cosmetics, weaving etc. simultaneously
Territory, is more beneficial for performance under mildly acidic conditions due to formula, if cosmetics are when pH value is 4.5-6.0 and human body skin
The compatibility best, textile dyeing and finishing can be only achieved under acid condition optimal using effect.On the other hand, with carbopol it is
Example, wherein trade mark carbopol 980 is applied most representative, and its optimal serviceability is in neutrality to alkalescence, and pH value is 6.8-7.8
Behave oneself best.Therefore, the acid resistance of macromolecule thickener seems extremely important in these fields.
Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) is that methyl vinyl ether and maleic anhydride are gathered by solvent
Close or the anhydride type copolymer that obtains of polymerisation in bulk, there is good chemical stability, good cohesive, cohesiveness, water conservation
Property, film property (institute's film forming is easily peeled), and to human non-toxic evil, be therefore used widely.At field of medicaments, ethylene methacrylic
Base ether/copolymer-maleic anhydride (PVM/MA), because having biological viscosity, is used as the binding agent of anastomosis, and tooth, dens supporter are fixed
The oral care products such as agent；In field of light chemical industry, the hydrolysis of Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) neutralizes produces
Thing is used as the thickening agent of surfactant, water-soluble material.
The acid anhydride structure of Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) has active anhydride bond, has the strongest
Reactivity, can react with water, alcohol etc., can react with water as adhesive as obtained product with methanol, ethanol synthesis
To product can have certain thickening power, but weak effect, and not salt tolerant.
Summary of the invention
It is an object of the invention to provide the macromolecule thickener of a kind of salt tolerant anti-acid, its preparation method and application.
Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) molecular weight, generally at 10-800 ten thousand, forms acid after hydrolysis
Formula structure, has certain suspension thickening power, but thickening effect is the least, and the viscosity of 0.5% concentration only has hundreds of mPa.s, no
Can use as thickening agent.Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) is modified by prior art, as made
Reacting formation half ester with alcohol, be used for adhesive, thickening effect is the most inconspicuous.The present invention is found by research, selects
Molecule contains the Long carbon chain compound of multiple oxygen elements, reacts with Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA)
The product obtained, exists easily due to a large amount of oxygen atoms in molecule and water forms hydrogen bond, be conducive to increasing high molecular Shu Shuineng
Power, can play obvious thickening effect in the application, and this compounds also has longer carbochain, at the netted knot forming Shu Shui
Structure plays skeleton function.The derivant of the Copolymer of Methyl Vinyl Ether/Maleic Anhydride of the present invention provides can be with carbopol phase
When viscosity, but salt tolerance and acid resistance are greatly improved.The described Long carbon chain compound containing multiple oxygen elements is typically derived from
Oxirane, expoxy propane, the addition product of polyglycereol or their mixing addition products, and in molecule, Long carbon chain derives from senior fat
Fat acid or fatty alcohol, this compounds derives from natural oil or synthetic ester oil.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of macromolecule thickener, is derivant or its salt of ethylene methacrylic ether/copolymer-maleic anhydride, and formula is:
In formula,
M is cation,
R1For CH2, CH (CH3) and/or CH2(OH)CH2,
R2For alkyl that carbon chain lengths is 6-22 and/or alkanoyl,
X is 1-30,
The monomer of esterification and non-esterified monomer random arrangement；Esterification yield is 10-50%, and described esterification yield is:
N/ [2* (n+m)] * 100%.
Preferably, M described in formula is H, Na, K, NH4Or N (CH2CH2OH)3(triethanolamine), or their mixing
Thing.
Preferably, R in formula2For alkyl that carbon chain lengths is 12-18 and/or alkanoyl.
Preferably, n+m described in formula is 5000-50000；X is 2-10.
In above-mentioned macromolecular compound, esterification yield is preferably 15-50%, more preferably 20-45%.
Described macromolecule thickener can be by Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) and Long carbon chain polyoxy
Hydroxy compounds carries out esterification in the presence of a catalyst and obtains, with in pH value regulator and its salt available.Described instead
Answer process can represent with following formula:
M, R in formula1、R2, x, n+m be defined as above.
In above-mentioned esterification, the most each copolymer anhydride group can be combined, all with two hydroxy compounds
Being 100% in conjunction with then esterification yield, esterification yield 50% then represents that each anhydride connects a hydroxy compounds.Esterification yield expression formula
For:
N/ [2* (n+m)] * 100%, can obtain actual esterification yield by detection.
Applicant studies discovery, and said derivative is when esterification yield is more than 50%, and product water solublity is greatly reduced, and thickening is imitated
Fruit is the best, and when esterification yield is less than 10%, product bundle outlet capacity is poor, thickening effect is bad, when esterification yield scope is 15-
50% can obtain preferable performance, and preferred esterification yield is 20-45%.
In the present invention, the Long carbon chain compound containing multiple oxygen elements of selection includes the addition of fatty alcohol and oxirane
Thing i.e. fatty alcohol-polyoxyethylene ether, the addition compound product i.e. fatty acid polyglycol glycerin ether of fatty acid and (+)-2,3-Epoxy-1-propanol, and fatty alcohol with
The addition compound product of expoxy propane i.e. fatty alcohol polyoxypropylene ether, or their mixture.
Fatty alcohol-polyoxyethylene ether chemical name is abbreviated as AEO, for commercial goods, is to be added with oxirane (EO) by higher alcohols
One-tenth obtains, and wherein higher alcohols carbon chain lengths is C8 to C18, derives from natural oil or synthol, includes but not limited to pungent
Alcohol, decanol, lauryl alcohol, tetradecyl alchohol, hexadecanol, stearyl alcohol, isooctadecanol, oleyl alcohol and their mixture, the adduct number of EO
Mesh is 1-25.Preferably fatty alcohol is C12-18 alcohol, and EO addition quantity is 2-10.The fatty alcohol-polyoxyethylene ether that the present invention mentions
(AEO) capryl alcohol polyoxyethylene ether-2 are included but not limited to, polyoxyethylene lauryl ether-5, polyoxyethylene lauryl ether-10, nonyl last of the ten Heavenly stems
Polyoxyethylenated alcohol-7, ten tetracosanol polyoxyethylene ether-10, Brij-721-5, Brij-721-15
Deng.
Fatty acid and polyglycereol addition compound product i.e. polyglyceryl fatty acid ester are that long-chain fatty acid obtains with polyglycereol addition, logical
Its carbon chain lengths of Chang Qizhong long-chain fatty acid is C8 to C22, derive from natural oil or synthesis acid, include but not limited to octanoic acid,
Capric acid, lauric acid, tetradecylic acid, hexadecylic acid, stearic acid, isostearic acid, oleic acid, behenic acid and their mixture, polyglycereol
Glycerol polymerization degree be 1-10.The fatty alcohol polyoxypropylene ether that the present invention mentions includes but not limited to lauric acid five polyglycereol, oil
Acid ten polyglycereol etc..
Fatty alcohol and expoxy propane addition compound product are fatty alcohol polyoxypropylene ether, are to be added with expoxy propane (PO) by higher alcohols
One-tenth obtains, and wherein higher alcohols carbon chain lengths is C8-18, derives from natural oil or synthol, include but not limited to capryl alcohol,
Decanol, lauryl alcohol, tetradecyl alchohol, hexadecanol, stearyl alcohol, isooctadecanol, oleyl alcohol and their mixture, the addition of expoxy propane
Number is 1-30.Preferably fatty alcohol is C12-18 alcohol, and PO addition quantity is 2-10.The fatty alcohol polyoxypropylene that the present invention mentions
Ether includes but not limited to lauryl alcohol polyethenoxy ether-5, lauryl alcohol polyethenoxy ether-7, lauryl alcohol polyethenoxy ether-10, Laurel
Alcohol polyethenoxy ether-15, ten tetracosanol polyethenoxy ether-2, oleyl alcohol polyethenoxy ether-5 etc..
The present inventor studies EO, PO, glycerol radical amount in discovery Long carbon chain polyoxy hydroxy compounds affects thickening agent
Thickening effect, EO, PO, glycerol group can obtain preferably performance in the range of quantity is 2-10.
Simultaneously those skilled in the art by known technology it is recognised that the molecule of ethylene methacrylic ether/copolymer-maleic anhydride
Measuring the biggest, thickening effect is the most obvious, selects molecular weight ethylene methacrylic ether/copolymer-maleic anhydride more than 800,000 can obtain preferably
Effect, preferred molecular weight ethylene methacrylic ether/copolymer-maleic anhydride more than 1,000,000.Commercially available ethylene methacrylic ether/maleic anhydride
Copolymer has the Gantrez AN of ISP company and the SuperGel MM001 of Sinolion company, and molecular weight is from 10-800 ten thousand
Available.
Macromolecule thickener involved in the present invention has good acidproof salt resistant character.Generally thickening agent uses environment many
Containing various electrolyte, such as sodium chloride, potassium chloride, sulfate and other salts, this can cause thickening agent thickening properties to decline, city
Vender flows thickener products carbopol, and such as Carbomer 980, in the electrolyte of 0.5%, viscosity decrease beyond 70%, and this
The macromolecule thickener that invention relates to declines only 10-20%, and salt resistant character is substantially better than Carbomer 980.Thickening agent is applied
In formula, in the formula that personal nursing and furniture are nursed, its pH environment is often faintly acid, and pH value is generally at 4.0-6.0.
This is that the pH of formulation product and human body are closer to the gentleest owing to human body skin pH value is faintly acid.Additionally formulation product is anti-
Microbial inoculum, quaternary ammonium salt softener must the preferable performances of competence exertion in acid condition.Industrial if part dyeing and finishing process is in acid
Competence exertion dyestuff colorability under the conditions of property.Thickening agent acid resistance is claimed by the application in these fields, and the present invention relates to
And macromolecule thickener there is extraordinary acid resistance, its optimal thickening effect is between 4.5-6.5 at pH value, and passes
The pH scope of the system optimal thickening properties of thickening agent Carbomer 980 is 6.8-7.8.
Using different pH value regulator can obtain different thickening properties, usual pH value regulator is NaOH, KOH,
NH4OH, Na2CO3, K2CO3, triethanolamine (TEA) etc., or their mixture, can select according to different use environment
Select.
The present invention also provides for the preparation method of a kind of described macromolecule thickener, by common for methyl vinyl ether/maleic anhydride
With Long carbon chain polyoxy hydroxy compounds in the presence of a catalyst, in polar solvent, at 50-150 DEG C, esterification is anti-for polymers (PVM/MA)
The derivant of ethylene methacrylic ether/copolymer-maleic anhydride should be obtained, neutralize by pH value regulator further and obtain described derivant
Salt.
Described Long carbon chain polyoxy hydroxy compounds is selected from fatty alcohol-polyoxyethylene ether, fatty alcohol polyoxypropylene ether or fat
Acid polyglyceryl ether, or their mixture.
Applicant of the present invention finds Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) and Long carbon chain polyoxy hydroxyl
The proportioning of compound affects the thickening properties of end product, and this proportioning affects the esterification yield of described copolymer.The most each common
Acid homopolymer anhydride group can be combined with two hydroxy compounds, all combines, and esterification yield is 100%, but conjugation is at certain model
In enclosing, better performance could be obtained.In the preparation method that the present invention mentions, esterification yield is 10-50%, preferably 15-50%, more
Preferably esterification yield is 20-45%.Esterification yield can be many with Long carbon chain by Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA)
The proportioning of oxygen hydroxy compounds controls, it is contemplated that the conversion ratio of esterification is less than 100%, Long carbon chain polyoxy hydroxy compounds
Used in amounts to increase 5-10% in right amount, and its mol ratio adjusts on the basis of theoretical mol ratio accordingly.When esterification yield is 10-
50%, mole joining of corresponding Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) and Long carbon chain polyoxy hydroxy compounds
Ratio is 20-45% for 1:0.22～1:1.1, preferably esterification yield, corresponding Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA)
It is 1:0.44～1:0.99 with the mol ratio of Long carbon chain polyoxy hydroxy compounds.Product may contain Determining Micro Acid anhydride group
The impurity of group's double esterification, will not produce impact to product thickening property.When determining above-mentioned mol ratio, the molal quantity of polymer leads to
Refer to the molal quantity of contained monomer, it is therefore apparent that the Copolymer of Methyl Vinyl Ether/Maleic Anhydride mentioned in the present invention
(PVM/MA) mol ratio with Long carbon chain polyoxy hydroxy compounds refers to Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/
MA) monomer contained by and the mol ratio of Long carbon chain polyoxy hydroxy compounds.
The catalyst mentioned in preparation method of the present invention is selected from p-methyl benzenesulfonic acid, concentrated sulphuric acid, Sodium ethylate, Feldalat NM
Deng, catalyst amount is the 0.5wt%-6wt% of copolymer (PVM/MA)；The pH value regulator mentioned be selected from sodium hydroxide,
Sodium carbonate, potassium hydroxide, potassium carbonate, ammonia, triethanolamine, or their mixture；The polar solvent mentioned includes but does not limits
Yu Shui, dimethylformamide, acetone, butanone, toluene, butyl ether etc..
Described pH value regulator is NaOH, KOH, NH4OH, Na2CO3, K2CO3, triethanolamine (TEA) etc., or they
Mixture.
The invention still further relates to the application as rheology control agent of the described macromolecule thickener.
The macromolecule thickener that the present invention provides has the good characteristic of salt anti-acid, and mild low-stimulation, can be used for individual
People's nursing product, detergent or other industrial circle play thickening, suspension effect as rheology control agent.As can be used for cosmetics,
Shampoo, bath gel, cleansing milk, handwashing liquid, liquid detergent, softener formula etc., and other industrial circles.Consumption is formula weight
The 0.1-10% of amount, preferred consumption is 0.2-5%.
Beneficial effect: the macromolecule thickener of the present invention, is the Long carbon chain chemical combination selecting to contain in molecule multiple oxygen elements
Thing, reacts the derivant obtained or its salt with Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA), at certain esterification yield
In the range of, there is excellent thickening properties or effect, and described macromolecule thickener has good acidproof salt resistant character.Institute
The macromolecule thickener stated is in its structure, by anhydride with the monomer reaction of hydroxyl, introduces nonionic long-chain monomer, long
The structure of chain monomer has good shielding action to the hydrophilic group carboxyl on main chain, thus inhibits the electricity in water
Solution matter affects；And its intermolecular heat resistance and salt tolerance, macromolecular chain can be made to be cross-linked to form the spatial networks with some strength
Structure so that it is there is the biggest hydrodynamic volume and the strongest thickening capabilities.Methyl vinyl ether/Malaysia according to the present invention
The derivant of acid anhydride copolymer provides viscosity that can be suitable with carbopol, but salt tolerance and acid resistance are greatly improved；And it is gentle low
Stimulate, can be used for personal care articles, detergent or other industrial circle and play thickening power as rheology control agent.
Accompanying drawing explanation
The infrared spectrogram of PVM/MA polyoxyethylene lauryl ether-3 ester of Fig. 1 embodiment 1 preparation.
Fig. 2 difference pH adjusting agent and the pH value impact on viscosity.
Macromolecule thickener and Ka Bo thickening agent acid resistance prepared by Fig. 3 present invention compare.
Macromolecule thickener and Ka Bo thickening agent salt tolerance prepared by Fig. 4 present invention compare.
Detailed description of the invention
Below by embodiment, the present invention will be described in detail, and following example are to the technical scheme is that
Premise, instantiation representational to part gives detailed embodiment and concrete operating process, but the present invention
Protection domain be not limited to following embodiment.
The preparation of embodiment 1PVM/MA polyoxyethylene lauryl ether-3 ester
Weigh Copolymer of Methyl Vinyl Ether/Maleic Anhydride (PVM/MA) the SuperGel MM001 that mol ratio is 1:0.85
(molecular weight 1,500,000), lauryl alcohol polyethylene glycol oxide base ether (AEO-3) are dissolved in DMF, and solid-to-liquid ratio is 1g:
5mL, fully dissolves after stirring, is warming up to 80 DEG C, add catalyst p-methyl benzenesulfonic acid, methyl vinyl ether/maleic anhydride
Copolymer (PVM/MA), the mass ratio of catalyst are 1:0.05.Stop heating after reaction 60min, after being cooled to room temperature, pour ice into
In water, leach the solid ester of precipitation, wash with water and be dried.Test its infrared spectrogram and see Fig. 1.
In spectrogram 1, the characteristic absorption peak of raw material Copolymer of Methyl Vinyl Ether/Maleic Anhydride is 1840cm-1And 1770cm-1, it is two infrared absorption peaks of anhydride in copolymer.And the characteristic absorption peak of raw material A EO-3 be concentrated mainly on 1050～
1210cm-1, 1050cm-1The broad peak gone out is the stretching vibration peak of primary alconol, 1050～1210cm-1It it is then the feature antisymmetry of ether
Stretching vibration peak, two peaks collectively constitute one 1050～1210cm-1Broad peak.And methyl vinyl ether/maleic anhydride
Thing, two kinds of raw materials of AEO-3 are mainly through the characteristic absorption peak of the water soluble polymer thickening agent obtained by single-esterification
1730cm-1The stretching vibration peak of place's ester group, and in the anhydride in raw material, the characteristic absorption peak of ether disappears；Product is at 1050cm-1
The feature broad peak of place's primary alconol disappears, and the substitute is 1050～1210cm-1In place's AEO-3 long-chain, the feature antisymmetry of ether is stretched
Contracting vibration peak.Infrared spectrogram proves, the water soluble polymer thickening agent product of gained be expectation gained methyl vinyl ether/
The esterification products of copolymer-maleic anhydride.
Esterification yield can be measured in following manner:
Take described esterification products to titrate with standard caustic soda solution, with phenolphthalein as indicator, be titrated to redness, 30s
The most do not fade for titration end-point, the standard caustic soda solution volume V that record consumes1, the content of carboxyl in sample can be represented.
It is subsequently adding volume V2Standard caustic soda solution, adds pyrohydrolysis and keeps 1h, be titrated to hydrochloric acid standard solution red proper while hot
Till disappearance, record consumes hydrochloric acid standard solution volume V3.The esterification yield of reaction can be expressed as:
Wherein, y is the esterification yield of Copolymer of Methyl Vinyl Ether/Maleic Anhydride；C1Rubbing for standard solution of sodium hydroxide
That concentration；C2Molar concentration for hydrochloric acid standard solution.
The esterification products esterification yield of above-mentioned prepared Copolymer of Methyl Vinyl Ether/Maleic Anhydride is 40.5%.
Viscosity test: by the solid esterification product of above-mentioned preparation, dispersing and dissolving is in a certain amount of distilled water, and stirring is to fully
After mixing, it is slowly added dropwise pH value regulator solution regulation pH value of solution while stirring, after stirring fully, i.e. obtains thick liquid, record
Thick liquid viscosity is with the variation tendency of pH value.Test mass percent be liquid viscosity when 0.5% be ηWater.Preparation wt%
(Na2SO4) be 0.05% solution, take this solution and thickening agent be made into the former paste that wt% (thickening agent) is 0.5%, survey its viscosity,
It is designated as ηSalt, it is calculated as follows viscosity retention rate μ.Viscosity retention ratio more high product salt tolerance is the best.
μ=ηSalt/ηWater× 100%
Viscosimetric analysis uses the digital rotating cylinder viscometer of NDJ-5S, No. 3 rotors, rotating speed 6rpm.
Testing result is the esterification products of 0.5wt% concentration, is pH adjusting agent with sodium hydroxide, viscosity when pH value is 5.6
For 13200mPa.s, viscosity retention ratio 81.5%.
Embodiment 2-7
According to the preparation method of embodiment 1, choose different fatty alcohol-polyoxyethylene ether and prepare different with PVM/MA reaction
The product of esterification yield, the viscosity of detection product, the results are shown in Table 1.
The viscosity (concentration 0.5wt%) of the different esterification products of table 1
Embodiment 8-12
According to the preparation method of embodiment 1, choose different Long carbon chain polyoxy hydroxy compounds and PVM/MA reaction is prepared not
With the product of esterification yield, the viscosity of detection product, the results are shown in Table 2.
The viscosity (concentration 0.5wt%) of the different esterification products of table 2
Embodiment 13
According to the esterification products of embodiment 2 preparation under 0.5wt% concentration, use different pH adjusting agents and different pH value
Under, the viscosity results of detection is shown in Fig. 2..
Fig. 2 shows, by different pH adjusting agents, can obtain different viscosity under same concentrations, and sodium salt is relatively low, ammonium
Salt is higher than sodium salt viscosity, and triethanolamine salt then shows the most prominent, and high viscosity is up to 7.6 ten thousand mPa.s, has well increasing
Thick effect, meets or exceeds the thickening properties of main flow thickening agent Carbomer 980.
Embodiment 14
The product prepared according to embodiment 2 and commercially available prod Carbomer 980 are made into the concentration of 0.2wt%, at different pH
Under, viscosity measurements comparing result is shown in Fig. 3.
Fig. 3 shows, thickening effect is had a direct impact by pH value, and embodiment 2 prepares product preferably increasing under faintly acid
Thick effect, main flow thickening agent card ripple then has preferable thickening effect in neutrality to alkalescence.The acid increasing of product is prepared in explanation
Thick effect is better than main flow thickening agent carbopol.
Embodiment 15
It is made into 0.5wt% concentration, containing variable concentrations with commercially available prod Carbomer 980 according to the product of embodiment 2 preparation
Potassium chloride, viscosity measurements comparing result is shown in Fig. 4.
Fig. 4 shows, along with the raising of system salinity, the viscosity of carbopol thickening agent drastically declines, and prepared by embodiment 2
The viscosity of product decline relatively mild, show preferable anti-salt property.Owing to salt is present in all kinds of formula, thickening agent resists
Salt performance is the best, and practical application effect is the best.
Application in embodiment 16 low viscosity emulsion formulations
Being applied in milky lotion formula according to the product of embodiment 2 preparation, formula is as follows:
Product is emulsion, and viscosity is 3100mPa.s.
Application in embodiment 17 high viscosity cream formula
Being applied in facial cleaning cream formula according to the product of embodiment 10 preparation, formula is as follows:
| Raw material | Mass percent w/w |
| Coco betaine | 8.0 |
| Sodium cocoyl glycinate | 12.0 |
| Polyoxyethylene lauryl ether (9) | 10.0 |
| Ethylene glycol and stearate | 3.0 |
| Glycerol | 1.8 |
| Salicylic acid | 1.0 |
| Essence | 0.2 |
| Embodiment 10 product | 3.5 |
| Deionized water | Surplus |
Product is stiff paste, viscosity 33000mPa.s, and oily skin cleaning function is good.
Claims (12)
1. a macromolecule thickener, is derivant or its salt of ethylene methacrylic ether/copolymer-maleic anhydride, and formula is:
In formula,
M is cation,
R1For CH2, CH (CH3) and/or CH2(OH)CH2,
R2For alkyl that carbon chain lengths is 6-22 and/or alkanoyl,
X is 1-30,
The monomer of esterification and non-esterified monomer random arrangement, esterification yield is 10-50%, and described esterification yield is: n/ [2* (n+
M)] * 100%.
Macromolecule thickener the most according to claim 1, it is characterised in that M described in formula for H, Na, K, NH4Or N
(CH2CH2OH)3, or their mixture.
Macromolecule thickener the most according to claim 1, it is characterised in that the R described in formula2It is 12-for carbon chain lengths
The alkyl of 18 and/or alkanoyl.
Macromolecule thickener the most according to claim 1, it is characterised in that n+m described in formula is 5000-50000；x
For 2-10.
Macromolecule thickener the most according to claim 1, it is characterised in that the esterification yield of described derivant is 20-45%.
6. the preparation method of the macromolecule thickener described in claim 1, it is characterised in that by methyl vinyl ether/maleic acid
With Long carbon chain polyoxy hydroxy compounds in the presence of a catalyst, in polar solvent, at 50-150 DEG C, esterification obtains anhydride copolymer
To the derivant of ethylene methacrylic ether/copolymer-maleic anhydride, neutralize the salt obtaining described derivant further by pH value regulator.
The preparation method of macromolecule thickener the most according to claim 6, it is characterised in that described Long carbon chain polyoxy hydroxyl
Based compound is selected from fatty alcohol-polyoxyethylene ether, fatty acid polyglycol glycerin ether or fatty alcohol polyoxypropylene ether, or their mixing
Thing.
The preparation method of macromolecule thickener the most according to claim 6, it is characterised in that described methyl ethylene
Ether/copolymer-maleic anhydride is 1:0.22～1:1.1 with the mol ratio of Long carbon chain polyoxy hydroxy compounds.
The preparation method of macromolecule thickener the most according to claim 6, it is characterised in that described polar solvent is N, N-
Dimethylformamide, toluene, water, acetone, butanone or butyl ether.
The preparation method of macromolecule thickener the most according to claim 6, it is characterised in that described catalyst is to first
One in benzenesulfonic acid, concentrated sulphuric acid, Sodium ethylate, the consumption of catalyst is Copolymer of Methyl Vinyl Ether/Maleic Anhydride quality
0.5～6wt%.
The preparation method of 11. macromolecule thickeners according to claim 6, it is characterised in that described pH value regulator
For NaOH, KOH, NH4OH、Na2CO3、K2CO3Or triethanolamine, or their mixture.
Macromolecule thickener described in 12. claim 1 is as the application of rheology control agent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322799B1 (en) * | 1997-07-22 | 2001-11-27 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Benefit agent compositions comprising mixtures of α-hydroxy esters |
| US20110274641A1 (en) * | 2009-06-29 | 2011-11-10 | Inolex Investment Corporation | Non-Petrochemically Derived Cationic Emulsifiers That Are Neutralized Amino Acid Esters and Related Compositions and Methods |
-
2016
- 2016-06-02 CN CN201610383925.8A patent/CN106046233B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322799B1 (en) * | 1997-07-22 | 2001-11-27 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Benefit agent compositions comprising mixtures of α-hydroxy esters |
| US20110274641A1 (en) * | 2009-06-29 | 2011-11-10 | Inolex Investment Corporation | Non-Petrochemically Derived Cationic Emulsifiers That Are Neutralized Amino Acid Esters and Related Compositions and Methods |
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