CN106432706B - A kind of self-emulsification aqueous polyester emulsion and preparation method thereof - Google Patents
A kind of self-emulsification aqueous polyester emulsion and preparation method thereof Download PDFInfo
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- CN106432706B CN106432706B CN201610929738.5A CN201610929738A CN106432706B CN 106432706 B CN106432706 B CN 106432706B CN 201610929738 A CN201610929738 A CN 201610929738A CN 106432706 B CN106432706 B CN 106432706B
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
The present invention provides a kind of self-emulsification aqueous polyester emulsions and preparation method thereof, include the following steps：By itaconic acid, 5 sodium sulfonate of dimethyl succinic acid, 1; 4 butanediols obtain terminal hydroxy group waterborne polyester through polycondensation reaction --- and poly- (5 sodium sulfonate butanediol of itaconic acid butanediol co dimethyl succinic acids) ester (PBIINa) is warming up to 110~160 DEG C under nitrogen protection with end olefin(e) acid; esterification is carried out, obtains end olefin(e) acid modified water-soluble polyester.The waterborne polyester that olefin(e) acid is held to be modified is dispersed in water, obtains waterborne polyester lotion.Waterborne polyester emulsion preparation method of the present invention is novel, has the function of self-emulsifying, does not need to add in emulsifier, without organic solvent, can be used as aqueous emulsion coating, have a vast market prospect.Step is simple and convenient to operate, is highly practical.
Description
Technical field
The invention belongs to water-based emulsion preparation field, more particularly to a kind of self-emulsification aqueous polyester emulsion and its preparation side
Method.
Background technology
With China's expanding economy, the yield of China's coating becomes global coating material production, disappears already close to 10,000,000 tons
Take the first big country.But presently used coating is mostly solvent based coating, and VOC content is high, is manufacturing and can caused in work progress
The serious pollution of environment, and damage the health of the mankind.Along with the continuous enhancing that human environment protection is realized, to environment
The research of friendly water paint and application are increasingly valued by people, and the solidification of coating, solvent free, Water-borne modification are
In development trend.
Water paint is a kind of environment-friendly type coating, is divided by the use of water that is cheap and deriving from a wealth of sources as solvent or conduct
The coating of dispersion media.Water paint is divided into water-soluble and two major class of aqueous emulsion.Water soluble paint is by water-soluble molecular resin
It is directly dissolved or dispersed in water, using water-soluble resin molecule as the coating of main film forming substance；Aqueous emulsion coating refers to set
Fat molecule is dispersed in water by way of additional emulsifier, and resin and emulsifier are jointly the coating of film forming matter.Wherein, water
Milkiness coating is due to the presence of emulsifier, and system poor storage stability, grain size is big, and gloss of film is poor.Therefore, how water and milk is improved
Property paint stability, be reduced or avoided emulsifier use have important research significance.
Hydrophilic segment or group are mainly introduced into the molecule of film forming matter by self-emulsification using the reactivity of group
On chain, the modification film forming matter of gained do not have to additional emulsifier can self-dispersing lotion is formed in water.Although self-emulsification
Preparation process is more, and cost is higher, but particle obtained is thinner in this way, usually nanoscale, and stability will
It is better than lotion made from additional emulsifier method.Thus more it is of practical significance.Patent CN103554509B discloses a kind of from breast
Change non-ion aqueous epoxy resin latex and preparation method thereof, the aqueous epoxy resin emulsion stability which obtains it is good and
It is nontoxic；Operating procedure is simple, and manufactured water paint has the characteristics that flexibility, water-tolerant.Patent CN102585152B is certainly
The preparation method of cation-type water-thinned polyurethane is emulsified, to contain only the tertiary amino compounds of an active function groups as hydrophily work(
Energy monomer prepares self-emulsifying cation type aqueous polyurethane, and products obtained therefrom self-emulsifying dispersion efficiency is high, has more superior performance.
It can be seen that self-emulsifying technology can overcome the harm of emulsifier in traditional water paint, the performance of lotion is effectively improved.
Polyester is to be esterified (or transesterification) instead by polyacid component (or the corresponding ester of polyacid) and polyol component
The resin containing a large amount of ester bonds that should be obtained.The Water-borne modification technology of polyester is to introduce ionic groups in polyester molecule chain to make it
Has hydrophily.Waterborne polyester has that gloss height, strong adhesive force, richness height, that impact resistance is good, VOC emission amount is low etc. is excellent
Point both can be configured to water-based stoving paint with water soluble amino resin, and can also be configured to room temperature with hydrophilic polyisocyanate
Cured water-borne wood coating.The comparison of the aqueous polyurethane of self-emulsifying and epoxy resin research at present is abundant, the water of self-emulsifying
Property polyester for coating report it is also less.Patent CN104231253B is related to a kind of preparation method of self-emulsifying polyester, by etc.
Mole polyethylene glycol and binary acid esterification generation polyethylene glycol dicarboxylic acid polyester occurs after, then sealed with aliphatic acid
End generates self-emulsifying polyester, but the polyester is mainly for the preparation of micro lubricating agent.
Invention content
In order to overcome above-mentioned deficiency, the present invention provides a kind of self-emulsification aqueous polyester emulsion and preparation method thereof, based on end
The advantages such as hydroxyl polyester end-group functionality is big, reactivity is high, viscosity is low, by being grafted leading-in end alkene on the terminal hydroxy group of polyester
Acid, by the way that reaction condition and rate of charge is controlled to adjust the dispersibility and automatic emulsifying performance of waterborne polyester, while leading-in end olefin(e) acid
Double bond increase the active group of film forming, and the performance of film can be effectively improved.Self-emulsification aqueous polyester emulsion is prepared at present
Correlative study report is less, and the raw materials used in the present invention abundance is easy to get, and the water-based emulsion of preparation is completely environmentally friendly, without organic molten
Agent, and performance adjustability section is wide.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of end olefin(e) acid modified water-soluble polyester, structural formula are as follows：
Wherein, x, y, n are the natural number more than zero.
" end olefin(e) acid " refers to containing CH in the present invention2The general designation of the organic compound of=CH-R-COOH functional groups.
Existing poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) although ester PBIINa have it is good
Good water solubility and environmental suitability, but it only has the side chain of itaconic acid in backbone molecule to carry double bond, and filming performance is poor, right
Matrix adhesive force is bad.For this purpose, the present invention has carried out system research to a variety of PBIINa graft-modification methods and experiment is groped, carry
Go out：Leading-in end olefin(e) acid is grafted on the terminal hydroxy group of polyester, esterification occurs using carboxyl and terminal hydroxy group, reaches closing end group
Effect, effectively prevent polarity terminal hydroxy group attract each other, adsorb, absorb caused by film forming characteristics it is bad the problem of.Simultaneously as
The double bond of leading-in end olefin(e) acid, it is double bond to make modified PBIINa macromolecular chains end, increases the density and activity of film forming
Radical amount effectively increases the performance of film, significantly reduces the deblocking temperature of PBIINa.
Preferably, the number-average molecular weight of the polyester is 2000-5000.
Preferably, the molecular weight distribution of the polyester is 1.10~1.95.
The present invention also provides a kind of preparation method of end olefin(e) acid modified water-soluble polyester, including：
Using olefin(e) acid and poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester PBIINa as raw material,
Carry out esterification to get.
Filming performance after emulsion film forming is related with polyester components and structure, therefore, currently preferred olefin(e) acid and poly- (clothing
Health acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester PBIINa molar ratio be 0.07~0.15:1.At this point,
The dispersibility and automatic emulsifying performance of polyester are best, and filming performance is good.
Preferably, the esterification condition is：Under inert gas shielding, 1~5h is reacted in 110~160 DEG C.
It is existing research shows that：The sealing end time of polyester generally in more than 5h, and in the present invention the preferred reaction time for 1~
5h.This be primarily due to during this period macromolecular chain end group in addition to other than blocking agent reaction, it is also mutually opposite between strand end group
Should, therefore the carboxyl concentration of final product is reduced, acid value also just reduces therewith.In addition, research also found：With regard to olefin(e) acid and gather
For the reaction of (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester PBIINa, react 110~160
When being carried out at DEG C, the generation of the side reactions such as ether, anti-esterification can be effectively reduced into, and ensures carboxyl and polyester in olefin(e) acid molecule
Esterification occurs for the terminal hydroxy group in molecule, plays end-blocked effect.
Preferably, the olefin(e) acid for undecenoic acid, acrylic acid, 11- lauroleic acids, (Z) -2- decylenic acids, trans- 2- hexenes
Acid, 2- phenylacrylic acids, parinaric acid, trans- -3- hexenoic acids or cis-9-hexadecenoic acid.
Undecenoic acid is 1 stable not only containing double bond but also containing the compound with carboxyl, and the polyester volume of synthesis is received
Shrinkage is small, intensity is high, heat resistance is good, water absorption rate is low.And the secondary carbon that alkenyl functional group double bond in molecular structure is neighbouring
On hydrogen atom have an autoxidizable ability, assign polyester air-drying property.Therefore, the preferred olefin(e) acid of the present invention is undecenoic acid.
The present invention also provides end olefin(e) acid modified water-soluble polyester prepared by the above-mentioned method of any one.
The present invention also provides a kind of self-emulsification aqueous polyester emulsion, including：The aqueous solution of the above-mentioned polyester of any one,
Wherein, solid content is 10%~60%.
The present invention also provides the above-mentioned polyester of any one, application of the polyester emulsion in water paint is prepared.
Beneficial effects of the present invention
(1) waterborne polyester emulsion preparation method of the present invention is novel, has the function of self-emulsifying, does not need to add in emulsification
Agent without organic solvent, can be used as aqueous emulsion coating, have a vast market prospect.
(2) the present invention is based on the advantages such as hydroxyl telechelic polyester end-group functionality is big, reactivity is high, viscosity is low, by poly-
Leading-in end olefin(e) acid is grafted on the terminal hydroxy group of ester, by control reaction condition and rate of charge adjust waterborne polyester dispersibility and from
Emulsifiability, while the double bond of leading-in end olefin(e) acid increases the active group of film forming, and can effectively improve the performance of film.At present
Prepare that self-emulsification aqueous polyester emulsion correlative study report is less, and the raw materials used in the present invention abundance is easy to get, preparation it is aqueous
Lotion is completely environmentally friendly, and without organic solvent, and performance adjustability section is wide.
(3) preparation method of the present invention is simple, highly practical, easy to spread.
Description of the drawings
Fig. 1 is the FTIR spectrum figure of polyester PBIINa-UA.
Fig. 2 is polyester PBIINa-UA's1H-NMR schemes.
Specific embodiment
Feature of present invention and other correlated characteristics are described in further detail by the following examples, in order to the same industry
The understanding of technical staff：
Embodiment 1
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
Undecenoic acid, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C are reacted and stirred 1 hour strongly,
It can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion, the lotion surface tension test measured
It the results are shown in Table 1.Critical micelle concentration is 4.6*10^-5g/L.
Embodiment 2
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To the PBIINa of terminal hydroxy group.Undecenoic acid is added dropwise thereto, addition is the 7% of Isosorbide-5-Nitrae butanediol mole, is protected in nitrogen
Under, 110 DEG C are reacted and stirred 5 hours strongly, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to
Lotion, the lotion surface tension test result measured are shown in Table 1.Critical micelle concentration is 2.615*10^-5g/L.
Embodiment 3
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To the PBIINa of terminal hydroxy group.Undecenoic acid is added dropwise thereto, addition is the 15% of Isosorbide-5-Nitrae butanediol mole, is protected in nitrogen
Under, 140 DEG C are reacted and stirred 4 hours strongly, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to
Lotion, the lotion surface tension test result measured are shown in Table 1.Critical micelle concentration is 2.255*10^-5g/L.
Embodiment 4
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
Acrylic acid, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reactions and strongly stirring 1 hour, i.e., and
It can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is 4.6*10^-5g/
L。
Embodiment 5
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
11- lauroleic acids, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C of reactions and strongly stirring 1 are small
When, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is 4.5*10
^-5g/L。
Embodiment 6
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
(Z) -2- decylenic acids, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C are reacted and stirred strongly 1
Hour, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is
4.32*10^-5g/L。
Embodiment 7
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
Trans- 2- hexenoic acids, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C of reactions and strongly stirring 1 are small
When, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is 4.5*10
^-5g/L。
Embodiment 8
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
2- phenylacrylic acids, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C are reacted and stirred strongly 1
Hour, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is 4.7*
10^-5g/L。
Embodiment 9
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
Parinaric acid, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C are reacted and stirred strongly 1
Hour, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is 4.6*
10^-5g/L。
Embodiment 10
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
Trans- -3- hexenoic acids, addition are the 10% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 160 DEG C are reacted and stirred strongly 1
Hour, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is 4.1*
10^-5g/L。
Embodiment 11
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester (PBIINa) of terminal hydroxy group.It is added dropwise thereto
Cis-9-hexadecenoic acid, addition are the 7% of Isosorbide-5-Nitrae butanediol mole, and under nitrogen protection, 110 DEG C are reacted and stirred strongly
1 hour, you can obtain the polyester of undecenoic acid modification.The polyester is added to the water and is configured to lotion.Critical micelle concentration is
4.6*10^-5g/L。
Comparative example
It is 1 by molar ratio：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonates and 1,4-butanediol are put
In 250ml four-hole boiling flasks, and catalyst stannous chloride is added in, addition is the 0.18% of methylene-succinic acid quality, is connect
Upper water knockout drum, thermometer and blender are warming up to 180 DEG C and stir strongly under nitrogen protection, when there is no water in water knockout drum
Esterification terminates during generation, is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours reaction time.
To the PBIINa of terminal hydroxy group.The polyester is added to the water and is configured to lotion, the lotion surface tension test result measured is shown in Table 1.
Critical micelle concentration is 1.2445*10^-4g/L.
It is compared by embodiment and comparative example it is found that the surface tension of polyester obtained is superior to comparative example in embodiment.
The surface tension of 1 aqueous polyester lotion of table
Continued
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to the technical solution recorded in previous embodiment or equivalent replacement is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (10)
1. a kind of end olefin(e) acid modified water-soluble polyester, which is characterized in that structural formula is as follows：
Wherein, x, y, n are the natural number more than zero.
2. polyester as described in claim 1, which is characterized in that the number-average molecular weight of the polyester is 2000-5000.
3. polyester as described in claim 1, which is characterized in that the molecular weight distribution of the polyester is 1.10~1.95.
4. a kind of preparation method of end olefin(e) acid modified water-soluble polyester, which is characterized in that including：
Using olefin(e) acid and poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonates butanediol) ester PBIINa as raw material, carry out
Esterification to get.
5. method as claimed in claim 4, which is characterized in that the olefin(e) acid and poly- (itaconic acid butanediol-co- methyl fourth two
Acid -5- sodium sulfonates butanediol) ester PBIINa molar ratio be 0.07~0.15:1.
6. method as claimed in claim 4, which is characterized in that the esterification condition is：Under inert gas shielding, in
110~160 DEG C of 1~5h of reaction.
7. method as claimed in claim 4, which is characterized in that the olefin(e) acid is undecenoic acid, acrylic acid, 11- lauroleic acids,
(Z) -2- decylenic acids, trans- 2- hexenoic acids, 2- phenylacrylic acids, parinaric acid, 16 carbon of trans- -3- hexenoic acids or cis- 9-
Olefin(e) acid.
8. end olefin(e) acid modified water-soluble polyester prepared by claim 4-7 any one of them method.
9. a kind of self-emulsification aqueous polyester emulsion, which is characterized in that including：The water of claim 1-3,8 any polyester
Property lotion, wherein, solid content be 10%~60%.
10. the polyester emulsion described in claim 1-3,8 any polyester or claim 9 is in water paint is prepared
Application.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610929738.5A CN106432706B (en) | 2016-10-31 | 2016-10-31 | A kind of self-emulsification aqueous polyester emulsion and preparation method thereof |
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| CN201610929738.5A CN106432706B (en) | 2016-10-31 | 2016-10-31 | A kind of self-emulsification aqueous polyester emulsion and preparation method thereof |
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| CN111848937B (en) * | 2020-07-30 | 2021-06-29 | 浙江大学 | Biodegradable polyester with high gas barrier property and preparation method and application thereof |
| CN113105607B (en) * | 2021-04-09 | 2022-04-22 | 青岛科技大学 | Self-repairing polyurethane cross-linked network containing UPy side chain, preparation method and application |
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| CN1185452A (en) * | 1996-12-18 | 1998-06-24 | 韦特科公司 | Functional group dead-end polymer containing sulfonation group and polymerized through sulfonation monomer |
| CN103936975A (en) * | 2014-05-07 | 2014-07-23 | 中国科学院化学研究所 | Sulfonate-anion-functionalized biodegradable polyester and preparation method thereof |
| CN105669959A (en) * | 2015-06-06 | 2016-06-15 | 青岛科技大学 | Water-soluble polyester and preparation method thereof |
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| CN1185452A (en) * | 1996-12-18 | 1998-06-24 | 韦特科公司 | Functional group dead-end polymer containing sulfonation group and polymerized through sulfonation monomer |
| CN103936975A (en) * | 2014-05-07 | 2014-07-23 | 中国科学院化学研究所 | Sulfonate-anion-functionalized biodegradable polyester and preparation method thereof |
| CN105669959A (en) * | 2015-06-06 | 2016-06-15 | 青岛科技大学 | Water-soluble polyester and preparation method thereof |
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