CN106432706A - Novel self-emulsifying water-based polyester emulsion and preparation method thereof - Google Patents
Novel self-emulsifying water-based polyester emulsion and preparation method thereof Download PDFInfo
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- CN106432706A CN106432706A CN201610929738.5A CN201610929738A CN106432706A CN 106432706 A CN106432706 A CN 106432706A CN 201610929738 A CN201610929738 A CN 201610929738A CN 106432706 A CN106432706 A CN 106432706A
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- Prior art keywords
- acid
- polyester
- water
- butanediol
- emulsion
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- 229920000728 polyester Polymers 0.000 title claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000839 emulsion Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004945 emulsification Methods 0.000 title claims description 12
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 29
- 239000011734 sodium Substances 0.000 claims abstract description 29
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 29
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005886 esterification reaction Methods 0.000 claims abstract description 21
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- 150000001336 alkenes Chemical class 0.000 claims description 22
- 230000032050 esterification Effects 0.000 claims description 19
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 18
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 18
- 229960002703 undecylenic acid Drugs 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- IJTNSXPMYKJZPR-UHFFFAOYSA-N parinaric acid Chemical compound CCC=CC=CC=CC=CCCCCCCCC(O)=O IJTNSXPMYKJZPR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 claims description 3
- OSFGNTLIOUHOKN-UHFFFAOYSA-N 4-[benzyl(methyl)sulfamoyl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1S(=O)(=O)N(C)CC1=CC=CC=C1 OSFGNTLIOUHOKN-UHFFFAOYSA-N 0.000 claims description 3
- IJTNSXPMYKJZPR-WVRBZULHSA-N alpha-parinaric acid Natural products CCC=C/C=C/C=C/C=CCCCCCCCC(=O)O IJTNSXPMYKJZPR-WVRBZULHSA-N 0.000 claims description 3
- GZZPOFFXKUVNSW-UHFFFAOYSA-N dodec-11-enoic acid Chemical compound OC(=O)CCCCCCCCCC=C GZZPOFFXKUVNSW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 claims description 2
- NIONDZDPPYHYKY-UHFFFAOYSA-N Z-hexenoic acid Natural products CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- -1 carbon Olefin Chemical class 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000003995 emulsifying agent Substances 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 23
- 230000004044 response Effects 0.000 description 13
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 12
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical compound OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000000693 micelle Substances 0.000 description 12
- 238000006068 polycondensation reaction Methods 0.000 description 12
- 239000001119 stannous chloride Substances 0.000 description 12
- 235000011150 stannous chloride Nutrition 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 230000001804 emulsifying effect Effects 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-HWKANZROSA-N 2E-hexene Chemical compound CCC\C=C\C RYPKRALMXUUNKS-HWKANZROSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000007519 polyprotic acids Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides novel self-emulsifying water-based polyester emulsion and a preparation method thereof. The preparation method includes the following steps that itaconic acid, methyl-butanedioic acid-5-sodium sulfonate and 1,4-butanediol are subjected to condensation polymerization, then terminal hydroxyl water-based polyester-poly(itaconic acid butanediol-co-methyl-butanedioic acid-5-sodium sulfonate butanediol)ester (PBIINa) is obtained, and the PBIINa and terminal olefine acid are heated to 110-160 DEG C under nitrogen protection, and terminal olefine acid modified water-based polyester is obtained after an esterification reaction. The terminal olefine acid modified water-based polyester is dispersed in water, and then the water-based polyester emulsion is obtained. The preparation method of the water-based polyester emulsion is novel and has a self-emulsifying function, an emulsifying agent does not need to be added, organic solvent is not contained, and the water-based polyester emulsion can be used as emulsion coating and has broad market prospects. The steps are simple, operation is convenient, and practicability is high.
Description
Technical field
The invention belongs to water-based emulsion preparation field, particularly to the new self-emulsification aqueous polyester emulsion of one kind and its preparation
Method.
Background technology
With China's expanding economy, the yield of China's coating, already close to 10,000,000 tons, becomes global coating material production, disappears
Take the first big country.But presently used coating mostly is solvent based coating, VOC content is high, can cause in manufacture and work progress
The severe contamination of environment, and damage the healthy of the mankind.Along with the continuous enhancing of human environment protection consciousness, to environment
The research of friendly water paint and application are increasingly subject to people's attention, 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 to be divided as solvent or conduct with cheap and wide material sources water
The coating of dispersion media.Water paint is divided into water solublity and aqueous emulsion two big class.Water soluble paint is by water miscible molecular resin
Directly it is 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 emulsifying agent, and resin and emulsifying agent are the coating of film forming matter jointly.Wherein, water
, due to the presence of emulsifying agent, system poor storage stability, particle diameter is big, and gloss of film is poor for milkiness coating.Therefore, how to improve water and milk
Property paint stability, the use that emulsifying agent be reduced or avoided have important Research Significance.
Self-emulsification, hydrophilic segment or group are incorporated into the molecule of film forming matter by the reactivity mainly using group
On chain, the modified film forming matter of gained can form emulsion by self-dispersing without additional emulsifying agent in water.Although self-emulsification
Preparation process is more, relatively costly, but the particle being obtained in this way is thinner, usually nanoscale, and stability will
It is better than the emulsion that additional emulsifying agent method is obtained.Thus be more of practical significance.Patent CN103554509B discloses a kind of breast certainly
Change non-ion aqueous epoxy resin latex and preparation method thereof, the aqueous epoxy resin emulsion good stability that this invention obtains and
Nontoxic；Operating procedure is simple, and the water paint made has the characteristics that pliability, water-tolerant.Patent CN102585152B is certainly
The preparation method of emulsifying cation-type water-thinned polyurethane, only to contain the tertiary amino compounds of active function groups for hydrophilic work(
Self-emulsifying cation type aqueous polyurethane can be prepared by monomer, products obtained therefrom self emulsifying dispersion efficiency is high, has more superior performance.
As can be seen here, self emulsifying technology can overcome the harm of emulsifying agent in traditional water paint, effectively improves the performance of emulsion.
Polyester is to be esterified (or ester exchange) instead by polyacid component (or the corresponding ester of polyprotic acid) and polyol component
The resin containing a large amount of ester bonds that should obtain.The Water-borne modification technology of polyester is to introduce ionic groups in polyester molecule chain to make it
Possesses hydrophilic.Waterborne polyester has gloss height, adhesive force is strong, richness is high, resistance to impact is good, VOC emission amount is low excellent
Point, both can be configured to water-based stoving paint with water soluble amino resin it is also possible to be configured to room temperature with hydrophilic polyisocyanate
The water-borne wood coating of solidification.The comparison of the aqueous polyurethane of self emulsifying and epoxy resin research is abundant at present, the water of self emulsifying
Property polyester be used for coating report also less.Patent CN104231253B is related to a kind of preparation method of self emulsifying polyester, by etc.
Mole Polyethylene Glycol and binary acid occur esterification to generate Polyethylene Glycol dicarboxylic acid polyester after, then sealed with fatty acid
End, generates self emulsifying polyester, but this polyester is mainly for the preparation of micro lubricating agent.
Content of the invention
In order to overcome above-mentioned deficiency, the present invention provides a kind of new self-emulsification aqueous polyester emulsion and preparation method thereof, base
In hydroxyl telechelic polyester end-group functionality big, reactivity is high, the low advantage of viscosity, by the terminal hydroxy group of polyester grafting introduce
End olefin(e) acid, adjusts dispersibility and the automatic emulsifying performance of waterborne polyester by controlling reaction condition and rate of charge, is simultaneously introduced end
The double bond of olefin(e) acid increased the active group of film forming, can effectively improve the performance of film again.Prepare self-emulsification aqueous polyester at present
Emulsion correlational study report is less, and the raw materials used abundance of the present invention is easy to get, the complete environmental protection of water-based emulsion of preparation, does not contain
Machine solvent, and performance adjustability is interval 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 is as follows：
Wherein, x, y, n are the natural number more than zero.
In the present invention, " end olefin(e) acid " refers to containing CH2The general designation of the organic compound of=CH-R-COOH functional group.
Existing poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) although ester PBIINa have good
Good water solublity and environmental suitability, but it only has the side chain in itaconic acid in backbone molecule to carry double bond, and filming performance is poor, right
Matrix adhesive force is not good.For this reason, the present invention has carried out systematic study to multiple 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, with terminal hydroxy group, esterification occurs using carboxyl, reach closing end group
Effect, effectively prevent polarity terminal hydroxy group and attracts each other, adsorbs, absorbing the not good problem of the film forming characteristicss leading to.Simultaneously as
The double bond of leading-in end olefin(e) acid, makes modified PBIINa macromolecular chain end be double bond, increased density and the 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 described polyester is 2000-5000.
Preferably, the molecular weight distribution of described polyester is 1.10～1.95.
Present invention also offers a kind of preparation method of end olefin(e) acid modified water-soluble polyester, including：
With olefin(e) acid and poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester PBIINa as raw material,
Carry out esterification, obtain final product.
Filming performance after emulsion film forming is relevant with polyester components and structure, therefore, currently preferred olefin(e) acid and poly- (clothing
Health acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester PBIINa mol ratio be 0.07～0.15:1.Now,
The dispersibility of polyester and automatic emulsifying performance are optimal, and filming performance is good.
Preferably, described esterification condition is：Under inert gas shielding, react 1～5h in 110～160 DEG C.
Now there are some researches show：The end-blocking time of polyester typically in more than 5h, and in the present invention the preferred response time be 1～
5h.It is in addition to reacting with end-capping reagent, also mutually contrary between strand end group that this is primarily due to macromolecular chain end group during this period
Should, therefore reduce the carboxyl concentration of final product, acid number also just reduces therewith.In addition, research also finds：With regard to olefin(e) acid and poly-
For the reaction of (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester PBIINa, react 110～160
When carrying out at DEG C, can effectively reduce into the generation of the side reactions such as ether, anti-esterification, and guarantee the carboxyl in olefin(e) acid molecule and polyester
There is esterification in the terminal hydroxy group in molecule, play end-blocked effect.
Preferably, described olefin(e) acid is undecylenic acid, acrylic acid, 11- lauroleic acid, (Z) -2- decylenic acid, trans- 2- hexene
Acid, 2- phenylacrylic acid, parinaric acid, trans -3- hexenoic acid or POA.
Undecylenic acid be 1 stable not only containing double bond but also containing the compound with carboxyl, the polyester volume of its synthesis is received
Shrinkage is little, intensity is high, heat resistance is good, water absorption rate is low.And the neighbouring secondary carbon of the thiazolinyl functional group double bond in molecular structure
On hydrogen atom have an autoxidizable ability, give polyester air-drying property.Therefore, the preferred olefin(e) acid of the present invention is undecylenic acid.
Present invention also offers the end olefin(e) acid modified water-soluble polyester of the above-mentioned method preparation of any one.
Present invention also offers a kind of new self-emulsification aqueous polyester emulsion, including：The aqueouss of the above-mentioned polyester of any one
Solution, wherein, solid content is 10%～60%.
Present invention also offers the above-mentioned polyester of any one, application in preparing water paint for the polyester emulsion.
Beneficial effects of the present invention
(1) waterborne polyester emulsion preparation method of the present invention is novel, has self emulsifying function it is not necessary to add emulsifying
Agent, without organic solvent, can be used as aqueous emulsion coating, has wide market prospect.
(2) present invention is based on that hydroxyl telechelic polyester end-group functionality is big, reactivity is high, the low advantage of viscosity, 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, the double bond being simultaneously introduced end olefin(e) acid increased the active group of film forming, can effectively improve the performance of film again.At present
Prepare that self-emulsification aqueous polyester emulsion correlational study report is less, the raw materials used abundance of the present invention is easy to get, the aqueouss of preparation
The complete environmental protection of emulsion, without organic solvent, and performance adjustability is interval wide.
(3) preparation method of the present invention simple, practical it is easy to promote.
Brief description
Fig. 1 is the FTIR spectrum figure of polyester PBIINa-UA.
Fig. 2 is polyester PBIINa-UA's1H-NMR schemes.
Specific embodiment
By the following examples feature of present invention and other correlated characteristic are described in further detail, in order to the same industry
The understanding of technical staff：
Embodiment 1
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
Undecylenic acid, addition is the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reaction simultaneously strong agitation 1 hours,
Can get the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion, the emulsion surface tension test recording
The results are shown in Table 1.Critical micelle concentration is 4.6*10^-5g/L.
Embodiment 2
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
PBIINa to terminal hydroxy group.Deca undecylenic acid thereto, addition is the 7% of Isosorbide-5-Nitrae butanediol mole, in nitrogen protection
Under, 110 DEG C of reaction simultaneously strong agitation 5 hours, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to
Emulsion, the emulsion surface tension test result recording is shown in Table 1.Critical micelle concentration is 2.615*10^-5g/L.
Embodiment 3
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
PBIINa to terminal hydroxy group.Deca undecylenic acid thereto, addition is the 15% of Isosorbide-5-Nitrae butanediol mole, in nitrogen protection
Under, 140 DEG C of reaction simultaneously strong agitation 4 hours, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to
Emulsion, the emulsion surface tension test result recording is shown in Table 1.Critical micelle concentration is 2.255*10^-5g/L.
Embodiment 4
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
Acrylic acid, addition is the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reaction simultaneously strong agitation 1 hours, that is,
Can get the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is 4.6*10^-5g/
L.
Embodiment 5
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
11- lauroleic acid, addition be Isosorbide-5-Nitrae butanediol mole 10%, under nitrogen protection, 160 DEG C reaction and strong agitation 1 little
When, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is 4.5*10
^-5g/L.
Embodiment 6
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
(Z) -2- decylenic acid, addition is the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reaction simultaneously strong agitation 1
Hour, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is
4.32*10^-5g/L.
Embodiment 7
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
Trans- 2- hexenoic acid, addition be Isosorbide-5-Nitrae butanediol mole 10%, under nitrogen protection, 160 DEG C reaction and strong agitation 1 little
When, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is 4.5*10
^-5g/L.
Embodiment 8
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
2- phenylacrylic acid, addition is the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reaction simultaneously strong agitation 1
Hour, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is 4.7*
10^-5g/L.
Embodiment 9
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
Parinaric acid, addition is the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reaction simultaneously strong agitation 1
Hour, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is 4.6*
10^-5g/L.
Embodiment 10
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
Trans -3- hexenoic acid, addition is the 10% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 160 DEG C of reaction simultaneously strong agitation 1
Hour, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is 4.1*
10^-5g/L.
Embodiment 11
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
Poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester (PBIINa) to terminal hydroxy group.Deca thereto
POA, addition is the 7% of Isosorbide-5-Nitrae butanediol mole, under nitrogen protection, 110 DEG C of reaction simultaneously strong agitation
1 hour, you can obtain the modified polyester of undecylenic acid.This polyester is added to the water and is configured to emulsion.Critical micelle concentration is
4.6*10^-5g/L.
Comparative example
Mol ratio is 1：0.2：1.25 methylene-succinic acid, dimethyl succinic acid -5- sodium sulfonate and BDO are put
In 250ml four-hole boiling flask, and add catalyst stannous chloride, its addition is the 0.18% of methylene-succinic acid quality, connects
Upper water knockout drum, thermometer and agitator, are warming up to 180 DEG C and strong agitation under nitrogen protection, when no longer there being water in water knockout drum
During generation, esterification terminates, and is then cooled to 160 DEG C, is decompressed to -0.1Mpa and carries out polycondensation reaction, 3 hours response time.?
PBIINa to terminal hydroxy group.This polyester is added to the water and is configured to emulsion, the emulsion surface tension test result recording is shown in Table 1.
Critical micelle concentration is 1.2445*10^-4g/L.
By embodiment and comparative example contrast, the surface tension of the polyester being obtained in embodiment is superior to comparative example.
The surface tension of table 1 aqueous polyester emulsion
Continued
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to this
Bright, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it is still
Technical scheme described in previous embodiment can be modified, or to wherein partly carrying out equivalent.All at this
Within bright spirit and principle, any modification, equivalent substitution and improvement made etc., should be included in protection scope of the present invention
Within.Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to the scope of the present invention
Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to
Various modifications that creative work to be paid can be made or deformation are still within protection scope of the present invention.
Claims (10)
1. a kind of end olefin(e) acid modified water-soluble polyester is it is characterised in that structural formula is as follows：
Wherein, x, y, n are the natural number more than zero.
2. polyester as claimed in claim 1 is it is characterised in that the number-average molecular weight of described polyester is 2000-5000.
3. polyester as claimed in claim 1 is it is characterised in that the molecular weight distribution of described polyester is 1.10～1.95.
4. a kind of preparation method of end olefin(e) acid modified water-soluble polyester is it is characterised in that include：
, carried out with olefin(e) acid and poly- (itaconic acid butanediol-co- dimethyl succinic acid -5- sodium sulfonate butanediol) ester PBIINa as raw material
Esterification, obtains final product.
5. method as claimed in claim 4 is it is characterised in that described olefin(e) acid and poly- (itaconic acid butanediol-co- methyl fourth two
Acid -5- sodium sulfonate butanediol) ester PBIINa mol ratio be 0.07～0.15:1.
6. method as claimed in claim 4 is it is characterised in that described esterification condition is：Under inert gas shielding, in
110～160 DEG C of reaction 1～5h.
7. method as claimed in claim 4 it is characterised in that described olefin(e) acid be undecylenic acid, acrylic acid, 11- lauroleic acid,
(Z) -2- decylenic acid, trans- 2- hexenoic acid, 2- phenylacrylic acid, parinaric acid, trans -3- hexenoic acid or cis- 9- 16 carbon
Olefin(e) acid.
8. the end olefin(e) acid modified water-soluble polyester of the method preparation described in any one of claim 4-7.
9. a kind of new self-emulsification aqueous polyester emulsion is it is characterised in that include：Claim 1-3,8 arbitrary described polyester
Water-based emulsion, wherein, solid content be 10%～60%.
10. claim 1-3,8 arbitrary described polyester, or the polyester emulsion described in claim 9 is in preparing water paint
Application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484891A (en) * | 2018-03-12 | 2018-09-04 | 吉林乾仁新材料有限公司 | The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application |
| CN111848937A (en) * | 2020-07-30 | 2020-10-30 | 浙江大学 | Biodegradable polyester with high gas barrier property and preparation method and application thereof |
| CN113105607A (en) * | 2021-04-09 | 2021-07-13 | 青岛科技大学 | Self-repairing polyurethane cross-linked network containing UPy side chain, preparation method and application |
| CN113789147A (en) * | 2021-08-23 | 2021-12-14 | 山西华傲工贸集团有限公司 | Double-component neoprene polyurethane composite rubber adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-10-31 CN CN201610929738.5A patent/CN106432706B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484891A (en) * | 2018-03-12 | 2018-09-04 | 吉林乾仁新材料有限公司 | The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application |
| CN111848937A (en) * | 2020-07-30 | 2020-10-30 | 浙江大学 | Biodegradable polyester with high gas barrier property and preparation method and application thereof |
| CN113105607A (en) * | 2021-04-09 | 2021-07-13 | 青岛科技大学 | Self-repairing polyurethane cross-linked network containing UPy side chain, preparation method and application |
| 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 |
| CN113789147A (en) * | 2021-08-23 | 2021-12-14 | 山西华傲工贸集团有限公司 | Double-component neoprene polyurethane composite rubber adhesive and preparation method thereof |
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