CN106397754A - Hydrophilic cationic modified polyester and preparation method thereof - Google Patents
Hydrophilic cationic modified polyester and preparation method thereof Download PDFInfo
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- CN106397754A CN106397754A CN201610774808.4A CN201610774808A CN106397754A CN 106397754 A CN106397754 A CN 106397754A CN 201610774808 A CN201610774808 A CN 201610774808A CN 106397754 A CN106397754 A CN 106397754A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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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
- C08G63/78—Preparation processes
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- Polymers & Plastics (AREA)
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- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention relates to a cationic modified polyester synthesized from polyol and polybasic acid and a preparation method thereof. By weight, the formula involves: 0-20 parts of polyhydric alcohol, 5-14 parts of polybasic acid, 30-100 parts of polyol, 0-30 parts of polyester, 0-15 parts of a surfactant, 5-20 parts of polyamine, and 20-40 parts of water. As the mixed stain of hydrophilic cationic modified polyester, polyol improves the solubility of modified polyester in an aqueous solution. The hydrophilic polyester prepared by the method provided by the invention has uniformly distributed hydrophilic functional groups, high molecular weight and strong water solubility, and can be used individually or compounded with other surfactants for use.
Description
Technical field
The invention belongs to chemical technology field, specifically, it is by cation-modified waterborne polyester and preparation method thereof.
Background technology
Hydrophilic polyester is increasingly widely used in printing and dyeing, washes and other due to having solvent-free pollution-free biological degraded
Field.Main hydrophilic polyester is all non-ionic currently on the market, although this polyester has hydrophily, certain molecule
The polyester water solubility of amount is not high, and solubility is very low, in-convenience in use, and its aqueous solution short life, long-time president Mucor change.
The primary synthetic methods of hydrophilic cationic modified poly ester are various polyalcohols or amine and polyacid addition polymerization, so
Dissolve in water afterwards.And polyester is the most universal and most important polyalcohol.When with polyester as polyalcohol, due to polyester itself
For hydrophobic, when molecular weight of polyesters is larger, it is greater than 5000 dalton, the waterborne polyester being synthesized by it is unstable, if
Increase hydrophilic group polyalcohols consumption, partly can improve stability of solution, but when polyester ratio also increases, solution is still unstable.
With water-soluble or water-dispersible polyester, hydrophilic sexual function base is distributed on whole polyester macromolecule chain by equal, thus holding very much
Easily it is dispersed in water, its bath life is just greatly enhanced.
Content of the invention
It is an object of the invention to provide a kind of cation-modified hydrophilic polyester and preparation method thereof, to overcome existing product
Disadvantages mentioned above existing for product and deficiency.The cationic hydrophilic polyester of the present invention in the case of certain molecular weight, the water of polyester
Dissolubility greatly improves, and solubility increases at least more than 1 times, and because containing cationic group, fungus and mildew resistance becomes, and increases the aqueous solution
Life-span.
Hydrophilic cationic modified poly ester of the present invention is it is characterised in that according to weight portion base, its formula includes
Material name：
Polyalcohol 0～20
Polyacid 5～14
Polyalcohols 30～100
Polyester 0～30
Surfactant 0～15
Polyamines 5～20
Water 20～40
Wherein above-mentioned polyalcohol is ethylene glycol, diethylene glycol, Isosorbide-5-Nitrae _ butanediol, isoprene, 1,6_ cyclohexane diol, season penta
Tetrol, one kind of trimethylolethane or any combination, polyalcohol includes polyester 0～30.Above-mentioned polyester is poly- right further
PET PET, one kind of polybutylene terephthalate (PBT) PBT or any combination.
Wherein above-mentioned polyacid is p- phthalic acid, m- phthalic acid, adipic acid, phthalic anhydride, inclined acid anhydride, one kind of citric acid
Or any combination,
Wherein above-mentioned polyalcohols is polyethylene glycol, polypropylene glycol, PolyTHF and their EVA, such as PEG1000-
8000.
Wherein above-mentioned water is deionized water.
Wherein above-mentioned polyamines is triethylamine diethylamine, N.N-2 Propylene Glycol amine, triethanolamine, diethanol amine, diethyl
One or more combinations of alkene triamine etc. polyamines.
A kind of preparation method of cation-modified hydrophilic polyesters is it is characterised in that comprise the following steps：
（a）In container, stirring motor, condenser and condensation water collector, nitrogen tube and temperature controller are installed, then distinguish
Add polyalcohol, polyacid, polyalcohols, polyester, polyamines, be warming up to 180-260 °C, react and be less than 10 to acid number；
（b）It is cooled to less than 100 °C, according to viscosity situation, appropriate addition part surface activating agent 0～15
（c）Load weighted deionized water is slowly added in container, stirring had both become the homogeneous transparent aqueous solution in a moment.
Two stages of above-mentioned steps (a) point：
(al) stirring motor, condenser and condensation water collector, nitrogen tube and temperature controller are installed in a reservoir, are initially charged
Polyalcohol is warming up to 240-300 °C and reacts and comprises 0 50 parts of polyester to the above-mentioned polyalcohol of no solid particle；
(a2) it is subsequently adding polyacid, polyamine, hydrophilic monomer, react at 180-260 °C and be less than 10 to acid number.
Beneficial effects of the present invention：
Due to there being the cation-modified hydrophilic polyester obtained by the present invention hydrophile function base all can be distributed, can be in water
Can be prepared by high molecular weight polyesters, such that it is able to super high molecular weight waterborne polyester be prepared by the present invention so as to bonding is strong before dispersion
Degree improves, and emphasizes all to improve.Aqueous polyester used by the present invention is that have polyamines, polyalcohol, polyacid polycondensation to form, and polyester etc.
Synthesis has water solubility or the waterborne polyester of water dispersible energy.
Cationic hydrophilic polyester hydrophile function base due to present invention preparation is evenly distributed, and molecular weight is high, and adhesion strength is high.
This waterborne polyester can individually or with other surfaces activating agent etc. be used in mixed way in printing and dyeing or washing field, has cost
Low, effect is good, the characteristic such as biodegradation environmental protection is pollution-free, the developing direction of green product after being.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is made with a step explanation invention not for restriction the scope of the present invention.Should
Understand, following examples are merely to illustrate the experimental technique of unreceipted actual conditions in this following example, generally according to routine
Condition, or manufacturer provide condition carry out
The cation-modified hydrophilic polyesters of embodiment 1, in parts by weight, it is filled a prescription as material name part diethylene glycol 3.18
Polyethylene glycol PEG-4000 32.4 polyethylene terephthalate, 10.8 adipic acid 3.24 N, N-hydroxyethyl-ethylenediamine 4.3
AEO AEO-3 8.5 water 37.5.On 250ml milliliter four-hole boiling flask, stirring motor, condenser are installed
And condensation water collector, nitrogen tube and temperature controller, it is subsequently adding diethylene glycol, polyethylene glycol PEG-4000, gather to benzene two
Formic acid glycol ester is warming up to 240-300 °C and reacts to no solid particle, addition adipic acid, N, N-hydroxyethyl-ethylenediamine,
180-260 °C is reacted to acid number less than 10, is cooled to 100 °C, after adding AEO AEO-3 to stir, delays
Slowly add water, stirring became sub-translucent cation-modified hydrophilic polyesters solution after 30 minutes.
The cation-modified hydrophilic polyesters of embodiment 2, in parts by weight, it is filled a prescription as material name part ethylene glycol
3.18 polyethylene glycol PEG-4000,32.4 polyethylene terephthalate, 10.8 terephthalic acid (TPA) diethanol amine 4.3 fat
Fat alcohol APEO AEO-9 8.5 water 37.5.On 250ml milliliter four-hole boiling flask, install stirring motor, condenser and
Condensation water collector, nitrogen tube and temperature controller, are subsequently adding ethylene glycol, polyethylene glycol PEG-4000, poly terephthalic acid
Glycol ester is warming up to 240-300 °C and reacts to no solid particle, adds terephthalic acid (TPA), diethanol amine, in 180-
260 °C are reacted to acid number less than 10, are cooled to 100 °C, after adding AEO AEO-9 to stir, slowly add
Enter water, stirring became sub-translucent cation-modified hydrophilic polyesters solution after 30 minutes.
The cation-modified hydrophilic polyesters of embodiment 3, in parts by weight, it is filled a prescription as material name part ethylene glycol 1.18
Zinn glutaric alcohol 2.0 polyethylene glycol PEG-4000,32.4 polyethylene terephthalate 10.8 M-phthalic acid 3.24 2
Monoethanolamine 4.3 octadecylamine APEO AN-12 8.5 water 37.5.On 250ml milliliter four-hole boiling flask, stirring horse is installed
Reach, condenser and condensation water collector, nitrogen tube and temperature controller, be subsequently adding ethylene glycol, zinn glutaric alcohol, polyethylene glycol
PEG-4000, polyethylene terephthalate are warming up to 240-300 °C and react to no solid particle, add isophthalic diformazan
Acid, diethanol amine, react at 180-260 °C and are less than 10 to acid number, be cooled to 100 °C, add octadecylamine APEO AN-
After 12 stir, it is slowly added to water, stirring became sub-translucent cation-modified hydrophilic polyesters solution after 30 minutes.
The cation-modified hydrophilic polyesters of embodiment 4, in parts by weight, it is filled a prescription as material name part ethylene glycol 3.18
Polyethylene glycol PEG-6000 32.4 polyethylene terephthalate, 10.8 adipic acid 3.24 diethylenetriamine 4.3 ten eight
Amine APEO AN-12 8.5 water 37.5.On 250ml milliliter four-hole boiling flask, stirring motor, condenser and condensation are installed
Water collector, nitrogen tube and temperature controller, are subsequently adding ethylene glycol, polyethylene glycol PEG-6000, poly terephthalic acid second two
Alcohol ester is warming up to 240-300 °C and reacts to no solid particle, adds adipic acid, diethylenetriamine, reacts at 180-260 °C
It is less than 10 to acid number, is cooled to 100 °C, after adding octadecylamine APEO AN-12 to stir, be slowly added to water, stirring
Become sub-translucent cation-modified hydrophilic polyesters solution after 30 minutes.
The cation-modified hydrophilic polyesters of embodiment 5, in parts by weight, it is filled a prescription as material name part ethylene glycol 3.18
Polyethylene glycol PEG-3000 32.4 polyethylene terephthalate, 10.8 adipic acid, 3.24 ethylenediamine 4.3 isomery 13
Alcohol APEO TDE-9 8.5 water 37.5., on 250ml milliliter four-hole boiling flask, installs stirring motor, condenser and condensation
Water collector, nitrogen tube and temperature controller, are subsequently adding ethylene glycol, polyethylene glycol PEG-3000, poly terephthalic acid second two
Alcohol ester is warming up to 240-300 °C and reacts to no solid particle, adds adipic acid, ethylenediamine, reacts to acid at 180-260 °C
Value is less than 10, is cooled to 100 °C, after adding isomerous tridecanol polyoxyethylene ether TDE-9 to stir, is slowly added to water, stirring
Become sub-translucent cation-modified hydrophilic polyesters solution after 30 minutes.
The cation-modified hydrophilic polyesters of embodiment 6, in parts by weight, it is filled a prescription as material name part diethylene glycol
3.18 polyethylene glycol PEG-5000,32.4 polyethylene terephthalate, 10.8 terephthalic acid (TPA) 3.24 triethanolamine
4.3 octadecylamine APEO AN-15 8.5 water 37.5., on 250ml milliliter four-hole boiling flask, installs stirring motor, condensation
Device and condensation water collector, nitrogen tube and temperature controller, are subsequently adding diethylene glycol, polyethylene glycol PEG-5000, gather to benzene
Naphthalate is warming up to 240-300 °C and reacts to no solid particle, adds terephthalic acid (TPA), triethanolamine,
180-260 °C is reacted to acid number less than 10, is cooled to 100 °C, after adding octadecylamine APEO AN-15 to stir, delays
Slow addition water, stirring became sub-translucent cation-modified hydrophilic polyesters solution after 30 minutes.
Subject cationic modified hydrophilic polyester, the molecular weight of polyester segments can also bring up to 10000- from 2000-3000
100000 dalton.Polyester segments hydrophilic radical has cation, carboxylic acid, nonionic polyoxyalkylene, and cation group, primary, secondary, uncle
With doped quaternary ammonium salt composition.All, molecular weight is high, adhesion strength for the cation-modified polyester hydrophile function base distribution prepared by the present invention
High.
The foregoing describe general principle, principal character and the advantages of the present invention of the present invention.The technical staff of the industry should
This understanding, the present invention is not restricted to the described embodiments, the simply explanation present invention's described in above-described embodiment and specification
Principle, without departing from the spirit and scope of the present invention the present invention also have various changes and modifications, these change and change
Enter to both fall within scope of the claimed invention.Claimed scope is by appending claims and its equivalent
Define.
Claims (16)
1. a kind of hydrophilic cationic modified poly ester is it is characterised in that according to parts by weight percentage, its formula includes following one-tenth
Point：
Polyalcohol 0～20
Polyacid 5～14
Polyalcohols 30～100
Polyester 0～30
Surfactant 0～15
Polyamines 5～20
Water 20～40.
2. according to claim 1 cation-modified hydrophilic polyesters it is characterised in that above-mentioned polyalcohol be ethylene glycol, diethyl two
Alcohol, Isosorbide-5-Nitrae _ butanediol, isoprene, 1,6_ cyclohexane diol, pentaerythrite, one kind of trimethylolethane or any group
Close.
3. according to claim 1 cation-modified hydrophilic polyesters it is characterised in that above-mentioned polyester be poly terephthalic acid second
Diol ester PET, one kind of polybutylene terephthalate (PBT) PBT or any combination.
4. according to claim 1 cation-modified hydrophilic polyesters it is characterised in that above-mentioned polyacid be p- phthalic acid,
M- phthalic acid, adipic acid, phthalic anhydride, inclined acid anhydride, one kind of citric acid or any combination.
5. according to claim 1 cation-modified hydrophilic polyesters it is characterised in that above-mentioned polyalcohols be polyethylene glycol, poly- the third two
Alcohol, PolyTHF and their EVA.
6. according to claim 1 cation-modified hydrophilic polyesters it is characterised in that above-mentioned surfactant includes isooctanol
APEO, certain herbaceous plants with big flowers alcohol APEO, AEO, isomerous tridecanol polyoxyethylene ether, stearyl alcohol polyoxy second
The one or any combination of alkene ether, Brij, aliphatic amine polyoxyethylene ether etc..
7. according to claim 1 cation-modified hydrophilic polyesters it is characterised in that above-mentioned water be deionized water.
8. preparation method according to claim 1 is it is characterised in that above-mentioned polyamines is triethylamine diethylamine, N.N-2 methyl
One or more combinations of ethylene glycol amine, triethanolamine, diethanol amine, diethylenetriamine etc. polyamines, such raw material is
Change the ionic of hydrophilic macromolecule polyester, greatly increase the dissolubility of hydrophilic polyesters.
9. the hydrophilic cationic modified poly ester preparation method kind as described in any one of claim 1～8 it is characterised in that
Comprise the following steps：
(a). stirring motor, condenser and condensation water collector, nitrogen tube and temperature controller, Ran Houfen are installed in a reservoir
Not Jia Ru polyalcohol, polyacid, polyalcohols, polyester, polyamines, be warming up to 180-260 °C, react to acid number be less than 10；
（b）It is cooled to less than 100 °C, according to viscosity situation, appropriate addition part surface activating agent 0～15：
（c）Load weighted deionized water is slowly added in container, stirring had both become the homogeneous transparent aqueous solution in a moment.
10. preparation method according to claim 9 is it is characterised in that above-mentioned steps (a) divide two stages：
(al) stirring motor, condenser and condensation water collector, nitrogen tube and temperature controller are installed in a reservoir, are initially charged
Polyalcohol is warming up to 240-300 °C and reacts and comprises 0 50 parts of polyester to the above-mentioned polyalcohol of no solid particle；
(a2) it is subsequently adding polyacid, polyamine, hydrophilic monomer, react at 180-260 °C and be less than 10 to acid number.
11. preparation methods according to claim 9 it is characterised in that above-mentioned polyalcohol be ethylene glycol, diethylene glycol, 1,
4_ butanediol, isoprene, 1,6_ cyclohexane diol, pentaerythrite, one kind of trimethylolethane or any combination.
12. preparation methods according to claim 9 are it is characterised in that above-mentioned polyester is polyethylene terephthalate
PET, one kind of polybutylene terephthalate (PBT) PBT or any combination, such raw material is not environmentally it is impossible to enough biologies drop
Solution, has substantial amounts of such discarded object in life, be mainly scrap concrete and recycle in the secondary invention of utilization.
13. preparation methods according to claim 9 are it is characterised in that above-mentioned polyacid is p- phthalic acid, m- benzene two
Formic acid, adipic acid, phthalic anhydride, inclined acid anhydride, one kind of citric acid or any combination.
14. preparation methods according to claim 9 it is characterised in that above-mentioned polyalcohols be polyethylene glycol, polypropylene glycol, poly-
Oxolane and their EVA, such raw material is to make polyester have certain water solubility.
15. preparation methods according to claim 9 are it is characterised in that above-mentioned polyamines is triethylamine diethylamine, N.N-2 first
One or more combinations of ethyl glycol amine, triethanolamine, diethanol amine, diethylenetriamine etc. polyamines, such raw material exists
In the ionic changing hydrophilic macromolecule polyester, greatly increase the dissolubility of hydrophilic polyesters.
16. preparation methods according to claim 9 are it is characterised in that above-mentioned surfactant includes isooctanol polyoxyethylene
Ether, certain herbaceous plants with big flowers alcohol APEO, AEO, isomerous tridecanol polyoxyethylene ether, Brij-721, oleyl alcohol
The one or any combination of APEO, aliphatic amine polyoxyethylene ether etc..
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610774808.4A CN106397754A (en) | 2016-08-31 | 2016-08-31 | Hydrophilic cationic modified polyester and preparation method thereof |
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| CN201610774808.4A CN106397754A (en) | 2016-08-31 | 2016-08-31 | Hydrophilic cationic modified polyester and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898550A (en) * | 2021-01-27 | 2021-06-04 | 唐山睿安科技有限公司 | Biodegradable polyester and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898635A (en) * | 2012-09-26 | 2013-01-30 | 重庆大学 | Amphipathic high polymer material and method for preparing same |
| CN103467729A (en) * | 2013-08-09 | 2013-12-25 | 四川大学 | Polyethylene glycol-poly amino acid-polyester triblock polymer, preparation method and use thereof |
| CN104788665A (en) * | 2015-04-21 | 2015-07-22 | 中国科学院化学研究所 | Alcohol water-soluble modified polyester ink resin and preparation method thereof |
-
2016
- 2016-08-31 CN CN201610774808.4A patent/CN106397754A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898635A (en) * | 2012-09-26 | 2013-01-30 | 重庆大学 | Amphipathic high polymer material and method for preparing same |
| CN103467729A (en) * | 2013-08-09 | 2013-12-25 | 四川大学 | Polyethylene glycol-poly amino acid-polyester triblock polymer, preparation method and use thereof |
| CN104788665A (en) * | 2015-04-21 | 2015-07-22 | 中国科学院化学研究所 | Alcohol water-soluble modified polyester ink resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898550A (en) * | 2021-01-27 | 2021-06-04 | 唐山睿安科技有限公司 | Biodegradable polyester and preparation method thereof |
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