CN109438685A - A kind of water-soluble copolyester and preparation method thereof - Google Patents
A kind of water-soluble copolyester and preparation method thereof Download PDFInfo
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- CN109438685A CN109438685A CN201811121511.3A CN201811121511A CN109438685A CN 109438685 A CN109438685 A CN 109438685A CN 201811121511 A CN201811121511 A CN 201811121511A CN 109438685 A CN109438685 A CN 109438685A
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- water
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- ester
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- soluble copolyester
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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
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- 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
Abstract
Present invention discloses a kind of water-soluble copolyesters and preparation method thereof, and this method comprises the following steps, are raw material by dicarboxylic acids or its ester, dihydric alcohol, dimethyl isophthalate -5- phosphate, and catalyst is added and is uniformly mixed in a kettle；Under inert environments normal pressure, 180 ~ 275 DEG C are warming up to, esterification or ester exchange reaction carry out 1 ~ 5 hour, and by-product collecting amount is greater than the 95% of theoretical value, maintains the temperature between 240 ~ 295 DEG C, are depressurized to 500Pa hereinafter, carrying out polycondensation reaction 0.5 ~ 5 hour.The copolyesters glass transition temperature of method preparation of the invention is 20 ~ 75 DEG C；Inherent viscosity at least 0.25dL/g.And there is excellent water solubility, organic solvent can not be used, VOC can be substantially reduced, is conducive to environmental protection.
Description
Technical field
The present invention relates to a kind of water-soluble copolyesters and preparation method thereof, belong to synthesis of polymer material field.
Background technique
Main binding or film forming matter of the polyester resin as paint, ink, coating, adhesive etc., have very big
Using.But need to be added various organic solvents in current use technique, so that it is had relatively good workability.Recently,
Environmental pollution and ensure the safety of workplace in order to prevent, gradually limits the use of organic solvent.For environmental protection and drop
Polyester resin is dispersed in water or its hydration is made to be current popular direction by the considerations of low VOC content.Water dispersed resin is formed
Coating there is water resistance similar with the coating formed by the resin of organic solvent and weatherability and excellent chemical resistance
It is also the same important.
Currently used waterborne polyester is usually then to be neutralized with amine using a large amount of carboxylic acid group is introduced；Either draw
Enter a large amount of sulfonate groups, but the obtained waterborne polyester, not only molecular weight is small, and dissolubility is limited, and obtained resin makes
With in performance, there are many restrictions and unfavorable factor.
Summary of the invention
In view of the prior art, there are drawbacks described above, and the purpose of the present invention is to provide a kind of water-soluble copolyester and its preparations
Method.
The purpose of the present invention will be realized through the following technical scheme:
A method of water-soluble copolyester is prepared, is included the following steps,
S1, by dicarboxylic acids or its ester, dihydric alcohol, dimethyl isophthalate -5- phosphate it is raw material, catalyst is added anti-
It answers in kettle and is uniformly mixed；
S2, under inert environments normal pressure, be warming up to 180 ~ 275 DEG C, esterification or ester exchange reaction carry out 1 ~ 5 hour, and by-product is received
Collection amount is greater than the 95% of theoretical value, maintains the temperature between 240 ~ 295 DEG C, is depressurized to 500Pa hereinafter, carrying out polycondensation reaction 0.5 ~ 5
Hour.
Electedly, at 220 ~ 270 DEG C, the reaction time is controlled 2 ~ 5 for esterification or transesterification reaction temperature control in the S2
Hour；The control of polycondensation reaction temperature is at 250 ~ 290 DEG C, and reaction pressure control is in 100Pa hereinafter, reaction time control is small 1 ~ 4
When.
Electedly, dicarboxylic acids or its ester are selected from terephthalic acid (TPA) or its ester, M-phthalic acid or its ester, neighbour in the S1
Phthalic acid or its ester, adipic acid, azelaic acid, decanedioic acid, 1,4 cyclohexanedicarboxylic acid.
Electedly, dihydric alcohol is selected from ethylene glycol, 1,4-butanediol, 1,3-PD, 1,2-PD, new penta in the S1
Glycol, hexylene glycol, 1,4 cyclohexane dimethanol, polyethylene glycol.
Electedly, dimethyl isophthalate -5- phosphate described in the S1 is selected from dimethyl isophthalate -5-
Sodium phosphate, dimethyl isophthalate -5- potassium phosphate, dimethyl isophthalate -5- lithium phosphate.
Electedly, the phosphatic dosage of dimethyl isophthalate -5- is based on acid and the total molar ratio example of ester
The mol% of 3mol% ~ 15.
Electedly, the catalyst is selected from butyl titanate, isopropyl titanate, Mg, Zn, Mn acetate, oxidation dibutyl
One of tin, antimony oxide, antimony acetate, antimony glycol, germanium dioxide or more than one composition.
Electedly, a kind of described in more than one prepares copolyesters made from the method for water-soluble copolyester, described water-soluble
Property copolyesters glass transition temperature be 20 ~ 75 DEG C；Inherent viscosity at least 0.25dL/g.
The beneficial effects of the present invention are embodied in: the present invention provides a kind of waterborne polyesters of phosphate monomer synthesis, pass through
Introduce phosphate monomer, water solubility be provided, since phosphate is multivalence functional group, a monomer be capable of providing 2 alkali metal from
Son can provide for excellent water solubility by the way that fewer ratio is added.Hydrophilic radical can be reduced in this way for resin
Water resistance originally, the influence of resistance etc..Monomer phosphorous simultaneously can also be capable of providing excellent flame retardant property.Side of the invention
The resin of method preparation has excellent water solubility, can not use organic solvent, can substantially reduce VOC, be conducive to environmental protection.
Below just in conjunction with the embodiments, the embodiment of the present invention is described in further detail, so that the technology of the present invention
Scheme is more readily understood, grasps.
Specific embodiment
Method of the invention is illustrated below by specific embodiment, so that technical solution of the present invention is easier to manage
Solution is grasped, but the present invention is not limited thereto.Experimental method described in following embodiments is unless otherwise specified conventional side
Method；The reagent and material commercially obtain unless otherwise specified.
Embodiment 1
By terephthalic acid (TPA) 8.3kg, M-phthalic acid 7.5kg, dimethyl isophthalate -5- sodium phosphate 1.5kg, ethylene glycol
3.7kg and neopentyl glycol 7.3kg are put into 50L stainless steel cauldron, and zinc acetate 8g is added, antimony oxide 7g, are used
Under nitrogen system, with the stirring of 55 ~ 80rpm revolving speed, it is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then it is warming up to 230 ~
270 DEG C are reacted 2.2 hours or so, and when amount of by-products reaches theoretical by-product 95% out, reaction was completed.Revolving speed is adjusted to 30
~50rpm, temperature are controlled between 255~285 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction.Sampling analysis, when
Polymer viscosity stops stirring when reaching desired value, eliminates vacuum, and product discharge obtains water-soluble copolyester product.
Visual inspection: product is transparent, tests to obtain sample characteristics of for example viscosity to be 0.45dL/g with Ubbelohde viscometer, be surveyed with DSC
Obtaining glass transition temperature (Tg) is 67 DEG C.
Embodiment 2
By terephthalic acid (TPA) 3.3kg, M-phthalic acid 8.3kg, adipic acid 2.9kg, dimethyl isophthalate -5- sodium phosphate
3kg, ethylene glycol 5.0kg and 1,4-CHDM 8.6kg are put into 50L stainless steel cauldron, and metatitanic acid four is added
Butyl ester 6.5g, antimony oxide 7.1g, under nitrogen system, with the stirring of 55 ~ 80rpm revolving speed, be gradually warmed up to 220 DEG C keep the temperature into
Row reaction 1 hour, then be warming up to 230 ~ 270 DEG C and react 2.2 hours or so, when amount of by-products reaches theoretical by-product 95% out
It waits, reaction was completed.Revolving speed is adjusted to 30~50rpm, and temperature is controlled between 255~285 DEG C, decompression step by step to 100Pa or less
Carry out polycondensation reaction.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates vacuum, and product discharge obtains
Water-soluble copolyester product.
Visual inspection: product is transparent, tests to obtain sample characteristics of for example viscosity to be 0.35 dL/g with Ubbelohde viscometer, be surveyed with DSC
Obtaining glass transition temperature (Tg) is 45 DEG C.
Embodiment 3
By M-phthalic acid 5.0kg, decanedioic acid 12.5kg, dimethyl isophthalate -5- potassium phosphate 2.4kg, 1,6-HD
3.5kg, 1 neopentyl glycol 8.3kg and diethylene glycol (DEG) 5.3kg are put into 50L stainless steel cauldron, and butyl titanate is added
6.5g, antimony glycol 7.1g, with the stirring of 55 ~ 80rpm revolving speed, are gradually warmed up to 220 DEG C of heat preservations and are reacted under nitrogen system
1 hour, then be warming up to 230 ~ 270 DEG C and react 2.2 hours or so, when amount of by-products reaches theoretical by-product 95% out, terminate
Reaction.Revolving speed is adjusted to 30~50rpm, and temperature is controlled between 255~285 DEG C, and decompression step by step to 100Pa or less carries out polycondensation
Reaction.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates vacuum, and product discharge obtains water-soluble total
Polyester product.
Visual inspection: product is transparent, tests to obtain sample characteristics of for example viscosity to be 0.5 dL/g with Ubbelohde viscometer, be surveyed with DSC
Obtaining glass transition temperature (Tg) is 21 DEG C.
Embodiment 4
By terephthalic acid (TPA) 6.6kg, phthalic anhydride 8.3kg, dimethyl isophthalate -5- potassium phosphate 1.2kg, ethylene glycol
2.5kg, hexylene glycol 4.7kg and diethylene glycol (DEG) 6.4kg are put into 50L stainless steel cauldron, and butyl titanate 6.5g is added,
Antimony glycol 7.1g with the stirring of 55 ~ 80rpm revolving speed, is gradually warmed up to 220 DEG C of heat preservations that carry out reaction 1 small under nitrogen system
When, then be warming up to 230 ~ 270 DEG C and react 2.2 hours or so, when amount of by-products reaches theoretical by-product 95% out, terminate anti-
It answers.Revolving speed is adjusted to 30~50rpm, and temperature is controlled between 255~285 DEG C, and it is anti-that decompression step by step to 100Pa or less carries out polycondensation
It answers.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates vacuum, and product discharge obtains water-soluble copolymer
Ester product.
Visual inspection: product is transparent, tests to obtain sample characteristics of for example viscosity to be 0.4 dL/g with Ubbelohde viscometer, be surveyed with DSC
Obtaining glass transition temperature (Tg) is 43 DEG C.
Comparative example
By terephthalic acid (TPA) 8kg, M-phthalic acid 8kg, Sodium Dimethyl Isophthalate-5-sulfonate 2kg, ethylene glycol 5.0kg and
Neopentyl glycol 8.6kg is put into 50L stainless steel cauldron, and butyl titanate 6.5g is added, antimony oxide 7.1g, is used
Under nitrogen system, with the stirring of 55 ~ 80rpm revolving speed, it is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then it is warming up to 230 ~
270 DEG C are reacted 2.2 hours or so, and when amount of by-products reaches theoretical by-product 95% out, reaction was completed.Revolving speed is adjusted to 30
~50rpm, temperature are controlled between 255~285 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction.Sampling analysis, when
Polymer viscosity stops stirring when reaching desired value, eliminates vacuum, and product discharge obtains comparative example.
Visual inspection: product is transparent, tests to obtain sample characteristics of for example viscosity to be 0.35 dL/g with Ubbelohde viscometer, be surveyed with DSC
Obtaining glass transition temperature (Tg) is 75 DEG C.
Below by the water solubility of embodiment and comparative example, aqueous stability, and it is prepared into the performance after coating and does
Comparison, specific as shown in table 1:
A, water solubility: excess sample is put into deionized water, is placed in conical flask, is dissolved by heating, and removes insoluble matter after cooling,
Test solution solids content；
B, aqueous stability: the aqueous solution of water-soluble polyester is stored at room temperature, observation how long have afterwards insoluble matter be precipitated or
Person's layering；
C, coating performance detects: curing agent (BL XP2706, Bayer) is added in resin aqueous solution, is coated in tinplate surface.
Then 160 degree, 10min baking and curing tests soaking-resistant, resistance to acid and alkali.
Table 1: the performance test table of embodiment and comparative example.
| Sample number into spectrum | Water-soluble (maximum contains admittedly) | The stabilized aqueous solution time | Water resistance | Resistance to acid and alkali |
| Embodiment 1 | 31% | > 6 months | It is excellent | It is excellent |
| Embodiment 2 | 37% | > 6 months | It is excellent | It is excellent |
| Embodiment 3 | 34% | > 6 months | It is excellent | It is excellent |
| Embodiment 4 | 30% | > 6 months | It is excellent | It is excellent |
| Comparative example | 21% | 2 months | It is good | Difference |
Show that the present invention provides scheme and can obtain good water solubility, and the water solubility that stability is high by above data
Copolyesters, while it being also able to maintain good coating performance, greatly improve service performance.
Still there are many specific embodiments by the present invention.All all skills formed using equivalent replacement or equivalent transformation
Art scheme, all falls within the scope of protection of present invention.
Claims (8)
1. a kind of preparation method of water-soluble copolyester, it is characterised in that: include the following steps,
S1, by dicarboxylic acids or its ester, dihydric alcohol, dimethyl isophthalate -5- phosphate it is raw material, catalyst is added anti-
It answers in kettle and is uniformly mixed；
S2, under inert environments normal pressure, be warming up to 180 ~ 275 DEG C, esterification or ester exchange reaction carry out 1 ~ 5 hour, and by-product is received
Collection amount is greater than the 95% of theoretical value, maintains the temperature between 240 ~ 295 DEG C, is depressurized to 500Pa hereinafter, carrying out polycondensation reaction 0.5 ~ 5
Hour.
2. a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that: in the S2 esterification or
At 220 ~ 270 DEG C, the reaction time was controlled at 2 ~ 5 hours for transesterification reaction temperature control；Polycondensation reaction temperature is controlled 250 ~ 290
DEG C, reaction pressure control is in 100Pa hereinafter, the reaction time controlled at 1 ~ 4 hour.
3. a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that: binary carboxylic in the S1
Acid or its ester be selected from terephthalic acid (TPA) or its ester, M-phthalic acid or its ester, phthalic acid or its ester, adipic acid, azelaic acid,
Decanedioic acid, 1,4 cyclohexanedicarboxylic acid.
4. a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that: dihydric alcohol in the S1
Selected from ethylene glycol, 1,4-butanediol, 1,3-PD, 1,2-PD, neopentyl glycol, hexylene glycol, 1,4-CHDM,
Polyethylene glycol.
5. a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that: described in the S1
Dimethyl isophthalate -5- phosphate is selected from dimethyl isophthalate -5- sodium phosphate, dimethyl isophthalate -5- phosphorus
Sour potassium, dimethyl isophthalate -5- lithium phosphate.
6. a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that: the M-phthalic acid
The phosphatic dosage of dimethyl ester -5- is 3mol% ~ 15mol% based on acid and the total molar ratio example of ester.
7. a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that: the catalyst is selected from
Butyl titanate, isopropyl titanate, Mg, Zn, Mn acetate, dibutyltin oxide, antimony oxide, antimony acetate, antimony glycol,
One of germanium dioxide or more than one composition.
8. polyester made from a kind of a kind of preparation method of water-soluble copolyester according to claim 1, it is characterised in that:
The glass transition temperature of the water-soluble polyester is 20 ~ 75 DEG C；Inherent viscosity at least 0.25dL/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811121511.3A CN109438685A (en) | 2018-09-26 | 2018-09-26 | A kind of water-soluble copolyester and preparation method thereof |
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| CN201811121511.3A CN109438685A (en) | 2018-09-26 | 2018-09-26 | A kind of water-soluble copolyester and preparation method thereof |
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| CN201811121511.3A Pending CN109438685A (en) | 2018-09-26 | 2018-09-26 | A kind of water-soluble copolyester and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378102A (en) * | 2020-04-22 | 2020-07-07 | 江门市制漆厂有限公司 | Hydrolysis-resistant water-based polyester resin and preparation method and application thereof |
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| CN101967225A (en) * | 2010-10-11 | 2011-02-09 | 苏州瀚海化学有限公司 | Method for preparing water-soluble sulfo-copolyester |
| CN102079812A (en) * | 2010-11-16 | 2011-06-01 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN106854275A (en) * | 2016-12-13 | 2017-06-16 | 苏州瀚海新材料有限公司 | Water paint polyester resin and preparation method thereof outside a kind of weather resistant room |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030153716A1 (en) * | 2002-02-05 | 2003-08-14 | Shenshen Wu | Golf ball compositions comprising a novel acid functional polyurethane, polyurea, or copolymer thereof |
| CN101967225A (en) * | 2010-10-11 | 2011-02-09 | 苏州瀚海化学有限公司 | Method for preparing water-soluble sulfo-copolyester |
| CN102079812A (en) * | 2010-11-16 | 2011-06-01 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN106854275A (en) * | 2016-12-13 | 2017-06-16 | 苏州瀚海新材料有限公司 | Water paint polyester resin and preparation method thereof outside a kind of weather resistant room |
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| CN111378102A (en) * | 2020-04-22 | 2020-07-07 | 江门市制漆厂有限公司 | Hydrolysis-resistant water-based polyester resin and preparation method and application thereof |
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Address after: 215000 Room 301, building 17, North West area, Suzhou nano City, No. 99, Jinjihu Avenue, Suzhou Industrial Park, Suzhou City, Jiangsu Province Applicant after: Zhonghan New Material Technology Co., Ltd Address before: 2, floor 215123, best building, 166 benevolence Road, Suzhou Industrial Park, Jiangsu, Suzhou Applicant before: SUZHOU CHANGYE MATERIAL TECHNOLOGY Co.,Ltd. |
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Application publication date: 20190308 |