CN107652421B - A kind of thiolated modified method of polyester - Google Patents
A kind of thiolated modified method of polyester Download PDFInfo
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- CN107652421B CN107652421B CN201710995080.2A CN201710995080A CN107652421B CN 107652421 B CN107652421 B CN 107652421B CN 201710995080 A CN201710995080 A CN 201710995080A CN 107652421 B CN107652421 B CN 107652421B
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention provides a kind of new thiolated modified method of polyester, the following steps are included: itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol are obtained a kind of unsaturated polyester (UP) containing double bonds through polycondensation reaction, sulfydryl-alkene click-reaction is carried out under ultraviolet light with mercaptoethane sulfonic acid compound, mercapto carboxy compounds or mercapto hydroxy compound and obtains water-soluble preferable waterborne polyester.After mixing by the water-soluble polyester, multifunctional sulfydryl polyester and photoinitiator, sulfydryl-alkene click-reaction occurs and obtains the macromolecule product of better performances.The method of the invention can efficiently solve the problem of control molecular weight, and accelerate curing rate, postponed the appearance of gel point, formed the structure of high crosslink density, product regularity obtained is higher, mechanical property is more excellent.
Description
Technical field
The invention belongs to the preparation method of high molecular material, in particular to a kind of thiolated modified method of new polyester.
Background technique
With the development of science and technology, the synthesis and application of high molecular material are increasingly focused on, wherein traditional
Free radical polymerization is to synthesize the important means of high molecular material, but the structure control of conventional free radical polymerizate is more difficult, easily
Biradical termination causes the molecular weight distribution of product wider, can not efficiently control molecular weight.
Click chemistry can effectively solve these problems, provide a kind of new way to prepare high-molecular organic material.It clicks
Chemistry has reaction raw materials and reagent is easy to get, is applied widely, reaction condition is simple mildly, hardly by external environment (oxygen
With water etc.) influence, yield is high, by-product is harmless, the easily separated purifying of product.Therefore, can use it is a series of it is simple, efficiently, can
Lean on and selective binding reaction come realize atom connect, make it in organic synthesis, material science, molecular biology and life
There is wide application in the fields such as object technology, Polymer Synthesizing.
Report that most click chemistries is alkynyl-azido cycloaddition of Cu catalysis, and click the most mature at present
Chemical type.But have been reported that, transiting state metal catalyst Cu can induce virus or oligonucleotide degradation, and Cu is used as and urges
Agent has cytotoxin, it is necessary to reduce application in vivo, and reaction condition required for preparation Cu is more complex, product
In purification Cu be difficult to remove, the formation for being unfavorable for macromolecular three-dimensional-structure etc..And sulfydryl-alkene clicking chemistry does not need that a huge sum of money is added
Metal catalyst can be chemically reacted rapidly under the action of ultraviolet or visible light, can be passed through under solvent-free conditions
The time of control light radiation achievees the purpose that control the extent of reaction, and raw material, without purifying, product structure is easily-controllable.In addition, with
Other kinds of click chemistry is compared, and sulfydryl-alkene curing reaction has simple, quick, the strong stereoselectivity of reaction condition, product
It is insensitive to water and oxygen, shrinkage stress is low, yield is high, easily forms the advantages that uniform polymer architecture.In Light Curing
Introducing sulfydryl not only can form new living radical by consuming peroxy radical, but also can accelerate curing rate, push away
The appearance of slow gel point, forms the structure of high crosslink density, polymer material obtained is than the production that general radical polymerize
Object regularity is higher, mechanical property is more excellent.
Chinese patent CN106700894A discloses the preparation method of the hyper-branched polyester of sulfydryl sealing end, including following step
It is rapid: hyper-branched polyester, thioacetic acid, dimethylamino naphthyridine tosilate being mixed with organic solvent, are heated to reflux
Divide water, stop reaction after reaching theoretical water yield, remove organic solvent, extraction obtains extraction phase and raffinate phase；It will be in raffinate phase
Remaining extractant removes, and obtains the hyper-branched polyester of sulfydryl sealing end.But preparation method is complicated, and polyester modification is inefficient.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention provides a kind of new thiolated modified method of polyester, and this method not only overcomes
The problem of conventional free radical solidification process structure control is more difficult, easy biradical termination, can not efficiently control molecular weight, Er Qiejia
Fast curing rate, has postponed the appearance of gel point, forms the structure of high crosslink density, and product regularity obtained is higher, power
It is more excellent to learn performance.
It is had the special feature that based on sulfydryl-alkene curing reaction, the present invention is directed to by drawing during curable unsaturated polyester
Enter macromolecular sulfhydryl compound, the performance of cured product is adjusted by control condition of cure and raw material proportioning, obtains having excellent
The high molecular polymer of mechanical performance.The research report for preparing high molecular material currently with sulfydryl-alkene clicking chemistry is less, this
The problem of structure control that invention solves conventional free radical polymerizate is more difficult, easy biradical termination, products therefrom mechanical performance
Well.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of thiolated modified method of new polyester, comprising:
By double bond containing unsaturated polyester (UP) and the sulfhydryl compound for having hydrophilic radical, such as: mercaptoethane sulfonic acid compound, mercapto
Base carboxyl compound, mercapto hydroxy compound in the presence of photoinitiators, carry out sulfydryl-double bond click-reaction, obtain a kind of water
Property polyester.The polyester and aqueous more sulfhydryl compounds are subjected to sulfydryl-double bond click-reaction, obtain that there is three-dimensional cross-linked netted knot
The high molecular polymer of structure.
Hydrophilically modified compound and sulfydryl end-caps are independently added not with traditional polyester hydrophilic modification method
Together, the research of the invention finds that: if introducing hydrophilic radical in advance in macromolecular sulfhydryl compound, recycle the solidification of sulfydryl-alkene
Reaction solidifies unsaturated polyester (UP), not only can more simply and effectively control condition of cure and radical polymerization product
Structure shortens the reaction time；Meanwhile the hydrophilic radical on sulfhydryl compound is living with reacting for polyester in click-reaction
Property and matching degree are higher, significantly improve the biocompatibility of final product (waterborne polyester) and biodegradability.
For most of double bond containing unsaturated polyester (UP)s, with the reduction of carbon-carbon double bond charge density, reaction rate is reduced,
Reaction mechanism also difference.In order to guarantee modified effect, reduces the cycloaddition reaction between double bond, improves reaction efficiency, originally
Inventing double bond and the molar ratio of sulfydryl in preferred double bond containing unsaturated polyester (UP) is 1: 0.5~1.
Structure, the type of hydrophilic radical of sulfhydryl compound with hydrophilic radical all can be to the biofacies of modified polyester
Capacitive and biodegradability have an impact.In order to obtain there is preferably the aqueous of biocompatibility and biodegradability to gather
Ester, the currently preferred sulfhydryl compound with hydrophilic radical are mercaptoethane sulfonic acid compound, mercapto carboxy compounds or sulfydryl
Hydroxy compounds.
It is furthermore preferred that the sulfhydryl compound with hydrophilic radical is 3- sulfydryl -1- propanesulfonate, 2- sulfydryl second sulphur
Acid, 7- Mucofluid Sodium, 4- sulfydryl -1- fourth sulfonic acid, 2- hydroxyl -3- mercaptopropanesulfonic acid sodium, bis--thio propane of 2,3- -1-
Potassium sulfonate or 2- mercapto ethane sulfonic acid sodium, 4- mercaptobenzoic acid, 3- mercaptopropionic acid are any in mercaptoethanol.
Preferably, the sulfydryl-double bond click-reaction condition are as follows: ultraviolet lamp power is 200~1000W, cure times 1
~10min, photocuring distance are 5~20cm.
Type, the ratio of hard and soft chain segment of polyester can all have an impact the final performance of product.Test result shows to produce
The elongation at break of object is related with the relative length of hard and soft chain segment in polyester.Therefore, currently preferred double bond containing unsaturation
Polyester by itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol in the presence of a catalyst polycondensation reaction and obtain, with obtain compared with
Excellent mechanical performance.
It is furthermore preferred that the polycondensation reaction condition are as follows: the esterification at nitrogen protection, 180 DEG C；160 DEG C are cooled to, is subtracted
It is depressed into -0.1Mpa polycondensation reaction 3 hours.
It is furthermore preferred that the catalyst is stannous chloride.
The present invention also provides the sulfhydryl modified polyester of any above-mentioned method preparation.
The present invention also provides above-mentioned sulfhydryl modified polyester to prepare the application in ultraviolet-curing paint.
The present invention also provides the application in terms of aqueous more sulfhydryl compound modified water-soluble polyester properties, the modifying process is logical
Sulfydryl-double bond click-reaction is crossed to realize.
Beneficial effects of the present invention
(1) hydrophilic radical is introduced unsaturated polyester (UP) by carrying out sulfydryl-alkene click-reaction under ultraviolet light by the present invention
In, a kind of novel waterborne polyester preparation method is obtained, is different from traditional with the strong dicarboxylic acids of hydrophily such as isophthalic two
Formic acid sodium sulfonate or dihydric alcohol 1,4-butanediol -2- sodium sulfonate substitute a part of binary acid or dihydric alcohol, and directly synthesis is unsaturated
Polyester.With extent of reaction height, reaction time short advantage, and waterborne polyester prepared by this method are compared to react with tradition
The polyester of preparation has higher biocompatibility and biodegradability, and the application of material is more extensive, safer, nontoxic.
(2) sulfydryl-alkene reaction of the present invention have simple, quick, the strong stereoselectivity of reaction condition, product to water and oxygen not
Sensitivity, shrinkage stress is low, yield is high, easily forms the advantages that uniform polymer architecture.Propose a kind of new polyester sulfhydrylation
Method of modifying, it is more difficult that this method not only overcomes conventional free radical solidification process structure control, easy biradical termination, can not be effectively
The problem of controlling molecular weight, and curing rate is accelerated, the appearance of gel point has been postponed, the structure of high crosslink density is formed,
Product regularity obtained is higher, mechanical property is more excellent.
(3) using double bond containing itaconic acid as raw material, the double bond of itaconic acid is individually located on branch the method for the present invention, double
Key is exposed with except main chain, and steric hindrance is low, and reaction is easier to carry out, and reactivity is higher, and required condition is simple, at low cost.
(4) preparation method of the present invention is simple, curing efficiency is high, practical, easy to spread.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the FTIR spectrum figure of waterborne polyester；
The FTIR spectrum figure of film after Fig. 2 is more sulfhydryl compounds and solidifies, wherein a: more sulfhydryl compounds,
B: cured film.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
The technical scheme adopted by the invention is that: a kind of new thiolated modified method of polyester, step include:
(1) the polyester synthesis stage: itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol are obtained through polycondensation reaction containing double bond
Unsaturated polyester (UP), then by click-reaction introduce mercaptoethane sulfonic acid compound, additional amount be dihydric alcohol integral molar quantity 10%
~50%, under ultraviolet light irradiation, obtain the waterborne polyester containing sulfonic acid group.
(2) solidify cross-linking stage: the solidification crosslinking of polyester carries out photocuring first to carry out heat cure again, and heat curing temperature is
40~100 DEG C, thermal curing time is 0.5~4h.The ultraviolet light curing power of photocuring is 200~1000W, cure times 1
~10min, photocuring distance are 5~20cm.
Embodiment 1
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 10% of dihydric alcohol mole, and distance 10cm irradiates 2min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1: 0.8 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
5wt% Irgacure2959 (BASF photoinitiator 2959) mixing, and persistently stirred 15 minutes with the speed of 250rpm.So
PU dispersion mixture is coated on the tinplate of ethyl alcohol cleaning by coating machine afterwards.Water evaporates 2h at 60 DEG C in an oven,
Distance 12cm solidification 5min obtains crosslinking curing product under 800W ultraviolet lamp.Properties of product are carried out according to relevant national standard
Contrast test, hardness 59, water absorption rate 70.26%, 74.17 ° of contact angle, tensile strength 0.982MPa, elongation at break is
90.25%, surface drying time 3h.
Embodiment 2
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 50% of dihydric alcohol mole, and distance 10cm irradiates 3min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1: 0.8 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
0.2wt%Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU is dispersed by coating machine
Body mixture is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 2h at 60 DEG C in an oven, distance 12cm under 800W ultraviolet lamp
Solidification 5min obtains crosslinking curing product.Test, hardness 54, water suction are compared to properties of product according to relevant national standard
Rate 79.35%, 63.17 ° of contact angle, tensile strength 0.962MPa, elongation at break 87.25%, surface drying time 2.6h.
Embodiment 3
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 13cm irradiates 2min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1: 0.5 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
0.8wt%Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU is dispersed by coating machine
Body mixture is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 2h at 40 DEG C in an oven, distance 12cm under 800W ultraviolet lamp
Solidification 5min obtains crosslinking curing product.Test, hardness 66, water suction are compared to properties of product according to relevant national standard
Rate 69.17%, 78.56 ° of contact angle, tensile strength 1.453MPa, elongation at break 94.26%, surface drying time 2.9h.
Embodiment 4
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 8cm irradiates 3min and obtains under 1000W ultraviolet lamp
Waterborne polyester.By the PU dispersion of waterborne polyester and multi-functional thiol's sealing end that molar ratio is 1: 1, deionized water and 0.8wt%
Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU dispersion is mixed by coating machine
Object is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 2h at 100 DEG C in an oven, and distance 12cm solidifies under 800W ultraviolet lamp
5min obtains crosslinking curing product.Test, hardness 66, water absorption rate are compared to properties of product according to relevant national standard
59.94%, 83.72 ° of contact angle, tensile strength 1.472MPa, elongation at break 96.92%, surface drying time 3.1h.
Embodiment 5
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 15cm irradiates 5min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1: 0.6 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
0.8wt%Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU is dispersed by coating machine
Body mixture is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 0.5h, distance under 1000W ultraviolet lamp at 70 DEG C in an oven
12cm solidification 5min obtains crosslinking curing product.Test compared to properties of product according to relevant national standard, hardness 66,
Water absorption rate 52.93%, 85.91 ° of contact angle, tensile strength 1.629MPa, elongation at break 98.16%, surface drying time is
2.7h。
Embodiment 6
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 12cm irradiates 4min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1: 0.6 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
0.8wt%Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU is dispersed by coating machine
Body mixture is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 4h at 70 DEG C in an oven, distance 12cm under 200W ultraviolet lamp
Solidification 5min obtains crosslinking curing product.Test, hardness 62, water suction are compared to properties of product according to relevant national standard
Rate 70.93%, 81.82 ° of contact angle, tensile strength 1.519MPa, elongation at break 90.43%, surface drying time 4.1h.
Embodiment 7
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 12cm irradiates 3min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1:0.6 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
0.8wt%Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU is dispersed by coating machine
Body mixture is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 1h at 70 DEG C in an oven, distance 20cm under 900W ultraviolet lamp
Solidification 1min obtains crosslinking curing product.Test, hardness 69, water suction are compared to properties of product according to relevant national standard
Rate 48.17%, 103.6 ° of contact angle, tensile strength 1.953MPa, elongation at break 104.086%, surface drying time 1.5h.
Embodiment 8
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 14cm irradiates 1min and obtains under 1000W ultraviolet lamp
To waterborne polyester.By molar ratio be 1: 0.6 waterborne polyester and multi-functional thiol sealing end PU dispersion, deionized water and
0.8wt%Irgacure2959 mixing, and persistently stirred 15 minutes with the speed of 250rpm.Then PU is dispersed by coating machine
Body mixture is coated on the tinplate of ethyl alcohol cleaning.Water evaporates 1h at 70 DEG C in an oven, and distance 5cm is solid under 900W ultraviolet lamp
Change 10min and obtains crosslinking curing product.Test compared to properties of product according to relevant national standard, hardness of film 72,
Water absorption rate 47.3%, 105.36 ° of contact angle, tensile strength 2.165MPa, elongation at break 124.255%, surface drying time is
1.3h。
Comparative example
Molar ratio is placed in tetra- mouthfuls of quartz of 250ml for 2: 1: 1: 2 itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol to burn
In bottle, and catalyst stannous chloride is added, additional amount is the 0.3% of itaconic acid quality, connects water segregator, thermometer and stirring
Device is warming up to 180 DEG C under nitrogen protection and stirs strongly, when there is water generation, esterification does not terminate in water segregator, so
After be cooled to 160 DEG C, be decompressed to -0.1Mpa carry out polycondensation reaction, the reaction time 3 hours.Obtain polyester.3- is added thereto
Sulfydryl -1- propanesulfonate, additional amount are the 30% of dihydric alcohol mole, and distance 15cm irradiates 2min and obtains under 1000W ultraviolet lamp
To waterborne polyester.The waterborne polyester of synthesis, deionized water, thermal initiator are mixed, and persistently stir 15 with the speed of 250rpm
Minute.Then dispersion mixture is coated on the tinplate of ethyl alcohol cleaning by coating machine.Water steams at 70 DEG C in an oven
48h is sent out, test, hardness of film 43, water absorption rate are compared to crosslinking curing product property according to relevant national standard
98.31%, 56.87 ° of contact angle, tensile strength 0.26MPa, elongation at break 35.78%, surface drying time 37h.
It is compared by embodiment and comparative example it is found that the crosslinking curing product property in embodiment is superior to comparative example, especially
Its curing time that cured product is greatly shortened in terms of surface drying time.
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 technical solution documented by previous embodiment, or part is equivalently replaced.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 specific embodiments of the present invention have been described, and it is not intended to limit the protection scope of the present invention, institute
Category field technical staff should be understood that based on the technical solutions of the present invention those skilled in the art do not need to pay wound
The various modifications or changes that the property made labour can be made are still within protection scope of the present invention.
Claims (5)
1. a kind of thiolated modified method of polyester characterized by comprising
Double bond containing unsaturated polyester (UP) and aqueous more sulfhydryl compounds are subjected to sulfydryl-double bond click-reaction, obtained sulfhydryl modified
Polyester；
Double bond and the molar ratio of aqueous more sulfhydryl compounds are 1:0.5 ~ 1 in the double bond containing unsaturated polyester (UP)；
Aqueous more sulfhydryl compounds are 3- sulfydryl -1- propanesulfonate；
The sulfydryl-double bond click-reaction condition are as follows: ultraviolet lamp power is 200 ~ 1000W, 1 ~ 10min of cure times, and light is solid
Changing distance is 5 ~ 20cm；
The double bond containing unsaturated polyester (UP) is carried out polycondensation reaction by itaconic acid, maleic acid, dipropylene glycol, neopentyl glycol and is obtained.
2. the method as described in claim 1, which is characterized in that the polycondensation reaction condition are as follows: at nitrogen protection, 180 DEG C
Esterification；160 DEG C are cooled to, is decompressed to -0.1MPa polycondensation reaction 3 hours.
3. method according to claim 2, which is characterized in that the esterification carries out in the presence of a catalyst, urges
Agent is stannous chloride.
4. the sulfhydryl modified polyester of the described in any item method preparations of claim 1-3.
5. sulfhydryl modified polyester as claimed in claim 4 is preparing the application in high molecular material.
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| CN112080241B (en) * | 2020-09-24 | 2021-12-21 | 广东普赛达密封粘胶有限公司 | Photo-curing adhesive and preparation method and application thereof |
| CN114133857B (en) * | 2021-10-19 | 2022-07-22 | 光易科技(无锡)有限公司 | Hyperbranched polyurethane acrylate photochromic composition and preparation method and application thereof |
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