CN109796420A - A kind of trihydroxyethyl isocyanuric 3(6- hydroxyl 1- caproic acid) ester and its synthetic method - Google Patents
A kind of trihydroxyethyl isocyanuric 3(6- hydroxyl 1- caproic acid) ester and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of 3 (6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric and its synthetic methods, belong to organic synthesis field.The synthetic method includes: that trihydroxyethyl isocyanuric ester, the 6-caprolactone that molar ratio is 2~4:1 are added into reactor, forms mixed system, and remove the moisture in mixed system；Under nitrogen atmosphere, mixed system is heated to 100 DEG C~180 DEG C, and catalyst is added into mixed system, reacted, generate trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester；The quality of catalyst is the 0.01%~2% of mixed system and catalyst gross mass.Obtained trihydroxyethyl isocyanuric 3 (the 6- hydroxyl 1- caproic acid) ester of the synthetic method provided through the embodiment of the present invention, it is as modified trihydroxyethyl isocyanuric ester, can obtain trihydroxyethyl isocyanuric triacrylate of good performance with acroleic acid esterification, for example, with good water resistance, curing rate, pigment dispersion performance.
Description
Technical field
The present invention relates to organic synthesis field, in particular to a kind of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester
And its synthetic method.
Background technique
Trihydroxyethyl isocyanuric triacrylate is a kind of common chemical products, can be used as curing agent, pigment dispersion
Agent, hydrophobing agent raw material.Trihydroxyethyl isocyanuric triacrylate is usually by trihydroxyethyl isocyanuric ester and acrylic acid
It is esterified.Since trihydroxyethyl isocyanuric ester does not dissolve in some common organic solvents, such as toluene etc. increases itself and third
The esterification difficulty of olefin(e) acid；In addition, the final viscosity of esterification products (i.e. trihydroxyethyl isocyanuric triacrylate) at normal temperature
It is very big, and it can be crystallized at low temperature, be unfavorable for the application of final esterification products.Currently, usually to trihydroxyethyl isocyanuric
Modifying agent is added in ester, to change the molecular structure of trihydroxyethyl isocyanuric ester, i.e., trihydroxyethyl isocyanuric ester is carried out
It is modified, and then the performance of final esterification products can be changed.Therefore, it is necessary to provide a kind of modification of trihydroxyethyl isocyanuric ester
Method.
The prior art provides a kind of method of modifying of trihydroxyethyl isocyanuric ester, this method are as follows: different to trihydroxyethyl
Ethylene oxide is added in cyanurate, and the two is subjected to ethoxylation, generates polyether intermediate.The polyether intermediate
Both it is soluble in toluene, esterification, and the trihydroxyethyl isocyanuric triacrylate that esterification obtains also easily are carried out with acrylic acid
Viscosity at normal temperature is little, and is not easy to crystallize at low temperature.
The inventor finds that the existing technology has at least the following problems:
The trihydroxyethyl isocyanuric triacrylate that obtains prepared by the method for modifying provided using the prior art, and not
The trihydroxyethyl isocyanuric triacrylate obtained is prepared using method of modifying to compare, the former water resistance significantly under
Drop, and the dispersibility of curing rate and pigment is also declined.
Summary of the invention
The embodiment of the invention provides a kind of 3 (6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric and its synthetic method,
To solve the above problems.The technical solution is as follows:
In a first aspect, providing a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the conjunction
Include: at method
It is (2~4) that molar ratio is added into reactor: 1 6-caprolactone, trihydroxyethyl isocyanuric ester, form mixing
System, and remove the moisture in the mixed system；
Under nitrogen atmosphere, the mixed system is heated to 100 DEG C~180 DEG C, and is added into the mixed system
Catalyst is reacted, and trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is generated；
The quality of the catalyst is the 0.01%~2% of the mixed system and the catalyst gross mass.
In a kind of possible design, the molar ratio of the 6-caprolactone and the trihydroxyethyl isocyanuric ester is (2.5
~3.5): 1.
A kind of moisture in possible design, in the removal mixed system, comprising:
The mixed system is heated to 80 DEG C~110 DEG C, and in the case where vacuum degree is at least -0.095MPa, described in extraction
Moisture in mixed system, until the quality of the moisture is less than the 0.05% of the mixed system quality.
It is defeated in Xiang Suoshu reactor after removing the moisture in the mixed system in a kind of possible design
The nitrogen for sending flow to be at least 0.1L/min, so that the mixed system is in the nitrogen atmosphere.
In a kind of possible design, the quality of the catalyst is the mixed system and the catalyst gross mass
0.05%~1%.
In a kind of possible design, the catalyst is stannous octoate, dibutyl tin dilaurate, zirconium-n-butylate, new
At least one of capric acid bismuth.
In a kind of possible design, after the mixed system is heated to 130 DEG C~140 DEG C, in Xiang Suoshu reactor
The catalyst is added.
Second aspect provides a kind of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, using described in first aspect
Synthetic method be prepared.
Technical solution provided in an embodiment of the present invention has the benefit that
The obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) of the synthetic method provided through the embodiment of the present invention
Ester can obtain trihydroxyethyl isocyanide of good performance as modified trihydroxyethyl isocyanuric ester with acroleic acid esterification
Uric acid triacrylate, such as the hydroxyethyl isocyanurate triacrylate have good water resistance, curing rate, pigment
Dispersion performance.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made below further
Ground detailed description.
In a first aspect, the embodiment of the invention provides a kind of conjunctions of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester
At method, which includes:
Step 101, molar ratio is added into reactor is (2~4): 1 6-caprolactone, trihydroxyethyl isocyanuric ester,
Mixed system is formed, and removes the moisture in mixed system.
Step 102, under nitrogen atmosphere, is heated to 100 DEG C~180 DEG C for mixed system, and be added into mixed system
Catalyst is reacted, and trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is generated；The quality of catalyst is mixed system
With the 0.01%~2% of catalyst gross mass.
Those skilled in the art can prepare (the 6- hydroxyl of trihydroxyethyl isocyanuric 3 using synthetic method provided in an embodiment of the present invention
Base 1- caproic acid) ester, wherein the chemical formula structure formula of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is as follows:
It can be seen that from the chemical formula structure formula of above-mentioned trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester due to not changing
Property 3 groups of trihydroxyethyl isocyanuric ester be to be arranged around intermediate cyclic structure, certain steric hindrance can be generated, and
Each hydroxyl of modified trihydroxyethyl isocyanuric ester is connected with the 6-caprolactone for having opened ring, that is, is connected to one
Steric hindrance can be reduced with free-moving segment, improve the curing rate of modified trihydroxyethyl isocyanuric ester, in turn
Also provide the curing rate of the esterification products of (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid；And due to
(the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 is polyester type organic, therefore (the 6- hydroxyl 1- of trihydroxyethyl isocyanuric 3
Caproic acid) product after ester and acroleic acid esterification is also polyester type organic, and polyester type organic and polyethers type organic (example
Such as, is produced from the polyethers centre that prior art ethylene oxide and trihydroxyethyl isocyanuric ester carry out ethoxylation and generate
Object) it compares, water resistance is stronger；In addition, since the number of the polyester segment of modified trihydroxyethyl isocyanuric ester increases,
This improves the dispersion performance of pigment.
As it can be seen that obtained 3 (the 6- hydroxyl 1- of trihydroxyethyl isocyanuric of the synthetic method provided through the embodiment of the present invention
Caproic acid) ester as modified trihydroxyethyl isocyanuric ester can obtain trihydroxyethyl of good performance with acroleic acid esterification
Isocyanuric acid triacrylate, for example, the hydroxyethyl isocyanurate triacrylate have good water resistance, curing rate,
The dispersion performance of pigment.
Each step of synthetic method provided in an embodiment of the present invention is illustrated below:
In a step 101, it is (2~4) that molar ratio is added into reactor: 1 6-caprolactone, trihydroxyethyl isocyanide urine
Acid esters forms mixed system, and removes the moisture in mixed system.
It is effectively modified in order to be carried out to trihydroxyethyl isocyanuric ester, need to guarantee the every of trihydroxyethyl isocyanuric ester
All connect a 6-caprolactone on a hydroxyl, and the additional amount of 6-caprolactone and trihydroxyethyl isocyanuric ester, 6-caprolactone
Impurities affect to the modified effect of trihydroxyethyl isocyanuric ester.
In terms of the additional amount of 6-caprolactone, the modified effect of trihydroxyethyl isocyanuric ester can be described as: when
When the additional amount of 6-caprolactone is too low, hydroxyl a part of in trihydroxyethyl isocyanuric ester can be prevented from connecting 6-caprolactone,
Also the hydroxyl of the part cannot be modified, and then weakens the modified effect to trihydroxyethyl isocyanuric ester；And work as ε-
When the additional amount of caprolactone is too high, a part of hydroxyl connection 2 or more in trihydroxyethyl isocyanuric ester 6-caprolactones can be made,
The double bond density fall of product after will lead to (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acroleic acid esterification
It is excessive, and then influence the curing rate of product.
Based on above-mentioned, after improving 6-caprolactone to the modified effect of trihydroxyethyl isocyanuric ester and above-mentioned esterification
The curing rate of product, in the embodiment of the present invention, the molar ratio of 6-caprolactone and trihydroxyethyl isocyanuric ester be may be configured as
2.5~3.5:1, for example, the molar ratio can be 2.5:1,2.6:1,2.7:1,2.8:1,2.9:1,3.0:1,3.1:
1,3.2:1,3.3:1,3.4:1,3.5:1 etc..
About trihydroxyethyl isocyanuric ester, 6-caprolactone purity in terms of, in order to ensure trihydroxyethyl isocyanuric ester
Each hydroxyl be connected with 6-caprolactone, it is pure that the purity of trihydroxyethyl isocyanuric ester and 6-caprolactone may be configured as chemistry.
Since 6-caprolactone is aqueous solution, the embodiment of the present invention imitates the modified of trihydroxyethyl isocyanuric ester to improve
Fruit, and remove trihydroxyethyl isocyanuric ester and be formed by the moisture of mixed system with 6-caprolactone.When implementing, pumping can be passed through
The method of water absorbing agent (such as molecular sieve) is added into mixed system to remove the moisture in mixed system in vacuum method.If adopting
With the moisture in the latter's method removal mixed system, a large amount of water absorbing agent is not only needed, but also need filtration step, this increase
Processing cost and time.Therefore, the embodiment of the present invention is using the moisture in the method removal mixed system vacuumized, the party
Method are as follows: mixed system is heated to 80 DEG C~110 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracted out in mixed system
Moisture, until the quality of moisture is less than 0.05%.
Specifically, mixed system is first heated to 80 DEG C~110 DEG C, make the moisture evaporation in mixed system；Then, it extracts
Air in reactor, until the vacuum degree in reactor is at least -0.095MPa；The air pressure in reactor is maintained later
More than -0.095MPa, and the moisture in mixed system is extracted, until the quality of moisture is less than the quality of mixed system
0.05%, such as 0.04%, 0.03%, 0.02%, 0.01% etc..
Wherein, time mixed system extracted with mixed system volume and to extract dynamics related, for example, this
The time that inventive embodiments extract mixed system is at least 2 hours, for example, 2 hours, 3 hours, 4 hours etc..
It should be noted that vacuum degree is more negative, value is bigger, for example, vacuum degree -0.095MPa is greater than vacuum degree -
0.085MPa。
In a step 102, under nitrogen atmosphere, mixed system is heated to 100 DEG C~180 DEG C, and into mixed system
Catalyst is added, is reacted, to generate trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, wherein the quality of catalyst
For mixed system and the 0.01%~2% of catalyst gross mass.
In the esterification process of trihydroxyethyl isocyanuric ester and 6-caprolactone, oxygen can occur for trihydroxyethyl isocyanuric ester
Change reaction, and then weakens the modified effect to trihydroxyethyl isocyanuric ester.For this problem, the embodiment of the present invention is by three hydroxyl second
Base chlorinated isocyanurates and 6-caprolactone carry out esterification in nitrogen atmosphere.Water when implementing, in removal mixed system
Point after, can into reactor feed flow be at least 0.1L/min (for example, may be configured as 0.1L/min, 0.2L/min,
0.3L/min, 0.4L/min, 0.5L/min etc.) nitrogen so that mixed system is in nitrogen atmosphere.
Wherein, reaction temperature, the type of catalyst and additional amount are equal to the modified effect of trihydroxyethyl isocyanuric ester
Have an impact, above three factor is illustrated one by one below.
In terms of reaction temperature, since the fusing point of trihydroxyethyl isocyanuric ester is 130 DEG C, at 130 DEG C hereinafter, three hydroxyls
With 6-caprolactone out-phase reaction can occur for ethyl chlorinated isocyanurates, be unfavorable for the progress of reaction.If at this point, different to trihydroxyethyl
Catalyst is added in cyanurate, will lead to a part of hydroxyl of trihydroxyethyl isocyanuric ester and do not react, and another part
Excessive 6-caprolactone has been gone up in connection on the alkyl of trihydroxyethyl isocyanuric ester, and then will lead to trihydroxyethyl isocyanuric ester
It is inhomogenous with the product composition after acroleic acid esterification；And since the product contains, there are many ester bonds, so that the product is in 140 DEG C of height
Temperature is lower easily to turn yellow, and will affect the application of the product, such as the application in varnish field.
In this regard, the embodiment of the present invention by mixed system be heated to 130 DEG C~140 DEG C (for example, can be set to 130 DEG C,
132 DEG C, 134 DEG C, 136 DEG C, 138 DEG C, 140 DEG C etc.), and catalyst is added into reactor.
In terms of catalyst charge, when catalyst charge is too low, it is unfavorable for the progress of reaction, reaction can be extended
Time, and then lead to the colour changed into yellow of mixed system and reaction product；And when catalyst charge is excessively high, due to trihydroxyethyl
The active difference of 3 hydroxyls of chlorinated isocyanurates is little, can generate by-product, reduce and change to trihydroxyethyl isocyanuric ester
Property effect.
To solve the above-mentioned problems, the quality of the catalyst in the embodiment of the present invention may be configured as mixed system and catalyst
Gross mass 0.05%~1%, for example, may be configured as 0.05%, 0.06%, 0.07%, 0.08%, 0.09%,
0.1% etc..
In terms of the type of catalyst, urged for be catalyzed that trihydroxyethyl isocyanuric ester and 6-caprolactone react
The type of agent can be set to it is a variety of, as long as the open loop of 6-caprolactone can be promoted.For example, in the embodiment of the present invention
Catalyst can be catalyst be at least one of stannous octoate, dibutyl tin dilaurate, zirconium-n-butylate, bismuth neodecanoate.
It should be noted that since the content of 6-caprolactone will affect trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid)
The performance of product after ester and acroleic acid esterification, such as mechanical performance.For this problem, trihydroxyethyl isocyanuric ester with
In the esterification process of 6-caprolactone, the embodiment of the present invention obtains the residual quantity of 6-caprolactone using gas chromatography, that is, judges
The extent of reaction.When the residual quantity of 6-caprolactone is 0.5%, it is believed that reaction is completed, at this point, stopping heating to mixed system.
Work as reaction product, i.e. trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, temperature is reduced to 60 DEG C hereinafter, discharging saves.
It should be noted that the residual quantity of above-mentioned 6-caprolactone refer to 6-caprolactone quality be overall reaction product with
And the 0.5% of 6-caprolactone gross mass.
Wherein, gas chromatography is used to measure constituent concentration to be known in the art.Since trihydroxyethyl isocyanide is urinated
The boiling point of sour 3 (6- hydroxyl 1- caproic acid) esters is higher, so the embodiment of the present invention obtains the residual of 6-caprolactone with the following method
Amount: a standard curve (point i.e. on the standard curve for 6-caprolactone residual quantity is first obtained first with the method for headspace sampling
A corresponding 6-caprolactone residual quantity), it is then carried out using residual quantity of the headspace injection method to the 6-caprolactone in the product real
It surveys, and brings measured result into standard curve and converse 6-caprolactone residual quantity.
As it can be seen that synthetic method provided in an embodiment of the present invention, not only easy to operate, but also there is no any waste water of output, gives up
Material and exhaust gas, are a kind of efficient synthetic methods.
Second aspect, the embodiment of the invention also provides a kind of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, benefits
The synthetic method described in first aspect is prepared.
The obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) of the synthetic method provided through the embodiment of the present invention
Ester can obtain trihydroxyethyl isocyanide of good performance as modified trihydroxyethyl isocyanuric ester with acroleic acid esterification
Uric acid triacrylate, such as the hydroxyethyl isocyanurate triacrylate have good water resistance, curing rate, pigment
Dispersion performance.
All the above alternatives can form the alternative embodiment of the disclosure, herein no longer using any combination
It repeats one by one.
Hereinafter the present invention will be further described through by specific embodiment.
In following specific embodiments, condition person is not specified in related operation, according to normal conditions or manufacturer
It is recommended that condition carry out.It is raw materials used production firm is not specified and specification person be can be with conventional products that are commercially available.
Wherein, trihydroxyethyl isocyanuric ester is purchased from Yangzhou Suntory Ltd., and 6-caprolactone is purchased from Japanese big respectively
Sai Lu plastics Co., Ltd.
Embodiment 1
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.5:1 are added into reactor, forms mixture
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
In, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen atmosphere
In enclosing.Mixed system is heated to 120 DEG C, and the tin dilaurate that quality is mixed system and catalyst gross mass 0.5% is added
Dibutyl tin catalyst, is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone is residual
When allowance is 0.5%, it is believed that reaction terminates；Reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl
Isocyanuric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 2
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.95:1 are added into reactor, forms mixing
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
Wherein, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen
In atmosphere.Mixed system is heated to 130 DEG C, and 2% n-butanol that quality is mixed system and catalyst gross mass is added
Zr catalyst is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity is
When 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanide
Uric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 3
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 3.0:1 are added into reactor, forms mixture
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
In, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen atmosphere
In enclosing.Mixed system is heated to 100 DEG C, and it is sub- that 0.5% octanoic acid that quality is mixed system and catalyst gross mass is added
Tin catalyst is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity is
When 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanide
Uric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 4
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 3.5:1 are added into reactor, forms mixture
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
In, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen atmosphere
In enclosing.Mixed system is heated to 180 DEG C, and 2% bismuth neodecanoate that quality is mixed system and catalyst gross mass is added
Catalyst is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity is
When 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanide
Uric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 5
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 3.0:1 are added into reactor, forms mixture
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
In, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen atmosphere
In enclosing.Mixed system is heated to 160 DEG C, and it is sub- that 0.05% octanoic acid that quality is mixed system and catalyst gross mass is added
Tin catalyst is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity is
When 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanide
Uric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 6
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.95:1 are added into reactor, forms mixing
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
Wherein, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen
In atmosphere.Mixed system is heated to 140 DEG C, and the 0.2% positive fourth that quality is mixed system and catalyst gross mass is added
Alcohol Zr catalyst, is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity
When being 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, it is different to can be obtained trihydroxyethyl
Cyanuric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 7
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.8:1 are added into reactor, forms mixture
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
In, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen atmosphere
In enclosing.Mixed system is heated to 135 DEG C, and 0.15% neodecanoic acid that quality is mixed system and catalyst gross mass is added
Bismuth catalyst is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity is
When 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanide
Uric acid 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 8
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.5:1 are added into reactor, forms mixture
System.Mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the moisture in mixed system,
In, extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that mixed system is in nitrogen atmosphere
In enclosing.Mixed system is heated to 120 DEG C, and it is sub- that 0.5% octanoic acid that quality is mixed system and catalyst gross mass is added
Tin catalyst is reacted.During the reaction, reaction end is judged using gas chromatography, when 6-caprolactone residual quantity is
When 0.5%, it is believed that reaction terminates；And reaction product is cooled to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanide
Uric acid 3 (6- hydroxyl 1- caproic acid) ester.
Reference examples 1
This reference examples provides a kind of trihydroxyethyl isocyanuric ester by after ethylene-oxide-modified.
Reference examples 2
This reference examples provides a kind of trihydroxyethyl isocyanuric ester without any modification.
Application Example
This application embodiment under the same reaction conditions, respectively will be modified provided by embodiment 8 and reference examples 1-2
Trihydroxyethyl isocyanuric ester and acrylic acid carry out esterification, and the trihydroxyethyl isocyanuric triacrylate that will be obtained
Sequentially number is No. 1, No. 2, No. 3.Later, the water suction for the trihydroxyethyl isocyanuric triacrylate for being respectively 1-10 to number
Rate, curing rate, viscosity are tested, as a result referring to table 1.
Table 1
It should be noted that the embodiment characterizes three hydroxyls corresponding to above-mentioned number 1-3 with the size of double bond conversion rate
Ethyl isocyanuric acid triacrylate curing rate.Wherein, double bond conversion rate is bigger, shows that curing rate is faster.
As can be seen from Table 1, the water absorption rate of the trihydroxyethyl isocyanuric triacrylate of number 1 is than number 2-3's
The water absorption rate of trihydroxyethyl isocyanuric triacrylate is low；The solidification of the trihydroxyethyl isocyanuric triacrylate of number 1
Speed is bigger than the curing rate of the trihydroxyethyl isocyanuric triacrylate of number 2-3；In addition, the trihydroxyethyl of number 1 is different
The pigment point of trihydroxyethyl isocyanuric triacrylate of the pigment dispersion of cyanuric acid triacrylate better than number 2-3
Dissipate performance.As it can be seen that the obtained modified trihydroxyethyl isocyanuric ester of the synthetic method provided through the embodiment of the present invention,
Trihydroxyethyl isocyanuric triacrylate of good performance can be obtained with acroleic acid esterification.
The foregoing is merely presently preferred embodiments of the present invention, the protection scope being not intended to limit the invention, 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.
Claims (8)
1. a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, which is characterized in that the synthetic method
Include:
It is (2~4) that molar ratio is added into reactor: 1 6-caprolactone, trihydroxyethyl isocyanuric ester form mixed system,
And remove the moisture in the mixed system；
Under nitrogen atmosphere, the mixed system is heated to 100 DEG C~180 DEG C, and catalysis is added into the mixed system
Agent is reacted, and trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is generated；
The quality of the catalyst is the 0.01%~2% of the mixed system and the catalyst gross mass.
2. synthetic method according to claim 1, which is characterized in that the 6-caprolactone and the trihydroxyethyl isocyanide are urinated
The molar ratio of acid esters is (2.5~3.5): 1.
3. synthetic method according to claim 1, which is characterized in that the moisture in the removal mixed system, packet
It includes:
The mixed system is heated to 80 DEG C~110 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the mixing out
Moisture in system, until the quality of the moisture is less than the 0.05% of the mixed system quality.
4. synthetic method according to claim 1, which is characterized in that removing the moisture in the mixed system
Afterwards, feed flow is at least the nitrogen of 0.1L/min in Xiang Suoshu reactor, so that the mixed system is in the nitrogen atmosphere
In enclosing.
5. synthetic method according to claim 1, which is characterized in that the quality of the catalyst be the mixed system with
The 0.05%~1% of the catalyst gross mass.
6. synthetic method according to claim 1, which is characterized in that the catalyst is stannous octoate, tin dilaurate two
At least one of butyl tin, zirconium-n-butylate, bismuth neodecanoate.
7. synthetic method according to claim 1, which is characterized in that the mixed system is heated to 130 DEG C~140 DEG C
Afterwards, the catalyst is added in Xiang Suoshu reactor.
8. a kind of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, utilizes the described in any item synthesis sides claim 1-7
Method is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
| CN115819783A (en) * | 2022-09-26 | 2023-03-21 | 山东天一化学股份有限公司 | Hyperbranched macromolecular flame retardant containing P, N and Si and preparation method thereof |
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| JPS6084274A (en) * | 1983-10-17 | 1985-05-13 | Toagosei Chem Ind Co Ltd | Production of acrylic acid ester |
| JP2015101606A (en) * | 2013-11-21 | 2015-06-04 | 関西ペイント株式会社 | Coating composition and coated article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6084274A (en) * | 1983-10-17 | 1985-05-13 | Toagosei Chem Ind Co Ltd | Production of acrylic acid ester |
| JPS6154788B2 (en) * | 1983-10-17 | 1986-11-25 | Toa Gosei Chem Ind | |
| JP2015101606A (en) * | 2013-11-21 | 2015-06-04 | 関西ペイント株式会社 | Coating composition and coated article |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
| CN115819783A (en) * | 2022-09-26 | 2023-03-21 | 山东天一化学股份有限公司 | Hyperbranched macromolecular flame retardant containing P, N and Si and preparation method thereof |
| CN115819783B (en) * | 2022-09-26 | 2023-08-22 | 山东天一化学股份有限公司 | Hyperbranched macromolecular flame retardant containing P, N, si and preparation method thereof |
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