CN116768726A - Unsaturated carbonate-containing compound, process for producing the same, cured product produced therefrom, and process for degrading the cured product - Google Patents
Unsaturated carbonate-containing compound, process for producing the same, cured product produced therefrom, and process for degrading the cured product Download PDFInfo
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- CN116768726A CN116768726A CN202210215878.1A CN202210215878A CN116768726A CN 116768726 A CN116768726 A CN 116768726A CN 202210215878 A CN202210215878 A CN 202210215878A CN 116768726 A CN116768726 A CN 116768726A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- C07—ORGANIC CHEMISTRY
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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Abstract
本发明提供一种含碳酸酯的不饱和化合物、其制备方法、其制备的固化物及降解固化物的方法。含碳酸酯的不饱和化合物具有如式(I)或式(II)所示之一结构，式(I)及式(II)中各符号如说明书中所定义。借此，以碳酸酯化合物为原料，分别和含有不饱和双键结构的环氧化合物或醇类化合物反应以制备出含碳酸酯的不饱和化合物，且其与树脂制得的固化物具有良好的热性质并提升可回收性。
The invention provides a carbonate-containing unsaturated compound, its preparation method, its prepared cured product and a method for degrading the cured product. The unsaturated compound containing carbonate has a structure represented by formula (I) or formula (II), and each symbol in formula (I) and formula (II) is as defined in the specification. In this way, the carbonate compound is used as a raw material and reacts with an epoxy compound or an alcohol compound containing an unsaturated double bond structure to prepare an unsaturated compound containing a carbonate, which has good properties with the cured product made from the resin. thermal properties and improve recyclability.
Description
Technical Field
The present invention relates to an unsaturated compound, a method for preparing the same, a cured product prepared by the same and a method for degrading the cured product, and more particularly, to an unsaturated compound containing carbonate, a method for preparing the same, a cured product prepared by the same and a method for degrading the cured product.
Background
Thermosetting materials have the characteristic of good resin processability before curing, and have the advantages of excellent thermal stability, mechanical strength, chemical resistance and the like after crosslinking and curing, so that the thermosetting materials are widely applied to various fields and are often used in fiber composite materials with high strength and light weight requirements. However, the characteristics of the thermosetting material such as non-reworkability and good chemical resistance also lead to the difficulty of recycling the thermosetting material after being discarded, and in addition, the burning of the fiber composite material easily shortens the service life of the incineration equipment, which causes a great deal of waste problems, so how to dispose of the discarded thermosetting material is an important improvement target in the current environmental protection issues.
At present, vinyl ester resin and unsaturated polyester resin are thermosetting materials commonly used in industry, and are widely applied to the fields of coating, transportation, construction and the like, so that the application market is continuously expanded due to the vigorous development of the transportation industry of automobiles, ships and other masses, and the treatment of resin waste becomes a serious issue facing to application and developers, so that the industry is thirsty about the technology capable of decomposing or recycling the resin waste.
The main current research is to depolymerize with acid water or alkaline water, which will lead to the problem of subsequent treatment of a large amount of wastewater, which is not friendly to industrial application and environment, but is limited by the limited content of structural ester groups in the prior art if organic degradation is used, and has the disadvantages of high degradation temperature, energy consumption and poor efficiency, so that the method has considerable application defects.
In view of this, it is an objective of related industries to synthesize a chemically degradable cured product and reuse waste materials.
Disclosure of Invention
The invention provides an unsaturated compound containing carbonate and a preparation method thereof, wherein the unsaturated compound is prepared by taking a carbonate compound as a raw material and respectively reacting with an epoxy compound or an alcohol compound containing unsaturated double bonds.
Another object of the present invention is to provide a cured product and a method for degrading the cured product, wherein the cured product is prepared by curing an unsaturated compound containing carbonate, and the cured product can be degraded, so that the product can be recycled and reused, and the environmental load is reduced.
An embodiment of the present invention provides a carbonate-containing unsaturated compound having a structure represented by formula (I) or formula (II):
wherein X is ethenyl, propenyl, acrylic or methacrylic, R 1 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and a is an integer of 0 to 5. A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a structure represented by formula (i):
wherein R is 2 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and b is an integer of 0 to 4. B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a structure represented by formula (i), a structure represented by formula (ii) or formula (iii):
wherein R is 3 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and c is an integer of 0 to 4. Y is a single bond, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, a sulfinyl group, an acyl group, a fluorenyl group or a hexafluoropropyl group. Z is an alkyl group having 1 to 12 carbon atoms,Alkoxy having 1 to 12 carbon atoms, ortho-phenylene, meta-phenylene or para-phenylene, n is an integer of 0 to 10.
In another embodiment, the present invention provides a method for preparing an unsaturated carbonate-containing compound, comprising providing a carbonate-containing compound, providing an unsaturated double bond-containing compound, and performing a catalytic step. The carbonate-containing compound is dimethyl carbonate or diphenyl carbonate. The unsaturated double bond-containing compound is a monofunctional alcohol compound containing an unsaturated double bond or a monofunctional epoxy compound containing an unsaturated double bond. The catalytic step is to mix a carbonate-containing compound with an unsaturated double bond-containing compound, and then obtain a carbonate-containing unsaturated compound under the catalysis of a catalyst, wherein the carbonate-containing unsaturated compound has a structure shown as a formula (I) or a formula (II):
wherein X is ethenyl, propenyl, acrylic or methacrylic, R 1 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and a is an integer of 0 to 5. A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a structure represented by formula (i):
wherein R is 2 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and b is an integer of 0 to 4. B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a structure represented by formula (i), a structure represented by formula (ii) or formula (iii):
wherein R is 3 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and c is an integer of 0 to 4. Y is a single bond, alkyl of 1 to 12 carbon atoms, cycloalkyl of 1 to 12 carbon atoms, oxygenAtom, sulfur atom, sulfonyl group, sulfinyl group, acyl group, fluorenyl group or hexafluoropropyl group. Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an ortho-phenylene group, a meta-phenylene group or a para-phenylene group, and n is an integer of 0 to 10.
The process for producing a carbonate-containing unsaturated compound according to the preceding paragraph, wherein the catalyst may be an ionic liquid or an organic base.
The process for producing a carbonate-containing unsaturated compound according to the preceding paragraph, wherein the equivalent ratio of the carbonate-containing compound to the unsaturated double bond-containing compound may be from 0.8 to 1.2.
In another embodiment, the present invention provides a method for preparing an unsaturated carbonate-containing compound, comprising performing a catalytic step and performing an addition step. The catalytic step is to mix diphenyl carbonate with a difunctional epoxy compound and then obtain a reactant under the catalysis of a catalyst. The addition step is to add the reactant acrylic acid or methacrylic acid to obtain a carbonate-containing unsaturated compound having a structure as shown in formula (II):
wherein X is ethenyl, propenyl, acrylic or methacrylic, R 1 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and a is an integer of 0 to 5. B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a structure represented by one of the formula (i), the formula (ii) or the formula (iii):
wherein R is 2 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, b is an integer of 0 to 4,R 3 is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and c is an integer of 0 to 4. Y is a single bond, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, a sulfinyl group, an acyl group, a fluorenyl group or a hexafluoropropyl group. Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an ortho-phenylene group, a meta-phenylene group or a para-phenylene group, and n is an integer of 0 to 10.
The process for producing a carbonate-containing unsaturated compound according to the preceding paragraph, wherein the catalyst may be an organic base and the equivalent ratio of the difunctional epoxy compound to diphenyl carbonate may be 2.0 to 8.0.
In still another embodiment, the present invention provides a cured product obtained by a curing reaction of the carbonate-containing unsaturated compound.
The cured product according to the preceding paragraph, wherein the curing reaction is completed by adding the carbonate-containing unsaturated compound to a resin and heating.
The cured product according to the preceding paragraph, wherein the resin may be an unsaturated polyester resin or a vinyl ester resin.
The cured product according to the preceding paragraph, wherein the carbonate-containing unsaturated compound may be added in an amount of 3 to 20 weight percent based on the resin content.
In a further embodiment of the present invention, a method for degrading a cured product is provided, comprising providing the cured product and performing a degradation step, wherein the degradation step is to react an amine compound with the cured product to degrade the cured product.
Therefore, the unsaturated compound containing the carbonic ester can participate in the free radical copolymerization of unsaturated resin or vinyl ester resin, the ester group density of a main structure is increased by introducing a high-activity carbonic ester structure into a network system, the material is endowed with good degradability, and a degradation method with mild conditions is provided, so that the high degradation efficiency can be achieved, no waste water is generated, and the industrialization is facilitated and the problem of derived environmental hazard can be avoided.
Drawings
The above and other objects, features, advantages and embodiments of the present invention will become more apparent by reading the following description of the accompanying drawings in which:
FIG. 1 is a flow chart showing the steps of a process for producing a carbonate-containing unsaturated compound according to an embodiment of the invention;
FIG. 2 is a flow chart showing the steps of a method for producing an unsaturated carbonate-containing compound according to another embodiment of the invention;
FIG. 3 is a flowchart showing steps of a method for producing a cured product according to still another embodiment of the present invention; and
fig. 4 is a flow chart showing steps of a method for degrading a cured product according to still another embodiment of the present invention.
Detailed Description
Embodiments of the invention will be discussed in more detail below. However, this embodiment may be an application of various inventive concepts and may be embodied within a wide variety of specific contexts. The particular embodiments are illustrative only and are not limiting to the scope of the disclosure.
In the present invention, the structure of the compound is sometimes represented by a bond wire (skeleton formula), and such a representation may omit a carbon atom, a hydrogen atom, and a carbon-hydrogen bond. If functional groups are explicitly depicted in the structural formula, the same shall apply.
In the present invention, the term "carbonate-containing unsaturated compound having a structure represented by the formula (I)" may be expressed as a carbonate-containing unsaturated compound represented by the formula (I) or a carbonate-containing unsaturated compound (I), for brevity and smoothness, and the other compounds or groups may be expressed in the same manner.
< unsaturated Compound containing carbonate >
The invention provides a carbonate-containing unsaturated compound, which has a structure shown as a formula (I) or a formula (II):
wherein X is vinyl group or propyleneA radical (all group), an acrylic radical (acrylate) or a methacrylic radical (methacrylate), R 1 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group (methoxy), a nitro group (nitro) or a halogen atom (halogen), a is an integer of 0 to 5. A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a structure represented by formula (i):
wherein R is 2 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and b is an integer of 0 to 4. B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a structure represented by formula (i), a structure represented by formula (ii) or formula (iii):
wherein R is 3 Is an alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, and c is an integer of 0 to 4. Y is a single bond, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group (sulfoxyl), a sulfinyl group (thio), an acyl group (carboyl), a fluorenyl group (fluorne) or a hexafluoropropyl group (hexafluoropane). Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an ortho (ortho-) phenylene group, a meta (meta-) phenylene group or a para (para-) phenylene group, and n is an integer of 0 to 10.
Therefore, the unsaturated compound containing carbonate of the invention can be used for endowing the thermosetting material with degradability by introducing the carbonate structure, so that the aim of recycling and degrading the material can be achieved.
< method for producing carbonate-containing unsaturated Compound >
Referring to FIG. 1, a process flow diagram of a process 100 for preparing carbonate-containing unsaturated compounds according to one embodiment of the invention is shown. In fig. 1, the method 100 for preparing unsaturated compounds containing carbonate includes a step 110, a step 120, and a step 130.
Step 110 provides a carbonate compound which is dimethyl carbonate (DMC) or diphenyl carbonate (DPC).
Step 120 provides an unsaturated double bond-containing compound which is a monofunctional alcohol compound containing an unsaturated double bond or a monofunctional epoxy compound containing an unsaturated double bond.
Step 130 is a catalytic step of mixing the carbonate-containing compound with the unsaturated double bond-containing compound to obtain a carbonate-containing unsaturated compound having a structure shown in formula (I) or formula (II):
concerning X, A, B, R 1 And a is defined by referring to the above, and is not described herein, and the catalyst may be an ionic liquid or an organic base.
Referring to FIG. 2, a flow chart of steps of a method 200 for preparing an unsaturated carbonate-containing compound according to another embodiment of the invention is shown. In fig. 2, a method 200 for preparing an unsaturated carbonate-containing compound includes a step 210 and a step 220.
Step 210 is a catalytic step of mixing diphenyl carbonate with a difunctional epoxy compound to obtain a reactant under the catalysis of a catalyst, wherein the catalyst may be an organic base.
Step 220 is an addition step of adding acrylic acid or methacrylic acid to the reactants to obtain a carbonate-containing unsaturated compound having a structure as shown in formula (II):
concerning X, B, R 1 And a is defined by referring to the above, and is not described herein.
Specifically, when the carbonate-containing unsaturated compound has a structure represented by formula (I), the preparation method comprises reacting dimethyl carbonate with a monofunctional alcohol compound containing an unsaturated double bond at an equivalent ratio of 0.8 to 1.2, using an ionic liquid as a catalyst, wherein the catalyst is added in an amount of 0.01 to 2 weight percent based on the total reactant content, and the reaction temperature is 60 to 90 ℃.
In addition, when the carbonate-containing unsaturated compound has a structure represented by formula (II), it has two preparation methods. The first preparation method is to react diphenyl carbonate with a monofunctional epoxy compound containing unsaturated double bonds at an equivalent ratio of 0.8 to 1.2, and use an organic base as a catalyst, wherein the catalyst is added in an amount of 0.01 to 2 weight percent of the content of the monofunctional epoxy compound containing unsaturated double bonds, and the reaction temperature is 80 to 140 ℃. The second preparation method is that the difunctional epoxy compound and diphenyl carbonate react at an equivalent ratio of 2.0 to 8.0, and organic base is used as a catalyst, the addition amount of the catalyst is 0.01 weight percent to 2 weight percent of the content of the difunctional epoxy compound, and then acrylic acid or methacrylic acid is added for reaction, wherein the equivalent ratio of the acrylic acid or the methacrylic acid to the difunctional epoxy compound is 0.4 to 0.6, and the reaction temperature is 80 ℃ to 140 ℃.
< cured product >
The present invention further provides a cured product obtained by performing a curing reaction of the carbonate-containing unsaturated compound, and the curing reaction is briefly described with reference to fig. 3, wherein fig. 3 is a flowchart illustrating a step of a method 300 for preparing a cured product according to still another embodiment of the present invention. In fig. 3, the method 300 for preparing a cured product includes steps 310 and 320.
Step 310 is a mixing step in which a carbonate-containing unsaturated compound is added to a resin. Specifically, the unsaturated carbonate-containing compound is added in an amount of 3 to 20 weight percent based on the resin content, which can improve the degradability of the cured product without affecting the basic physical properties. For details of the carbonate-containing unsaturated compound, reference is made to the foregoing, and details are not repeated herein, but the resin may be, but is not limited to, an unsaturated polyester resin or a vinyl ester resin.
Step 320 is a curing step in which the carbonate-containing unsaturated compound is free-radically copolymerized with the resin to form a cured product, and the curing temperature by heating may be 25 ℃ to 80 ℃. The curing temperature and heating time of the heating can be flexibly adjusted according to the types of the unsaturated compound containing carbonate and the resin used, and the invention is not limited thereto.
< method of degrading cured product >
Referring to FIG. 4, a flowchart illustrating steps of a method 400 for degrading a cured product according to another embodiment of the invention is shown. In fig. 4, a method 400 of degrading a cured product includes a step 410 and a step 420.
Step 410 provides the cured product. Step 420 is a degradation step, which is to react an amine compound with the cured product to degrade the cured product. Specifically, the degradation step can be carried out at 80-150 ℃ without adding any catalyst, and the degraded liquid can be distilled and purified to recycle amine compounds and recover the produced urea derivatives for further use in paint or polyurethane materials, thereby achieving the aim of recycling application.
The present invention is further illustrated by the following specific examples, which are presented to facilitate a person of ordinary skill in the art to which the invention pertains and to make and practice the invention without undue interpretation, and are not to be construed as limiting the scope of the present invention, but as illustrating how the materials and methods of the present invention may be practiced.
< example/comparative example >
< preparation of carbonate-containing unsaturated Compound >
Example 1: 10 g of dimethyl carbonate and 28.89 g of hydroxyethyl methacrylate (2-Hydroxyethyl methacrylate, HEMA) are taken so that the two form reactants in an equivalent ratio of 1:1, followed by the addition of trioctylmethyl phosphonium methyl carbonate in an amount of 0.5% by weight based on the total amount of reactants (trioctylmethylphosphonium methyl carbonate, P 8881 CH 3 OCOO) ionic liquid and heating to 80 ℃ for 8 hours to obtain the unsaturated compound containing carbonic ester of the example 1, the yield is about 60%. Data of FTIR spectra: 1748cm -1 (carbonate C＝O)、1715cm -1 (acrylate c=o). The reaction equation for example 1 is shown in Table one below.
Example 2: 10 g of diphenyl carbonate and 13.27 g of glycidyl methacrylate (Glycidyl methacrylate, GMA) were taken so that the two were formed into a uniform solution at an equivalent ratio of 1:1 in a nitrogen atmosphere at 110℃and 0.027 g of pyridine (0.2 wt% of GMA) was further added thereto to react for 3 hours, whereby the carbonate-containing unsaturated compound of example 2 was obtained in a yield of about 90%. Data of FTIR spectra: 1749cm -1 (aliphatic carbonate C＝O)、1715cm -1 (acrylate c=o). The reaction equation for example 2 is shown in Table two below.
Example 3: 10 g of diphenyl carbonate and 34.54 g of bisphenol A type epoxy resin (commercial product No. BE188 of vinca resin) were taken so that the two were formed into a homogeneous solution at an equivalent ratio of 1:2 in a nitrogen atmosphere at 110℃and further 0.1727 g of pyridine (0.5 wt% BE 188) was added to react for 3 hours. Next, 8.04 g of methacrylic acid was further added in an equivalent ratio of 0.5:1 to BE188 and reacted for 4 hours, whereby the carbonate-containing unsaturated compound of example 3 was obtained. Data of FTIR spectra: 1749cm -1 (carbonate C＝O)、1719cm -1 (acrylate c=o). The reaction equation for example 3 is shown in Table three below.
< preparation of cured product >
The carbonate-containing unsaturated compounds of examples 1 to 3 were added to the unsaturated polyester resin (UP 1) or the bisphenol a-type vinyl ester resin (VE 1), respectively, diluted with Styrene (SM), and 1phr of peroxide MEKPO and 1phr of cobalt octoate were added, stirred uniformly, poured into a mold, cured at room temperature for 12 hours, and then cured at 80 ℃ for 4 hours to obtain cured products of examples 4 to 9 and comparative examples 1 to 4.
The formulations and contents used in examples 4 to 9 and comparative examples 1 to 4 are shown in the following Table IV.
< evaluation of thermal Properties >
Thermal property evaluation was performed for examples 4 to 9 and comparative examples 1 to 4 by using a thermal differential scanning calorimeter (Differential Scanning Calorimeter, DSC) to perform glass transition temperature (T) at a temperature rise rate of 10 ℃/min g ) And T is measured g The results of the (. Degree. C.) measurements are shown in Table five below.
As can be seen from the results in table five, the glass transition temperature of comparative example 4 is low, and the molecular weight of example 3 is large and the viscosity is high, and the mixed viscosity after addition is significantly increased, so that if the addition ratio of example 3 is too high, the required operation viscosity can be achieved by adding more diluent SM, which is rather unfavorable for the physical properties of the cured product, whereas examples 4 to 9 achieve the proper operation viscosity by adjusting the addition ratio of diluent SM and unsaturated compound containing carbonate, and maintain the good glass transition temperature.
< degradation cured product >
The cured product of the present invention can be degraded by an amine compound. First, 0.2 g of the cured products of examples 4 to 9 and comparative examples 1 to 4 and 4 g of hexylamine were placed in a container, respectively, and after heating to 130℃in an oven for 24 hours, the remaining solids were taken out to observe the residual amount, and the residual weight (%) was shown in Table six below.
From the results in Table six, it can be seen that the introduction of carbonate into the network structure in examples 4 to 9 effectively provides a degradation point, so that the disintegration efficiency of the network structure is significantly increased, and the complete degradation effect can be achieved at 130 ℃ without catalyst. In comparative examples 1 and 2, the carbonate-containing unsaturated compound of the present invention was not added, and the degradation effect was not good, whereas in comparative example 3, the content of the carbonate-containing unsaturated compound was low, and the purpose of complete degradation was not achieved, but a significant improvement in degradability was observed with the carbonate-containing unsaturated compound of the present invention.
In summary, the carbonate-containing unsaturated compound of the present invention is prepared from a carbonate compound and an epoxy compound or an alcohol compound containing an unsaturated double bond, and can be introduced into a commercially available unsaturated polyester resin or vinyl ester resin for curing, and the carbonate-containing unsaturated compound can be degraded under mild conditions through an amine compound, so that the carbonate-containing unsaturated compound can be recovered as a thermosetting material.
While the invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto but may be variously modified and modified by those skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention is accordingly defined by the appended claims.
Symbol description
100,200 Process for the preparation of carbonate-containing unsaturated compounds
300 method for preparing solidified material
400 method for degrading cured product
110,120,130,210,220,310,320,410,420, step.
Claims (11)
1. A carbonate-containing unsaturated compound having a structure represented by formula (I) or formula (II):
wherein X is ethenyl, propenyl, acrylic or methacrylic;
wherein R is 1 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, a being an integer of 0 to 5;
wherein A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a structure represented by formula (i):
wherein R is 2 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, b is an integer of 0 to 4;
wherein B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, the structure represented by formula (i), one of the structures represented by formula (ii) or formula (iii):
wherein R is 3 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, c is an integer of 0 to 4;
wherein Y is a single bond, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, a sulfinyl group, an acyl group, a fluorenyl group or a hexafluoropropyl group;
wherein Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an ortho-phenylene group, a meta-phenylene group or a para-phenylene group; and
wherein n is an integer of 0 to 10.
2. A process for producing a carbonate-containing unsaturated compound, comprising:
providing a carbonate-containing compound which is dimethyl carbonate or diphenyl carbonate;
providing an unsaturated double bond-containing compound which is a monofunctional alcohol compound containing unsaturated double bonds or a monofunctional epoxy compound containing unsaturated double bonds; and
performing a catalytic step of mixing the carbonate-containing compound with the unsaturated double bond-containing compound to obtain a carbonate-containing unsaturated compound having a structure shown in formula (I) or formula (II) under the catalysis of a catalyst:
wherein X is ethenyl, propenyl, acrylic or methacrylic;
wherein R is 1 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, a being an integer of 0 to 5;
wherein A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a structure represented by formula (i):
wherein R is 2 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, b is an integer of 0 to 4;
wherein B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, the structure represented by formula (i), one of the structures represented by formula (ii) or formula (iii):
wherein R is 3 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, c is an integer of 0 to 4;
wherein Y is a single bond, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, a sulfinyl group, an acyl group, a fluorenyl group or a hexafluoropropyl group;
wherein Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an ortho-phenylene group, a meta-phenylene group or a para-phenylene group;
wherein n is an integer of 0 to 10.
3. The method for producing a carbonate-containing unsaturated compound according to claim 2, wherein the catalyst is an ionic liquid or an organic base.
4. The method for producing a carbonate-containing unsaturated compound according to claim 2, wherein the equivalent ratio of the carbonate-containing compound to the unsaturated double bond-containing compound is 0.8 to 1.2.
5. A process for producing a carbonate-containing unsaturated compound, comprising:
performing a catalytic step, namely mixing diphenyl carbonate with a difunctional epoxy compound, and obtaining a reactant under the catalysis of a catalyst; and
an addition step is performed in which the reactant is added with acrylic acid or methacrylic acid to obtain a carbonate-containing unsaturated compound having a structure represented by formula (II):
wherein X is ethenyl, propenyl, acrylic or methacrylic;
wherein R is 1 Is of carbon number 1 to4, a is an integer from 0 to 5;
wherein B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a structure represented by one of the formula (i), the formula (ii) or the formula (iii):
wherein R is 2 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, b is an integer of 0 to 4;
wherein R is 3 An alkyl group having 1 to 4 carbon atoms, a methoxy group, a nitro group or a halogen atom, c is an integer of 0 to 4;
wherein Y is a single bond, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, a sulfinyl group, an acyl group, a fluorenyl group or a hexafluoropropyl group;
wherein Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an ortho-phenylene group, a meta-phenylene group or a para-phenylene group;
wherein n is an integer of 0 to 10.
6. The method for producing a carbonate-containing unsaturated compound according to claim 5, wherein the catalyst is an organic base, and the equivalent ratio of the difunctional epoxy compound to the diphenyl carbonate is 2.0 to 8.0.
7. A cured product obtained by subjecting the carbonate-containing unsaturated compound according to claim 1 to a curing reaction.
8. The cured product of claim 7, wherein the curing reaction is accomplished by adding the carbonate-containing unsaturated compound to a resin and heating.
9. The cured product of claim 8, wherein the resin is an unsaturated polyester resin or a vinyl ester resin.
10. The cured product according to claim 8, wherein the carbonate-containing unsaturated compound is added in an amount of 3 to 20% by weight based on the resin content.
11. A method of degrading a cured product comprising:
providing a cured product according to claim 7; and
and performing a degradation step, namely reacting an amine compound with the cured product to degrade the cured product.
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