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WO2023168562A1 - 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 - Google Patents

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 Download PDF

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WO2023168562A1
WO2023168562A1 PCT/CN2022/079570 CN2022079570W WO2023168562A1 WO 2023168562 A1 WO2023168562 A1 WO 2023168562A1 CN 2022079570 W CN2022079570 W CN 2022079570W WO 2023168562 A1 WO2023168562 A1 WO 2023168562A1
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carbon atoms
carbonate
formula
compound
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PCT/CN2022/079570
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French (fr)
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汪孟纬
陈俊安
张孟庭
张家豪
郑名尧
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上纬创新育成股份有限公司
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • 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
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation

Definitions

  • the present invention relates to an unsaturated compound, its preparation method, its prepared cured product and a method for degrading the cured product.
  • it relates to an unsaturated compound containing carbonate, its preparation method, its prepared cured product and its degradation method. Curing method.
  • Thermosetting materials have the characteristics of good resin processability before curing, and have excellent thermal stability, mechanical strength and chemical resistance after cross-linking and curing. Therefore, they are widely used in various fields and are often used for high strength and lightweight. fiber composite materials in demand. However, due to the non-reprocessability and good chemical resistance of thermoset materials, it is difficult to recycle and reuse them after disposal. In addition, the burning of fiber composite materials can easily shorten the life of incineration equipment, causing a large number of waste problems. Therefore, how to deal with waste thermosetting materials has become a key improvement target in today's environmental protection issues.
  • vinyl ester resin and unsaturated polyester resin are commonly used thermosetting materials in industry. They are widely used in coatings, transportation and construction and other fields. Due to the booming development of automobiles, ships and other mass transportation industries, their application markets continue to expand. , for applications and developers, the treatment of this resin waste has become a major issue that has to be faced, making the industry thirsty for knowledge on technologies that can decompose or recycle this resin waste.
  • One object of the present invention is to provide a carbonate-containing unsaturated compound and its preparation method, which is prepared by using a carbonate compound as a raw material and reacting with an epoxy compound or an alcohol compound containing an unsaturated double bond respectively.
  • Another object of the present invention is to provide a cured product and a method for degrading the cured product, which involves subjecting an unsaturated compound containing carbonate to a curing reaction to prepare a cured product, and the cured product can be degraded so that the product can be recycled and reused. Utilize and reduce environmental burden.
  • One embodiment of the present invention provides a carbonate-containing unsaturated compound, which has a structure shown in formula (I) or formula (II):
  • A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or one of the structures shown in formula (i):
  • R 2 is an alkyl group with 1 to 4 carbon atoms, methoxy group, nitro group or halogen atom, and b is an integer from 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):
  • R 3 is an alkyl group with 1 to 4 carbon atoms, methoxy group, nitro group or halogen atom, and c is an integer from 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 thionyl group, an acyl group, a fluorenyl group or a hexafluoropropanyl 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 from 0 to 10.
  • Another embodiment of the present invention provides a method for preparing a carbonate-containing unsaturated compound, which includes 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 compound containing unsaturated double bonds is a monofunctional alcohol compound containing unsaturated double bonds or a monofunctional epoxy compound containing unsaturated double bonds.
  • the catalytic step is to mix a carbonate-containing compound with an unsaturated double bond-containing compound, and then catalyze it with a catalyst to obtain an unsaturated carbonate-containing compound, which has a structure shown in formula (I) or formula (II) :
  • A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or one of the structures shown in formula (i):
  • R 2 is an alkyl group with 1 to 4 carbon atoms, methoxy group, nitro group or halogen atom, and b is an integer from 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):
  • R 3 is an alkyl group with 1 to 4 carbon atoms, methoxy group, nitro group or halogen atom, and c is an integer from 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 thionyl group, an acyl group, a fluorenyl group or a hexafluoropropanyl 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 from 0 to 10.
  • the catalyst may be an ionic liquid or an organic base.
  • the equivalent ratio of the carbonate-containing compound to the unsaturated double bond-containing compound may be 0.8 to 1.2.
  • Another embodiment of the present invention provides a method for preparing a carbonate-containing unsaturated compound, which includes performing a catalyzing step and performing an adding step.
  • the catalytic step is to mix diphenyl monocarbonate and a difunctional epoxy compound, and then catalyze it with a catalyst to obtain a reactant.
  • the addition step is to add acrylic acid or methacrylic acid to the reactant to obtain an unsaturated compound containing carbonate, which has a structure shown in formula (II):
  • B is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or one of the structures represented by formula (i), formula (ii) or formula (iii):
  • R 2 is an alkyl group, methoxy group, nitro group or halogen atom with 1 to 4 carbon atoms
  • b is an integer from 0 to 4
  • R 3 is an alkyl group, methoxy group, nitro group with 1 to 4 carbon atoms.
  • a halogen atom c is an integer from 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 thionyl group, an acyl group, a fluorenyl group or a hexafluoropropanyl 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 from 0 to 10.
  • the catalyst can be an organic base, and the equivalent ratio of the bifunctional epoxy compound to diphenyl carbonate can be from 2.0 to 8.0.
  • Another embodiment of the present invention provides a cured product, which is obtained by subjecting the aforementioned unsaturated compound containing carbonate to a curing reaction.
  • the curing reaction is completed by adding an unsaturated compound containing carbonate to a resin and heating.
  • the resin may be unsaturated polyester resin or vinyl ester resin.
  • the added amount of the carbonate-containing unsaturated compound may be 3 to 20 weight percent of the resin content.
  • Another embodiment of the present invention provides a method for degrading a cured product, which includes providing the aforementioned 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.
  • the carbonate-containing unsaturated compound of the present invention can participate in the free radical copolymerization of unsaturated resin or vinyl ester resin.
  • the ester group density of the main structure is increased, and the The material has good degradability, and a degradation method under mild conditions is proposed, which can achieve high degradation efficiency and produce no waste water, which facilitates industrialization and avoids derived environmental hazards.
  • Figure 1 is a flow chart illustrating a method for preparing a carbonate-containing unsaturated compound according to an embodiment of the present invention
  • Figure 2 is a flow chart illustrating a method for preparing a carbonate-containing unsaturated compound according to another embodiment of the present invention
  • Figure 3 is a flow chart illustrating a method for preparing a cured product according to yet another embodiment of the present invention.
  • FIG. 4 is a flow chart illustrating a method for degrading cured matter according to another embodiment of the present invention.
  • the compound structure is sometimes represented by a skeleton formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If there is a functional group clearly drawn in the structural formula, the one shown shall prevail.
  • the carbonate-containing unsaturated compound has a structure represented by formula (I)".
  • formula (I) the carbonate-containing unsaturated compound represented by formula (I)
  • the representation of the carbonate-containing unsaturated compound (I) other compounds or groups can be deduced by analogy.
  • the present invention provides a carbonate-containing unsaturated compound, which has a structure shown in formula (I) or formula (II):
  • A is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or one of the structures shown in formula (i):
  • R 2 is an alkyl group with 1 to 4 carbon atoms, methoxy group, nitro group or halogen atom, and b is an integer from 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):
  • R 3 is an alkyl group with 1 to 4 carbon atoms, methoxy group, nitro group or halogen atom, and c is an integer from 0 to 4.
  • Y is a single bond, an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, a thionyl group, an acyl group, or a fluorenyl group. (fluorene) or hexafluoropropane.
  • Z is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, ortho- (ortho-) phenylene, meta (meta-) phenylene or para (para-) phenylene.
  • n is an integer from 0 to 10.
  • the carbonate-containing unsaturated compound of the present invention imparts degradability to the thermal cured product by introducing a carbonate structure, thereby achieving the purpose of recycling and degrading the material in the future.
  • FIG. 1 is a step flow chart illustrating a method 100 for preparing a carbonate-containing unsaturated compound according to an embodiment of the present invention.
  • the method 100 for preparing a carbonate-containing unsaturated compound includes step 110 , step 120 and step 130 .
  • Step 110 is to provide a carbonate-containing compound, which is dimethylcarbonate (DMC) or diphenylcarbonate (DPC).
  • DMC dimethylcarbonate
  • DPC diphenylcarbonate
  • Step 120 is to provide a compound containing an unsaturated double bond, 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, which involves mixing a carbonate-containing compound with an unsaturated double bond-containing compound, and then catalyzing it with a catalyst to obtain a carbonate-containing unsaturated compound having formula (I) or formula ( II)
  • a catalytic step which involves mixing a carbonate-containing compound with an unsaturated double bond-containing compound, and then catalyzing it with a catalyst to obtain a carbonate-containing unsaturated compound having formula (I) or formula ( II)
  • FIG. 2 is a step flow chart illustrating a method 200 for preparing a carbonate-containing unsaturated compound according to another embodiment of the present invention.
  • the method 200 for preparing a carbonate-containing unsaturated compound includes step 210 and step 220 .
  • Step 210 is a catalytic step, which involves mixing diphenyl monocarbonate and a difunctional epoxy compound to obtain a reactant under the catalysis of a catalyst.
  • the catalyst may be an organic base.
  • Step 220 is an addition step, which is to add acrylic acid or methacrylic acid to the reactant to obtain an unsaturated compound containing carbonate, which has a structure shown in formula (II):
  • the unsaturated compound containing carbonate has a structure represented by formula (I)
  • its preparation method is to combine dimethyl carbonate and a monofunctional alcohol compound containing an unsaturated double bond at an equivalent ratio of 0.8 to 1.2, and use ionic liquid as a catalyst, and the amount of catalyst added is 0.01 to 2 weight percent of the total reactant content, and the reaction temperature is 60°C to 90°C.
  • 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, and the amount of catalyst added is 0.8 to 1.2.
  • the content of the bonded monofunctional epoxy compound is 0.01 to 2 weight percent, and the reaction temperature is 80°C to 140°C.
  • the second preparation method is to react a bifunctional epoxy compound with diphenyl carbonate at an equivalent ratio of 2.0 to 8.0, and use an organic base as a catalyst, and the amount of catalyst added is 0.01 weight of the bifunctional epoxy compound. percentage to 2 weight percent, and then add acrylic acid or methacrylic acid for reaction, wherein the equivalent ratio of acrylic acid or methacrylic acid to the bifunctional epoxy compound is 0.4 to 0.6, and the reaction temperature is 80°C to 140°C.
  • the present invention further provides a cured product, which is obtained by subjecting the aforementioned unsaturated compound containing carbonate to a curing reaction.
  • the aforementioned curing reaction is briefly described as follows with reference to Figure 3, wherein Figure 3 illustrates yet another implementation of the present invention.
  • the cured product preparation method 300 includes step 310 and step 320 .
  • Step 310 is a mixing step in which the carbonate-containing unsaturated compound is added to a resin.
  • the addition amount of the carbonate-containing unsaturated compound is 3 to 20 weight percent of the resin content, which can improve the degradability of the cured product without affecting the basic physical properties.
  • the aforementioned resin may be, but is not limited to, unsaturated polyester resin or vinyl ester resin.
  • Step 320 is a curing step, which involves free radical copolymerization of the unsaturated compound containing carbonate and the resin to form a cured product, and the heating curing temperature may be 25°C to 80°C.
  • the heating curing temperature and heating time can be flexibly adjusted according to the types of the carbonate-containing unsaturated compound and resin used, and the present invention is not limited thereto.
  • FIG. 4 is a flow chart illustrating a method 400 for degrading cured matter according to another embodiment of the present invention.
  • the method 400 for degrading cured matter includes step 410 and step 420 .
  • Step 410 is to provide the aforementioned cured product.
  • Step 420 is a degradation step, which involves reacting an amine compound with the aforementioned cured product to degrade the cured product.
  • the above-mentioned degradation step can be performed at 80°C to 150°C without adding any catalyst, and the degraded liquid can be purified by distillation, the amine compounds can be reused, and the produced urea derivatives can be recovered , further used in coatings or polyurethane materials to achieve the goal of recycling.
  • Example 1 Take 10 grams of dimethyl carbonate and 28.89 grams of hydroxyethyl methacrylate (2-Hydroxyethyl methacrylate, HEMA), so that the two form a reactant at an equivalent ratio of 1:1, and then , add 0.5 weight percent of trioctylmethylphosphonium methyl carbonate (P 8881 CH 3 OCOO) ionic liquid to the total amount of the reactants, and raise the temperature to 80°C and react for 8 hours to obtain the carbonic acid-containing carbonate of Example 1
  • the yield of the unsaturated compound of ester is about 60%.
  • the reaction equation of Example 1 is shown in Table 1 below.
  • Example 2 Take 10 grams of diphenyl carbonate and 13.27 grams of glycidyl methacrylate (GMA), so that the two are in an equivalent ratio of 1:1, and in nitrogen at 110°C A uniform solution was formed in the environment, and 0.027 g of pyridine (0.2 wt% GMA) was added, and the reaction was carried out for 3 hours to obtain the carbonate-containing unsaturated compound of Example 2, with a yield of about 90%.
  • the reaction equation of Example 2 is shown in Table 2 below.
  • Example 3 Take 10 grams of diphenyl carbonate and 34.54 grams of bisphenol A-type epoxy resin (Changchun artificial resin product code BE188), so that the two are in an equivalent ratio of 1:2, and at 110 A uniform solution was formed in a nitrogen atmosphere at °C, and then 0.1727 g of pyridine (0.5 wt% BE188) was added and the reaction was carried out for 3 hours. Then, 8.04 grams of methacrylic acid was added, the equivalent ratio of which to BE188 was 0.5:1, and the mixture was reacted for 4 hours to obtain the carbonate-containing unsaturated compound of Example 3.
  • the reaction equation of Example 3 is shown in Table 3 below.
  • the carbonate-containing unsaturated compounds of Examples 1 to 3 were added to unsaturated polyester resin (UP1) or bisphenol A vinyl ester resin (VE1) respectively, and then diluted with styrene (SM), and Add 1 phr of peroxide MEKPO and 1 phr of cobalt octoate, stir evenly, pour into the mold, cure at room temperature for 12 hours, and then cure at 80°C for 4 hours to obtain Examples 4 to 9 and Comparative Example 1 to the cured product of Comparative Example 4.
  • UP1 unsaturated polyester resin
  • VE1 bisphenol A vinyl ester resin
  • SM styrene
  • Add 1 phr of peroxide MEKPO and 1 phr of cobalt octoate stir evenly, pour into the mold, cure at room temperature for 12 hours, and then cure at 80°C for 4 hours to obtain Examples 4 to 9 and Comparative Example 1 to the cured product of Comparative Example 4.
  • Examples 4 to 9 and Comparative Examples 1 to 4 were evaluated by using a differential scanning calorimeter (DSC) to measure the glass transition temperature at a heating rate of 10°C/min. (T g ) measurement, and the T g (°C) measurement results are listed in Table 5 below.
  • DSC differential scanning calorimeter
  • the cured product of the present invention can undergo a degradation reaction using amine compounds.
  • 0.2 grams of the cured products of Examples 4 to 9 and Comparative Examples 1 to 4 and 4 grams of hexylamine were placed in a container, and heated to 130°C in an oven. After heating for 24 hours, the remaining Take out the solid and observe the residual amount, and list the residual weight (%) in Table 6 below.
  • the carbonate-containing unsaturated compound of the present invention is prepared by using a carbonate compound and an epoxy compound or alcohol compound containing an unsaturated double bond, which can be introduced into a commercially available unsaturated polyester resin or Curing in vinyl ester resin makes the cured product degradable and can be degraded through amine compounds under mild conditions to address the recycling issues of thermosetting materials.

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Abstract

提供一种含碳酸酯的不饱和化合物，其具有如式（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。

Description

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 技术领域
本发明是关于一种不饱和化合物、其制备方法、其制备的固化物及降解固化物的方法，尤其是关于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。
背景技术
热固性材料具有固化前树脂加工性佳的特性，且交联固化后具有优异的热稳定性、机械强度以及耐化性等优点，因此广泛应用于各种领域，并且经常用于高强度与轻量化需求的纤维复合材料中。然而，因热固性材料自身不可再加工性与良好的耐化性等特性，也导致其在废弃后难以回收重新利用，此外，纤维复合材料的燃烧容易缩短焚化设备的寿命，造成大量废弃物问题，故如何处理废弃热固性材料为当今环保议题中的重点改善目标。
目前，乙烯基酯树脂与不饱和聚酯树脂为工业上常用的热固性材料，其广泛应用于涂料、运输与建筑等领域，因汽车、船舶与其他大众运输工业蓬勃发展，使得其应用市场不断扩张，对于应用与开发商来说，该树脂废弃物的处理成为不得不面对的重大议题，使得业界对于能够将该树脂废弃物分解或回收再利用的技术求知若渴。
现今研究主流以酸水或碱水进行解聚，该作法将会衍生出后续大量废 水处理等问题，对于工业应用与环境较不友善，而如要利用有机物降解，以现今技术而言，受限于结构酯基含量有限，须施以相当高的降解温度，具有耗能且效率不佳的缺点，故仍存有相当大的应用缺陷。
有鉴于此，如何合成出具有化学降解性的固化物，并可将废弃物重复利用，于是成相关业者努力的目标。
发明内容
本发明之一目的在于提供一种含碳酸酯的不饱和化合物及其制备方法，其是以碳酸酯化合物为原料，分别和含有不饱和双键的环氧化合物或醇类化合物反应制得。
本发明之另一目的在于提供一种固化物以及降解固化物的方法，其是将含碳酸酯的不饱和化合物进行固化反应制备出固化物，且此固化物可进行降解，使产品能够回收再利用，减轻环境负担。
本发明的一实施方式提供一种含碳酸酯的不饱和化合物，其具有如式(I)或式(II)所示之一结构：
Figure PCTCN2022079570-appb-000001
其中，X为乙烯基、丙烯基、丙烯酸基或甲基丙烯酸基，R 1为碳数1至4的烷基、甲氧基、硝基或卤素原子，a为0至5的整数。A为碳数1至12的烷基、碳数1至12的烷氧基或式(i)所示之一结构：
Figure PCTCN2022079570-appb-000002
其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数。B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)所示之结构、式(ii)或式(iii)所示之一结构：
Figure PCTCN2022079570-appb-000003
其中，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4的整数。Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基、亚硫酰基、酰基、芴基或六氟丙烷基。Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位亚苯基、间位亚苯基或对位亚苯基，n为0至10的整数。
本发明的另一实施方式提供一种含碳酸酯的不饱和化合物的制备方法，包含提供一含碳酸酯化合物、提供一含不饱和双键化合物以及进行一催化步骤。含碳酸酯化合物为碳酸二甲酯或碳酸二苯酯。含不饱和双键化合物为含不饱和双键的单官能醇类化合物或含不饱和双键的单官能环氧化合物。催化步骤是将含碳酸酯化合物与含不饱和双键化合物混合后，在一催化剂催化下得到一含碳酸酯的不饱和化合物，其具有如式(I)或式(II)所示之一结构：
Figure PCTCN2022079570-appb-000004
其中，X为乙烯基、丙烯基、丙烯酸基或甲基丙烯酸基，R 1为碳数1至4的烷基、甲氧基、硝基或卤素原子，a为0至5的整数。A为碳数1至12的烷基、碳数1至12的烷氧基或式(i)所示之一结构：
Figure PCTCN2022079570-appb-000005
其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数。B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)所示之结构、式(ii)或式(iii)所示之一结构：
Figure PCTCN2022079570-appb-000006
其中，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4的整数。Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基、亚硫酰基、酰基、芴基或六氟丙烷基。Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位亚苯基、间位亚苯基或对位亚苯基， n为0至10的整数。
依据前段所述的含碳酸酯的不饱和化合物的制备方法，其中催化剂可为离子液体或有机碱。
依据前段所述的含碳酸酯的不饱和化合物的制备方法，其中含碳酸酯化合物与含不饱和双键化合物的当量比值可为0.8至1.2。
本发明的又一实施方式提供一种含碳酸酯的不饱和化合物的制备方法，包含进行一催化步骤以及进行一添加步骤。催化步骤是将一碳酸二苯酯与一双官能环氧化合物混合后，在一催化剂催化下得到一反应物。添加步骤是将反应物添加丙烯酸或甲基丙烯酸，以得到一含碳酸酯的不饱和化合物，其具有如式(II)所示之一结构：
Figure PCTCN2022079570-appb-000007
其中，X为乙烯基、丙烯基、丙烯酸基或甲基丙烯酸基，R 1为碳数1至4的烷基、甲氧基、硝基或卤素原子，a为0至5的整数。B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)、式(ii)或式(iii)所示之一结构：
Figure PCTCN2022079570-appb-000008
Figure PCTCN2022079570-appb-000009
其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4的整数。Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基、亚硫酰基、酰基、芴基或六氟丙烷基。Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位亚苯基、间位亚苯基或对位亚苯基，n为0至10的整数。
依据前段所述的含碳酸酯的不饱和化合物的制备方法，其中催化剂可为有机碱，且双官能环氧化合物与碳酸二苯酯的当量比值可为2.0至8.0。
本发明的再一实施方式提供一种固化物，其是通过前述含碳酸酯的不饱和化合物进行一固化反应而得。
依据前段所述的固化物，其中固化反应是将含碳酸酯的不饱和化合物添加至一树脂中并加热而完成。
依据前段所述的固化物，其中树脂可为不饱和聚酯树脂或乙烯基酯树脂。
依据前段所述的固化物，其中含碳酸酯的不饱和化合物的添加量可为树脂含量的3重量百分比至20重量百分比。
本发明的更一实施方式提供一种降解固化物的方法，包含提供前述固化物以及进行一降解步骤，其中降解步骤是将一胺类化合物与固化物反应，以降解固化物。
借此，本发明的含碳酸酯的不饱和化合物可参与不饱和树脂或乙烯基 酯树脂自由基共聚反应，通过导入高活性碳酸酯结构于网状系统中，增加主体结构的酯基密度，赋予材料良好的降解性，且提出一种条件温和的降解方法，可达到高降解效率且无废水产生，以利工业化并可避免衍生的环境危害问题。
附图说明
为让本发明的上述和其他目的、特征、优点与实施例能更明显易懂，所附图式的说明如下：
图1是绘示依照本发明的一实施方式的含碳酸酯的不饱和化合物的制备方法的步骤流程图；
图2是绘示依照本发明的另一实施方式的含碳酸酯的不饱和化合物的制备方法的步骤流程图；
图3是绘示依照本发明的再一实施方式的固化物的制备方法的步骤流程图；以及
图4是绘示依照本发明的又一实施方式的降解固化物的方法的步骤流程图。
具体实施方式
下述将更详细讨论本发明各实施方式。然而，此实施方式可为各种发明概念的应用，可被具体实行在各种不同的特定范围内。特定的实施方式是仅以说明为目的，且不受限于揭露的范围。
本发明中，有时以键线式(skeleton formula)表示化合物结构，此种表示法可以省略碳原子、氢原子以及碳氢键。倘若，结构式中有明确绘出官能基的，则以绘示者为准。
本发明中，「含碳酸酯的不饱和化合物，具有如式(I)所示之一结构」，为了简洁与通顺，有时会表达为式(I)所示的含碳酸酯的不饱和化合物或含碳酸酯的不饱和化合物(I)，其他化合物或基团的表示方式依此类推。
<含碳酸酯的不饱和化合物>
本发明提供一种含碳酸酯的不饱和化合物，其具有如式(I)或式(II)所示之一结构：
Figure PCTCN2022079570-appb-000010
其中，X为乙烯基(vinyl group)、丙烯基(allyl group)、丙烯酸基(acrylate)或甲基丙烯酸基(methacrylate)，R 1为碳数1至4的烷基、甲氧基(methoxy)、硝基(nitro)或卤素原子(halogen)，a为0至5的整数。A为碳数1至12的烷基、碳数1至12的烷氧基或式(i)所示之一结构：
Figure PCTCN2022079570-appb-000011
其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数。B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)所示之结构、式(ii)或式(iii)所示之一结构：
Figure PCTCN2022079570-appb-000012
其中，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4的整数。Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基(sulfonyl)、亚硫酰基(thionyl)、酰基(carbonyl)、芴基(fluorene)或六氟丙烷基(hexafluoropropane)。Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位(ortho-)亚苯基、间位(meta-)亚苯基或对位(para-)亚苯基，n为0至10的整数。
借此，本发明的含碳酸酯的不饱和化合物通过导入碳酸酯结构赋予热固化物可降解性，可达到日后材料回收降解的目的。
<含碳酸酯的不饱和化合物的制备方法>
配合参照图1，其是绘示依照本发明的一实施方式的含碳酸酯的不饱和化合物的制备方法100的步骤流程图。在图1中，含碳酸酯的不饱和化合物的制备方法100包含步骤110、步骤120以及步骤130。
步骤110为提供一含碳酸酯化合物，其为碳酸二甲酯(Dimethylcarbonate,DMC)或碳酸二苯酯(Diphenylcarbonate,DPC)。
步骤120为提供一含不饱和双键化合物，其为含不饱和双键的单官能醇类化合物或含不饱和双键的单官能环氧化合物。
步骤130为进行一催化步骤，其是将含碳酸酯化合物与含不饱和双键化合物混合后，在一催化剂催化下得到一含碳酸酯的不饱和化合物，其具 有如式(I)或式(II)所示之一结构：
Figure PCTCN2022079570-appb-000013
关于X、A、B、R 1以及a的定义请参照上文，在此不另赘述，且前述催化剂可为离子液体或有机碱。
请参阅图2，其是绘示依照本发明的另一实施方式的含碳酸酯的不饱和化合物的制备方法200的步骤流程图。在图2中，含碳酸酯的不饱和化合物的制备方法200包含步骤210以及步骤220。
步骤210为进行一催化步骤，其是将一碳酸二苯酯与一双官能环氧化合物混合后，在一催化剂催化下得到一反应物，前述催化剂可为有机碱。
步骤220为进行一添加步骤，其是将反应物添加丙烯酸或甲基丙烯酸，以得到一含碳酸酯的不饱和化合物，其具有如式(II)所示之一结构：
Figure PCTCN2022079570-appb-000014
关于X、B、R 1以及a的定义请参照上文，在此不另赘述。
具体而言，当含碳酸酯的不饱和化合物为式(I)所示之结构时，其制备方法是将碳酸二甲酯与含不饱和双键的单官能醇类化合物在当量比值为0.8至1.2下反应，并使用离子液体作为催化剂，且催化剂的添加量为总反 应物含量的0.01重量百分比至2重量百分比，反应温度为60℃至90℃。
另外，当含碳酸酯的不饱和化合物为式(II)所示之结构时，其具有两种制备方法。第一种制备方法是将碳酸二苯酯与含不饱和双键的单官能环氧化合物在当量比值为0.8至1.2下反应，并使用有机碱作为催化剂，且催化剂的添加量为含不饱和双键的单官能环氧化合物含量的0.01重量百分比至2重量百分比，反应温度为80℃至140℃。第二种制备方法则是将双官能环氧化合物与碳酸二苯酯在当量比值为2.0至8.0下反应，并使用有机碱作为催化剂，且催化剂的添加量为双官能环氧化合物含量的0.01重量百分比至2重量百分比，再添加丙烯酸或甲基丙烯酸进行反应，其中丙烯酸或甲基丙烯酸与双官能环氧化合物的当量比值为0.4至0.6，反应温度为80℃至140℃。
<固化物>
本发明进一步提供一种固化物，其是通过前述含碳酸酯的不饱和化合物进行一固化反应而得，而前述固化反应参照图3简单说明如下，其中图3绘示依照本发明的再一实施方式的固化物的制备方法300的步骤流程图。在图3中，固化物的制备方法300包含步骤310与步骤320。
步骤310是进行一混合步骤，其是将含碳酸酯的不饱和化合物添加至一树脂中。具体来说，含碳酸酯的不饱和化合物的添加量为树脂含量的3重量百分比至20重量百分比，其可在不影响基础物性的情况下提升固化物的可降解性。关于含碳酸酯的不饱和化合物的细节请参照前文，在此不予以赘述，而前述树脂可为但不限于不饱和聚酯树脂或乙烯基酯树脂。
步骤320是进行一固化步骤，其是使含碳酸酯的不饱和化合物与树脂 进行自由基共聚后以形成固化物，且加热的固化温度可为25℃至80℃。关于加热的固化温度与加热时间可随所使用的含碳酸酯的不饱和化合物与树脂的种类弹性调整，本发明并不以此为限。
<降解固化物的方法>
请参阅图4，其是绘示依照本发明的又一实施方式的降解固化物的方法400的步骤流程图。在图4中，降解固化物的方法400包含步骤410以及步骤420。
步骤410为提供前述固化物。步骤420为进行一降解步骤，其是将一胺类化合物与前述固化物反应，以降解固化物。具体来说，上述降解步骤可于80℃至150℃下且不添加任何催化剂进行降解，而降解后的液体可经过蒸馏提纯，将胺类化合物重复使用，并回收产生的脲(urea)衍生物，进一步用于涂料或聚氨酯材料中，达到循环应用的目标。
兹以下列具体实施例进一步示范说明本发明，用以有利于本发明所属技术领域通常知识者，可在不需过度解读的情形下完整利用并实践本发明，而不应将这些实施例视为对本发明范围的限制，但用于说明如何实施本发明的材料及方法。
<实施例/比较例>
<含碳酸酯的不饱和化合物的制备>
实施例1：取10克的碳酸二甲酯与28.89克的甲基丙烯酸羟乙酯(2-Hydroxyethyl methacrylate,HEMA)，以使前述两者在当量比1:1的比例下形成反应物，接着，加入反应物总量0.5重量百分比的三辛基甲基鏻碳酸甲酯(trioctylmethylphosphonium methyl carbonate,P 8881CH 3OCOO)离子液 体，并升温至80℃反应8小时，可得到实施例1的含碳酸酯的不饱和化合物，其产率约为60％。FTIR光谱的数据：1748cm -1(carbonate C＝O)、1715cm -1(acrylate C＝O)。实施例1的反应方程式如下表一所示。
Figure PCTCN2022079570-appb-000015
实施例2：取10克的碳酸二苯酯与13.27克的甲基丙烯酸缩水甘油酯(Glycidyl methacrylate,GMA)，以使前述两者在当量比1:1的比例下，并在110℃的氮气环境中形成均匀溶液，再加入0.027克的吡啶(0.2wt％的GMA)，反应3小时，可得到实施例2的含碳酸酯的不饱和化合物，其产率约为90％。FTIR光谱的数据：1749cm -1(aliphatic carbonate C＝O)、1715cm -1(acrylate C＝O)。实施例2的反应方程式如下表二所示。
Figure PCTCN2022079570-appb-000016
实施例3：取10克的碳酸二苯酯与34.54克的双酚A型环氧树脂(长春人造树脂商品代号BE188)，以使前述两者在当量比1:2的比例下，并在110℃的氮气环境中形成均匀溶液，再加入0.1727克的吡啶(0.5wt％的BE188)，反应3小时。接着，再加入8.04克的甲基丙烯酸，其与BE188的当量比为0.5:1，并反应4小时，可得到实施例3的含碳酸酯的不饱和化合物。FTIR光谱的数据：1749cm -1(carbonate C＝O)、1719cm -1(acrylate C＝O)。实施例3的反应方程式如下表三所示。
Figure PCTCN2022079570-appb-000017
<固化物的制备>
将实施例1至实施例3的含碳酸酯的不饱和化合物分别添加至不饱和聚酯树脂(UP1)或双酚A型乙烯基酯树脂(VE1)，再以苯乙烯(SM)稀释，并加入1phr的过氧化物MEKPO与1phr的辛酸钴，搅拌均匀后倒入模具中，在室温下固化12小时，之后在80℃下固化4小时，以得到实施例4至实施例9以及比较例1至比较例4的固化物。
关于实施例4至实施例9以及比较例1至比较例4所使用的配方及含量如下表四所示。
Figure PCTCN2022079570-appb-000018
<热性质评估>
将实施例4至实施例9以及比较例1至比较例4进行热性质评估，其是利用热示差扫描卡量计(Differential Scanning Calorimeter,DSC)在10℃/min的升温速率下进行玻璃转移温度(T g)的量测，并将T g(℃)量测结果列于下表五。
Figure PCTCN2022079570-appb-000019
由表五的结果可见，比较例4的玻璃转移温度较低，其是由于实施例3的分子量较大且黏度较高，添加后混合黏度会明显上升，因此若实施例3的添加比例过高，则会导致需添加较多稀释剂SM方可达到所需的操作黏度，反而不利于固化物的物性表现，而实施例4至实施例9则透过稀释剂SM与含碳酸酯的不饱和化合物添加比例的调整达到合适的操作黏度，并保有良好的玻璃转移温度。
<降解固化物>
本发明的固化物可利用胺类化合物进行降解反应。首先，分别取0.2克的实施例4至实施例9以及比较例1至比较例4的固化物与4克的己胺置于容器中，并于烘箱加热至130℃，加热24小时后将剩余的固体取出观察残余量，并将残留重量(％)列于下表六。
Figure PCTCN2022079570-appb-000020
由表六的结果可见，实施例4至实施例9通过导入碳酸酯于网状结构中，可有效提供降解点，使网状结构瓦解效率明显上升，最终在130℃且无催化剂催化下即可达到完全降解之功效。另外，比较例1及比较例2则未添加本发明的含碳酸酯的不饱和化合物，其降解效果不佳，而比较例3则因为添加含碳酸酯的不饱和化合物的含量偏低，未达完全降解之目的，但仍可观察到添加本发明的含碳酸酯的不饱和化合物对于降解性有显著的改善。
综上所述，本发明的含碳酸酯的不饱和化合物是利用碳酸酯化合物与含有不饱和双键的环氧化合物或醇类化合物制备而得，其可导入市售的不饱和聚酯树脂或乙烯基酯树脂中进行固化，赋予固化物具有可降解性，并可在温和条件下透过胺类化合物进行降解，因应热固材料回收议题。
虽然本发明已以实施方式揭露如上，然其并非用以限定本发明，任何熟习此技艺者，在不脱离本发明之精神和范围内，当可作各种之更动与润饰，因此本发明之保护范围当视后附之申请专利范围所界定者为准。
符号说明
100,200:含碳酸酯的不饱和化合物的制备方法
300:固化物的制备方法
400:降解固化物的方法
110,120,130,210,220,310,320,410,420:步骤

Claims (11)

  1. 一种含碳酸酯的不饱和化合物，其特征在于，具有如式(I)或式(II)所示之一结构：
    Figure PCTCN2022079570-appb-100001
    其中，X为乙烯基、丙烯基、丙烯酸基或甲基丙烯酸基；
    其中，R 1为碳数1至4的烷基、甲氧基、硝基或卤素原子，a为0至5的整数；
    其中，A为碳数1至12的烷基、碳数1至12的烷氧基或式(i)所示之一结构：
    Figure PCTCN2022079570-appb-100002
    其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数；
    其中，B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)所示之该结构、式(ii)或式(iii)所示之一结构：
    Figure PCTCN2022079570-appb-100003
    其中，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4的整数；
    其中，Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基、亚硫酰基、酰基、芴基或六氟丙烷基；
    其中，Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位亚苯基、间位亚苯基或对位亚苯基；以及
    其中，n为0至10的整数。
  2. 一种含碳酸酯的不饱和化合物的制备方法，其特征在于，包含：
    提供一含碳酸酯化合物，其为碳酸二甲酯或碳酸二苯酯；
    提供一含不饱和双键化合物，其为含不饱和双键的单官能醇类化合物或含不饱和双键的单官能环氧化合物；以及
    进行一催化步骤，其是将该含碳酸酯化合物与该含不饱和双键化合物混合后，在一催化剂催化下得到一含碳酸酯的不饱和化合物，其具有如式(I)或式(II)所示之一结构：
    Figure PCTCN2022079570-appb-100004
    其中，X为乙烯基、丙烯基、丙烯酸基或甲基丙烯酸基；
    其中，R 1为碳数1至4的烷基、甲氧基、硝基或卤素原子，a为0至5的整数；
    其中，A为碳数1至12的烷基、碳数1至12的烷氧基或式(i)所示之一结构：
    Figure PCTCN2022079570-appb-100005
    其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数；
    其中，B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)所示之该结构、式(ii)或式(iii)所示之一结构：
    Figure PCTCN2022079570-appb-100006
    其中，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4 的整数；
    其中，Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基、亚硫酰基、酰基、芴基或六氟丙烷基；
    其中，Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位亚苯基、间位亚苯基或对位亚苯基；
    其中，n为0至10的整数。
  3. 如权利要求2所述的含碳酸酯的不饱和化合物的制备方法，其特征在于，该催化剂为离子液体或有机碱。
  4. 如权利要求2所述的含碳酸酯的不饱和化合物的制备方法，其特征在于，该含碳酸酯化合物与该含不饱和双键化合物的当量比值为0.8至1.2。
  5. 一种含碳酸酯的不饱和化合物的制备方法，其特征在于，包含：
    进行一催化步骤，其是将一碳酸二苯酯与一双官能环氧化合物混合后，在一催化剂催化下得到一反应物；以及
    进行一添加步骤，其是将该反应物添加丙烯酸或甲基丙烯酸，以得到一含碳酸酯的不饱和化合物，其具有如式(II)所示之一结构：
    Figure PCTCN2022079570-appb-100007
    其中，X为乙烯基、丙烯基、丙烯酸基或甲基丙烯酸基；
    其中，R 1为碳数1至4的烷基、甲氧基、硝基或卤素原子，a为0至5的整数；
    其中，B为碳数1至12的烷基、碳数1至12的烷氧基、式(i)、式(ii)或式(iii)所示之一结构：
    Figure PCTCN2022079570-appb-100008
    其中，R 2为碳数1至4的烷基、甲氧基、硝基或卤素原子，b为0至4的整数；
    其中，R 3为碳数1至4的烷基、甲氧基、硝基或卤素原子，c为0至4的整数；
    其中，Y为单键、碳数1至12的烷基、碳数1至12的环烷基、氧原子、硫原子、磺酰基、亚硫酰基、酰基、芴基或六氟丙烷基；
    其中，Z为碳数1至12的烷基、碳数1至12的烷氧基、邻位亚苯基、间位亚苯基或对位亚苯基；
    其中，n为0至10的整数。
  6. 如权利要求5所述的含碳酸酯的不饱和化合物的制备方法，其特征 在于，该催化剂为有机碱，且该双官能环氧化合物与该碳酸二苯酯的当量比值为2.0至8.0。
  7. 一种固化物，其特征在于，是通过如权利要求1所述的含碳酸酯的不饱和化合物进行一固化反应而得。
  8. 如权利要求7所述的固化物，其特征在于，该固化反应是将该含碳酸酯的不饱和化合物添加至一树脂中并加热而完成。
  9. 如权利要求8所述的固化物，其特征在于，该树脂为不饱和聚酯树脂或乙烯基酯树脂。
  10. 如权利要求8所述的固化物，其特征在于，该含碳酸酯的不饱和化合物的添加量为该树脂含量的3重量百分比至20重量百分比。
  11. 一种降解固化物的方法，其特征在于，包含：
    提供如权利要求7所述的固化物；以及
    进行一降解步骤，其是将一胺类化合物与该固化物反应，以降解该固化物。
PCT/CN2022/079570 2022-03-07 2022-03-07 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 WO2023168562A1 (zh)

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