A 7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method and application

A technology for oxabicyclo and alkene monomers, which is applied in the field of 7-oxabicyclo[2.2.1]hept-5-ene monomers and their preparation, and achieves the advantages of short process, getting rid of high dependence and few by-products. Effect

Active Publication Date: 2017-11-24
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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Problems solved by technology

However, since the molecular structure of furoic acid compounds only contains a single functional group, direct polymerization cannot be achieved in the reaction, so there has been no relevant technical report on the preparation of high-performance bio-based engineering plastics using biomass raw material furoic acid compounds

Method used

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  • A 7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method and application
  • A 7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method and application
  • A 7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] In a 1L reactor, blow nitrogen, add 25.2g methyl furoate, 17.2g methyl acrylate, 0.055g hydroquinone, reflux at 80°C for 20h, remove methyl acrylate and methyl furoate by distillation under reduced pressure, 1,2-Diacetylmethyl-7-oxabicyclo[2.2.1]hept-5-ene and 1,3-diacetylmethyl-7-oxabicyclo[2.2.1]hept-5 were obtained -ene mixture, the ratio is 41:59, the product is white crystal, the yield is 70%. through 1 H-NMR (400MHz, CDCl 3 ) test, δ(2.58-3.48), the CH connected to the ester group on the ring, 1H; δ(3.60-3.89), CH 3 , 6H; δ(5.27-5.33), CH on the ring, 1H; δ(6.34-6.60), CH on the ring with a double bond, 2H; δ(7.29), CDCl 3 , 1H. Such as figure 1 shown.

[0035]At room temperature, 332.2 g of terephthalic acid, 173.8 g of ethylene glycol and 1,2-diacetylmethyl ester-7-oxabicyclo[2.2.1]hept-5-ene prepared in Example 1 and 1, Add 84.8g of a mixture of 3-diacetylmethyl-7-oxabicyclo[2.2.1]hept-5-ene and anhydrous zinc acetate into a 1000mL stainless steel reacto...

Embodiment 2

[0037] In a 1L reactor, blow nitrogen, add 22.4g furoic acid, 17.2g acrylic acid, 0.11g hydroquinone, react at 160°C for 10h, and remove acrylic acid and furoic acid by distillation under reduced pressure to obtain 1,2-dicarboxy-7- A mixture of oxabicyclo[2.2.1]hept-5-ene and 1,3-dicarboxy-7-oxabicyclo[2.2.1]hept-5-ene in a ratio of 32:68, the product is white Crystals, 62% yield. through 1 H-NMR (400MHz, CDCl 3 ) test, CH on the δ(1.95-2.61) ring 2 , 2H; δ(2.58-3.68), CH on the ring with a carboxyl group, 1H; δ(5.27-5.33), CH on the ring, 1H; δ(6.34-6.60), CH with a double bond on the ring, 2H; (7.29), CDCl 3 , 1H.

[0038] At room temperature, 332.2g of terephthalic acid, 173.8g of ethylene glycol and 1,2-dicarboxy-7-oxabicyclo[2.2.1]hept-5-ene and 1,3- Add 36.8 g of a mixture of dicarboxy-7-oxabicyclo[2.2.1]hept-5-ene and anhydrous zinc acetate into a 1000 mL stainless steel reactor, and after three times of vacuuming and nitrogen replacement, start stirring. Raise t...

Embodiment 3

[0040] In a 1L reactor, blow nitrogen, add 25.2g methyl furoate, 34.4g methyl acrylate, 0.44g hydroquinone, react at 190°C for 6h, remove methyl acrylate and methyl furoate by distillation under reduced pressure, and obtain 1 , 2-Diacetylmethyl-7-oxabicyclo[2.2.1]hept-5-ene and 1,3-Diacetylmethyl-7-oxabicyclo[2.2.1]hept-5-ene The mixture, the ratio is 38:62, the product is white crystal, and the yield is 84%. through 1 H-NMR (400MHz, CDCl 3 ) test, δ(2.58-3.48), CH connected to the carboxyl group on the ring, 1H; δ(3.60-3.89), CH 3 , 6H; δ(5.27-5.33), CH on the ring, 1H; δ(6.34-6.60), CH on the ring with a double bond, 2H; δ(7.29), CDCl 3 , 1H.

[0041] At room temperature, 332.2 g of terephthalic acid, 173.8 g of ethylene glycol, and 1,2-diacetylmethyl ester-7-oxabicyclo[2.2.1]hept-5-ene prepared in Example 3 and 1 , 127.2g of a mixture of 3-diacetylmethyl-7-oxabicyclo[2.2.1]hept-5-ene and anhydrous zinc acetate were added to a 1000mL stainless steel reactor. After three...

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Abstract

The invention discloses a 7-oxabicyclo[2.2.1]hept-5-ene monomer, its preparation method and application. The 7-oxabicyclo[2.2.1]hept-5-ene monomer adopts bio-based furoic acid compound as a raw material, and undergoes a Diels-Alder reaction with acrylic acid and acrylate in the presence of a polymerization inhibitor and a Lewis acid catalyst. Unreacted raw materials were removed by vacuum distillation to obtain 7-oxabicyclo[2.2.1]hept-5-ene monomer. The preparation method of the invention is simple, efficient and has few by-products. The furoic acid compound as a raw material is obtained by oxidation of furfural prepared by a corn cob fermentation method. The raw material has wide sources, low cost and sustainable development. The monomer structure prepared by the invention contains carboxylic acid or carboxylate difunctional groups, and can be widely used in the fields of bio-based polyester, epoxy resin, polyamide, polyurethane and the like.

Description

technical field [0001] The present invention relates to the technical field of preparation of polymer monomers such as high-performance bio-based polyester, bio-based epoxy resin, bio-based polyamide and bio-based polyurethane, in particular to a 7-oxabicyclo[2.2.1]heptane -5-ene monomers and methods for their preparation. Background technique [0002] At present, the alcohol, acid, and ester monomers containing rigid ring structures used in the synthesis of high-performance engineering plastics such as polyester, epoxy resin, polyamide, and polyurethane are mainly derived from petroleum. However, petroleum is a non-renewable resource, and with the continuous increase of its exploitation and production, the total reserves of such resources are gradually decreasing. Due to the continuous depletion of petroleum resources, the source of raw materials for the synthesis of various engineering plastics will be severely impacted in the future, which will inevitably lead to fatal d...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D493/08C08G63/676
Inventor 王静刚马松琪刘小青朱锦那海宁倪金平
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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