A 4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method

A technology of oxabicyclo and hydroxymethyl, applied in the field of 4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation, can solve the problem of high performance Bio-based engineering plastics and other issues to achieve the effect of getting rid of high dependence, short process and improving manufacturing level

Active Publication Date: 2016-08-03
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Application Information

AI Technical Summary

Problems solved by technology

However, since the molecular structure of furfuryl alcohol only contains a single functional group, it cannot be directly polymerized in the reaction, so there has been no relevant technical report on the preparation of high-performance bio-based engineering plastics from biomass raw material furfuryl alcohol.

Method used

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  • A 4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method
  • A 4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method
  • A 4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] In a 1L reactor, blow nitrogen, add 294g furfuryl alcohol, 258g methyl acrylate, 0.22g hydroquinone, reflux at 90°C for 24 hours, remove methyl acrylate and furfuryl alcohol by distillation under reduced pressure, and obtain 2-methoxyacyl-4 -Hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene and 3-methoxyyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene The mixture, the ratio is 41:59, the product is light yellow viscous liquid, and the yield is 62%. through 1 H-NMR (400MHz, CDCl 3 ) test, CH on the δ(1.52-2.22) ring 2 , 2H; δ(2.52, 3.05, 3.24), CH on the ring, 1H; δ(3.61, 3.70), CH 3 , 3H; δ(3.91-4.24), CH in hydroxymethyl 2 , 2H; δ(4.95-5.14), CH on the ring, 1H; δ(6.13-6.45), CH on the ring with a double bond, 2H.

[0029] At room temperature, 332.2 g of terephthalic acid, 173.8 g of ethylene glycol and 2-methoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene prepared in Example 1 Add 36.8g of 3-methoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer mixtu...

Embodiment 2

[0031] In a 1L reactor, blow nitrogen, add 294g furfuryl alcohol, 216g acrylic acid, 0.05g hydroquinone, reflux at 60°C for 12h, remove acrylic acid and furfuryl alcohol by distillation under reduced pressure, and obtain 2-carboxy-4-hydroxymethyl-7 - A mixture of oxabicyclo[2.2.1]hept-5-ene and 3-carboxy-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene in a ratio of 32:68 , the product was a colorless viscous liquid with a yield of 70%. through 1 H-NMR (400MHz, CDCl 3 ) test, CH on the δ(1.52-2.22) ring2 , 2H; δ(2.52, 3.05, 3.24), CH on the ring, 1H; δ(3.61, 3.70), CH 3 , 3H; δ(3.91-4.24), CH in hydroxymethyl 2 , 2H; δ(4.95-5.14), CH on the ring, 1H; δ(6.13-6.45), CH on the ring with a double bond, 2H.

[0032] At room temperature, 332.2 g of terephthalic acid, 173.8 g of ethylene glycol, and 2-methoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5- Add 73.6g of alkene and 3-methoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer mixture and anhydrous zinc acetate i...

Embodiment 3

[0034] In a 1L reactor, blow nitrogen, add 294g furfuryl alcohol, 300g ethyl acrylate, 0.33g 2,6-dinitrohydroquinone, reflux at 100°C, 0.1MPa for 18h, distill off ethyl acrylate and furfuryl alcohol under reduced pressure to obtain 2-Ethoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene and 3-ethoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2. 1] A mixture of hept-5-enes in a ratio of 71:29. The product is a colorless viscous liquid with a yield of 81%. through 1 H-NMR (400MHz, CDCl 3 ) test, CH on the δ(1.52-2.22) ring 2 , 2H; δ(2.52, 3.05, 3.24), CH on the ring, 1H; δ(3.61, 3.70), CH 3 , 3H; δ(3.91-4.24), CH in hydroxymethyl 2 , 2H; δ(4.95-5.14), CH on the ring, 1H; δ(6.13-6.45), CH on the ring with a double bond, 2H.

[0035] At room temperature, 332.2g of terephthalic acid, 173.8g of ethylene glycol and 2-methoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene prepared in Example 3 Add 110.4g of 3-methoxyacyl-4-hydroxymethyl-7-oxabicyclo[2.2.1]hept-5-ene monomer mixtur...

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Abstract

The invention discloses a 4-hydroxymethyl-7-oxa bicyclo[2.2.1]hept-5-ene monomer and a preparation method thereof. The preparation method comprises the following steps: carrying out Diels-Alder reaction between biological-based furfuryl alcohol as a raw material and acrylic acid and acrylate in the presence of a polymerization inhibitor; and distilling under reduced pressure to remove the unreacted raw material to obtain the 4-hydroxymethyl-7-oxa bicyclo[2.2.1]hept-5-ene monomer. The preparation method is simple, efficient and fewer in byproducts. The raw material furfuryl alcohol is obtained by fermenting corn cobs, so that the raw material source is extensive, the cost is low and the sustainable development can be carried out. Moreover, the monomer prepared by the preparation method structurally contains hydroxyl and carboxylic acid or carboxylic ester bifunctional groups, and can be extensively applied to the fields of biological-based polyester, epoxy resin, 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 and bio-based polyurethane, in particular to a 4-hydroxymethyl-7-oxabicyclo[2.2.1] Hep-5-ene monomer and method for its preparation. Background technique [0002] At present, alcohol, acid, and ester monomers containing rigid ring structures are mainly derived from petroleum for the synthesis of engineering plastics such as polyester, epoxy resin, and polyurethane. 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 damage to the entire engineering plastics industry...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D493/08C08G63/21C08G63/20C08G63/183
CPCC07D493/08C08G63/21
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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