CN1162419C - Synthesis of cardanol glycidyl ether - Google Patents

Abstract

The present invention belongs to a synthesis method of cardanol glycidyl ether. 0.8 to 1.1 mol% of adopted cashew nut shell oil and 1.5 to 3.0 mol% of epoxy chloropropane react under the existence of 0.8 to 2.0 mol% of sodium hydroxide, and an epoxy group, phenyl and a long-chain substituent group are contained in the molecular structure of the diluent. The diluent has good electrochemical corrosion resistance and water resistance in a wet corrosion environment for a long time.

Description

Synthesizing of cardanol glycidyl ether

Technical field: the synthetic method that the invention belongs to cardanol glycidyl ether.

Background technology: there is more than 100,000,000 ton organic volatile every year in the whole world to the discharging of ground ring, and wherein 70% comes from coating.Serious pollution the Nature, destroyed the environment of human survival.Why seriously polluted coating is, is that in the drying and forming-film process, these solvents all volatilize in air, have not only polluted environment, and have also caused great waste for resource because it contains a large amount of solvents.Therefore develop high solid coating, it is very significant particularly developing solventless coatings.

Because epoxy resin cured product has many advantages, particularly its adhesivity and chemical-resistant are particularly outstanding, so epoxy-resin systems coating occupies critical positions all the time in industrial coating, even solventless coatings is no exception.Because the no solution paint viscosity ratio of liquid is bigger, the viscosity that regulate coating is fit to the requirement of construction technology, must add a certain amount of low viscosity reactive thinner, and its adding can not influence the fundamental property index of coating.At present at home in the existing products, as n-butyl glycidyl ether, glycidyl allyl ether etc., all more available aspect outward appearance, viscosity, smell, toxicity, but because of structural reason, for a long time under the wet corrosion environment, use when electrochemically resistant is learned corrosion, its water resistance is not ideal enough, generally uses better under the dry corrosion environment.

Summary of the invention: the synthetic method that the purpose of this invention is to provide a kind of cardanol glycidyl ether.In the molecular structure of this thinner, contain epoxy group(ing), phenyl and long-chain substituting group.The end epoxy group(ing) has been given high reaction activity and high; Phenyl helps improving resist chemical performance and intensity; C on the phenyl ring ₁₅The straight chain substituting group has been given fabulous water tolerance and snappiness; Unsaturated double-bond on the long carbochain is compared its epoxy compounds with the same molecular amount, has lower viscosity, has given good dilution and wettability; The fatty clan elder's carbon-chain structure and the aromatic benzene ring structure that are contained in the molecule have been given this product and fats Resins, epoxy and the good intermiscibility of aromatics Resins, epoxy.

The cashew nut shell oil that the present invention adopts: epoxy chloropropane: hydrogen sodium hydride (mol ratio)=0.8-1.1: 1.5-3.0: 0.8-2.0;

Cashew nut shell oil and epoxy chloropropane react as follows in the presence of sodium hydroxide:

Structure 1

Structure 2

Wherein: structure 1=90%, structure 2=10%

Five steps of synthetic branch of cardanol glycidyl ether carry out:

The first step: get cashew nut shell oil in molar ratio, epoxy chloropropane stirs, leads to N ₂Gas, it is to drip behind 30% the solution that sodium hydroxide is mixed with concentration, and temperature is controlled at 50-55 ℃, and the dropping time is 3-4h;

Second step: be warmed up to 70-75 ℃, insulation 3-4h;

The 3rd step: epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, 80 ± 2 ℃ of temperature, vacuum tightness 160mmHg is up to no overhead product, and the epoxy chloropropane of recovery and moisture cool off the back layering, and the epoxy chloropropane of separating out can be used again;

The 4th step: after product centrifuging, batch product of promptly winning;

The 5th goes on foot: after filter residue is filtered with the toluene extraction, steam toluene and promptly obtain second batch of product, measure oxirane value and viscosity.

Embodiment is as follows:

Embodiment 1

On the reaction flask of a 500ml, agitator, condenser, thermometer, charging opening and ventpipe are housed, drop into cashew nut shell oil 193.3g, epoxy chloropropane 111g stirs, leads to N ₂Gas is opened water of condensation.Begin to drip the sodium hydroxide solution 85.3g of 30% concentration then, temperature is controlled at 50 ℃, and the dropping time is 3h.

Be warming up to 73 ± 2 ℃, insulation 4h.

Be warming up to 80 ± 2 ℃, epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, vacuum tightness 160mmHg.

After product centrifuging, obtain firstling.

Filter residue is extracted, filters, steams toluene with toluene, obtain second batch of product.

Oxirane value=0.17 viscosity=160cps/25 ℃ yield=85%

Embodiment 2

In device with example 1, drop into cashew nut shell oil 193.3, epoxy chloropropane 111g stirs, leads to N ₂Gas, unlatching water of condensation.Begin to drip the sodium hydroxide solution 106.7g of 30% concentration then, temperature is controlled at 50 ℃, and the dropping time is 4h.

Be warmed up to 73 ± 2 ℃, insulation 4h.

Be warming up to 80 ± 2 ℃, epoxy chloropropane that reclaim under reduced pressure is excessive and water.Vacuum tightness 160mmHg.

With product centrifuging, obtain firstling.

Filter residue is extracted, filters, steams toluene with toluene, obtain second batch of product.

Oxirane value=0.18 viscosity=160cps/25 ℃ yield=85%

Embodiment 3

In device, drop into cashew nut shell oil 151g, epoxy chloropropane 92.5g, stirring, logical N with example 1 ₂Gas is opened water of condensation.Begin to drip the sodium hydroxide solution 88.7g of 30% concentration then, temperature is controlled at 50 ℃, and the dropping time is 3h.

Be warming up to 73 ± 2 ℃, insulation 3h.

Be warming up to 80 ± 2 ℃, epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, vacuum tightness is 160mmHg.

With product centrifuging, obtain firstling.

Filter residue is extracted with toluene, filter and steam toluene, obtain second batch of product.

Oxirane value=0.21 viscosity=160cps/25 ℃ yield=87.7%

Embodiment 4

In device with example 1, drop into cashew nut shell oil 151g, epoxy chloropropane 115.6g stirs, leads to N ₂Gas is opened water of condensation.Begin to drip the sodium hydroxide solution 100g of 30% concentration then, temperature is controlled at 50 ℃, and the dropping time is 3.5h.

Be warming up to 73 ± 2 ℃, insulation 3.5h.

Be warming up to 80 ± 2 ℃, epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, vacuum tightness is 160mmHg.

With product centrifuging, obtain firstling.

Filter residue is extracted with toluene, filter and steam toluene, obtain second batch of product.

Oxirane value=0.20 viscosity=160cps/25 ℃ yield=87.7%

Embodiment 5

In device with example 1, drop into cashew nut shell oil 120.8g, epoxy chloropropane 111g stirs, leads to N ₂Gas is opened water of condensation.Begin to drip the sodium hydroxide solution 106.7g of 30% concentration then, temperature is controlled at 55 ℃, and the dropping time is 3.5h.

Be warming up to 73 ± 2 ℃, insulation 3.5h.

Be warming up to 80+2 ℃, epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, vacuum tightness is 160mmHg.

With product centrifuging, obtain firstling.

Filter residue is extracted with toluene, filter and steam toluene, obtain second batch of product.

Oxirane value=0.18 viscosity=160cps/25 ℃ yield=87.8%

Embodiment 6

In device with example 1, drop into cashew nut shell oil 133g, epoxy chloropropane 111g stirs, leads to N ₂Gas is opened water of condensation.Begin to drip the sodium hydroxide solution 106.7g of 30% concentration then, temperature is controlled at 55 ℃, and the dropping time is 3.5h.

Be warming up to 73 ± 2 ℃, insulation 4h.

Be warming up to 80 ± 2 ℃, epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, vacuum tightness is 160mmHg.

With product centrifuging, obtain firstling.

Filter residue is extracted with toluene, filter and steam toluene, obtain second batch of product.

Oxirane value=0.18 viscosity=160cps/25 ℃ yield=87.8%

Claims (1)

1. a cardanol glycidyl ether is synthetic, it is characterized in that the cashew nut shell oil that adopts: epoxy chloropropane: hydrogen sodium hydride (mol ratio)=0.8-1.1: 1.5-3.0: 0.8-2.0; Cashew nut shell oil and epoxy chloropropane react as follows in the presence of sodium hydroxide:

Structure 1

Structure 2

Wherein: structure 1=90%, structure 2=10%

Five steps of synthetic branch of cardanol glycidyl ether carry out:

The first step: get cashew nut shell oil in molar ratio, epoxy chloropropane stirs, leads to N ₂Gas, it is to drip behind 30% the solution that sodium hydroxide is mixed with concentration, and temperature is controlled at 50-55 ℃, and the dropping time is 3-4h;

Second step: be warmed up to 70-75 ℃, insulation 3-4h;

The 3rd step: epoxy chloropropane that reclaim under reduced pressure is excessive and moisture, 80 ± 2 ℃ of temperature, vacuum tightness 160mmHg is up to no overhead product, and the epoxy chloropropane of recovery and moisture cool off the back layering, and the epoxy chloropropane of separating out can be used again;

The 4th step: after product centrifuging, batch product of promptly winning;

The 5th goes on foot: after filter residue is filtered with the toluene extraction, steam toluene and promptly obtain second batch of product, measure oxirane value and viscosity.