Epoxy diluent

The invention discloses a method for synthesizing C12/14 alkyl glycidyl ether, which comprises the following steps:
(1) fatty alcohol is taken as a raw material and is subjected to addition ring-opening with epoxy chloropropane under
the catalysis of Lewis acid catalysts to obtain an intermediate with a chlorophydrin ether structure; and (2) the
intermediate with the chlorophydrin ether structure reacts with alkali to perform the ring-closure removal to chlorine
hydride to obtain a product. In the step (1), one to two of the Lewis acid catalysts, namely AlCl3, SnCl4 and ZnCl2
are adopted first, the adding amount of the catalysts is 0.05 to 5 percent of the mass of the fatty alcohol, the
temperature is increased to be between 40 and 80 DEG C, and an epoxy compound is dripped to continue reacting
for 1 to 7 hours; and one Lewis acid catalyst, BF3.Et2O which accounts for 0.05 to 1.5 percent of the mass of the
fatty alcohol is added into the mixture. The method well solves the problems of lower epoxy value of the product
and more residual raw material, namely the fatty alcohol existing in the prior art that the fatty alcohol and the epoxy
chloropropane are taken as raw materials to synthesize alkyl glycidyl ether.

Description

C 12/14The synthetic method of alkyl glycidyl ether

Technical field

The present invention relates to a kind of synthetic method of epoxide resin reactive diluent.

Background technology

The synthetic industrial Fatty Alcohol(C12-C14 and C12-C18) (primary alconol) that mostly adopts at
present of alkyl glycidyl ether is a raw material, at Lewis acid (as BF 3Et 2O, AlCl 3, SnCl 4, ZnCl 2Deng)
under the catalysis, obtain the intermediate of chloropharin ether structure with epoxy chloropropane
addition open loop, again with alkali reaction (generally using NaOH), the closed loop
dehydrochlorination obtains product.Reaction equation is as follows:

As everyone knows, do not have at normal temperature under the condition of catalyzer existence, the
hydroxyl of Fatty Alcohol(C12-C14 and C12-C18) is difficult to react with epoxy group(ing), even (greater
than 170 ℃) reaction is also very slow under comparatively high temps.At Lewis acid (as BF 3Et 2O)
catalyzer exists down, and the reactive behavior of epoxy group(ing) strengthens greatly, 50 ℃ down
just can be successfully and the hydroxyl reaction of Fatty Alcohol(C12-C14 and C12-C18), the
intermediate of generation chloropharin ether structure.Though the reactive behavior of primary
hydroxyl is low in reactivity ratio's feedstock fat alcohol of the secondary hydroxyl in the intermediate
product chloropharin ether, but still the competitive opening that participates in epoxy group(ing) of
meeting generates undesirable chainpropagation by product.When Fatty Alcohol(C12-C14 and C12-C18)
that adopts equivalent and epoxy compounds reaction, because the generation of chainpropagation by
product, cause having a large amount of feedstock fat alcohol to remain in the product, even adopt
excessive epoxide to participate in reaction, still can not eliminate the residual of feedstock fat alcohol
fully, and the oxirane value of product is lowered further.
Though can adopt the distillatory method from middle product, to remove and reclaim feedstock fat alcohol, when
boiling point of fatty alcohols during greater than 200 ℃ as (C 12/14Fatty Alcohol(C12-C14 and C12-C18)), the
method for this Separation and Recovery becomes difficult.
Though can adopt the method that epoxy compounds (general for epoxy chloropropane) is slowly splashed into
reaction system to improve the reaction preference of primary hydroxyl, also can adopt and add the reaction
preference (thermosetting resin that inert solvent improves primary hydroxyl, the 19th the 6th phase of volume, in
November, 2004, the 18th～19 page), but all can not well address the above problem

Summary of the invention

Is that the product oxirane value that exists of raw material synthesis of alkyl glycidyl ether technology is lower for
solving existing with Fatty Alcohol(C12-C14 and C12-C18) and epoxy chloropropane, the more problem of residual
feedstock fat alcohol.The inventor adopts the method with the different compound uses of catalyzer, has well solved
the problems referred to above.

With Fatty Alcohol(C12-C14 and C12-C18) and epoxy chloropropane is that the step of raw material synthesis of
alkyl glycidyl ether comprises:

(1) adopting Fatty Alcohol(C12-C14 and C12-C18) is raw material, under lewis acid catalyst catalysis, obtains
the intermediate of chloropharin ether structure with epoxy chloropropane addition open loop;
(2) (2) intermediate of chloropharin ether structure again with alkali reaction (generally using NaOH), the
closed loop dehydrochlorination obtains product.

The inventor has adopted following method:

n the reaction of (1) Fatty Alcohol(C12-C14 and C12-C18) that goes on foot and epoxy ring-opening
addition, adopt lewis acid catalyst AlCl earlier 3, SnCl 4, ZnCl 2In one or both mix as catalyst A, adopt
simultaneously epoxy compounds (as: epoxy chloropropane) slowly is added drop-wise to method in the
reaction system, improve the reaction preference of epoxy group(ing) to primary hydroxyl; (for example:
BF add a kind of lewis acid catalyst B afterwards again 3Et 2O), reaction is further carried out, and made
and add epoxy compounds and react completely, reduce raw material epoxy chloropropane residual in
product, reduce the loss of raw material.

The detailed process of reaction is:

(1) add Fatty Alcohol(C12-C14 and C12-C18) and catalyst A in reactor, the add-on of catalyst A is 0.05%
～5% of a Fatty Alcohol(C12-C14 and C12-C18) quality.The temperature to 40 of rising reaction mass
℃～80 ℃, and keep this temperature of reaction, drip epoxy compounds, 1～4 hour dropping
time.After being added dropwise to complete, keeping this temperature of reaction and continue
reaction 1～7 hour; Afterwards, add a kind of lewis acid catalyst B again, the add-on of B is 0.05%～
1.5% of a Fatty Alcohol(C12-C14 and C12-C18) quality.30～100 ℃ of temperature of reaction, 1～4
hour reaction times.

Described lewis acid catalyst A is AlCl 3, SnCl 4, ZnCl 2In a kind of or two kinds mixture.
Described lewis acid catalyst B is BF 3Et 2O.
The mol ratio of described epoxy compounds and Fatty Alcohol(C12-C14 and C12-C18) is preferably
0.9～1.4:1.
(2) intermediate of chloropharin ether structure and alkali reaction, the closed loop dehydrochlorination
obtains product.Described alkali is preferably NaOH.

Expriment 1
In the 10L reaction flask, add 3918 gram C 12/14Mixed fatty alcohol, 25 gram SnCl 4, stir, be warmed up
to 80 ℃.Keep 80 ℃ of temperature of reaction, in 4 hours, drip epoxy chloropropane 2410 grams,
after being added dropwise to complete, continued stirring reaction 2 hours in this temperature.Cool to
60 ℃, add 7.3 gram BF 3Et 2O, 60 ℃ were reacted 2 hours down.Keep 60 ℃ of temperature of
reaction, in 3 hours, drip 1777 gram 50.0%NaOH, under equality of temperature, reacted 3 hours
again.Afterwards, add 80 ℃ of hot water of 3500 grams, stir, leave standstill, divide sub-cloud salt
solution, add 80 ℃ of deionized waters of 1000 grams again, stir, add the 2.50% phosphoric acid pH
value that neutralizes and equal 6, leave standstill, divide sub-cloud water.Add 80 ℃ of deionized
waters of 1000 grams again, stir, leave standstill, divide sub-cloud water.Vacuum (100Torr), 120 ℃
down dehydration to moisture less than 1000ppm after, filter product 5270 grams.Epoxy equivalent
(weight) 278, raw material C 12/14The mixed fatty alcohol residual quantity is less than 2.50%.

Expriment 2
In the 10L reaction flask, add 3918 gram C 12/14Mixed fatty alcohol, 5 gram AlCl 3, 10 gram ZnCl 2,
stir, be warmed up to 65 ℃.Keep 65 ℃ of temperature of reaction, in 3 hours, drip epoxy
chloropropane 2410 grams, after being added dropwise to complete, continued stirring reaction 7 hours
in this temperature.Cool to 60 ℃, add 7.3 gram BF 3Et 2O, 60 ℃ were reacted 2 hours down.Keep 60
℃ of temperature of reaction, in 3 hours, drip 1777 gram 50.00%NaOH, under equality of
temperature, reacted 3 hours again.Afterwards, add 80 ℃ of hot water of 3500 grams, stir, leave
standstill, divide sub-cloud salt solution, add 80 ℃ of deionized waters of 1000 grams again, stir, add
the 2.50% phosphoric acid pH value that neutralizes and equal 6, leave standstill, divide sub-cloud
water.Add 80 ℃ of deionized waters of 1000 grams again, stir, leave standstill, divide sub-cloud
water.Vacuum (100Torr), 120 ℃ down dehydration to moisture less than 1000ppm after, filter product
5270 grams.Epoxy equivalent (weight) 280, raw material C 12/14The mixed fatty alcohol residual
quantity is less than 3.50%.

Expriment 3

In the 10L reaction flask, add 3918 gram C 12/14Mixed fatty alcohol, 195.9 gram ZnCl 2, stir, be
warmed up to 40 ℃.Keep 40 ℃ of temperature of reaction, in 3 hours, drip epoxy chloropropane 2410
grams, after being added dropwise to complete, continued stirring reaction 2 hours in this
temperature.Cool to 30 ℃, add 58.7 gram BF 3Et 2O, 30 ℃ were reacted 4 hours down.Intensification
is also kept 60 ℃ of temperature of reaction, drips 1777 gram 50.00%NaOH in 3 hours, reacts 3 hours
under equality of temperature again.Afterwards, add 80 ℃ of hot water of 3500 grams, stir, leave
standstill, divide sub-cloud salt solution, add 80 ℃ of deionized waters of 1000 grams again, stir, add
the 2.50% phosphoric acid pH value that neutralizes and equal 6, leave standstill, divide sub-cloud
water.Add 80 ℃ of deionized waters of 1000 grams again, stir, leave standstill, divide sub-cloud
water.Vacuum (100Torr), 120 ℃ down dehydration to moisture less than 1000ppm after, filter product
5270 grams.Epoxy equivalent (weight) 276, raw material C 12/14The mixed fatty alcohol residual
quantity is less than 2.40%.

Expriment 4

In the 10L reaction flask, add 3918 gram C 12/14Mixed fatty alcohol, 1.959 gram ZnCl 2, stir, be
warmed up to 40 ℃.Keep 40 ℃ of temperature of reaction, in 1 hour, drip epoxy chloropropane 2410
grams, after being added dropwise to complete, continued stirring reaction 1 hour in this
temperature.Be warmed up to 100 ℃, add 1.959 gram BF 3Et 2O, 100 ℃ were reacted 1 hour
down.Cooling is also kept 60 ℃ of temperature of reaction, drips 1777 gram 50.00%NaOH in 3 hours,
reacts 3 hours under equality of temperature again.Afterwards, add 80 ℃ of hot water of 3500 grams,
stir, leave standstill, divide sub-cloud salt solution, add 80 ℃ of deionized waters of 1000 grams again,
stir, add the 2.50% phosphoric acid pH value that neutralizes and equal 6, leave standstill, divide sub-
cloud water.Add 80 ℃ of deionized waters of 1000 grams again, stir, leave standstill, divide sub-cloud
water.Vacuum (100Torr), 120 ℃ down dehydration to moisture less than 1000ppm after, filter product
5270 grams.Epoxy equivalent (weight) 324, raw material C 12/14The mixed fatty alcohol residual
quantity is less than 18.80%.

Expriment 5
In the 10L reaction flask, add 3918 gram C 12/14Mixed fatty alcohol, 98 gram SnCl 4, 97.9 gram
ZnCl 2Stir, be warmed up to 80 ℃.Keep 80 ℃ of temperature of reaction, in 3 hours, drip epoxy
chloropropane 2410 grams, after being added dropwise to complete, continued stirring reaction 2 hours
in this temperature.Be warmed up to 100 ℃, add 7.3 gram BF 3Et 2O, 100 ℃ were reacted 2 hours
down.Cooling is also kept 60 ℃ of temperature of reaction, drips 1777 gram 50.00%NaOH in 3 hours,
reacts 3 hours under equality of temperature again.Afterwards, add 80 ℃ of hot water of 3500 grams,
stir, leave standstill, divide sub-cloud salt solution, add 80 ℃ of deionized waters of 1000 grams again,
stir, add the 2.50% phosphoric acid pH value that neutralizes and equal 6, leave standstill, divide sub-
cloud water.Add 80 ℃ of deionized waters of 1000 grams again, stir, leave standstill, divide sub-cloud
water.Vacuum (100Torr), 120 ℃ down dehydration to moisture less than 1000ppm after, filter product
5270 grams.Epoxy equivalent (weight) 275, raw material C 12/14The mixed fatty alcohol residual
quantity is less than 2.10%.

Expriment 6

In the 10L reaction flask, add 3918 gram C 12/14Mixed fatty alcohol, 88 gram SnCl 4, 50 gram
AlCl 3Stir, be warmed up to 70 ℃.Keep 70 ℃ of temperature of reaction, in 3 hours, drip epoxy
chloropropane 2410 grams, after being added dropwise to complete, continued stirring reaction 2 hours
in this temperature.Be warmed up to 90 ℃, add 7.3 gram BF 3Et 2O, 90 ℃ were reacted 2 hours
down.Cooling is also kept 60 ℃ of temperature of reaction, drips 1777 gram 50.00%NaOH in 3 hours,
reacts 3 hours under equality of temperature again.Afterwards, add 80 ℃ of hot water of 3500 grams,
stir, leave standstill, divide sub-cloud salt solution, add 80 ℃ of deionized waters of 1000 grams again,
stir, add the 2.50% phosphoric acid pH value that neutralizes and equal 6, leave standstill, divide sub-
cloud water.Add 80 ℃ of deionized waters of 1000 grams again, stir, leave standstill, divide sub-cloud
water.Vacuum (100Torr), 120 ℃ down dehydration to moisture less than 1000ppm after, filter product
5270 grams.Epoxy equivalent (weight) 276, raw material C 12/14The mixed fatty alcohol residual
quantity is less than 2.20%.