CN110042421A - A kind of preparation method of the alkoxylate intermediate based on dibutoxyethyl sebacate NO free radical - Google Patents
A kind of preparation method of the alkoxylate intermediate based on dibutoxyethyl sebacate NO free radical Download PDFInfo
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Abstract
The present invention relates to light stabilizer preparation technical field, in particular to the preparation method of a kind of alkoxylate intermediate based on dibutoxyethyl sebacate NO free radical；The following steps are included: by (2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical of decanedioic acid two existing for water, alcohol, alkali, the HCOOH under the conditions of catalytic and oxidative electrolysis technology, alkoxylate intermediate is made；The invention has the following advantages: this reaction is low compared with popular response temperature, without using catalyst and it is swift in response；Raw material sources are extensive, inexpensively；And product ultimate yield is high, so that having more economic value.
Description
Technical field
It is the present invention relates to light stabilizer preparation technical field, in particular to a kind of based on dibutoxyethyl sebacate NO free radical
The preparation method of alkoxylate intermediate.
Background technique
In order to improve the weatherability of plastic products, light stabilizer usually is added in its manufacturing process.And it is existing
Light stabilizer is mostly hindered amine light stabilizer, such as bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls) sebacates
It is a kind of hindered amine light stabilizer.Such as the Chinese patent of Publication No. CN106699639A discloses a kind of light stabilizer
The synthetic method of HS-112.It should be noted that: light stabilizer HS-112 is bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperazines
Piperidinyl) sebacate trade name.The patent is mentioned, by being catalyst by molybdenum trioxide, normal octane be raw material and solvent with
Bis- (2,2,6,6- tetramethyl-piperidyl) sebacate NO free radicals react to obtain light stabilizer HS112 --- bis- (pungent oxygen of 1-
Base -2,2,6,6- tetramethyl -4- piperidyl) sebacate.
Since traditional hindered amine light stabilizer generally has very high alkalinity, high alkalinity limits hindered amines light and stablizes
Agent halogen resin, acidic resins and acidic materials may be bred stabilising system in synergistic stability effect.HS-112 be with-
OC8H17 replaces the hydrogen atom on UV-770 (bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacic acid esters) nitrogen, to pass through structure
On change with become hindered amine N- alkyl oxide, make its alkalinity reduce.
But this alkoxylated hindered amine synthesis of N- is progress substitution reaction under the effect of the catalyst, so that
The process is more complicated and yield is relatively low.If replaced with increasingly complex group, with test synthesis, other are effective
N- alkoxylate light stabilizer replaces difficulty directly proportional to the complexity of substituent group, so that yield more reduces.Cause
This, is necessary and prepares a kind of alkoxylate intermediate based on dibutoxyethyl sebacate NO free radical, in order to increasingly complex
Group is replaced, to improve light stabilizer ultimate yield.
Summary of the invention
The present invention solves the above-mentioned technical problems in the prior art, provides a kind of free based on dibutoxyethyl sebacate nitrogen oxygen
The preparation method of the alkoxylate intermediate of base.
To solve the above problems, technical scheme is as follows:
A kind of preparation method of the alkoxylate intermediate based on dibutoxyethyl sebacate NO free radical, comprising the following steps:
(2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical of decanedioic acid two is existed in water, alcohol, alkali, HCOOH
Under conditions of catalytic and oxidative electrolysis technology, be made alkoxylate intermediate；The structural formula of the alkoxylate intermediate are as follows:
Reaction equation are as follows:
Preferably, the alcohol is methanol, ethyl alcohol, ethylene glycol, propyl alcohol, any one in propylene glycol；Methanol is optimal.
Preferably, the alkali is NaOH, KOH, Ba (OH)2In any one；KOH is optimal.
Preferably, decanedioic acid two (2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical: water: alcohol: alkali:
The mass ratio of the material of HCOOH is 1~60:1~20:80~150:1~5:1~40；Two (the 2,2,6,6- tetramethyl of decanedioic acid
Base -4- hydroxy piperidine) ester NO free radical: water: alcohol: alkali: the mass ratio of the material of HCOOH is 1~20:10~20:120~150:
2~3:20~40 are optimal.
Preferably, the electrolysis temperature of the catalytic and oxidative electrolysis technology is 10~70 DEG C；40~50 DEG C are optimal.
Preferably, the anode material of the catalytic and oxidative electrolysis technology is BDD electrode, vitreous carbon, any one in diamond, excellent
Select BDD electrode.
Preferably, the cathode material of the catalytic and oxidative electrolysis technology is titanium plate, stainless steel, any one in stereotype, preferably titanium
Plate.
Preferably, the current density of the catalytic and oxidative electrolysis technology is maintained at 300~2600A/m3；It is preferred that current density is
600~1200A/m3。
More specifically, recommending method of the present invention is to follow the steps below: the decanedioic acid two of 100g (2,
2,6,6- tetramethyl -4- hydroxy piperidines) ester NO free radical is put into cell reaction bottle, then puts into water, the 60g first of 30g respectively
Alcohol, 16g sodium hydroxide, 30g formic acid, in 800A/m3Catalytic and oxidative electrolysis technology under current density, anode material are BDD electrode, cathode
Material is titanium plate, and electrolyte is filtered in electrolysis afterwards for 24 hours, can obtain decanedioic acid two (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester nitrogen
The NOH type hindered amine light stabilizer intermediate of oxygen radical.
Compared with the existing technology, advantages of the present invention is as follows,
(1) present invention is for the first time in a manner of catalytic and oxidative electrolysis technology in the alkoxylate of synthesis of sebacic acid diester NO free radical
Mesosome, the intermediate are simplest NOH type hindered amine light stabilizer intermediate, and H group therein is easy more multiple by other
Miscellaneous R group is replaced, to further synthesize NOR type hindered amine light stabilizer intermediate.In above process, by with
The mode high yield of catalytic and oxidative electrolysis technology formerly prepares NOH type hindered amine light stabilizer intermediate so that the NOH type prepared by
H group in resistance amine light stabilizer intermediate is more readily replaced by other complexity group R, thus the synthesis of high yield
NOR type hindered amine light stabilizer intermediate；
(2) this reaction is low compared with popular response temperature, without using catalyst and is swift in response；
(3) raw material sources are extensive, inexpensively；And product ultimate yield is high, so that having more economic value.
Detailed description of the invention
Fig. 1 is product infrared spectrogram obtained under formic acid environment；
Lower curve is decanedioic acid two (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester NO free radical in figure；
Top curve is electrolysate decanedioic acid two (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester NO free radical in figure
Alkoxylate intermediate.
Specific embodiment
Embodiment 1:
(2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical of decanedioic acid two of 100g is put into cell reaction bottle
In, then water, 60g methanol, 16g sodium hydroxide, the 30g formic acid of 30g is put into respectively, in 800A/m3Electrolytic catalysis under current density
Oxidation, anode material are BDD electrode, and cathode material is titanium plate, and electrolyte is filtered in electrolysis afterwards for 24 hours, and dibutoxyethyl sebacate can be obtained
The product 97g of the alkoxylate intermediate of NO free radical, content (GC) 97.40%, yield about 89%.
Fig. 1 is the product infrared spectrogram obtained under formic acid environment；Before electrolysis, there is no hydroxyl (ν in functional group region
OH) characteristic peak, corresponding 3405 (the ν OH) in the infrared peak of product after electrolysis have hydroxyl characteristic peak；Illustrate in cell reaction, nitrogen oxygen is free
Base is electrolyzed to produce hydroxyl (ν OH).
The alkoxylate midbody product of dibutoxyethyl sebacate NO free radical is prepared in aforementioned manners, catalytic and oxidative electrolysis technology
Electrolysis temperature is 10~70 DEG C, and current density is maintained at 200~2600A/m3, reacting can all go on smoothly；Wherein electrolysis temperature
40~50 DEG C of selection, current density select 600~1200A/m3It is optimal.
Embodiment 2:
(2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical of decanedioic acid two of 100g is put into cell reaction bottle
In, then water, 40g methanol, 8g sodium hydroxide, the 30g formic acid of 15g is put into respectively, in 300A/m3Electrolytic catalysis oxygen under current density
Change, anode material is BDD electrode, and cathode material is titanium plate, and electrolyte is filtered in electrolysis afterwards for 24 hours, and dibutoxyethyl sebacate nitrogen can be obtained
The product 88g of the alkoxylate intermediate of oxygen radical, content (GC) 88.35%, yield about 82%.
Embodiment 3:
(2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical of decanedioic acid two of 100g is put into cell reaction bottle
In, then water, 50g methanol, 6g potassium hydroxide, the 50g formic acid of 45g is put into respectively, in 600A/m3Electrolytic catalysis oxygen under current density
Change, anode material is BDD electrode, and cathode material is titanium plate, and electrolyte is filtered in electrolysis afterwards for 24 hours, and dibutoxyethyl sebacate nitrogen can be obtained
The product 93g of the alkoxylate intermediate of oxygen radical, content (GC) 93.25%, yield about 85%.
Embodiment 4:
With embodiment 1 method prepare dibutoxyethyl sebacate NO free radical alkoxylate intermediate product, difference
It is in the selection in alcohol；Product assay (GC) is made and yield result is as follows:
Embodiment 5:
The alkoxylate midbody product of dibutoxyethyl sebacate NO free radical, difference are prepared with the method for embodiment 1
It is NO free radical: water: alcohol: alkali: the mass ratio of the material of HCOOH；The alkoxy of dibutoxyethyl sebacate NO free radical obtained
Change midbody product content (GC) and yield result be as follows:
Comparative example 1:
With embodiment 1 method prepare dibutoxyethyl sebacate NO free radical alkoxylate intermediate product, difference
It is in the selection of anode material；Product assay (GC) is made and yield result is as follows:
Use vitreous carbon as anode: by-product is more, and is easy passivation, and the constant pressure the case where, electric current decline is obvious, needs
Often cleaning vitreous carbon pole plate, could improve electrolytic current density.
Use platinum as anode: after electrolysis 12 hours, electric current decline is obvious, and product yield is low.
Use pb-ag alloy as anode: almost no current is generated almost without product.
Comparative example 2:
With embodiment 1 method prepare dibutoxyethyl sebacate NO free radical alkoxylate intermediate product, difference
It is in the selection of cathode material；Product assay (GC) is made and yield result is as follows:
Use stainless steel as cathode: stainless steel polar plate is electrolysed in same time easily by electrolytic etching, and product is less.
Use stereotype as cathode: stereotype surface is easily corroded to form irregular male and fomale(M&F), reduces the pole plate service life, no
It is recommended that using for a long time.
Use nickel plate as cathode: almost no current is generated almost without product.
Use cadmium plate as cathode: almost no current is generated almost without product.
Comparative example 3:
With embodiment 1 method prepare dibutoxyethyl sebacate NO free radical alkoxylate intermediate product, difference
It is in the selection of concentration of electrolyte；Product assay (GC) is made and yield result is as follows:
NO free radical: water: alcohol: alkali: when the mass ratio of the material of HCOOH is 20:10:40:3:20, since electroanalysis solvent is
The amount of the mixture of first alcohol and water, alcohol is less, makes NO free radical be not easy to be dissolved, electrolysate is caused to decline.
NO free radical: water: alcohol: alkali: when the mass ratio of the material of HCOOH is 20:10:240:3:20, in this feed ratio, though
The usage amount of right alcohol is 2 times of optimum charging ratio, and NO free radical can be completely dissolved at this time, still, since the amount of methanol increases
It is more, reduce the moisture in electrolyte, electrolytic efficiency is caused to lower, electrolysate decline.
NO free radical: water: alcohol: alkali: when the mass ratio of the material of HCOOH is 20:10:120:20:20, in this feed ratio,
Since the amount of alkali is excessive, keep the pH value in electrolyte higher, be electrolysed in very short time, pole plate meeting heavy corrosion reduces electrolysis effect
Rate, product generate seldom.
Comparative example 4:
With embodiment 1 method prepare dibutoxyethyl sebacate NO free radical alkoxylate intermediate product, difference
It is in the selection of current density；Product assay (GC) is made and yield result is as follows:
How low current density is, reduces yield.
Current density is much, punctures anode, can not be electrolysed, keep electrolytic pole board unstable, influence quality of anode.
The critical that the technical program succeeds is: choosing specific electrode material, i.e. selection BDD electrode conduct
Anode material, titanium plate are as cathode material；The concentration of accurate control electrolyte, i.e. alkali: the mass ratio of the material 20:10 of HCOOH:
120:3:20；Under the conditions ofs specific current density, electrolysis temperature etc., i.e. current density A/m3For 800A/m3.It can get highest
Yield.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of the alkoxylate intermediate based on dibutoxyethyl sebacate NO free radical, which is characterized in that including
Following steps:
By decanedioic acid two (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester NO free radical item existing for water, alcohol, alkali, HCOOH
Alkoxylate intermediate is made in catalytic and oxidative electrolysis technology under part；The structural formula of the alkoxylate intermediate are as follows:
2. preparation method as described in claim 1, which is characterized in that the alcohol is methanol, ethyl alcohol, ethylene glycol, propyl alcohol, the third two
Any one in alcohol.
3. preparation method as described in claim 1, which is characterized in that the alkali is NaOH, KOH, Ba (OH)2In any one.
4. preparation method as described in claim 1, which is characterized in that two (2,2,6, the 6- tetramethyl -4- hydroxyls of decanedioic acid
Piperidines) ester NO free radical: water: alcohol: alkali: the mass ratio of the material of HCOOH is 1~60:1~20:80~150:1~5:1~40.
5. preparation method as described in claim 1, which is characterized in that two (2,2,6, the 6- tetramethyl -4- hydroxyls of decanedioic acid
Piperidines) ester NO free radical: water: alcohol: alkali: the mass ratio of the material of HCOOH be 1~20:10~20:120~150:2~3:20~
40。
6. preparation method as described in claim 1, which is characterized in that the electrolysis temperature of the catalytic and oxidative electrolysis technology is 10~70
℃。
7. preparation method as described in claim 1, which is characterized in that the anode material of the catalytic and oxidative electrolysis technology is BDD electricity
Pole, vitreous carbon, any one in diamond.
8. preparation method as described in claim 1, which is characterized in that the cathode material of the catalytic and oxidative electrolysis technology be titanium plate,
Any one in stainless steel, stereotype.
9. preparation method as described in claim 1, which is characterized in that the current density of the catalytic and oxidative electrolysis technology is maintained at
300~2600A/m3。
10. preparation method as described in claim 1, which comprises the following steps:
(2,2,6,6- tetramethyl -4- hydroxy piperidine) the ester NO free radical of decanedioic acid two of 100g is put into cell reaction bottle,
Water, 60g methanol, 16g sodium hydroxide, the 30g formic acid for putting into 30g respectively again, in 800A/m3Electrolytic catalysis oxygen under current density
Change, anode material be BDD electrode, cathode material is titanium plate, electrolysis filter electrolyte afterwards for 24 hours, can obtain decanedioic acid two (2,2,6,
6- tetramethyl -4- hydroxy piperidine) ester NO free radical NOH type hindered amine light stabilizer intermediate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850596A (en) * | 2020-07-13 | 2020-10-30 | 万华化学集团股份有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| CN111996546A (en) * | 2020-07-28 | 2020-11-27 | 宿迁联盛科技股份有限公司 | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester |
| CN112609201A (en) * | 2020-12-11 | 2021-04-06 | 万华化学(四川)有限公司 | Method for pair-wise synthesizing carbonic diester and sebacic diester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850596A (en) * | 2020-07-13 | 2020-10-30 | 万华化学集团股份有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| CN111850596B (en) * | 2020-07-13 | 2021-04-20 | 万华化学(四川)有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| CN111996546A (en) * | 2020-07-28 | 2020-11-27 | 宿迁联盛科技股份有限公司 | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester |
| CN111996546B (en) * | 2020-07-28 | 2021-06-29 | 宿迁联盛科技股份有限公司 | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester |
| CN112609201A (en) * | 2020-12-11 | 2021-04-06 | 万华化学(四川)有限公司 | Method for pair-wise synthesizing carbonic diester and sebacic diester |
| CN112609201B (en) * | 2020-12-11 | 2023-09-19 | 万华化学(四川)有限公司 | Method for synthesizing carbonic acid diester and sebacic acid diester in pair |
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