CN107141271B - A kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate - Google Patents
A kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate Download PDFInfo
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- CN107141271B CN107141271B CN201710485903.7A CN201710485903A CN107141271B CN 107141271 B CN107141271 B CN 107141271B CN 201710485903 A CN201710485903 A CN 201710485903A CN 107141271 B CN107141271 B CN 107141271B
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- oxygen hydrochlorate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Abstract
The present invention relates to a kind of synthetic methods of epoxy plasticizer based on molybdenum multi-metal oxygen hydrochlorate.The technical solution adopted is that: formic acid or acetic acid are mixed with raw oil material, anion Mo8O26 4‑Molybdenum multi-metal oxygen phosphate catalyst be dissolved in H2O2In, it is slowly added to reaction system and is reacted, reaction temperature is at 30~60 DEG C, 2~6h of reaction time.With H in reaction process2O2Consumption, molybdenum multi-metal oxygen phosphate catalyst is gradually precipitated from reaction system, is centrifugated out catalyst after reaction, and reaction solution is washed with deionized to neutrality, and epoxy product can be obtained in distillation.Catalyst used herein has then separation function, and easily recycling uses, and free from environmental pollution, gained epoxy plasticizer quality is higher.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to a kind of conjunction of the epoxy plasticizer based on molybdenum multi-metal oxygen hydrochlorate
At method.
Background technique
Plasticizer is always world wide production, the maximum plastic processing additives of consumption figure with its necessity in plastic processing
One of, it will be more than 19,500,000,000 dollars to the expection of the year two thousand twenty world market.In recent years, China has become Asian-Pacific area plasticizer production
Amount and the most country of consumption figure.Type includes phthalate (DOP or DEHP), benzene polyester class, epoxies, aliphatic
Binary acid esters, citric acid ester type, phenyl alkylsulf class, phosphoric acid ester, polyesters, chlorinated paraffin class etc., wherein DEHP makes
With the most extensively, but stepping up with countries in the world environmental consciousness finds that adjacent benzene class plasticizer has latent carcinogenicity.
So research and development new plasticizer and the existing environment-friendly plasticizer synthesis technology of Optimal improvements are extremely urgent.
Epoxy plasticizer is the compound for having epoxy group in the molecular structure, processes work in industrial Corvic
In industry, it not only has plasticization to PVC, but also the active chlorine atom in polyvinyl chloride chain can be made to stablize, the epoxy in structure
The hydrogen chloride for degrading out because of light and heat can be absorbed in group, so that the continuous decomposition of PVC be prevented to act on, plays stabilizer
Effect, can extend the service life of PVC product.Epoxy plasticizer has excellent water resistance, oil resistivity, while still good
Auxiliary stabilizer.According to the difference of used catalyst, epoxy plasticizer synthetic method mainly has sulfuric acid process, ion exchange resin to urge
Change method, solid superacid as catalyst oxidizing process etc..Such acid catalysis production method, process flow is long and complicated, and product quality is unstable
Fixed, epoxide number is 5% or so, and high production cost, equipment is more, and " three wastes " treating capacity is big, and solvent benzol has toxicity, at present this method
It has been eliminated.And no-solvent process synthesizing epoxy soybean oil is used to become the hot spot researched and developed.Although solventless method overcomes
Many shortcomings of solvent method, but that there is also reaction stabilities is poor, and finished product epoxide number is lower, and product color is deep, and equipment is rotten
Erosion and the disadvantages of environmental pollution is serious.
Summary of the invention
The purpose of the present invention is to provide one kind using molybdenum multi-metal oxygen hydrochlorate as catalyst, H2O2For oxidant, method letter
List, catalyst amount are less and environmentally protective, the high epoxy plasticizer based on molybdenum multi-metal oxygen hydrochlorate of plasticizer epoxide number closes
At method.
The technical solution adopted by the present invention is that: a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate, packet
It includes following steps: a certain amount of organic carboxyl acid being taken to mix with raw oil material, be Mo with anion8O26 4-Molybdenum multi-metal oxygen hydrochlorate
For catalyst, H2O2For oxidant, catalyst is dissolved in H2O2In, then it is added dropwise to the mixed of organic carboxyl acid and raw oil material
In zoarium system, it is centrifugated out catalyst after reaction in 30~60 DEG C of 2~6h of reaction, reaction solution is washed with deionized
It is dry to neutrality, obtain target product.
A kind of above-mentioned epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate, the organic carboxyl acid are formic acid
Or acetic acid.
A kind of above-mentioned epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate, the raw oil material is insatiable hunger
With vegetable oil or fatty acid methyl ester.Preferably, the polyunsaturated vegetable oil is soybean oil.
A kind of above-mentioned epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate, the anion are Mo8O26 4-
Molybdenum multi-metal oxygen hydrochlorate be: tetra-allkylammonium class molybdenum multi-metal oxygen hydrochlorate, imidazoles molybdenum multi-metal oxygen hydrochlorate or pyridines molybdenum are more
Oxometallate.
Preferably, the structural formula of the tetra-allkylammonium class molybdenum multi-metal oxygen hydrochlorate is as follows:
Wherein, R1、R2、R3And R4For methyl, ethyl, normal-butyl or n-hexadecyl.
Preferably, the structural formula of the imidazoles molybdenum multi-metal oxygen hydrochlorate is as follows:
Wherein, n=1~8.
Preferably, the structural formula of the pyridines molybdenum multi-metal oxygen hydrochlorate is as follows:
Wherein, n=1~8.
A kind of upper epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate, catalyst amount is feedstock oil
The 1~20% of lipid amount, organic carboxyl acid dosage are 10~50%, H of raw oil material quality2O2Dosage is raw oil material quality
10~100%
The beneficial effects of the present invention are:
1. the present invention, will be based on Mo8O26 4-The molybdenum multi-metal oxygen hydrochlorate of anion is used for the synthesis of epoxy plasticizer for the first time,
Catalyst activity is high, dosage is few.
2. the present invention, catalyst soluble is in oxidant H2O2In, with H in reaction process2O2Consumption, molybdenum multi-metal oxygen
Phosphate catalyst is gradually precipitated from reaction system, and centrifugation may separate out catalyst after reaction, and separation method is simple.It urges
Agent is i.e. reusable after being washed with ether, being dry.
3. the present invention, is centrifugated out catalyst after reaction, oil is mutually washed with deionized to neutrality, vacuum distillation
Epoxy product can be obtained, last handling process is simple.
4. the present invention, synthetic method uses solventless method, avoids the use of organic solvent.
5. carrying out the synthetic reaction of epoxy plasticizer using method of the invention, gained epoxides quality is preferable, epoxy
Value > 5.5%, acid value < 1mg KOH/g.Not only epoxida tion catalyst effect is good for the invention, but also catalyst easily recycles use, no
Pollute environment.
Specific embodiment
Below by embodiment, the present invention is described in further detail, but embodiment is not to limit of the invention
It is fixed.
Embodiment 1 is based on 1- hexyl -3- methylimidazole molybdate ([Hmim]4Mo8O26) Plasticizer Epoxidized Soybean Oil
[Hmim]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [Hmim]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, temperature are being housed
20g refined soybean oil and 7g formic acid (88%) are added in the 50mL three-necked flask of meter, under agitation, is slowly added dropwise dissolved with urging
The H of agent2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, it is cooled to room temperature to reaction solution
Afterwards, it is centrifugated out catalyst, reaction solution is washed with water to neutrality, dry to get yellow oily product, as target product.
It being measured according to GB/T 1677-2008, target product epoxide number is 6.22%, it is measured according to GB/T 1668-2008,
Target product acid value is 0.36mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.12%, 6.10%, 6.05%, 6.01% and 5.98%.
Embodiment 2 is based on 1,2- dimethyl -3- hexyl imidazolium molybdate ([DHmim]4Mo8O26) epoxidized soybean oil plasticising
Agent
[DHmim]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [DHmim]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, temperature are being housed
20g refined soybean oil and 7g formic acid (88%) are added in the 50mL three-necked flask of meter, under agitation, is slowly added dropwise dissolved with urging
The H of agent2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, it is cooled to room temperature to reaction solution
Afterwards, it is centrifugated out catalyst, reaction solution is washed with water to neutrality, dry to get yellow oily product, as target product.
It being measured according to GB/T 1677-2008, target product epoxide number is 6.18%, it is measured according to GB/T 1668-2008,
Target product acid value is 0.41mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.10%, 6.05%, 6.00%, 6.96% and 5.93%.
Embodiment 3 is based on 1,2- dimethyl -3- hexyl imidazolium molybdate ([DHmim]4Mo8O26) epoxy aliphatic acid methyl ester
Plasticizer
[DHmim]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [DHmim]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, temperature are being housed
20g fatty acid methyl ester and 7g formic acid (88%) are added in the 50mL three-necked flask of meter, under agitation, is slowly added dropwise dissolved with urging
The H of agent2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, it is cooled to room temperature to reaction solution
Afterwards, it is centrifugated out catalyst, reaction solution is washed with water to neutrality, dry to get yellow oily product, as target product.
It being measured according to GB/T 1677-2008, target product epoxide number is 6.47%, it is measured according to GB/T 1668-2008,
Target product acid value is 0.39mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.45%, 6.40%, 6.31%, 6.24% and 6.16%.
Embodiment 4 is based on 1- hexyl pyridine molybdate ([Hpy]4Mo8O26) Plasticizer Epoxidized Soybean Oil
[Hpy]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [Hpy]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, thermometer are being housed
50mL three-necked flask in 20g refined soybean oil and 7g formic acid (88%) be added be slowly added dropwise under agitation dissolved with catalysis
The H of agent2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, it is cooled to room temperature to reaction solution
Afterwards, it is centrifugated out catalyst, reaction solution is washed with water to neutrality, dry to get yellow oily product, as target product.
Measuring target product epoxide number according to GB/T 1677-2008 is 6.39%, measures mesh according to GB/T 1668-2008
Mark product acid value is 0.38mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.35%, 6.29%, 6.21%, 6.14% and 6.06%.
Embodiment 5 is based on 1- hexyl pyridine molybdate ([Hpy]4Mo8O26) epoxy aliphatic acid methyl ester plasticizer
[Hpy]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [Hpy]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, thermometer are being housed
50mL three-necked flask in 20g fatty acid methyl ester and 7g formic acid (88%) be added be slowly added dropwise under agitation dissolved with catalysis
The H of agent2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, it is cooled to room temperature to reaction solution
Afterwards, it is centrifugated out catalyst, reaction solution is washed with water to neutrality, dry to get yellow oily product, as target product.
Measuring target product epoxide number according to GB/T 1677-2008 is 6.45%, measures mesh according to GB/T 1668-2008
Mark product acid value is 0.44mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.38%, 6.32%, 6.25%, 6.17% and 6.11%.
Embodiment 6 is based on tetrabutylammonium molybdate ([(C4H9)4N]4Mo8O26) Plasticizer Epoxidized Soybean Oil
[(C4H9)4N]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [Hpy]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, thermometer are being housed
50mL three-necked flask in 20g refined soybean oil and 7g formic acid (88%) be added be slowly added dropwise under agitation dissolved with catalysis
The H of agent2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, it is cooled to room temperature to reaction solution
Afterwards, it is centrifugated out catalyst, reaction solution is washed with water to neutrality, dry to get yellow oily product, as target product.
Measuring target product epoxide number according to GB/T 1677-2008 is 6.34%, measures mesh according to GB/T 1668-2008
Mark product acid value is 0.41mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.28%, 6.22%, 6.15%, 6.07% and 6.02%.
Embodiment 7 is based on tetrabutylammonium molybdate ([(C4H9)4N]4Mo8O26) epoxy aliphatic acid methyl ester plasticizer
[(C4H9)4N]4Mo8O26Structural formula is shown below:
(1) synthetic method
Weigh 0.5g [Hpy]4Mo8O26Catalyst is dissolved in 5g H2O2(30%) in, reflux condensing tube, thermometer are being housed
50mL three-necked flask in 20g epoxy aliphatic acid methyl ester and 7g formic acid (88%) is added, under agitation, be slowly added dropwise dissolved with
The H of catalyst2O2Solution, and 60 DEG C are to slowly warm up to, 6h is stirred in 60 DEG C of constant temperature.After reaction, room is cooled to reaction solution
Wen Hou is centrifugated out catalyst, and reaction solution is washed with water to neutrality, and dry to get yellow oily product, as target produces
Object.
Measuring target product epoxide number according to GB/T 1677-2008 is 6.42%, measures mesh according to GB/T 1668-2008
Mark product acid value is 0.43mg KOH/g.
The catalyst isolated is reusable after being washed with ether, being dry.Use the epoxide number point of five target products
It Wei 6.37%, 6.30%, 6.25%, 6.19% and 6.12%.
Examples detailed above shows using a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate of the present invention, can
So that the polyunsaturated vegetable oils such as soybean oil and fatty acid methyl ester are in H2O2Oxidation is lower to carry out epoxidation reaction, and obtaining has compared with epipodium
Oxygen value and lower acid value obtain epoxy plasticizer product.Molybdenum multi-metal oxygen phosphate catalyst is dissolved in oxidant during the reaction
H2O2, with reacting to carry out, catalyst can be voluntarily precipitated from reaction system, and catalyst is easily recycled and again after reaction
It is multiple to use.The catalytic process is avoided using traditional strong acid catalyst, and reaction process is simple to operation, is the conjunction of epoxy plasticizer
At providing a new process route.
Claims (7)
1. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate, which comprises the steps of: take one
Quantitative organic carboxyl acid is mixed with raw oil material, is Mo with anion8O26 4-Molybdenum multi-metal oxygen hydrochlorate be catalyst, with H2O2
For oxidant, catalyst is dissolved in H2O2In, it is then added dropwise in the mixed system of organic carboxyl acid and raw oil material, 30
~60 DEG C of 2~6h of reaction are centrifugated out catalyst after reaction, and reaction solution is washed with deionized to neutrality, dry,
Obtain target product；The anion is Mo8O26 4-Molybdenum multi-metal oxygen hydrochlorate be: tetra-allkylammonium class molybdenum multi-metal oxygen hydrochlorate, miaow
Azole molybdenum multi-metal oxygen hydrochlorate or pyridines molybdenum multi-metal oxygen hydrochlorate；The raw oil material is polyunsaturated vegetable oil or fatty acid
Methyl esters；The epoxide number > 5.5% of gained epoxy plasticizer.
2. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate according to claim 1, feature exist
In the organic carboxyl acid is formic acid or acetic acid.
3. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate according to claim 1, feature exist
In the polyunsaturated vegetable oil is soybean oil.
4. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate according to claim 1, feature exist
In the structural formula of the tetra-allkylammonium class molybdenum multi-metal oxygen hydrochlorate is
Wherein, R1、R2、R3And R4For methyl, ethyl, normal-butyl or n-hexadecyl.
5. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate according to claim 1, feature exist
In the structural formula of the imidazoles molybdenum multi-metal oxygen hydrochlorate are as follows:
Wherein, n=1~8.
6. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate according to claim 1, feature exist
In the structural formula of the pyridines molybdenum multi-metal oxygen hydrochlorate are as follows:
Wherein, n=1~8.
7. a kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate according to claim 1-6,
It is characterized by: catalyst amount be raw oil material quality 1~20%, organic carboxyl acid dosage be raw oil material quality 10~
50%, H2O2Dosage is the 10~100% of raw oil material quality.
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