CN109265361A - Amide groups is applied to the method that plant oil base plasticizer carries out micro- reaction continuous flow preparation - Google Patents
Amide groups is applied to the method that plant oil base plasticizer carries out micro- reaction continuous flow preparation Download PDFInfo
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- CN109265361A CN109265361A CN201811168490.0A CN201811168490A CN109265361A CN 109265361 A CN109265361 A CN 109265361A CN 201811168490 A CN201811168490 A CN 201811168490A CN 109265361 A CN109265361 A CN 109265361A
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- epoxidized soybean
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Abstract
The invention discloses amide groups to be applied to the method that plant oil base plasticizer carries out micro- reaction continuous flow preparation, epoxidized soybean oil is dissolved in organic solvent and obtains solution A, amides Ring Opening Reagent and ring-opening reaction catalyst are dissolved in organic solvent and obtain solution B, solution A and solution B are pumped into the first mixer of micro-reaction device simultaneously to be mixed, it reacts to obtain epoxidized soybean oil open-loop products subsequently into the first microreactor of micro-reaction device, acetylation reagent and acetylization reaction catalyst are dissolved in organic solvent and obtain solution C, it is pumped into the second mixer of micro-reaction device and mixes simultaneously with epoxidized soybean oil open-loop products, subsequently into being reacted in the second microreactor of micro-reaction device, reaction product is through rotating to obtain the final product.The method of the present invention is compared with traditional preparation process, and using the particularity of amide group, and ring-opening reaction successively occurs for the micro- reaction continuous flow device of combination and acetylization reaction prepares the more superior new plasticizer of performance.
Description
Technical field
The present invention relates to amide groups to be applied to the method that plant oil base plasticizer carries out micro- reaction continuous flow preparation, belonging to
Learn synthesis field.
Background technique
Epoxidized soybean oil (ESO) is a kind of common plasticizer and stabilizer, is mainly characterized by cheap, green ring
The advantages of guarantor, furthermore it and polyvinyl chloride resin compatibility preferably make stability aspect, is more prominent compared with other plasticizer.But epoxy
Soybean oil is there is also many disadvantages, and unstable three-membered ring makes its resistance to migration and volatility there is certain ask in structure
Topic, especially the intersolubility of pure epoxy soybean oil and epoxy resin is not that can not play its optimal plasticising performance very well, still
The epoxy group and long flexible chain of epoxidized soybean oil make it with good modified condition.
Inherently a kind of plasticizer of many amides compounds, amide is usually the compound of weakly acidic pH, and structure is more
Stablize, many low molecule liquid amides such as NN dimethylformamide is not only excellent aprotic polar solvent, it is also possible to which work increases
Mould agent, lubricant additive etc..Compared to the plasticizer of ester-containing base class, stability and resistance to migration are higher, such as erucic acid acyl
Amine, the fatty acid amide that many N- sulfoalkyls replace all are widely used in plasticizer, field of lubricant.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, by ring-opening polymerisation, in epoxy soybean
The modification that amide group is carried out on the long-chain of oil, makes it have the two-fold advantage of ester group class and amide base class plasticizer, and combine
Micro- reaction continuous flow preparation process develops a kind of novel excellent plant oil base plasticizer.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:
A kind of method that amide groups carries out micro- reaction continuous flow preparation applied to plant oil base plasticizer, including walk as follows
It is rapid:
Step 1: epoxidized soybean oil being dissolved in organic solvent and obtains solution A, by amides Ring Opening Reagent and ring-opening reaction
Catalyst, which is dissolved in organic solvent, obtains solution B；
Step 2: solution A and solution B that step 1 obtains while being pumped into the first mixer of micro-reaction device is mixed
It closes, reacts to obtain epoxidized soybean oil open-loop products subsequently into the first microreactor of micro-reaction device；
Step 3: being dissolved in organic solvent by acetylation reagent and acetylization reaction catalyst and obtain solution C, with step 2
It obtained epoxidized soybean oil open-loop products while mixing in the second mixer for being pumped into micro-reaction device, is filled subsequently into micro- reaction
It is reacted in the second microreactor set, reaction product is through rotating to obtain the final product.
The present invention chooses suitable amides Ring Opening Reagent and acetylation reagent is reacted with epoxidized soybean oil, designs
With the modified plasticizer haveing excellent performance out.But select different amides Ring Opening Reagent and acetylation reagent that can all make it
It is different to be plasticized performance.It also will affect the side reaction of open loop efficiency and acetylization reaction using different catalyst simultaneously.
The present invention designs reasonable plasticizer synthetic route first, and more representative several structural formulas are as follows:
Or
Traditional still reaction reaction time first is very long, and side reaction is more in reaction process, the product finally synthesized
It can be unable to reach expection, and yield is not high, it is economical to have a greatly reduced quality.Even some amides Ring Opening Reagents and epoxidized soybean oil
It is difficult to react in reaction flask, and what the present invention designed improves yield using miniflow field system, but also solves very
Influence of more side reactions for end product quality.Some reagents for being difficult to react in reaction flask also can in microreactor
It carries out.
In addition, the violent time length of acylation process heat release leads to many side reactions.Compared to traditional autoclave intermittent reaction, benefit
It can make being greatly improved for mass-and heat-transfer efficiency with miniflow field system, it is not only efficiently but also safe.Traditional still reaction is
Can not a step realize ring-opening reaction and acetylation, and in micro flow field, the establishment of reasonable microreactor can be designed so that
This two-step reaction can be carried out with serialization.
Compared with other kinds of Ring Opening Reagent, the finally obtained product of amides Ring Opening Reagent plasticising aspect of performance with
Other modification groups also have better promotion.
In step 1, the amides Ring Opening Reagent is in acetamide, caproamide, phthalimide or benzamide
Any one.
The ring-opening reaction catalyst is sodium hydrogen or sodium ethoxide, preferred alcohol sodium.
Epoxide and amides Ring Opening Reagent and ring-opening reaction catalyst in step 2, in the epoxidized soybean oil
Mixing molar ratio be 1:5~15:0.01~0.1, preferably 1:5~10:0.02~0.1.
Ring-opening reaction temperature in first microreactor is 50~90 DEG C, preferably 60~80 DEG C, reaction time is 5~
15min, preferably 8~12min.
In step 3, the acetylation reagent is acetic anhydride.
The acetylization reaction catalyst is perchloric acid or 4-dimethylaminopyridine (DMAP), preferably perchloric acid.
The mixing molar ratio of the epoxidized soybean oil open-loop products and acetylation reagent and acetylization reaction catalyst is 1:5
~20:0.01~0.1, preferably 1:5~15:0.02~0.1.
Acetylization reaction temperature in second microreactor is 10~30 DEG C, preferably 20~30 DEG C, reaction time 5
~15min, preferably 8~12min.
In step 3, reaction product uses NaHCO before revolving3It is 6.5~7.5 that aqueous solution, which adjusts reaction product pH value,
NaHCO3The concentration of aqueous solution is 5wt%.
The product of revolving is preferably further washed, and is dried.
In step 1 and step 3, the organic solvent is tetrahydrofuran (THF).
Microchannel in the micro-reaction device in microreactor is polyfluortetraethylene pipe, and caliber is 0.5~1mm, each
Microreactor interior conduit total volume is 5~8mL.
The utility model has the advantages that
1, the present invention is using epoxidized soybean oil as raw material, using the particularity of amide group, and micro- reaction continuous flow is combined to fill
It sets successively generation ring-opening reaction and acetylization reaction and prepares the more superior new plasticizer of performance.From a cost perspective, very
Multiamide class Ring Opening Reagent is more economical；For product effect, the modification of amide group is passed through on epoxidized soybean oil long-chain,
It is more prominent to be plasticized resistance to migration in performance.In addition, entire synthesis process is obtained further excellent using miniflow field system
Change and simplify, hence it is evident that so that mass-and heat-transfer efficiency is greatly improved, it is long caused all to avoid the acylation process heat release violent time
More side reactions not only solve the problem of some Ring Opening Reagents can not carry out in reaction flask, and two-step reaction are become one
Continuous flow is walked, has higher meaning for industrialized production later；
2, the present invention selects amides Ring Opening Reagent, the alkalescent of amide groups, and the wherein hydridization conjugation of N atom, makes
4 atoms for obtaining amide are in same plane, it is easier to be inserted into polymer molecule, be used for Plasticizer Epoxidized Soybean Oil
Preparation in, compared to aliphatic radical Ring Opening Reagent have better plasticization effect.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is the reaction principle figure that the present invention prepares plant oil base plasticizer using micro-reaction device.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Structure depicted in Figure of description, ratio, size etc., only to cooperate the revealed content of specification, with
Understand for those skilled in the art and read, be not intended to limit the invention enforceable qualifications, therefore does not have technically
Essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size can be generated not influencing the present invention
Under effect and the purpose that can reach, should all still it fall in the range of disclosed technology contents can cover.Meanwhile
Cited such as "upper", "lower", "front", "rear", " centre " term in this specification are merely convenient to being illustrated for narration, and
It is non-that to limit the scope of the invention, relativeness is altered or modified, under the content of no substantial changes in technology, when
Also it is considered as the enforceable scope of the present invention.
The preparation step of the method for the present invention are as follows:
Step 1: epoxidized soybean oil being dissolved in organic solvent and obtains solution A, by amides Ring Opening Reagent and ring-opening reaction
Catalyst, which is dissolved in organic solvent, obtains solution B；
Step 2: solution A and solution B that step 1 obtains while being pumped into the first mixer of micro-reaction device is mixed
It closes, reacts to obtain epoxidized soybean oil open-loop products subsequently into the first microreactor of micro-reaction device；
Step 3: being dissolved in organic solvent by acetylation reagent and acetylization reaction catalyst and obtain solution C, with step 2
It obtained epoxidized soybean oil open-loop products while mixing in the second mixer for being pumped into micro-reaction device, is filled subsequently into micro- reaction
It is reacted in the second microreactor set, reaction product is through rotating to obtain the final product.
As shown in Figure 1, the micro-reaction device that uses of the present invention includes three syringe pumps, two mixers and two it is micro-
Reactor.Syringe pump 1 is provided with solution A, and syringe pump 2 is provided with solution B, and the two is pumped into mixing in mixer 1 simultaneously, then into
Enter reaction in microreactor 1 and obtains epoxidized soybean oil open-loop products；Syringe pump 3 is provided with solution C, with epoxidized soybean oil open loop
Product is pumped into mixing in mixer 2 simultaneously, obtains final product subsequently into reaction in microreactor 2.
Microchannel in microreactor is polyfluortetraethylene pipe, caliber 1mm, and each microreactor interior conduit total volume is
8mL。
Embodiment 1
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, acetamide is dissolved in THF, sodium ethoxide is added and makees
It is poured in syringe pump for another phase, two-phase is injected in microreactor simultaneously, 15min is reacted at 50 DEG C, wherein epoxidized soybean oil
The molar ratio of middle epoxide and acetamide is 1:5, and two-phase flow velocity is respectively 0.146,0.054, catalyst sodium ethoxide and ring
The molar ratio of epoxide in oxygen soybean oil is 0.01:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another section
Microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, reacted at 10 DEG C
15min, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:5, perchloric acid and epoxidized soybean oil open-loop products
Molar ratio is 0.2:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then be plasticized
The detection of agent performance.
Embodiment 2
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, acetamide is dissolved in THF, sodium ethoxide is added and makees
It is poured in syringe pump for another phase, two-phase is injected in microreactor simultaneously, 10min is reacted at 100 DEG C, wherein epoxidized soybean oil
The molar ratio of middle epoxide and acetamide is 1:10, and two-phase flow velocity is respectively 0.176,0.074, catalyst sodium ethoxide and ring
The molar ratio of epoxide in oxygen soybean oil is 0.08:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another section
Microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, reacted at 25 DEG C
10min, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, perchloric acid and epoxidized soybean oil open-loop products
Molar ratio is 0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then increased
Mould the detection of agent performance.
Embodiment 3
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, acetamide is dissolved in THF, sodium ethoxide is added and makees
It is poured in syringe pump for another phase, two-phase is injected in microreactor simultaneously, 5min is reacted at 110 DEG C, wherein epoxidized soybean oil
The molar ratio of middle epoxide and acetamide is 1:15, and two-phase flow velocity is respectively 0.321,0.117, catalyst sodium ethoxide and ring
The molar ratio of epoxide in oxygen soybean oil is 0.1:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another section
Microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, react 5min at 30 DEG C,
Wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:20, the molar ratio of perchloric acid and epoxidized soybean oil open-loop products
For 0.1:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then carry out plasticizer performance
Detection.
Embodiment 4
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, benzamide is dissolved in THF, sodium ethoxide is added
It is poured in syringe pump as another phase, two-phase is injected in microreactor simultaneously, 12min is reacted at 80 DEG C, wherein epoxy soybean
In oil the molar ratio of epoxide and benzamide be 1:5, two-phase flow velocity is respectively 0.321,0.117, catalyst sodium hydrogen with
The molar ratio of epoxide in epoxidized soybean oil is 0.02:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another
Section microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, reacted at 10 DEG C
12min, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:5, perchloric acid and epoxidized soybean oil open-loop products
Molar ratio is 0.02:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then increased
Mould the detection of agent performance.
Embodiment 5
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, benzamide is dissolved in THF, sodium ethoxide is added
It is poured in syringe pump as another phase, two-phase is injected in microreactor simultaneously, 10min is reacted at 100 DEG C, wherein epoxy soybean
The molar ratio of epoxide and benzamide is 1:10 in oil, and two-phase flow velocity is respectively 0.153,0.097, catalyst sodium ethoxide
Molar ratio with the epoxide in epoxidized soybean oil is 0.08:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another
One section of microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, reacted at 25 DEG C
10min, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, perchloric acid and epoxidized soybean oil open-loop products
Molar ratio is 0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then increased
Mould the detection of agent performance.
Embodiment 6
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, benzamide is dissolved in THF, sodium ethoxide is added
It is poured in syringe pump as another phase, two-phase is injected in microreactor simultaneously, 8min is reacted at 110 DEG C, wherein epoxy soybean
The molar ratio of epoxide and benzamide is 1:15 in oil, and two-phase flow velocity is respectively 0.176,0.104, catalyst sodium ethoxide
Molar ratio with the epoxide in epoxidized soybean oil is 0.01:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another
One section of microreactor, with acetic anhydride and catalyst 4-dimethylaminopyridine be used as it is another mix through microreactor, in 30
5min is reacted at DEG C, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:15, and perchloric acid is opened with epoxidized soybean oil
The molar ratio of ring product is 0.1:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then
Carry out the detection of plasticizer performance.
Embodiment 7
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, phthalimide is dissolved in THF, is added
Sodium ethoxide pours in syringe pump as another phase, and two-phase is injected in microreactor simultaneously, and 10min, middle ring are reacted at 100 DEG C
The molar ratio of epoxide and phthalimide is 1:10 in oxygen soybean oil, and two-phase flow velocity is respectively 0.47,0.23, is urged
The molar ratio of epoxide in agent sodium ethoxide and epoxidized soybean oil is 0.08:1, obtained epoxidized soybean oil open-loop products
Continue to be passed through another section of microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, in
10min is reacted at 25 DEG C, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, perchloric acid and epoxidized soybean oil
The molar ratio of open-loop products is 0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, is finally produced through revolving
Object, then carry out the detection of plasticizer performance.
Embodiment 8
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, caproamide is dissolved in THF, sodium ethoxide is added and makees
It is poured in syringe pump for another phase, two-phase is injected in microreactor simultaneously, 10min is reacted at 100 DEG C, wherein epoxidized soybean oil
The molar ratio of middle epoxide and caproamide is 1:10, and two-phase flow velocity is respectively 0.47,0.23, catalyst sodium ethoxide and epoxy
The molar ratio of epoxide in soybean oil is 0.08:1, obtained epoxidized soybean oil open-loop products continue to be passed through another section it is micro-
Reactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, react 10min at 25 DEG C,
Wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, the molar ratio of perchloric acid and epoxidized soybean oil open-loop products
For 0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then carry out plasticizer
The detection of energy.
Comparative example 1
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, benzoic acid is dissolved in THF, fluoboric acid is added and makees
It is poured in syringe pump for another phase, two-phase is injected in microreactor simultaneously, 10min is reacted at 100 DEG C, wherein epoxidized soybean oil
The molar ratio of middle epoxide and benzoic acid is 1:10, and two-phase flow velocity is respectively 0.138,0.145, catalyst fluoboric acid and ring
The molar ratio of epoxide in oxygen soybean oil is 0.08:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another section
Microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, reacted at 25 DEG C
10min, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, perchloric acid and epoxidized soybean oil open-loop products
Molar ratio is 0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then increased
Mould the detection of agent performance.
Comparative example 2
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, furancarboxylic acid is dissolved in THF, fluoboric acid is added
It is poured in syringe pump as another phase, two-phase is injected in microreactor simultaneously, 10min is reacted at 100 DEG C, wherein epoxy soybean
The molar ratio of epoxide and furancarboxylic acid is 1:10 in oil, and two-phase flow velocity is respectively 0.13,0.153, catalyst fluoboric acid
Molar ratio with the epoxide in epoxidized soybean oil is 0.08:1, and obtained epoxidized soybean oil open-loop products continue to be passed through another
One section of microreactor, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, reacted at 25 DEG C
10min, wherein epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, perchloric acid and epoxidized soybean oil open-loop products
Molar ratio is 0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then increased
Mould the detection of agent performance.
Comparative example 3
Epoxidized soybean oil is used into THF dilution as a phase and pours syringe pump, acetic acid is dissolved in THF, fluoboric acid conduct is added
Another phase pours in syringe pump, and two-phase is injected in microreactor simultaneously, 10min is reacted at 100 DEG C, wherein in epoxidized soybean oil
The molar ratio of epoxide and acetic acid is 1:10, and two-phase flow velocity is respectively 0.209,0.191, and catalyst fluoboric acid and epoxy are big
The molar ratio of epoxide in soya-bean oil is 0.08:1, obtained epoxidized soybean oil open-loop products continue to be passed through another section it is micro- anti-
Answer device, with acetic anhydride and catalyst perchloric acid be used as it is another mix through microreactor, react 10min at 25 DEG C,
Middle epoxidized soybean oil open-loop products and acetic anhydride molar ratio are 1:10, and the molar ratio of perchloric acid and epoxidized soybean oil open-loop products is
0.08:1.Product adjusts pH to 7 or so through sodium bicarbonate aqueous solution, obtains final product through revolving, then carry out plasticizer performance
Detection.
Comparative example 4
Inherently a kind of plasticizer of reference substance pure epoxy soybean oil plasticizer (ESO), directly using ESO as plasticizer, system
The detection of plasticising performance is carried out at plastics.
Comparative example 5
0.03mol epoxidized soybean oil is weighed as in 50ml three-necked bottle, then the benzamide of 0.3mol is dissolved in 20mL's
THF is added in three-necked bottle after dissolution, and the sodium ethoxide of 0.0024mol is added, the agitating and heating 48 hours in 100 degree of oil baths,
Product adjusts ph to 7.0 or so with sodium bicarbonate, and revolving is extracted with ethyl acetate.By obtained product as another three-necked bottle
In, ph value is adjusted to 7.0 or so, and revolving is extracted with ethyl acetate and obtains final product, then carries out the detection of plasticising performance.
Comparative example 6
0.03mol epoxidized soybean oil is weighed as in 50ml three-necked bottle, then the benzamide of 0.15mol is dissolved in 20mL's
THF is added in three-necked bottle after dissolution, and the sodium ethoxide of 0.0024mol is added, the agitating and heating 48 hours in 100 degree of oil baths,
Product adjusts pH to 7.0 or so with sodium bicarbonate, and revolving is extracted with ethyl acetate.By obtained product as another three-necked bottle
In, the perchloric acid of 0.0024mol is added in the acetic anhydride of 0.15mol and is put in constant pressure funnel, is added drop-wise to three dropwise
The reaction was continued with open-loop products in neck bottle, reaction 48 hours under 10 degree.PH value 7 is adjusted, revolving is extracted with ethyl acetate and obtains most
Final product, then carry out the detection of speedup performance.
By the PVC of obtained plasticizer and proper proportion, adjuvant, lubricant etc. is mixed, is cooked, vulcanization pressure
System, is finally cut again, tearing strength, the detection of the indexs such as strained tensile power is carried out to it.Wherein, tearing strength utilizes drawing
Power machine is detected, and presses the standard of GB/T 528-2009；Wherein tensile strength is detected using extensometer, and presses DB37/
The standard of T 2263-2012 is detected；The test method of water imbibition is that each sample is cut into the little shape of difference, records each matter
Amount, then duck in drink 48 hours, then claim quality, calculate the difference for impregnating front and back.
Table 1 has measured Examples 1 to 8 respectively, the tearing strength parameter for the plasticizer that comparative example 1~6 is prepared into:
Table 1
As can be seen from Table 1: it is compared with epoxidized soybean oil and ester-containing base class open-loop products, what by open loop, treated
Amide-containing product is enhanced in terms of tearing strength, and three kinds of amides open-loop products are in the comparison of this index
Advantage is similar.And the product made in micro flow field than still reaction to obtain properties of product more preferable.And in epoxy soybean
Oil is 1 to 10 with open-loop products molar ratio, and reaction temperature is that 100 degree of lower effects are best.
Table 2 is Examples 1 to 8 respectively, the tension test parameter for the plasticizer that comparative example 1~6 is prepared into:
Table 2
It can be seen from the data in Table 2 that compared with epoxidized soybean oil, it is each to change surname product in strained tensile power and stretch strong
It has spent aspect all and has improved, wherein optimal with the effect that benzamide does Ring Opening Reagent.And the optimum response mole in micro flow field
Than for 1:10, wherein catalyst fluoboric acid and perchloric acid are more preferable, optimal reaction temperature is 100 degree.
In addition, the mechanism of action of plasticizer is that plasticizing molecule is inserted between polymer molecular chain, polymer molecule is weakened
The stress of chain reduces the crystallinity of polymer molecular chain to reach plasticization effect.Compare aliphatic radical and amide groups Ring Opening Reagent, acyl
The alkalescent of amido, and the wherein hydridization conjugation of N atom, so that 4 atoms of amide are in same plane, it is easier to be inserted into
Into polymer molecule.The inherently good plasticizer of substance of many amide-containings, such as exist in Li Wei, Xu Zhenzhen et al.
Pacify in micro- engineering college journal just studies have reported that NN dimethylformamide has good plasticization effect to starch serous coat.Separately
Outside, the resistance to migration of some plasticizer of the class containing aliphatic radical is not fine.Therefore, containing possible with the epoxidized soybean oil of amoyl modified
With more superior than the performance only with the modified epoxidized soybean oil plasticising product of aliphatic radical.
Table 3 is Examples 1 to 8 respectively, the water imbibition detection data for the plasticizer that comparative example 1~6 is prepared into:
Table 3
3 (Continued) of table
It can be seen from the data in Table 3 that the resistance to migration of remodeling product is also improved, the reference substance with epoxidized soybean oil
It compares, including compared with containing only ester group class plasticizer, advantage is become apparent.
The present invention provides amide groups to be applied to the think of that plant oil base plasticizer carries out the method for micro- reaction continuous flow preparation
Road and method, there are many method and the approach for implementing the technical solution, the above is only a preferred embodiment of the present invention,
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, can also do
Several improvements and modifications out, these modifications and embellishments should also be considered as the scope of protection of the present invention.What is be not known in the present embodiment is each
The available prior art of component part is realized.
Claims (10)
1. amide groups is applied to the method that plant oil base plasticizer carries out micro- reaction continuous flow preparation, which is characterized in that including such as
Lower step:
Step 1: epoxidized soybean oil being dissolved in organic solvent and obtains solution A, and amides Ring Opening Reagent and ring-opening reaction are catalyzed
Agent, which is dissolved in organic solvent, obtains solution B；
Step 2: solution A and solution B that step 1 obtains while being pumped into the first mixer of micro-reaction device is mixed, so
It reacts to obtain epoxidized soybean oil open-loop products into the first microreactor of micro-reaction device afterwards；
Step 3: acetylation reagent and acetylization reaction catalyst are dissolved in organic solvent and obtain solution C, is obtained with step 2
Epoxidized soybean oil open-loop products be pumped into the second mixer of micro-reaction device and mix simultaneously, subsequently into micro-reaction device
It is reacted in second microreactor, reaction product is through rotating to obtain the final product.
2. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 1, the amides Ring Opening Reagent is acetamide, caproamide, phthalimide or benzene first
Any one in amide.
3. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 1, the ring-opening reaction catalyst is sodium hydrogen or sodium ethoxide.
4. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that epoxide and amides Ring Opening Reagent and ring-opening reaction in step 2, in the epoxidized soybean oil
The mixing molar ratio of catalyst is 1:5~15:0.01~0.1.
5. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 2, the ring-opening reaction temperature in the first microreactor is 50~90 DEG C, reaction time 5
~15min.
6. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 3, the acetylation reagent is acetic anhydride.
7. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 3, the acetylization reaction catalyst is perchloric acid or 4-dimethylaminopyridine.
8. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 3, the epoxidized soybean oil open-loop products and acetylation reagent and acetylization reaction catalyst
Mixing molar ratio is 1:5~20:0.01~0.1.
9. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 3, the acetylization reaction temperature in the second microreactor is 10~30 DEG C, reaction time
For 5~15min.
10. amide groups according to claim 1 is applied to the side that plant oil base plasticizer carries out micro- reaction continuous flow preparation
Method, which is characterized in that in step 3, reaction product uses NaHCO before revolving3Aqueous solution adjust reaction product pH value be 6.5~
7.5。
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