CN109970597B - Polyhydroxy trihydric hydrazide initiator and preparation method thereof - Google Patents
Polyhydroxy trihydric hydrazide initiator and preparation method thereof Download PDFInfo
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- C07C241/04—Preparation of hydrazides
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- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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Abstract
The invention relates to a polyhydroxy trihydric hydrazide initiator and a preparation method and a use method thereof. An amphiphilic compound containing three hydrazide groups is synthesized, the compound has the characteristic of being positioned on a water/oil two-phase interface, meanwhile, hydrazide of a hydrophilic part can perform redox reaction with potassium persulfate at normal temperature, and free radicals can be generated repeatedly for many times, so that a multiphase tandem polymerization mode is flexibly controlled, the polymerization of styrene, vinyl acetate, styrene and N-vinyl pyrrolidone is initiated on the water/oil interface in sequence, a multi-block copolymer is obtained, experiments prove that the feeding ratio of monomers is very consistent with the composition ratio of the copolymer, the initiation efficiency of the initiator is higher, the polymerization reaction conditions in the mode are mild and controllable, the energy consumption is low, other organic solvents and emulsifiers are not used, and the product is pure and completely meets the requirements of green chemistry.
Description
Technical Field
The invention relates to the technical field of synthesis of high polymer materials, in particular to a polyhydroxy ternary hydrazide initiator and a preparation method and a use method thereof.
Background
Polyolefin is a very important high molecular material, and has a wide variety and wide application. The materials are generally obtained by homopolymerizing or copolymerizing olefin monomers through an initiator, and the free radical initiator can be divided into two categories of oil solubility and water solubility according to different polymerization occasions, and is respectively used for the polymerization of the oil solubility monomer and the water solubility monomer, and the water solubility initiator can also be diffused into a tiny emulsion micelle to initiate the polymerization of the oil solubility monomer. In the existing high molecular polymerization technology, a free radical initiator must be matched with the physical and chemical properties of monomers, one initiator can only initiate a specific polymerization reaction, and few initiators can polymerize monomers in both water phase and oil phase. If the initiator is endowed with more and stronger functions, the collocation of the initiator and the monomer is not restricted by the interface of a water phase and an oil phase, thereby being very beneficial to the preparation of polyolefin polymer materials. In the development process of polymer materials, people often leave no residual force on the design of a polymer structure, but the improvement of an initiator is insufficient, and in fact, the design of the initiator is also a very important link, and the initiator can bring unexpected convenience to the molecular design of the polymer materials. For example, the living radical polymerization technology can make the synthesis of a block copolymer simple and convenient, but the living radical polymerization can only be generally carried out in an organic phase, and cannot realize cross-phase polymerization, the synthesized block polymer has insufficient adaptability and limited application value, and cannot be widely popularized so far.
The first condition for achieving a heterogeneous tandem polymerisation mode is the strict positioning of the initiator, whose molecules are at the interface between the aqueous phase and the oil phase only if the initiator has the characteristics of a surfactant, thus making it possible to initiate the tandem polymerisation of the two phases water/oil. On the other hand, the initiator as a radical generating source should be controllable in advance, that is, the radical is generated many times by the design of the chemical reaction, which is very similar to the radical living polymerization. In contrast, the reactive species of free radical living polymerization are generally generated only at a specific site, which limits the chemical design. The repeated generation of free radicals at different places can be completely realized by using redox reaction, wherein the reducing agent is an organic compound, and the oxidizing agent is a water-soluble inorganic compound such as K2S2O8. One of the alkylated nitrogen atoms of the monohydrazide compound is still reducing, the redox reaction first takes place on this nitrogen atom, which after oxidation first forms a cationic radical and then ionizes a hydrogen ion on the adjacent carbon atom, forming a carbon radical, the nitrogen atomThe oxidation may also be repeated after being reduced until all of the hydrogens on the adjacent carbon atoms are ionized, the initiation mechanism of which is shown in FIG. 2. Although the initiator with the hydrazide structure has similar redox reaction characteristics with the organic tertiary amine compound, the hydrazide compound is more stable than the organic amine compound, and cannot be oxidized after being contacted with air for a long time, and meanwhile, the initiator with the hydrazide structure has high initiation efficiency and is not easy to generate a gelation phenomenon in the polymerization process.
The invention relates to a case of the new polymerization mode, the designed initiator is a polyhydroxy three-membered hydrazide initiator, the structure of which is shown in figure 1, and K is used at normal temperature2S2O8The oxidation can generate free radicals to successfully initiate the polymerization of styrene, vinyl acetate and hydrophilic monomer N-vinyl pyrrolidone to obtain a multi-block copolymer which is difficult to obtain by other polymerization means, and the polymerization mode completely accords with the standard of green chemistry-the normal-temperature reaction has low energy consumption, no organic solvent and no other surfactant.
Disclosure of Invention
The invention provides a polyhydroxy trihydric hydrazide initiator which has the characteristic of water/oil interface positioning, and free radicals generated at normal temperature can bidirectionally initiate water-soluble and oil-soluble monomers through the redox reaction with potassium persulfate so as to realize multiphase tandem polymerization and finally form a multi-block copolymer.
The invention aims to solve another technical problem of providing a preparation method of the polyhydroxy trihydric hydrazide initiator, which is feasible, simple and convenient to operate and easy for mass preparation.
The invention aims to solve another technical problem of providing a specific application of the polyhydroxy trihydric hydrazide initiator in the preparation of a styrene/vinyl acetate/N-vinyl pyrrolidone multi-block copolymer.
1. The technical scheme adopted by the invention for solving the primary technical problems is as follows: a polyhydroxy trihydric hydrazide initiator is an organic compound with amphipathy characteristics, can be well dispersed in water, is compatible with oil-soluble monomers, and generates free radicals to initiate the polymerization of water/oil two-phase monomers under the oxidation action of potassium persulfate, wherein the chemical structure of the polyhydroxy trihydric hydrazide initiator is shown in figure 1.
The initiator reacts with the potassium persulfate at normal temperature to generate interface free radicals, so that the water-based and oil-based monomers can be initiated in a two-way manner to realize a multi-phase tandem polymerization mode, and a multi-block copolymer can be formed very easily;
the initiator can generate free radicals on adjacent carbon atoms for multiple times through continuous nitrogen oxide atoms, can flexibly and variously control polymerization reaction, can ensure that various monomers are polymerized according to the feeding sequence, and is beneficial to the molecular design of polyolefin polymer materials;
the polyhydroxy ternary hydrazide initiator has good stability, is not oxidized after being contacted with air for a long time, and the obtained polymer is not easy to generate gel after the polymerization is initiated.
2. The technical scheme adopted by the invention for solving another technical problem is as follows: the preparation method of the polyhydroxy trihydric hydrazide initiator has a synthetic route shown in figure 3, and is characterized by comprising the following steps: 1) mixing and dissolving trimethylolpropane triglycidyl ether and benzoyl hydrazine in absolute ethyl alcohol according to the molar ratio of 1: 3, controlling the mass ratio of the trimethylolpropane triglycidyl ether to the ethyl alcohol to be within the range of 1: 3.5-1: 4, and keeping the reaction liquid to reflux for 3-4 hours under stirring; 2) transferring the reaction liquid into a high-pressure reaction kettle, adding ethylene oxide, controlling the molar ratio of the ethylene oxide to the benzoyl hydrazine to be 1.2: 1, sealing the reaction kettle, controlling the reaction temperature to be 45-50 ℃, controlling the reaction time to be 3-4 hours, and then cooling the reaction kettle to room temperature; 3) and (3) concentrating the solution in the reaction kettle by using a rotary evaporator to remove ethanol, and finally obtaining a light yellow viscous substance, wherein the product is the polyhydroxy trihydric hydrazide initiator which can be well dispersed in water.
3. The technical scheme adopted by the invention for solving the other technical problem is as follows: the application method of the polyhydroxy trihydric hydrazide initiator in polyolefin synthesis is characterized by comprising the following steps: 1) dissolving a polyhydroxy trihydric hydrazide initiator in water to prepare an aqueous solution with the mass concentration of 1.0-1.5 per thousand, wherein the amount of the initiator is 1.0-1.5% of the weight of the first monomer; 2) adding an oil-soluble monomer into an aqueous solution, fully stirring, adding potassium persulfate solid powder with the dosage of 1.0-1.3% of the mass of the added monomer, carrying out dispersion polymerization reaction after 5-10 minutes, raising the temperature of the system and quickly forming a polymer dispersion liquid; 3) adding a second monomer, wherein the second monomer is absorbed by the formed polymer if the second monomer is oil-soluble, and after adding a second batch of potassium persulfate, the polymerization reaction is restarted, the polymer particle size is increased, and finally the segmented copolymer is obtained; if the second monomer is water-soluble, an amphiphilic block copolymer is obtained after the same procedure.
The method has the advantages that the free radicals are only generated at the interface, the initiation efficiency is high, the concentration of the oil phase monomer is high, the polymerization reaction is fast, the conversion rate is high, the monomers can be added in sequence in the polymerization process, and the composition and the structure of the polymer are very easy to control;
it is very beneficial that no other organic solvent is added in the whole polymerization process, no harsh conditions are needed, and the requirements of green chemistry are completely met.
The invention has the advantages that: 1) the new initiator can be used for realizing a multiphase tandem polymerization mode, namely, one initiator can complete polymerization in various modes; 2) the composition and the structure of the polymer are easy to control, and various blocks can be randomly matched according to actual requirements; 3) the polymerization reaction condition is mild and controllable, the energy consumption is low, other organic solvents and emulsifiers are not used, the product is pure, and the requirements of green chemistry are completely met.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation of polyhydroxy trihydric hydrazide initiator:
1. mixing trimethylolpropane triglycidyl ether and benzoyl hydrazine according to a molar ratio of 1: 3, dissolving the mixture in absolute ethyl alcohol, controlling the mass ratio of the trimethylolpropane triglycidyl ether to the ethyl alcohol within a range of 1: 3.5-1: 4, and keeping a reaction solution to reflux for 3-4 hours under stirring;
2. transferring the reaction liquid into a high-pressure reaction kettle, adding ethylene oxide, controlling the molar ratio of the ethylene oxide to the benzoyl hydrazine to be 1.2: 1, sealing the reaction kettle, controlling the reaction temperature to be 45-50 ℃, controlling the reaction time to be 3-4 hours, and then cooling the reaction kettle to room temperature;
3. and (3) concentrating the solution in the reaction kettle by using a rotary evaporator to remove ethanol to obtain a light yellow viscous substance, wherein the product is the polyhydroxy trihydric hydrazide initiator and can be well dispersed in water.
The initiator is used according to the following operation steps:
a. dissolving 1.0g of polyhydroxy trihydric hydrazide initiator in 1000mL of water to prepare aqueous solution with mass concentration of 1.0-1.5 per mill;
b. adding 80g of oil-soluble monomer styrene into an aqueous solution, fully stirring, adding 1.0g of potassium persulfate solid powder, wherein the dosage of the potassium persulfate solid powder is 1.0-1.3% of the mass of the added monomer, performing dispersion polymerization reaction after 5-10 minutes, raising the temperature of a system from 20-25 ℃ to 40-45 ℃, quickly forming a white polystyrene dispersion liquid, finishing the polymerization reaction within half an hour generally, and then basically exhausting the styrene;
c. adding different amounts of a second monomer of vinyl acetate, quickly absorbing the monomer by polystyrene particles, then adding a second batch of potassium persulfate, wherein the dosage of the potassium persulfate is 1 percent of the mass of the vinyl acetate, restarting the polymerization reaction, starting to rise the system temperature, increasing the size of polymer particles, and finally obtaining a copolymer containing styrene and vinyl acetate blocks;
d. after the second step is finished, adding N-vinyl pyrrolidone with different weight as a second monomer, adding potassium persulfate after the potassium persulfate is dissolved, wherein the dosage of the potassium persulfate is 1 percent of the mass of the N-vinyl pyrrolidone, restarting the reaction after a short induction period, obviously increasing the viscosity of the system, finally obtaining the amphiphilic copolymer with the polystyrene and the poly N-vinyl pyrrolidone block, and precipitating the product by using methanol to obtain solid products.
And (3) product analysis: by comparisonThe actual effect of the initiator is measured by the consistency of the monomer feeding ratio and the copolymer composition ratio after two times of polymerization, after each time of polymerization, the reaction mixture with unit volume is precipitated by methanol, the obtained polymer is weighed after being washed and dried, the yield of the polymer is obtained, the yield of polystyrene is obtained by the first polymerization, the yield of the copolymer is obtained by the second polymerization, and the mass composition ratio M of two blocks in the copolymer is calculated1/M2And a batch feed ratio m1/m2Is the ratio of the masses of the two monomers added in the experiment. The results of four copolymerization experiments for each of the second monomers are shown in the table below, and it can be seen that the ratio of the charge to the composition is very consistent, which means that each polymerization reaction is relatively complete, i.e. the initiator has a relatively high initiation efficiency.
The charge ratio of the polymerization reaction is compared with the composition ratio of the copolymer
Drawings
FIG. 1 chemical structure of polyhydroxy trihydric hydrazide initiators.
FIG. 2 redox initiation principle.
FIG. 3 is a synthetic route for polyhydroxy trihydric hydrazide initiators.
Claims (2)
1. A preparation method of polyhydroxy trihydric hydrazide initiator is disclosed, and the initiator has the structural formula:
the preparation method of the polyhydroxy trihydric hydrazide initiator is characterized by comprising the following steps in sequence:
1) mixing and dissolving trimethylolpropane triglycidyl ether and benzoyl hydrazine in absolute ethyl alcohol according to the molar ratio of 1: 3, controlling the mass ratio of the trimethylolpropane triglycidyl ether to the ethyl alcohol to be within the range of 1: 3.5-1: 4, and keeping the reaction liquid to reflux for 3-4 hours under stirring;
2) transferring the reaction liquid into a high-pressure reaction kettle, adding ethylene oxide, controlling the molar ratio of the ethylene oxide to the benzoyl hydrazine to be 1.2: 1, sealing the reaction kettle, controlling the reaction temperature to be 45-50 ℃, controlling the reaction time to be 3-4 hours, and then cooling the reaction kettle to room temperature;
3) and (3) concentrating the solution in the reaction kettle by using a rotary evaporator to remove ethanol, and finally obtaining a light yellow viscous substance, wherein the product is the polyhydroxy trihydric hydrazide initiator which can be well dispersed in water.
2. A method of using the polyhydroxy trihydric hydrazide initiator of claim 1. The method comprises the following steps in sequence:
1) dissolving 1.0g of the polyhydroxy trihydric hydrazide initiator as defined in claim 1 in 1000mL of water to prepare an aqueous solution;
2) adding 80g of oil-soluble monomer styrene into the aqueous solution obtained in the step 1), fully stirring, adding 1.0g of potassium persulfate solid powder, wherein the dosage of the potassium persulfate solid powder is 1.0-1.3% of the mass of the added monomer, performing dispersion polymerization reaction after 5-10 minutes, raising the system temperature from 20-25 ℃ to 40-45 ℃, quickly forming a white polystyrene dispersion liquid, finishing the polymerization reaction within half an hour generally, and basically exhausting the styrene at this moment;
3) adding different amounts of a second monomer of vinyl acetate, quickly absorbing the monomer by polystyrene particles, then adding a second batch of potassium persulfate, wherein the dosage of the potassium persulfate is 1 percent of the mass of the vinyl acetate, restarting the polymerization reaction, starting to rise the system temperature, increasing the size of polymer particles, and finally obtaining a copolymer containing styrene and vinyl acetate blocks;
4) after the second step is finished, adding N-vinyl pyrrolidone with different weight as a second monomer, adding potassium persulfate after the potassium persulfate is dissolved, wherein the dosage of the potassium persulfate is 1 percent of the mass of the N-vinyl pyrrolidone, restarting the reaction after a short induction period, obviously increasing the viscosity of the system, finally obtaining the amphiphilic copolymer with the polystyrene and the poly N-vinyl pyrrolidone block, and precipitating the product by using methanol to obtain solid products.
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| CN101585929A (en) * | 2009-06-25 | 2009-11-25 | 嘉兴荣泰雷帕司绝缘材料有限公司 | Hydrazide latency improving curing agent and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic surface active initiator and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101585929A (en) * | 2009-06-25 | 2009-11-25 | 嘉兴荣泰雷帕司绝缘材料有限公司 | Hydrazide latency improving curing agent and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic surface active initiator and preparation method thereof |
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