阅读说明：本技术 双亲性超支化聚合物的制备方法 (Preparation method of amphiphilic hyperbranched polymer ) 是由 宰少波 金晖 张志华 于 2020-06-15 设计创作，主要内容包括：本发明公开一种双亲性超支化聚合物的制备方法,主要解决现有技术中双亲性超支化聚合物合成复杂的问题。通过采用一种双亲性超支化聚合物的制备方法,以活性氢化合物为起始剂,在催化剂存在下,将包括环氧烯烃和带有羟基的环氧化合物的原料,进行反应,得到双亲性超支化聚合物；其中,所述催化剂为具有式(1)通式结构的氧化磷腈：R-(1)、R-(2)各自独立地表示碳原子数为1～10的烷基、未取代的或者具有取代基的碳原子数为6～10的苯基、或未取代的或者具有取代基的碳原子数6～10的苯基烷基；x为0～5.0的技术方案,较好地解决了该问题,可用于双亲性超支化聚合物的工业化生产中。。(The invention discloses a preparation method of an amphiphilic hyperbranched polymer, which mainly solves the problem that the synthesis of the amphiphilic hyperbranched polymer is complex in the prior art. By adopting a preparation method of the amphiphilic hyperbranched polymer, taking an active hydrogen compound as an initiator, and reacting raw materials comprising epoxy olefin and an epoxy compound with hydroxyl in the presence of a catalyst to obtain the amphiphilic hyperbranched polymer; wherein the catalyst is a phosphazene oxide having the general structure of formula (1): r 1 、R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted phenyl group having 6 to 10 carbon atoms, or an unsubstituted or substituted phenylalkyl group having 6 to 10 carbon atoms; the technical scheme that x is 0-5.0 better solves the problem and can be used for industrial production of the amphiphilic hyperbranched polymer.)

1. A preparation method of an amphiphilic hyperbranched polymer comprises the steps of taking an active hydrogen compound as an initiator, and reacting raw materials including epoxy olefin and an epoxy compound with hydroxyl in the presence of a catalyst to obtain the amphiphilic hyperbranched polymer; wherein the catalyst is a phosphazene oxide having the general structure of formula (1):

in the formula (1), R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted phenyl group having 6 to 10 carbon atoms, or an unsubstituted or substituted phenylalkyl group having 6 to 10 carbon atoms; x represents the amount of water molecules in terms of molar ratio, and the value of x is within the range of 0-5.0.

2. The method of claim 1, wherein R is selected from the group consisting of₁And R₂Or R₂And R₂Are bonded to each other to form a ring structure.

3. The method for preparing amphiphilic hyperbranched polymer according to claim 1, wherein R is₁And R₂At least one or a mixture of more than two of aliphatic hydrocarbon groups with 1-8 carbon atoms; more preferably at least one or a mixture of two or more of alkyl groups having 1 to 8 carbon atoms; most preferably said R₁And R₂Preferably methyl.

4. The method for preparing an amphiphilic hyperbranched polymer according to claim 1, wherein x is in the range of 0 to 2.0.

5. The method of claim 1, wherein the active hydrogen compound is at least one selected from the group consisting of an-OH-containing active hydrogen compound and an-NH-containing active hydrogen compound.

6. The method of claim 5, wherein the-OH-containing active hydrogen compound is at least one selected from the group consisting of alcohols having 1 to 20 carbon atoms, polyhydric alcohols having 2 to 20 carbon atoms and having 2 to 8 hydroxyl groups, saccharides, and derivatives thereof, and polyether polyols having 2 to 8 terminal groups, having 1 to 8 hydroxyl groups on the terminal groups, and having a number average molecular weight of 200 to 30000.

7. The method of claim 5, wherein the-NH-containing active hydrogen compound is at least one selected from the group consisting of primary aliphatic or aromatic amines having 1 to 20 carbon atoms, secondary aliphatic or aromatic amines having 2 to 20 carbon atoms, polyamines having 2 to 20 carbon atoms and having 2 to 3 primary or secondary amino groups, unsaturated cyclic secondary amines having 4 to 20 carbon atoms, cyclic polyamines having 4 to 10 carbon atoms and having 2 to 3 secondary amino groups, substituted or N-monosubstituted acid amides having 2 to 20 carbon atoms, and imides of dicarboxylic acids having 4 to 10 carbon atoms.

8. The method for preparing amphiphilic hyperbranched polymer according to claim 1, wherein the alkylene oxide is one or more selected from ethylene oxide, propylene oxide, styrene oxide, and cyclohexene oxide.

9. The method for preparing amphiphilic hyperbranched polymer according to claim 1, wherein the epoxy compound having a hydroxyl group is one or more selected from glycidol, 2-cyclopropylethanol, and 3-methyl-3-oxetanemethanol.

10. The method for preparing the amphiphilic hyperbranched polymer according to claim 1, wherein the reaction temperature is 10 to 180 ℃, the reaction pressure is not higher than 3.0MPa, and the reaction time is 0.1 to 50 hours.

Technical Field

The invention discloses a preparation method of an amphiphilic hyperbranched polymer, in particular to a method for preparing a lipophilic and hydrophilic amphiphilic hyperbranched polymer by using a phosphazene catalyst one-step method.

Background

Hyperbranched polymers are a class of macromolecules with highly branched, three-dimensional spherical structures. Hyperbranched polymers have a much lower solution viscosity than traditional linear polymers. This lower viscosity indicates that the molecular chains of the hyperbranched molecules are less entangled and have a spherical molecular structure. Due to the unique physical and chemical properties and the potential application performance in many fields, the hyperbranched polymer has good industrial application performance.

In recent years, the application research of hyperbranched polymers is also widely regarded by researchers. The intercalation of dye molecules into hyperbranched polymers has been partially studied, and linear molecules have been blended with hyperbranched molecules. The hyperbranched molecules can be purposefully designed into novel functional polymers, such as cross-linking agents, nonlinear photoelectric materials, high-optical-activity organic macromolecules and the like.

Hyperbranched polymers generally exhibit properties similar to dendritic polymers, have lower melt and solution viscosities, better solubility and thermal properties, higher chemical reactivity, and the like. Hyperbranched polymers are therefore an economical alternative to dendrimers in some fields of application.

The existing preparation methods of hyperbranched polymers include condensation reaction, addition reaction, ring-opening polymerization, graft polymerization and the like.

The amphiphilic hyperbranched polymer is a macromolecular compound containing a hydrophilic chain segment and an oleophilic chain segment in the same molecular chain, and the compound can reduce the surface tension of an oil-water interface. They may phase separate in selective solvents, surfaces or bulk, forming spherical, rod-like, lamellar and worm-like structures. The complex structure formed after phase separation endows the materials with special performance, and is often applied to the fields of nano particle preparation, drug delivery, oilfield chemistry, textile auxiliary agents and the like.

The amphiphilic hyperbranched polymer combines the characteristics of the hyperbranched polymer and the amphiphilic polymer, and has good application prospects in the aspects of drug carriers, in-vitro detection and surfactants.

Disclosure of Invention

The invention utilizes the self-made phosphazene catalyst, uses the conventional monomer and adopts a one-step method to prepare the amphiphilic hyperbranched polymer, thereby solving the problem of complex synthesis of the hyperbranched polymer.

The invention provides a preparation method of an amphiphilic hyperbranched polymer, which is a method for preparing the hyperbranched polymer by a one-step method by using a phosphazene catalyst as a catalyst and an epoxy compound as a raw material.

In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of an amphiphilic hyperbranched polymer comprises the steps of taking an active hydrogen compound as an initiator, and reacting raw materials including epoxy olefin and an epoxy compound with hydroxyl in the presence of a catalyst to obtain the amphiphilic hyperbranched polymer; wherein the catalyst is a phosphazene oxide having the general structure of formula (1):

in the formula (1), R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted phenyl group having 6 to 10 carbon atoms, or an unsubstituted or substituted phenylalkyl group having 6 to 10 carbon atoms; x represents the amount of water molecules in terms of molar ratio, and the value of x is within the range of 0-5.0.

In the above technical scheme, R₁And R₂Or R₂And R₂Preferably, they are bonded to each other to form a ring structure.

In the above technical scheme, R₁And R₂Preferably at least one or a mixture of more than two of aliphatic hydrocarbon groups with 1-8 carbon atoms; more preferably at least one or a mixture of two or more of alkyl groups having 1 to 8 carbon atoms

In the above technical scheme, R₁And R₂Preferably methyl.

In the above-mentioned embodiment, these phosphine oxide nitrile compounds represented by the general formula (1) are generally easily converted into their water-containing compounds or hydrates due to their water absorption properties, and the symbol x representing the amount of water molecules contained in the compounds is a molar ratio based on the phosphazene oxide compound and is in the range of 0 to 5.0, preferably 0 to 2.0.

In the above technical solution, the active hydrogen compound is preferably selected from an-OH-containing or-NH-containing active hydrogen compound.

First, the active hydride is water. The organic compound having a partial structural formula-OH includes, for example, carboxylic acids having 1 to 20 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid and the like; polycarboxylic acids having 2 to 20 carbon atoms and 2 to 6 carboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid terephthalic acid, etc.; alcohols having 1 to 20 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, isoamyl alcohol, etc.; polyhydric alcohols having 2 to 20 carbon atoms and 2 to 8 hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, diglycerin, butylene glycol, pentaerythritol, and the like; saccharides or derivatives thereof, such as glucose, sorbitol, fructose, sucrose, bisphenol A, and the like.

Organic compounds having a partial structure of-NH-as the active hydrogen compound include, for example, primary aliphatic or aromatic amines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, benzylamine, aniline, etc.; secondary aliphatic or aromatic amines having 2 to 20 carbon atoms, such as diethylamine, methylethylamine, di-n-propylamine, diphenylamine and the like; polyamines having 2 to 20 carbon atoms and having 2 to 3 primary or secondary amino groups, such as ethylenediamine, hexamethylenediamine, melamine, N, N' -dimethylethyleneamine, etc.; unsaturated cyclic secondary amines having 4 to 20 carbon atoms, such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, purine, etc.; cyclic polyamines having 4 to 20 carbon atoms and having 2 to 3 secondary amine groups, such as pyrazine, piperazine, etc.; substituted or N-monosubstituted acid amides having 2-20 carbon atoms, such as acetamide, propionamide, N-methylpropionamide, 2-pyrrolidone, etc.; and imides of dicarboxylic acids having 4 to 10 carbon atoms, such as succinimide, maleimide, etc.

Among these active hydrogen compounds, preferred are compounds having a partial structural formula of-OH including, for example, polyhydric alcohols having 2 to 20 carbon atoms and having 2 to 8 hydroxyl groups, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethylene glycol, propylene glycol, 1-4 butylene glycol, etc.; saccharides or derivatives thereof, such as glucose, sorbitol, fructose, sucrose, etc.

Other active hydrides useful in the present invention include polymers having terminal active hydrogen atoms such as polyalkylene oxides, polylactides, polyamides, polycarbonates, polysiloxanes, and copolymers thereof.

In the above technical solution, the epoxyolefin compound is preferably selected from ethylene oxide, propylene oxide, 1, 2-butylene oxide, styrene oxide and other compounds. Two or more of these compounds may be used in combination. When a mixture thereof is used, a method of using several phosphazene oxide compounds simultaneously, a method of using them together in order, or a method of repeating the order can be used. Ethylene oxide and propylene oxide are more preferred. Propylene oxide is more preferred.

In the above technical solution, the epoxy compound having a hydroxyl group is preferably selected from: glycidol, 2-cyclopropylethanol, 3-methyl-3-oxetanemethanol and the like.

In the above-mentioned embodiment, the amount of the phosphazene oxide compound represented by the general formula (1) is not particularly limited, but the range of the amount to be used is usually 1X 10^-10～1×10^-1Preferably 1X 10^-7～1×10^-1Per mol of epoxy compound.

In the above-mentioned embodiment, the type of the polymerization reaction in the method of the present invention is not particularly limited. A method of feeding the epoxy compound to the reactor in a lump, intermittently or continuously is usually employed, in which the phosphazene oxide compound represented by the general formula (1) or the phosphazene oxide compound and the active hydrogen compound are fed together with the solvent when used. The reaction temperature is 10-180 ℃, preferably 30-150 ℃, and more preferably 60-130 ℃. The reaction pressure is not higher than 3.0MPa, preferably 0.01 to 1.5MPa, and more preferably 0.1 to 1.0 MPa. The reaction time varies depending on the type of substance used, the amount used, the polymerization temperature and the pressure, and is preferably 0.1 to 50 hours, more preferably in the range of 0.5 to 30 hours.

In the process of the present invention, a solvent may also be used, if necessary. The solvent used includes, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and the like; aromatic hydrocarbons such as benzene, toluene, etc.; ethers such as diethyl ether, tetrahydrofuran, anisole and the like; aprotic solvents such as dimethylsulfoxide, N, N-dimethylformamide and the like. In addition to these, any solvent can be used as long as it does not inhibit the polymerization reaction of the process of the present invention.

The polymerization reaction in the process of the present invention can also be carried out in the presence of an inert gas such as nitrogen, argon, etc., as required.

The invention adopts the phosphazene catalyst to catalyze the ring-opening polymerization of epoxy olefin and epoxy compound with hydroxyl group, thereby preparing the amphiphilic hyperbranched polymer, and adjusting the HLB value according to the monomer structure and the proportion in the polymer. The following formula is a structural schematic general formula of the amphiphilic hyperbranched polymer prepared by the self-made phosphazene catalyst.

The amphiphilic hyperbranched polymer prepared by the invention has narrow molecular weight distribution and wide HLB value adjusting range, can be used for preparing lipophilic and hydrophilic polymers, and has better application prospect in the aspects of drug carriers, in-vitro detection and surfactants.

The molecular weight and molecular weight distribution of the amphiphilic hyperbranched polymer are measured by coacervation permeation chromatography using polyethylene oxide with narrow distribution as a standard sample. The HLB value is calculated by an empirical formula HLB being 7 +. SIGMA H +. SIGMA L, wherein SIGMA H is the hydrophilic base number, and SIGMA L is the lipophilic base number.

By adopting the technical scheme of the invention, the amphiphilic hyperbranched polymer can be prepared by a one-step method, the process is simple, the molecular weight distribution of the prepared amphiphilic hyperbranched polymer is narrow, the HLB value adjusting range is wide, and the prepared amphiphilic hyperbranched polymer has better application prospect in the aspects of drug carriers, in-vitro detection and surfactants and obtains better technical effect.

The present invention will be described in more detail with reference to examples, but the present invention is not to be construed as being limited to the examples.

Detailed Description

[ example 1 ]

A2.5L autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and an epoxy compound feed port was charged with 7.78g (0.02mol) of tris (tetramethylguanidino) phosphine oxide { [ (Me) as the phosphazene oxide compound represented by the general formula (1)₂N)₂C＝N]₃P ═ O } and 50g (0.37mol) of trihydroxymethylpropane. After nitrogen displacement, the temperature was raised to 100 ℃. Then, 400g (6.90mol) of propylene oxide and 216g (2.9mol) of glycidol were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. Thereafter, 580g (10.0mol) of propylene oxide were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. After the end of the propylene oxide feed, the mixture was reacted at 100 ℃ for 12 hours. The pressure was reduced to 0 MPa. After the low boiling fraction in the system was extracted by a vacuum pump, the polymer was transferred to a separate vessel and cooled to room temperature. As a result, 1180g of a transparent polymer having no odor was obtained. Number average molecular weight 3100, molecular weight distribution 1, 20, HLB value 16.

[ example 2 ]

A2.5L autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and an epoxy compound feed port was charged with 7.78g (0.02mol) of tris (tetramethylguanidino) phosphine oxide { [ (Me) as the phosphazene oxide compound represented by the general formula (1)₂N)₂C＝N]₃P ═ O } and 50g (0.37mol) of trihydroxymethylpropane. After nitrogen displacement, the temperature was raised to 100 ℃. 980g (16.90mol) of propylene oxide and 216g (2.9mol) of glycidol were then added continuously over a period of 4 hours, so that the reaction pressure did not exceed 0.35 MPa. After the end of the feed, the mixture was reacted at 100 ℃ for 12 hours. The pressure was reduced to 0 MPa. After the low boiling fraction in the system was extracted by a vacuum pump, the polymer was transferred to a separate vessel and cooled to room temperature. As a result, 1200g of a clear polymer having no odor was obtainedA compound (I) is provided. Number average molecular weight 3210, molecular weight distribution 1.18, HLB value 16.

[ example 3 ]

A2.5L autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and an epoxy compound feed port was charged with 7.78g (0.02mol) of tris (tetramethylguanidino) phosphine oxide { [ (Me) as the phosphazene oxide compound represented by the general formula (1)₂N)₂C＝N]₃P ═ O } and 50g (0.37mol) of trihydroxymethylpropane. After nitrogen displacement, the temperature was raised to 100 ℃. Then, 400g (5.56mol) of butylene oxide and 216g (2.9mol) of glycidol were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. Thereafter, 500g (6.94mol) of butylene oxide were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. After the end of the butylene oxide feed, the mixture was reacted at 100 ℃ for 12 hours. The pressure was reduced to 0 MPa. After the low boiling fraction in the system was extracted by a vacuum pump, the polymer was transferred to a separate vessel and cooled to room temperature. As a result, 1100g of a transparent polymer having no odor was obtained. Number average molecular weight 2950, molecular weight distribution 1.15, HLB value 2.4.

[ example 4 ]

A2.5L autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and an epoxy compound feed port was charged with 7.78g (0.02mol) of tris (tetramethylguanidino) phosphine oxide { [ (Me) as the phosphazene oxide compound represented by the general formula (1)₂N)₂C＝N]₃P ═ O } and 50g (0.37mol) of trihydroxymethylpropane. After nitrogen displacement, the temperature was raised to 100 ℃. Then, 400g (5.56mol) of butylene oxide and 216g (2.9mol) of glycidol were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. Thereafter, 500g (8.62mol) of propylene oxide were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. After the end of the propylene oxide feed, the mixture was reacted at 100 ℃ for 12 hours. The pressure was reduced to 0 MPa. After the low boiling fraction in the system was extracted by a vacuum pump, the polymer was transferred to a separate vessel and cooled to room temperature. As a result, 1100g of a transparent polymer having no odor was obtained. Number average molecular weight 2960, molecular weight distribution 1.18, HLB value 10.

[ example 5 ]

A2.5L autoclave equipped with a pressure gauge, a temperature gauge, a stirring device and an epoxy compound feed port was charged with 7.78g (0.02mol) of tris (tetramethylguanidino) phosphine oxide { [ (Me) as the phosphazene oxide compound represented by the general formula (1)₂N)₂C＝N]₃P ═ O } and 50g (0.37mol) of trihydroxymethylpropane. After nitrogen displacement, the temperature was raised to 100 ℃. Then, 600g (8.33mol) of butylene oxide and 216g (2.9mol) of glycidol were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. Thereafter, 300g (5.17mol) of propylene oxide were continuously added over 4 hours so that the reaction pressure did not exceed 0.35 MPa. After the end of the propylene oxide feed, the mixture was reacted at 100 ℃ for 12 hours. The pressure was reduced to 0 MPa. After the low boiling fraction in the system was extracted by a vacuum pump, the polymer was transferred to a separate vessel and cooled to room temperature. As a result, 1100g of a transparent polymer having no odor was obtained. Number average molecular weight 2950, molecular weight distribution 1.20, HLB value 7.4.

According to the method, the phosphazene catalyst is used for preparing the hyperbranched polymer, and the HLB value can be adjusted by adjusting the structure and the content of the monomer.