WO2020014887A1

WO2020014887A1 - Preparation method for dendritic or hyperbranched polymer, and prepared polymer thereof

Info

Publication number: WO2020014887A1
Application number: PCT/CN2018/096124
Authority: WO
Inventors: 李武松; 刘聪聪; 谭志
Original assignee: 威海晨源分子新材料有限公司
Priority date: 2018-07-18
Filing date: 2018-07-18
Publication date: 2020-01-23
Also published as: CN112105660A

Abstract

The present application provides a preparation method for a dendritic or hyperbranched polymer, comprising: adding components in a reaction system to a hypergravity reactor; and controlling a reaction temperature and a hypergravity level to prepare the required dendritic or hyperbranched polymer. Compared with the dendritic or hyperbranched polymer synthesized by a traditional process, the present application enhances a mass transfer process of a polymer molecule, improves the mass transfer efficiency, greatly shortens a reaction period, and ensures that the product purity is not reduced; the present application further has advantages such as low energy consumption, small space occupied by a device, large operation elasticity, simple production procedure, high efficiency, and low material consumption.

Description

Method for preparing dendritic or hyperbranched polymer and polymer obtained by preparing same

Technical field

The present application belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a dendritic or hyperbranched polymer and a polymer obtained by preparing the same.

Background technique

Dendritic and hyperbranched polymers are important chemical products. Because of their low viscosity, high solubility, excellent film-forming properties, and easy modification, they are currently used in ink coatings, biomedicine, plastics, rubber, and petrochemicals. , Water treatment and other fields have a wide range of applications. For example, coating curing agents, toughening agents, dispersants, etc., plastic lubricants, etc., flocculants for water treatment, demulsifiers, scale inhibitors, heavy metal water treatment agents, and the like.

The methods for synthesizing dendrimers are generally divided into two categories, one is from the core of the dendrimer, and it is synthesized by diffusion from the inside to the outside (divergence method); the other is from the outer layer of the dendrimer. A method of stepwise convergence from outside to inside (convergence method). Whether it is synthesized by divergent method or synthesized by convergence method, it needs to undergo multiple steps of reaction and purification. Hyperbranched polymers do not have a perfect molecular structure but have structures and characteristics similar to dendrimers, and do not require multiple steps of synthesis and purification in the synthesis. The required hyperbranched polymer can be synthesized from the monomers through the "quasi-one-step method", thereby greatly reducing the cost of synthesis. However, the current conventional production processes of the two polymers still have the problems of high industrialization costs caused by long synthesis cycles, low conversion rates, low production efficiency, and high energy consumption, thus limiting the industrial production and dendritic and hyperbranched polymers. The pace of industrialization promotion. At present, an efficient production equipment or production process is urgently needed to solve the problems of low efficiency and high cost of industrial production of dendritic and hyperbranched polymers, thereby accelerating the widespread industrialization of dendritic and hyperbranched polymers worldwide and promoting related industries. The rapid development of the chain.

Summary of the invention

In view of the above technical problems, the present application proposes a new method for preparing a dendritic or hyperbranched polymer and the polymer obtained by the preparation.

In order to achieve the above-mentioned object, on the one hand, the present application provides a method for preparing a dendritic or hyperbranched polymer. Each component of the reaction system is added to a hypergravity reactor, and the reaction temperature is controlled to be 0 to 250 ° C and the hypergravity level It is (2 ~ 500) × g, and g is the acceleration of gravity, and a dendritic or hyperbranched polymer having the following molecular formula is prepared:

among them:

[C] means nuclear;

Nc is the multiplicity of the kernel, and Nc is a positive integer;

[FF] represents the functional group of the core, X is the total number of functional groups of the core [FF], where X is a positive integer multiple of 0 or 1 to Nc-1, and when X is not equal to 0, [FF] is -OH , -NH ₂ ,

Or one or more of -COOH;

[BR] represents a branching unit, P is the total number of branching units [BR], where P is 0 or a positive integer, and when p is greater than 1, [BR] is a plurality of identical or different branching units;

[IF] represents internal functional groups, q is the total number of internal functional groups [IF], where q is 0 or a positive integer, when q is greater than 1, then [IF] is a plurality of the same or different internal functional groups; [IF] is

One or more of them;

[EX] represents a chain extender, m is the total number of chain extenders [EX], where m is 0 or a positive integer, and when m is greater than 1, [EX] is a plurality of identical or different chain extenders;

[TF] represents terminal functional groups, z is the total number of terminal functional groups [TF], where z is 0 or a positive integer, and when z is greater than 1, [TF] is a plurality of identical or different terminal functional groups;

When both p and m are greater than 1, [BR] and [EX] are connected alternately or multiple [BR] are connected and then connected with multiple [EX].

As a preference, when [IF] is

, The method for preparing the dendritic polymer includes the following steps:

The polyamine monomer, solvent, and acrylate monomer are introduced into the hypergravity reactor. Under the protection of an inert gas, the reaction is carried out at a temperature of 0 to 80 ° C and a hypergravity level of (5 to 500) × g. From 1 to 14 hours, G-0.5-terminated terminal dendritic polyamide amine polymers are formed;

The G-0.5-terminated ester-terminated dendritic polyamide amine polymer, solvent, and polyamine monomer were introduced into a hypergravity reactor, and the above reaction was repeated under the protection of an inert gas to generate a G0-terminated amino-terminated dendrimer. Amidoamine polymers;

The G0-terminated amino-terminal dendritic polyamide amine polymer, solvent, and acrylate monomers are introduced into a hypergravity reactor, and the above reaction is repeated under the protection of an inert gas to generate G0.5-generation dendritic polyamide amine polymerization. Thing

By analogy, a GN-generation dendritic polyamide amine polymer is obtained, where N = n × 0.5, and n is −1.0 or a positive integer.

Preferably, in the step of obtaining a G-0.5-terminated terminal dendritic polyamide amine polymer, the molar ratio of the polyamine monomer to the acrylate monomer is 1: (4 to 40) ;

In the step of obtaining a G0-terminated amino-terminated dendritic polyamide amine polymer, the molar ratio of the G-0.5-terminated ester-terminated dendritic polyamide amine polymer to the polyamine monomer is 1 :( 4 to 40);

In the step of obtaining a G0.5-terminated ester-terminated dendritic polyamide amine polymer, the molar ratio of the G0-terminated amino-terminated dendritic polyamide amine polymer to the acrylate monomer is 1 :( 8 ~ 80);

By analogy, for the synthesis of the entire generation of amino-terminated dendritic polyamide amine polymers with N being an integer, the moles of the semi-terminated ester-terminated dendritic polyamide amine polymers and the polyamine monomer in the reactants The ratio is 1: (4 × 2 ^N ～ 40 × 2 ^N ). For the synthesis of half-generation ester-terminated dendritic polyamide amine polymers in which N is a non-integer, polyamine monomers or whole generation terminals in the reaction The molar ratio of the amino dendritic polyamide amine polymer to the acrylate monomer is 1: (4 × 2 ^{N + 0.5} to 40 × 2 ^{N + 0.5} ).

As a preference, when [IF] is

, The method for preparing the hyperbranched polymer includes the following steps:

The polyamine monomer, solvent, and acrylate monomer were introduced into the hypergravity reactor. Under the protection of an inert gas, the reaction was carried out at a temperature of 0-30 ° C and a hypergravity level of (5 to 500) × g. 0.5 ～ 12h, forming prepolymer;

The solvent was removed at a temperature of 40 to 70 ° C, and then the temperature was raised to 80 to 160 ° C, and the reaction was performed for 0.5 to 5 hours to obtain a hyperbranched polyamide amine polymer.

Preferably, the molar ratio of the polyamine monomer to the acrylate monomer is 1: (1 to 3.5).

Preferably, the polyamine monomer includes ethylenediamine, propylenediamine, succindiamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, o-phenylenediamine, m-phenylenediamine and p-diamine One of phenylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, piperazine, N-aminoethylpiperazine, polyethylenepolyamine, melamine Or more; the acrylate monomers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, trimethylolpropane triacrylate One or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate.

As a preference, when [IF] is

The preparation method includes the following steps:

Prepolymerization reaction: Polyol, polycarboxylic acid / polyacid anhydride and solvent are introduced into a hypergravity reactor, and the hypergravity level of the hypergravity reactor is (2 to 400) × g, and then a catalyst is added thereto. Under the protection of an inert gas, at a temperature of -10 to 140 ° C, the reaction is performed for 0.1 to 24 hours to prepolymerize to form a polymerized monomer;

Polymerization reaction: The temperature is increased to 20-250 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions. The reaction time is 0.1-24 hours to obtain a dendritic or hyperbranched polymer.

As a preference, when [IF] is

At this time, the hypergravity level of the hypergravity reactor is (5 to 300) × g, the temperature of the prepolymerization reaction is -10 to 120 ° C, and the reaction time is 0.1 to 10h. The obtained dendritic or hyperbranched polymer is prepared It is a dendritic or hyperbranched polyester.

Preferably, the polyhydric alcohol includes glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, tris (hydroxymethyl) amine, and tris (hydroxy) Ethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol, bis (trimethylolpropane), bis (pentaerythritol), tris (hydroxymethyl) isocyanurate, tris (hydroxy) One or more of ethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, glyceride of ricinoleic acid (castor oil), inositol, sugar, sugar alcohol.

As a preference, when [IF] is

At this time, the hypergravity level of the hypergravity reactor is (2 to 200) × g, the temperature of the prepolymerization reaction is -10 to 120 ° C, and the reaction time is 0.1 to 10h. The obtained dendritic or hyperbranched polymer is prepared It is a dendritic or hyperbranched polyester amide or polyester amine.

Preferably, the polyol is an amino alcohol having at least one amino group and at least two hydroxyl groups, and the amino alcohol includes diethanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, dibutanolamine, diisobutanolamine, bis (2-hydroxy-1-butyl) amine, bis (2-hydroxy- One or more of 1-propyl) amine and dicyclohexanolamine.

Preferably, a molar ratio of the added amount of the polyhydric alcohol to the polycarboxylic acid / polyacid anhydride is 15: (1 to 225); the polycarboxylic acid / polyacid anhydride includes oxalic acid, citric acid, and malonic acid , Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, acetic anhydride, succinic anhydride, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, meta Phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ether tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic dianhydride and 3,3 ', 4,4' -One or more of diphenylsulfone tetracarboxylic dianhydride.

As a preference, when [IF] is

When the polyol is a polyether polyol, the hypergravity level of the hypergravity reactor is (10 to 400) × g, the temperature of the prepolymerization reaction is 20 to 140 ° C, and the reaction time is 1 to 24 hours; polymerization The reaction temperature is from 40 ° C to 250 ° C, and the reaction time is from 0.5 to 24 hours. A dendritic or hyperbranched polyether ester is prepared.

Preferably, the molar ratio of the polyether polyol to the polycarboxylic acid / polyanhydride is 1: (0.1 to 20); the polyether polyol includes diethylene glycol and triethylene glycol , Polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentylene glycol and polyhexanediol, polyglyceryl ether, trimethylolpropane polyether, polypentaerythritol, polyxylitol, polysorbate, polysucrose The polycarboxylic acid includes glyceric acid; the polybasic acid anhydride includes trimellitic anhydride, pyromellitic anhydride, diphenyl ether tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, biphenyl One or more of pyromellitic dianhydride and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride.

Another aspect of the present application provides a dendritic or hyperbranched polymer prepared by the preparation method according to any one of the foregoing technical solutions.

Compared with the prior art, the advantages and positive effects of this application are:

1. The use of hypergravity technology to synthesize dendritic or hyperbranched polymers can greatly improve the mass and heat transfer efficiency, increase the reaction rate by 1 to 10 times, greatly reduce the reaction time, reduce reaction by-products, and avoid product causes. Reduced quality caused by prolonged heating time, while reducing energy consumption, cost, and energy efficiency.

2. The use of hypergravity technology to synthesize dendritic or hyperbranched polymers can simplify the process and be safe and reliable. At the same time, the equipment used is small in size, light in weight, and easy to maintain, which can significantly reduce investment in equipment and production sites.

detailed description

The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

The embodiment of the present application provides a method for preparing a dendritic or hyperbranched polymer. Each component of the reaction system is added to a hypergravity reactor, and the reaction temperature is controlled to be 0 to 250 ° C. and the hypergravity level is (2 to 500). ) × g, where g is the acceleration of gravity, and a dendritic or hyperbranched polymer having the following molecular formula is prepared:

among them:

[C] means nuclear;

Nc is the multiplicity of the nucleus, and Nc is a positive integer, indicating the number of repeated occurrences;

Or one or more of -COOH;

One or more of them;

[TF] represents terminal functional groups, z is the total number of terminal functional groups [TF], where z is 0 or a positive integer, when z is greater than 1, [TF] is a plurality of identical or different terminal functional groups, [TF] includes All functional groups as the functional group at the end of the polymer may be, for example, -OH, -NH ₂ , -COOH, -COOM (carboxylate),

R4NX (quaternary ammonium salt, R represents four identical or different hydrocarbon groups, X represents a halogen atom or acid group), -R (hydrocarbon group of different carbon atoms),

(Double bond) or

(Ester group) one or more, but not limited to these functional groups;

Hypergravity technology is a new technology that uses a hypergravity environment that is much larger than the acceleration of the earth's gravity to enhance the mass transfer and micro mixing processes. It is obtained by rotating the earth to simulate a hypergravity environment. Under hypergravity, the molecular diffusion and interphase mass transfer between molecules of different sizes are much faster than under conventional gravity fields, which can greatly improve the mass and heat transfer efficiency of reactants, thereby increasing the reaction rate and shortening. Reaction cycle. In the above preparation method, components such as monomers, solvents and the like are added to the hypergravity reactor, and by controlling the reaction temperature and the level of hypergravity, the synthesis process of applying the hypergravity technology to dendritic or hyperbranched polymers is successfully achieved. Compared with the existing preparation method, the reaction period can be greatly shortened, the energy consumption of the reaction can be reduced, and the raw materials can be saved. The size of the hypergravity level is related to the size and rotation speed of the hypergravity reactor. For the same hypergravity reactor, it can be controlled by adjusting the rotation speed. The relationship between the hypergravity level and the size and rotation speed of the hypergravity reactor is common knowledge in the art, not The focus of this application is not described here in detail. In addition, it can be understood that, in the above preparation method, those skilled in the art can control the structure of the polymer in the reaction according to the common knowledge and common technical means in the art, such as adjusting the amount of reactants and reaction conditions, etc. It is formed into a dendritic structure or a hyperbranched structure as required.

In a preferred embodiment, the hypergravity reactor is one of a horizontal hypergravity reactor, a vertical hypergravity reactor, and an internal circulation hypergravity reactor, but is not limited to these types. Those skilled in the art may select according to the type of the actual reaction monomer and the needs of the reaction mechanism.

In the above preparation method, when the obtained polymer is a dendritic polyamide amine polymer, that is, when [IF] in the molecular formula of the dendritic polymer is

In this case, the embodiment of the preparation method specifically includes the following steps:

a1: Introduce polyamine monomer, solvent, and acrylate monomer into the hypergravity reactor. Under the protection of inert gas, the temperature is 0 ～ 80 ℃, and the supergravity level is (5 ～ 500) × g. , Reaction for 1 to 14h, to obtain G-0.5-terminated terminal dendritic polyamide amine polymers;

a2: G-0.5 generation dendritic polyamide amine polymer, solvent and polyamine monomer are introduced into the hypergravity reactor, under the protection of an inert gas, at a temperature of 0 to 80 ° C, and the supergravity level is ( 5 ~ 500) × g, reaction for 1 ~ 14h, the reaction yields G0-terminated amino terminal dendritic polyamide amine polymer;

a3: The G0-terminated amino-terminated dendritic polyamide amine polymer, solvent, and acrylate monomers are introduced into a supergravity reactor, under the protection of an inert gas, at a temperature of 0 to 80 ° C, and the supergravity level is (5 ~ 500) × g, reaction for 1 ~ 14h, the reaction produces G0.5 generation of terminal ester-based dendritic polyamide amine polymer;

a4: By analogy, a GN-generation dendritic polyamide amine polymer is obtained, where N = n × 0.5, and n is -1, 0, or a positive integer.

In the above method for preparing a dendritic polyamide amine polymer, a desired dendritic polyamide amine polymer is obtained through multiple iterative reactions in a super-gravity environment, and the reaction speed is fast and the efficiency is high. In the above steps a1-a4, in order to facilitate the generation of dendritic polyamide amine polymers, the level of hypergravity is limited to the above range, but it can be understood that those skilled in the art can also be within the above range according to the actual reaction situation. It can also be adjusted within, for example, 10g, 50g, 100g, 150g, 200g, 250g, 300g, 350g, 400g, 450g, etc. and any other point value within this range. In addition, in order to match the environment of hypergravity, the reaction temperature and reaction time are limited to the above-mentioned range, but it can be understood that those skilled in the art can also adjust within the above-mentioned range according to the actual reaction situation, and the temperature can also be 10 ° C, 20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C, etc. and any other point in the range; the reaction time may also be 2h, 4h, 5h, 6h, 8h, 10h , 12h, and any other point value within that range.

In a preferred embodiment, the mass of the reactant in each step accounts for 20% to 80% of the total mass of the reaction system, wherein the reactant is a substance after removing the solvent in the reaction system of each step. The reaction system refers to all components added to the hypergravity reactor in each step.

In the above embodiments, the percentages of the mass of the reactants to the total mass of the reaction system are respectively limited to the above ranges, which is beneficial to the full reaction of the reactants and avoids the waste of raw materials. However, it can be understood that the mass of the reactant may also be 30%, 40%, 50%, 60%, 70%, etc. of the total mass of the reaction system, and those skilled in the art may select within the above range according to the actual reaction situation. .

In a preferred embodiment, in the step of obtaining a G-0.5-terminated ester-group dendritic polyamide amine polymer, the molar ratio of the polyamine monomer to the acrylate monomer is 1 :( 4 to 40); in the step of obtaining a G0-terminated amino-terminated dendritic polyamide amine polymer, the molar ratio of the G-0.5-generation ester-terminated dendritic polyamide amine polymer and the polyamine monomer The ratio is 1: (4 to 40); in the step of obtaining a G0.5-terminated ester-terminated dendritic polyamide amine polymer, the G0-terminated amino-terminated dendritic polyamide amine polymer and the acrylate The molar ratio of the monomers is 1: (8 ~ 80); and so on, for the synthesis of the entire generation of amino-terminated dendritic polyamide amine polymers where N is an integer, the semi-terminally ester-terminated dendrimers in the reaction are synthesized. The molar ratio of the amidoamine polymer to the polyamine monomer is 1: (4 × 2 ^N to 40 × 2 ^N ), and for a non-integer half-terminated ester-based dendrimer polyamide polymer, In the synthesis, the molar ratio of the polyamine monomer or the amino-terminated dendritic polyamideamine polymer to the acrylate monomer in the reactant is 1: (4 × 2 ^{N + 0.5} to 4 0 × 2 ^{N + 0.5} ).

In the above embodiments, in order to facilitate the sufficient polymerization reaction between the monomers and the progress of the iterative reaction, the content of each component in each step of the reaction is limited to the above range, but it can be understood that the technology in the art Personnel can also adjust within the above range according to actual conditions. Specifically, in a1, the molar ratio of the polyamine monomer to the acrylate monomer can also be 1: 5, 1:10, 1 : 15, 1:20, 1:25, 1:30, 1:35, etc. and any ratio within the above range; in a2, the G-0.5-generation end-terminated dendritic polyamide amine polymer and The molar ratio of the polyamine monomer may also be 1: 5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, etc. and any ratio within the above range; In a3, the molar ratio of the G0-terminated amino-terminal dendritic polyamide amine polymer to the acrylate monomer may also be 1:10, 1:20, 1:30, 1:40, 1: 50, 1:60, 1:70, etc. and any ratio within the above range.

In the above preparation method, when the polymer obtained is a hyperbranched polyamide amine polymer, that is, when the molecular formula of the hyperbranched polymer is [IF],

b1: Introduce polyamine monomer, solvent and acrylate monomer into the supergravity reactor, under the protection of inert gas, at a temperature of 0-30 ° C and a supergravity level of (5-500) × g , React for 0.5 ~ 12h to form a prepolymer;

b2: The solvent is removed at a temperature of 40 to 70 ° C, and then the temperature is raised to 80 to 160 ° C, and the reaction is performed for 0.5 to 5 hours to obtain a hyperbranched polyamide amine polymer.

In the above method for preparing a hyperbranched polyamidoamine polymer, the required hyperbranched polyamidoamine polymer is prepared in a hypergravity environment, and the reaction speed is fast and the efficiency is high. In order to facilitate the generation of hyperbranched polyamidoamine polymers, the level of hypergravity is limited to the above range, but it can be understood that those skilled in the art can also adjust within the above range according to the actual reaction situation, for example, it can also be 10g, 50g, 100g, 150g, 200g, 250g, 300g, 350g, 400g, 450g, etc. and any other point value within this range. In addition, in order to match the environment of hypergravity, the reaction temperature and reaction time are limited to the above-mentioned range, but it can be understood that those skilled in the art can also adjust within the above-mentioned range according to the actual reaction situation, specifically, in step b1 In addition, the temperature may also be 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, etc. and any other point in the range, and the reaction time may also be 2h, 4h, 5h, 6h, 8h , 10h, and any other point value within this range; in step b2, the temperature for removing the solvent may also be 50 ° C, 55 ° C, 60 ° C, 65 ° C, etc. and any other point value within this range, reaction temperature It can also be 90 ° C, 100 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, etc. and any other point in the range. The reaction time can also be 1h, 1.5h, 2h, 2.5h, 3h , 3.5h, 4h, and any other point value within this range.

In a preferred embodiment, the mass of the reactant accounts for 20% to 80% of the total mass of the reaction system, wherein the reactant is a substance after removing the solvent in the reaction system. In this embodiment, the percentages of the mass of the reactants to the total mass of the reaction system are respectively limited to the above ranges, which is beneficial to the full reaction of the reactants and avoids the waste of raw materials. However, it can be understood that the mass of the reactant may also be 30%, 40%, 50%, 60%, 70%, etc. of the total mass of the reaction system, and those skilled in the art may select within the above range according to the actual reaction situation. .

In a preferred embodiment, the molar ratio of the polyamine monomer to the acrylate monomer is 1: (1 to 3.5). In this embodiment, in order to facilitate a sufficient reaction between the monomers, the molar ratio of the polyamine monomer and the acrylate monomer is limited to the above range, but it can be understood that those skilled in the art It can also be adjusted within the above range according to actual conditions, for example, it can also be 1: 1.5, 1: 2, 1: 2.5, 1: 3, etc., and any ratio within this range.

In the above-mentioned preparation method for preparing a dendritic or hyperbranched polyamide amine polymer, preferably, the polyamine monomer includes ethylenediamine, propylenediamine, succindiamine, pentanediamine, hexamethylenediamine, Heptanediamine, octanediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, piperazine One or more of N-aminoethylpiperazine, polyethylene polyamine; the acrylate monomers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate , One or more of ethyl acrylate, butyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate.

In the above examples, the polyamine monomers and acrylate monomers listed are all preferred compounds that are beneficial to the reaction, but it can be understood that the compounds that can be used in the present application are not limited to those listed above. As long as the compound is in accordance with the above reaction mechanism, those skilled in the art can replace it according to actual needs.

When the molecular formula [IF] of the dendritic or hyperbranched polymer is

c1 prepolymerization reaction: introducing a polyol, a polycarboxylic acid / polyacid anhydride, and a solvent into a hypergravity reactor, the hypergravity level of the hypergravity reactor is (2 to 400) × g, and then adding a catalyst thereto; Under the protection of an inert gas, at a temperature of -10 to 140 ° C, the reaction is performed for 0.1 to 24 hours to prepolymerize to form a polymerized monomer;

c2 Polymerization reaction: The temperature is increased to 20-250 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction time is 0.1 to 24 hours to obtain a dendritic or hyperbranched polymer.

In the above-mentioned method for preparing a dendritic or hyperbranched polymer, firstly, a polymerization monomer is generated through a prepolymerization reaction in a hypergravity environment, and then the temperature is raised and reduced to continue the reaction to finally prepare a desired dendritic or hyperbranched polymer. Fast and efficient.

In the above preparation method, when the obtained dendritic or hyperbranched polymer is a dendritic or hyperbranched polyester, that is, when [IF] is

At this time, the hypergravity level of the hypergravity reactor is (5 to 300) × g, the temperature of the prepolymerization reaction is -10 to 120 ° C, and the reaction time is 0.1 to 10 hours; as mentioned above, the polymerization reaction is 20 to 250 ° C, reaction time is 0.1 to 24h.

In the above-mentioned embodiments for preparing dendritic or hyperbranched polyesters, it can be understood that, in order to facilitate the generation of dendritic or hyperbranched polyesters, the hypergravity level of the hypergravity reactor is limited to the above range. The supergravity level can also be 10g, 50g, 100g, 150g, 200g, 250g, etc. Those skilled in the art can choose within the above range. In addition, in order to facilitate the generation of dendritic or hyperbranched polyester and cooperate with the environment of hypergravity, the temperature and reaction time are limited to the above ranges, but it can be understood that those skilled in the art can also according to the actual reaction situation Adjust within the above range. Specifically, in step c1, the temperature may also be -5 ° C, 0 ° C, 10 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 80 ° C, 100 ° C, etc., The reaction time may also be 0.5h, 1h, 2h, 3h, 5h, 6h, 8h, etc .; in step c2, the temperature may also be 40 ° C, 50 ° C, 60 ° C, 80 ° C, 100 ° C, 120 ℃, 150 ° C, 180 ° C, 200 ° C, 220 ° C, etc., the reaction time may also be 0.5h, 1h, 5h, 10h, 15h, 20h, etc.

As a preferred embodiment of the method for preparing a dendritic or hyperbranched polyester, the polyhydric alcohol includes glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol Alcohol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol, bis (trimethylolpropane), bis (pentaerythritol), tris ( Hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, glyceryl ricinoleate (castor oil), inositol, sugar, One or more of the sugar alcohols. The polyhydric alcohols listed in this example are all preferred compounds that are beneficial to the formation of dendritic or hyperbranched polyesters, but it can be understood that the optional compounds in this application are not limited to the compounds listed above, but may also be Other compounds known in the art can be used by those skilled in the art as long as they meet the above reaction mechanism.

In the above preparation method, when the obtained dendritic or hyperbranched polymer is a dendritic or hyperbranched polyester amide or polyester amine, that is, when [IF] is

At this time, the hypergravity level of the hypergravity reactor is (2 to 200) × g, the temperature of the prepolymerization reaction is -10 to 120 ° C, and the reaction time is 0.1 to 10h; the polymerization reaction is as described above, and the temperature is 20 ° C ～ 250 ℃, reaction time is 0.1 ～ 24h.

In the above embodiments for preparing dendritic or hyperbranched polyesteramides or polyesteramines, it can be understood that, in order to facilitate the generation of dendritic or hyperbranched polyesteramides or polyesteramines, the supergravity reactor The gravity level is limited to the above range, and the supergravity level may also be 5g, 10g, 30g, 50g, 80g, 100g, 120g, 150g, etc. Those skilled in the art can select within the above range. In addition, in order to facilitate the formation of dendritic or hyperbranched polyester amides or polyester amines and cooperate with the environment of hypergravity, the temperature and reaction time are limited to the above ranges, but it can be understood that those skilled in the art also It can be adjusted within the above range according to the actual reaction situation. Specifically, in step c1, the temperature may also be -5 ° C, 0 ° C, 10 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 80 ° C. , 100 ° C, etc., the reaction time may also be 0.5h, 1h, 2h, 3h, 5h, 6h, 8h, etc .; in step c2, the temperature may also be 40 ° C, 50 ° C, 60 ° C, 80 ° C , 100 ° C, 120 ° C, 150 ° C, 180 ° C, 200 ° C, 220 ° C, etc., the reaction time may also be 0.5h, 1h, 5h, 10h, 15h, 20h, etc.

As a preference of the above embodiment for preparing dendritic or hyperbranched polyester amide or polyester amine, the polyol is an amino alcohol having at least one amino group and at least two hydroxyl groups, and the amino alcohol includes diethanolamine, dipropanolamine , Diisopropanolamine, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, dibutanolamine, diisobutanolamine, di ( One or more of 2-hydroxy-1-butyl) amine, bis (2-hydroxy-1-propyl) amine, and dicyclohexanolamine. The polyhydric alcohols listed in this example are all preferred compounds that are beneficial to the formation of dendritic or hyperbranched polyester amides or polyester amines, but it can be understood that the optional compounds in this application are not limited to those listed above. The compound can also be other compounds known in the art, and those skilled in the art can use it alternately as long as it complies with the above reaction mechanism.

As a preference of the above embodiment for preparing dendritic or hyperbranched polyester, polyester amide and polyester amine, the molar ratio of the added amount of the polyol to the polycarboxylic acid / polyacid anhydride is 15: (1 to 225) ; The polycarboxylic acid / polyanhydride includes oxalic acid, citric acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, acetic anhydride, succinic anhydride, orthobenzene Dicarboxylic acid, isophthalic acid, terephthalic acid, phthalic anhydride, metaphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ether tetracarboxylic anhydride, benzophenone One or more of tetracarboxylic anhydride, biphenyltetracarboxylic dianhydride, and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride.

In the above embodiments, in order to make the reactants fully react, the molar ratio of the added amount of the polyhydric alcohol to the polycarboxylic acid / polyacid anhydride is limited to the above range, but it can be understood that those skilled in the art can also Need to select within the above range, for example, it can also be 15:10, 15:15, 15:50, 15: 100, 15: 150, 15: 200, and so on. In addition, the polycarboxylic acids / polyacid anhydrides listed in the above examples are all preferred compounds that are beneficial to the above reaction, but it can be understood that the optional compounds in this application are not limited to the compounds listed above, and may also be Other compounds known in the art can be used by those skilled in the art as long as they meet the above reaction mechanism.

In the above preparation method, when the obtained dendritic or hyperbranched polymer is a dendritic or hyperbranched polyether ester, [IF] is

When the polyol is a polyether polyol, the hypergravity level of the hypergravity reactor is (10 to 400) × g, the temperature of the prepolymerization reaction is 20 to 140 ° C, and the reaction time is 1 to 24 hours. The reaction temperature is 40 to 250 ° C, and the reaction time is 0.5 to 24 hours.

In the above embodiments, in order to facilitate the generation of dendritic or hyperbranched polyether esters, the hypergravity level of the hypergravity reactor is limited to the above range, and the hypergravity level may also be 20g, 50g, 100g, 150g , 200g, 250g, 300g, etc., those skilled in the art can select within the above range. In addition, in order to facilitate the reaction and cooperate with the environment of hypergravity, the temperature and reaction time in steps c1 and c2 are respectively limited to the above ranges, but it can be understood that those skilled in the art may also Adjust within the above range. Specifically, in step c1, the temperature may also be 30 ° C, 60 ° C, 90 ° C, 120 ° C, etc., and the reaction time may also be 5h, 10h, 15h, 20h, etc .; in In step c2, the temperature may also be 70 ° C, 100 ° C, 150 ° C, 200 ° C, and the like, and the reaction time may also be 5h, 10h, 15h, 20h, and the like.

As a preference of the above embodiment, the molar ratio of the polyether polyol to the polycarboxylic acid / polyhydric anhydride is 1: (0.1 to 20); the polyether polyol includes diethylene glycol, diethylene glycol Triethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentylene glycol, polyhexanediol, polyglyceryl ether, trimethylolpropane polyether, polypentaerythritol, polyxylitol, polysorbate One or more of alcohol and polysucrose; the polycarboxylic acid includes glyceric acid; the polybasic acid anhydride includes trimellitic anhydride, pyromellitic anhydride, diphenyl ether tetracarboxylic anhydride, benzophenone One or more of tetracarboxylic anhydride, biphenyltetracarboxylic dianhydride, and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride.

Further, the polyethylene glycol is preferably polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 (PEG400) or polyethylene glycol 600; the polypropylene glycol is preferably polypropylene glycol 400 or polypropylene glycol 1000, more preferably polypropylene glycol 400.

In the above embodiments, in order to make the reactants fully react, the molar ratio of the polyether polyol to the polycarboxylic acid / polyacid anhydride is limited to the above range, but it can be understood that those skilled in the art can also Select within the above range as required, for example, it can also be 1: 0.2, 1: 0.5, 1: 1, 1: 5, 1:10, 1:15, and so on. In addition, the polyether polyol, polycarboxylic acid, and polybasic acid anhydride listed in the above examples are all preferred compounds that are beneficial to the above reaction, but it can be understood that the optional compounds in this application are not limited to those mentioned above. The listed compounds can also be other compounds known in the art, and those skilled in the art can use them alternately as long as they conform to the above reaction mechanism.

In the above-mentioned embodiments of the preparation methods, preferably, the solvent includes one of methanol, ethanol, propanol, n-butanol, isobutanol, N, N-dimethylformamide, and dimethylsulfoxide, or Multiple. It can be understood that the compounds that can be selected as solvents in the present application are not limited to those listed above, as long as the compounds that can dissolve the reactants and facilitate the reaction can be used by those skilled in the art.

In the embodiments of the above preparation methods, as a preference, the catalyst includes one or more of p-toluenesulfonic acid, butyl titanate, dibutyltin dilaurate, stannous chloride and stannous octoate; The added amount of the catalyst is 0.1% to 5% of the total mass of the polyol and the polycarboxylic acid / polyacid anhydride. It can be understood that the compounds that can be selected as catalysts in this application are not limited to those listed above, as long as the compounds that can catalyze the reaction can be replaced by those skilled in the art. In each of the above embodiments, the amount of the catalyst does not need to be too much, and it only needs to play a catalytic role. Within the above range, it can also be 0.5% of the total mass of the polyol and polycarboxylic acid / polyacid anhydride, 1%, 2%, 3%, 4%, etc., those skilled in the art can select within the above range according to the actual reaction needs.

In the above embodiments of the preparation methods, preferably, the inert gas is at least one of nitrogen, helium, and argon. It can be understood that it may also be another inert gas as a reaction shielding gas.

The embodiment of the present application further provides a dendritic or hyperbranched polymer prepared by the preparation method described in any one of the above embodiments. Dendritic or hyperbranched polymers prepared by hypergravity technology can be widely used in coatings, biomedicine, environmental protection and other fields.

In order to introduce the method for preparing the dendritic or hyperbranched polymer provided in the examples of the present application in more detail, the following description will be given in combination with specific examples.

1. Preparation of dendritic polyamide amine

Example 1

25.3mol of methanol, 0.5mol of ethylenediamine and 2mol of methyl acrylate were added to the supergravity reactor, and protected by argon. The supergravity level of the supergravity reactor was 5g, and the reaction was performed at 0 ° C for 12 hours, that is, A G-0.5 generation dendritic PAMAM (polyamide amine polymer) is obtained; wherein the sum of the mass of the ethylenediamine and methyl acrylate is 20% of the total mass of the reaction system, and the ethylenediamine and the methyl acrylate are The molar ratio of the ester was 1: 4.

Example 2

Add 50mol of methanol, 10mol of ethylenediamine and 40mol of methyl acrylate to the hypergravity reactor, and protect it with argon. The hypergravity level of the hypergravity reactor is 5g, and the reaction is performed at 25 ° C for 6 hours to obtain G. -0.5 generation dendritic PAMAM; wherein the sum of the mass of the ethylenediamine and methyl acrylate is 20% of the total mass of the reaction system, and the molar ratio of the ethylenediamine to the methyl acrylate is 1: 4.

Example 3

16.7mol of methanol, 0.2mol of ethylenediamine and 4mol of methyl acrylate were added to the hypergravity reactor, and protected by argon. The supergravity level of the hypergravity reactor was 250g, and the reaction was performed at 40 ° C for 4 hours, that is, G-0.5 generation dendritic PAMAM is obtained; wherein the sum of the mass of the ethylenediamine and methyl acrylate is 40% of the total mass of the reaction system, and the molar ratio of the ethylenediamine to the methyl acrylate is 1:20 .

Example 4

9.4mol of methanol, 0.2mol of ethylenediamine and 8mol of methyl acrylate were added to the hypergravity reactor, and protected by argon. The supergravity level of the hypergravity reactor was 500g, and the reaction was performed at 80 ° C for 2 hours, that is, G-0.5 generation dendritic PAMAM is obtained; wherein the sum of the mass of the ethylenediamine and methyl acrylate is 80% of the total mass of the reaction system, and the molar ratio of the ethylenediamine to the methyl acrylate is 1:40 .

Example 5

34 mol of ethanol, 0.5 mol of propylene diamine, and 5 mol of methyl methacrylate were added to the hypergravity reactor, protected by nitrogen, the hypergravity level of the hypergravity reactor was 50g, and the reaction was performed at 30 ° C for 4 hours, that is, G-0.5 generation dendritic PAMAM is obtained; wherein the mass of the propylene diamine and methyl methacrylate is 30% of the total mass of the reaction system, and the molar ratio of the propylene diamine to the methyl methacrylate Is 1:10;

0.2mol of the above-mentioned G-0.5 generation dendrimer, 12.4mol of ethanol, and 0.8mol of propylene diamine were added to the hypergravity reactor, and protected by nitrogen. The hypergravity level of the hypergravity reactor was 5g, and the reaction was performed at 0 ° C for 4 hours. The G0 generation dendritic PAMAM is obtained; wherein the mass of the G-0.5 generation dendritic PAMAM and the propylene diamine is 20% of the total mass of the reaction system, and the G-0.5 generation dendritic PAMAM and the The molar ratio of propylene diamine is 1: 4.

Example 6

Add 11.6mol of ethanol, 0.1mol of butanediamine, 0.1mol of pentanediamine, and 6mol of methyl methacrylate to the hypergravity reactor, and protect it with nitrogen. The hypergravity level of the hypergravity reactor is 100g, at 60 After reacting for 6 hours at ℃, G-0.5 generation dendritic PAMAM is obtained; wherein the mass of the succindiamine, pentanediamine and methyl methacrylate is 50% of the total mass of the reaction system, and the succindiamine The molar ratio of pentanediamine to the methyl methacrylate is 1:30;

1.25 mol of the above-mentioned G-0.5 generation dendritic PAMAM, 56.5 mol of ethanol, and 25 mol of pentanediamine were added to the hypergravity reactor and protected by nitrogen. The supergravity level of the hypergravity reactor was 250g, and the reaction was performed at 40 ° C for 8 hours. The G0 generation dendritic PAMAM is obtained; wherein the mass of the G-0.5 generation dendritic PAMAM and the pentanediamine is 50% of the total mass of the reaction system, and the G-0.5 generation dendritic PAMAM and the The molar ratio of pentanediamine is 1:20.

Example 7

8.9 mol of ethanol, 0.2 mol of propylene diamine and 6 mol of methyl methacrylate were added to the hypergravity reactor and protected by nitrogen. The hypergravity level of the hypergravity reactor was 300g, and the reaction was performed at 50 ° C for 10 hours. That is, a G-0.5 generation dendritic PAMAM is obtained; wherein the mass of the propylene diamine and methyl methacrylate is 60% of the total mass of the reaction system, and the molar ratio of the propylene diamine to methyl methacrylate is 1:30;

Add 0.125 mol of the above-mentioned G-0.5 generation dendritic PAMAM, 2.3 mol of ethanol, and 5 mol of propylene diamine to the hypergravity reactor and protect it with nitrogen. The supergravity level of the hypergravity reactor is 500g, and the reaction is performed at 80 ° C for 5 hours The G0 generation dendritic PAMAM is obtained; wherein the mass of the G-0.5 generation dendritic PAMAM and the propylene diamine is 80% of the total mass of the reaction system, and the G-0.5 generation dendritic PAMAM and the The molar ratio of propylene diamine is 1:40.

Example 8

4.4 mol of n-butanol, 0.1 mol of o-phenylenediamine, and 1 mol of butyl acrylate were added to the hypergravity reactor, and protected by nitrogen. The supergravity level of the hypergravity reactor was 50g, and the reaction was performed at 30 ° C for 12 hours. To obtain a G-0.5 generation dendritic PAMAM; wherein the mass of the o-phenylenediamine and butyl acrylate is 30% of the total mass of the reaction system, and the molar ratio of the o-phenylenediamine to the butyl acrylate Is 1:10;

Add 0.2 mol of the above-mentioned G-0.5 generation dendritic PAMAM, 3.8 mol of n-butanol, and 1 mol of o-phenylenediamine to the hypergravity reactor and protect it with nitrogen. The hypergravity level of the hypergravity reactor is 50g at 30 ° C. After 12 hours of reaction, G0 generation dendritic PAMAM is obtained; wherein the mass of the G-0.5 generation dendritic PAMAM and the o-phenylenediamine is 30% of the total mass of the reaction system, and the G-0.5 generation dendritic The molar ratio of PAMAM to the o-phenylenediamine is 1: 5.

Add 0.1 mol of the above-mentioned G0-dendritic PAMAM, 6.5 mol of n-butanol, and 0.8 mol of butyl acrylate into the hypergravity reactor, and protect it by nitrogen. In one hour, the G0.5 generation dendritic PAMAM is obtained; wherein the mass of the G0 generation dendritic PAMAM and the butyl acrylate is 20% of the total mass of the reaction system, and the G0 generation dendritic PAMAM and the acrylic acid The molar ratio of butyl ester was 1: 8.

Example 9

Add 0.1mol of the above-mentioned G-0.5 generation dendritic PAMAM, 3mol of n-butanol, and 1mol of o-phenylenediamine into the hypergravity reactor, and protect it with nitrogen. The supergravity level of the hypergravity reactor is 100g, and the reaction is performed at 60 ° C. 6 hours, the G0 generation dendritic PAMAM is obtained; wherein the mass of the G-0.5 generation dendritic PAMAM and the o-phenylenediamine is 40% of the total mass of the reaction system, and the G-0.5 generation dendritic PAMAM The molar ratio to the o-phenylenediamine is 1:10.

Add 0.125 mol of the above-mentioned G0 dendritic PAMAM, 9 mol of n-butanol, and 5 mol of butyl acrylate to a hypergravity reactor, and protect it with nitrogen. The hypergravity level of the hypergravity reactor is 250g, and the reaction is performed at 40 ° C for 4 hours. The G0.5 generation dendritic PAMAM is obtained; wherein the mass of the G0 generation dendritic PAMAM and the butyl acrylate is 50% of the total mass of the reaction system, and the G0 generation dendritic PAMAM and the butyl acrylate The molar ratio is 1:40.

Example 10

8.7 mol of n-butanol, 0.2 mol of o-phenylenediamine, and 2 mol of butyl acrylate were added to the hypergravity reactor, and protected by nitrogen. The hypergravity level of the hypergravity reactor was 50g, and the reaction was performed at 30 ° C for 6 hours. To obtain a G-0.5 generation dendritic PAMAM; wherein the mass of the o-phenylenediamine and butyl acrylate is 30% of the total mass of the reaction system, and the molar ratio of the o-phenylenediamine to the butyl acrylate Is 1:10;

0.2mol of the above-mentioned G-0.5 generation dendritic PAMAM, 6.1mol of n-butanol, and 6mol of o-phenylenediamine were added to the hypergravity reactor, protected by nitrogen, and the hypergravity level of the hypergravity reactor was 300g at 50 ° C. After 4 hours of reaction, G0 generation dendritic PAMAM is obtained; wherein the mass of the G-0.5 generation dendritic PAMAM and the o-phenylenediamine is 60% of the total mass of the reaction system, and the G-0.5 generation dendritic The molar ratio of PAMAM to the o-phenylenediamine is 1:30.

Add 0.125 mol of the above-mentioned G0 dendritic PAMAM, 4.5 mol of n-butanol, and 10 mol of butyl acrylate to the hypergravity reactor and protect it with nitrogen. The hypergravity level of the hypergravity reactor is 500g, and the reaction is performed at 80 ° C for 1 hour To obtain the G0.5 generation dendritic PAMAM; wherein the mass of the G0 generation dendritic PAMAM and the butyl acrylate is 80% of the total mass of the reaction system, and the G0 generation dendritic PAMAM and the butyl acrylate The molar ratio of the ester was 1:80.

Comparative Example 1

50 mol of methanol, 10 mol of ethylenediamine and 40 mol of methyl acrylate were added to the reaction kettle. After mixing well, it was protected by argon and reacted at 25 ° C for 48 hours to obtain -0.5 generation dendritic PAMAM.

2.Preparation of hyperbranched polyamide amine

Example 11

(1) Introduce 1mol ethylenediamine, 6.5mol methanol and 1mol methyl methacrylate into the hypergravity reactor. The hypergravity level of the hypergravity reactor is 5g. Under the protection of nitrogen, the reaction is carried out at 0 ° C for 12h. A prepolymer is formed; wherein the molar ratio of ethylenediamine and methyl methacrylate is 1: 1, and the mass of ethylenediamine and methyl methacrylate accounts for 20% of the total mass of the reaction system.

(2) The methanol was removed at a temperature of 40 ° C, and then the temperature was raised to 80 ° C, and the reaction was performed for 5 hours to obtain a hyperbranched PAMAM.

Example 12

(1) Introduce 1 mol of o-phenylenediamine, 10 mol of methanol and 2.25 mol of methyl acrylate into the hypergravity reactor. The hypergravity level of the hypergravity reactor is 250g. Under the protection of nitrogen, the reaction is carried out at 15 ° C for 6 hours. A prepolymer is formed; wherein the molar ratio of o-phenylenediamine to methyl acrylate is 1: 2.25, and the mass of o-phenylenediamine and methyl acrylate accounts for 50% of the total mass of the reaction system.

(2) The methanol is removed at a temperature of 55 ° C., and then the temperature is raised to 120 ° C., and the reaction is performed for 2.75 h to obtain a hyperbranched PAMAM.

Example 13

(1) 1 mol of diethylene triamine, 36 mol of methanol, and 3.5 mol of pentaerythritol triacrylate were introduced into the hypergravity reactor. The hypergravity level of the hypergravity reactor was 500 g. Under the protection of nitrogen, the reaction was carried out at 30 ° C for 0.5. h, forming a prepolymer; wherein the molar ratio of diethylenetriamine to pentaerythritol triacrylate is 1: 3.5, and the mass of diethylenetriamine and pentaerythritol triacrylate accounts for 80% of the total mass of the reaction system.

(2) The methanol was removed at a temperature of 70 ° C., and then the temperature was raised to 160 ° C., and the reaction was performed for 0.5 h to obtain a hyperbranched PAMAM.

Example 14

(1) Introduce 1mol ethylenediamine, 11.3mol methanol and 3.5mol methyl acrylate into the hypergravity reactor. The hypergravity level of the hypergravity reactor is 200g. Under the protection of nitrogen, the reaction is carried out at 25 ° C for 4h. A prepolymer is formed; wherein the molar ratio of ethylenediamine to methyl acrylate is 1: 3.5, and the mass of ethylenediamine and methyl acrylate accounts for 50% of the total mass of the reaction system.

(2) The methanol was removed at a temperature of 60 ° C., and then the temperature was raised to 160 ° C., and the reaction was performed for 1 h to obtain a hyperbranched PAMAM.

Comparative Example 2

(1) Dissolve 1 mol of ethylenediamine and 3.5 mol of methyl acrylate in 11.3 mol of methanol and add it to the reaction kettle. Under nitrogen protection, react at room temperature (25 ° C) for 10 hours, and then reduce the pressure at 60 ° C Distillation to obtain a prepolymer;

(2) The temperature was raised to 160 ° C, and the reaction was performed for 5 hours to obtain hyperbranched PAMAM.

3.Preparation of hyperbranched polyester

Example 15

(1) Add 1.5 mol of glycerol, 0.1 mol of oxalic acid and 4.6 mol of methanol to the hypergravity reactor, and add p-0.1% toluenesulfonic acid to it. The hypergravity level of the hypergravity reactor is 5g, protected under nitrogen. Next, prepolymerize at a temperature of -10 ° C for 10 hours to form a polymerized monomer; wherein the molar ratio of the glycerol to the oxalic acid is 15: 1;

(2) The temperature is then raised to 20 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions. When the reaction is performed for 24 hours, a hyperbranched polyester is obtained.

Example 16

(1) 0.15 mol of 1, 2, 4-butanetriol, 1 mol of acetic anhydride and 2.6 mol of ethanol were added to the hypergravity reactor, and 2.5% butyl titanate was added thereto. The hypergravity level of the hypergravity reactor was 150 g, under nitrogen protection, at 55 ° C. for 5 h to pre-polymerize to form a polymerized monomer; wherein the molar ratio of the 1,2,4-butanetriol to the acetic anhydride is 15: 100;

(2) The temperature is then raised to 115 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions. When the reaction is performed for 12 hours, a hyperbranched polyester is obtained.

Example 17

(1) 0.1 mol of 1, 2, 4-butanetriol, 0.05 mol of pentaerythritol, 2.25 mol of acetic anhydride, and 5.4 mol of ethanol are added to a hypergravity reactor, and 5% stannous chloride is added to the hypergravity reactor. The supergravity level is 300g, under the protection of nitrogen, at a temperature of 120 ° C and reacted for 0.1h to prepolymerize to form a polymerized monomer; wherein the added amount of the 1,2,4-butanetriol and pentaerythritol and the acetic anhydride The molar ratio of the added amount is 15: 225;

(2) The temperature is then increased to 250 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions. When the reaction is performed for 0.1 h, a hyperbranched polyester is obtained.

Example 18

(1) Add 1mol 1,2,4-butanetriol, 5mol metaphthalic anhydride and 23.2mol ethanol to the hypergravity reactor, and add 5% stannous chloride to it, the hypergravity level of the hypergravity reactor 300 g, under nitrogen protection, at 60 ° C. for 2 h to pre-polymerize to form a polymerized monomer; wherein the molar amount of the 1,2,4-butanetriol added and the molar amount of the metaphthalic anhydride added The ratio is 1: 5;

Comparative Example 3

1 mol of 1, 2, 4-butanetriol and 5 mol of metaphthalic anhydride were added to the reactor, and 5% stannous chloride was added thereto. The reaction was performed at 60 ° C for 4 hours under the protection of nitrogen. Monomer; then the temperature is increased to 250 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 8 hours to prepare a hyperbranched polyester.

4. Preparation of hyperbranched polyester amide

Example 19

(1) Add 1.5 mol of diethanolamine, 0.1 mol of succinic acid and 2.8 mol of propanol to the hypergravity reactor, and add 2% dibutyltin dilaurate. The hypergravity level of the hypergravity reactor is 2g. Under the protection of nitrogen gas, it is prepolymerized at -10 ° C for 10 hours to form a polymerization monomer; wherein the molar ratio of the added amount of the diethanolamine to the succinic acid is 15: 1;

(2) The temperature is then raised to 20 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 24 hours to obtain a hyperbranched polyester amide.

Example 20

(1) Add 0.3mol of 2-amino-1,3-propanediol, 2mol of acetic anhydride and 4mol of propanol to the supergravity reactor, and add 3% butyl titanate to it, the supergravity level of the supergravity reactor It is 100g, and under the protection of nitrogen gas, it is prepolymerized at 55 ° C. for 5 hours to form a polymerization monomer; wherein the molar ratio of the added amount of 2-amino-1,3-propanediol to the acetic anhydride is 15: 100;

(2) The temperature is then raised to 115 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 12 hours to obtain a hyperbranched polyester amide.

Example 21

(1) Add 0.15mol of diisobutanolamine, 2.25mol of terephthalic acid and 6.5mol of propanol to the hypergravity reactor, and add 4% butyl titanate to the hypergravity reactor. It is 200g, and under the protection of nitrogen gas, it is prepolymerized at 120 ° C and reacted for 0.1h to form a polymerization monomer; wherein the molar ratio of the added amount of the diisobutanolamine and the terephthalic acid is 15: 225 ;

(2) The temperature is then increased to 250 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions for 0.1 h to obtain a hyperbranched polyester amide.

Example 22

(1) Add 2mol diethanolamine, 3mol succinic acid and 9.4mol propanol to the hypergravity reactor, and add 2.5% butyl titanate to it. The supergravity level of the hypergravity reactor is 2g. Under gas protection, at 80 ° C. for 1 h, the polymer is first prepolymerized to form a polymerized monomer; wherein the molar ratio of the added amount of the diethanolamine to the succinic acid is 2: 3;

(2) The temperature is then raised to 150 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 1 hour to obtain a hyperbranched polyester amide.

Example 23

(1) Add 5 mol of methyl acrylate, 5 mol of diethanolamine, and 30 mol of methanol to a hypergravity reactor. Add 3% p-toluenesulfonic acid. The hypergravity level of the hypergravity reactor is 10g. Under the protection of nitrogen, At 50 ° C for 2h, the polymer is first prepolymerized to form a polymerized monomer; wherein the molar ratio of the methyl acrylate to the diethanolamine is 1: 1;

(2) The temperature is increased to 100 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 0.5 h to obtain a yellow viscous hyperbranched polyesteramine.

Comparative Example 4

2mol of diethanolamine and 3mol of adipic acid were added to the reaction kettle, and a catalyst of butyl titanate with a total mass of 2.5% of the raw material was added thereto. The reaction was performed at 80 ° C for 2 hours under the protection of argon gas, and then prepolymerized. Polymerized monomers are formed; then the temperature is raised to 150 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions. The reaction is performed for 12 hours to prepare a hyperbranched polyester amide.

5.Preparation of hyperbranched polyetherester

Example 24

(1) 3 mol of polyethylene glycol, 0.3 mol of malonic acid and 3.3 mol of n-butanol are added to a hypergravity reactor, the hypergravity level of the hypergravity reactor is 10 g, and then 0.5% p-toluene is added thereto. Sulfonic acid, under the protection of argon gas, was slowly heated to 20 ° C. and reacted for 24 hours to prepolymerize to form a polymerized monomer; wherein the molar ratio of the polyethylene glycol to the malonic acid was 1: 0.1;

(2) The temperature is increased to 40 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 24 hours to obtain a hyperbranched polyether ester.

Example 25

(1) adding 0.5 mol of polypropylene glycol, 5 mol of trimellitic anhydride, and 11.3 mol of ethanol to a hypergravity reactor having a hypergravity level of 200 g, and then adding 1.5% p-toluenesulfonic acid thereto, Under the protection of argon gas, the temperature was slowly raised to 80 ° C. and the reaction was carried out for 12 h to form a polymerization monomer; wherein the molar ratio of the polypropylene glycol to the trimellitic anhydride was 1:10;

(2) The temperature is increased to 145 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 12 hours to obtain a hyperbranched polyether ester.

Example 26

(1) 0.5 mol of polyhexanediol, 10 mol of pyromellitic anhydride and 25 mol of ethanol were added to a hypergravity reactor, and the hypergravity level of the hypergravity reactor was 400 g, and then 2.5% p-toluenesulfonic acid was added thereto. Under the protection of argon gas, the acid is slowly heated to 140 ° C. and reacted for 1 hour to prepolymerize to form a polymerized monomer; wherein the molar ratio of the polyhexanediol to the pyromellitic anhydride is 1:20;

(2) The temperature is increased to 250 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 0.5 h to obtain a hyperbranched polyether ester.

Example 27

(1) Add 3mol of PEG400, 3mol of malonic acid and 23.4mol of n-butanol to a hypergravity reactor, the hypergravity level of the hypergravity reactor is 10g, and then add 0.1% stannous octoate to the Under gas protection, slowly raise the temperature to 60 ° C. and react for 2 h to pre-polymerize to form a polymerized monomer; wherein the molar ratio of the PEG400 to the malonic acid is 1: 1;

(2) The temperature is increased to 240 ° C., and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions, and the reaction is performed for 0.5 h to obtain a hyperbranched polyether ester.

Comparative Example 5

Add 3mol of malonic acid, 3mol of PEG400 and stannous octoate to the reaction kettle, slowly increase the temperature to 60 ° C under the protection of argon, and react for 12h to obtain the pre-polymerized monomer, then raise the temperature to 240 ° C, polymerize for 4h, vacuum treat the product, and obtain The brown transparent solid is a hyperbranched polyether ester, and the amount of stannous octoate added is 0.1% of the total mass of the raw materials.

Comparison of experimental results

Table 1 Comparison of experimental results between the examples and comparative examples

As can be seen from Table 1, compared with the traditional production method, the dendritic or hyperbranched polymer prepared by the hypergravity technology in this application can shorten the reaction time by 6 to 8 times, greatly improving the reaction rate, saving energy, and shortening. Response cycle, improve production efficiency and reduce production costs.

The above are only the preferred embodiments of the present application, and are not intended to limit the present application in any other form. Any person skilled in the art may use the disclosed technical content to change or modify the equivalent equivalent. The embodiments are applied in other fields, but as long as they do not depart from the technical solution of the present application, any simple modifications, equivalent changes, and modifications made to the above embodiments according to the technical essence of the present application still belong to the protection scope of the technical solution of the present application.

Claims

A method for preparing a dendritic or hyperbranched polymer, which is characterized in that each component of the reaction system is added to a hypergravity reactor, and the reaction temperature is controlled to be 0 to 250 ° C, and the hypergravity level is (2 to 500) × g, g is the acceleration of gravity, and a dendritic or hyperbranched polymer having the following molecular formula is prepared:

among them:

[C] means nuclear;

Nc is the multiplicity of the kernel, and Nc is a positive integer;

[FF] represents the functional group of the core, X is the total number of functional groups of the core [FF], where X is a positive integer multiple of 0 or 1 to Nc-1, and when X is not equal to 0, [FF] is -OH , -NH 2 ,
Or one or more of -COOH;

[BR] represents a branching unit, P is the total number of branching units [BR], where P is 0 or a positive integer, and when p is greater than 1, [BR] is a plurality of identical or different branching units;

[IF] represents internal functional groups, q is the total number of internal functional groups [IF], where q is 0 or a positive integer, when q is greater than 1, then [IF] is a plurality of the same or different internal functional groups; [IF] is

One or more of them;

[EX] represents a chain extender, m is the total number of chain extenders [EX], where m is 0 or a positive integer, and when m is greater than 1, [EX] is a plurality of identical or different chain extenders;

[TF] represents terminal functional groups, z is the total number of terminal functional groups [TF], where z is 0 or a positive integer, and when z is greater than 1, [TF] is a plurality of identical or different terminal functional groups;

When both p and m are greater than 1, [BR] and [EX] are connected alternately or multiple [BR] are connected and then connected with multiple [EX].
The preparation method according to claim 1, wherein when [IF] is
, The method for preparing the dendritic polymer includes the following steps:

The polyamine monomer, solvent, and acrylate monomer are introduced into the hypergravity reactor. Under the protection of an inert gas, the reaction is carried out at a temperature of 0 to 80 ° C and a hypergravity level of (5 to 500) × g. From 1 to 14 hours, G-0.5-terminated terminal dendritic polyamide amine polymers are formed;

The G-0.5-terminated ester-terminated dendritic polyamide amine polymer, solvent, and polyamine monomer were introduced into a hypergravity reactor, and the above reaction was repeated under the protection of an inert gas to generate a G0-terminated amino-terminated dendrimer. Amidoamine polymers;

The G0-terminated amino-terminal dendritic polyamide amine polymer, solvent, and acrylate monomers are introduced into a hypergravity reactor, and the above reaction is repeated under the protection of an inert gas to generate G0.5-generation dendritic polyamide amine polymerization. Thing

By analogy, a GN-generation dendritic polyamide amine polymer is obtained, where N = n × 0.5, and n is −1.0 or a positive integer.
The preparation method according to claim 2, wherein in the step of obtaining a G-0.5-terminated ester-group dendritic polyamide amine polymer, the polyamine monomer and the acrylate monomer The molar ratio is 1: (4 to 40);

In the step of obtaining a G0-terminated amino-terminated dendritic polyamide amine polymer, the molar ratio of the G-0.5-terminated ester-terminated dendritic polyamide amine polymer to the polyamine monomer is 1 :( 4 to 40);

In the step of obtaining a G0.5-terminated ester-terminated dendritic polyamide amine polymer, the molar ratio of the G0-terminated amino-terminated dendritic polyamide amine polymer to the acrylate monomer is 1 :( 8 ~ 80);

By analogy, for the synthesis of the entire generation of amino-terminated dendritic polyamide amine polymers with N being an integer, the moles of the semi-terminated ester-based dendritic polyamide amine polymers and the polyamine monomers in the reactants The ratio is 1: (4 × 2 N ～ 40 × 2 N ). For the synthesis of half-generation ester-terminated dendritic polyamide amine polymers in which N is a non-integer, polyamine monomers or whole generation terminals in the reaction The molar ratio of the amino dendritic polyamide amine polymer to the acrylate monomer is 1: (4 × 2 N + 0.5 to 40 × 2 N + 0.5 ).
The preparation method according to claim 1, wherein when [IF] is
, The method for preparing the hyperbranched polymer includes the following steps:

The polyamine monomer, solvent, and acrylate monomer were introduced into the hypergravity reactor. Under the protection of an inert gas, the reaction was carried out at a temperature of 0-30 ° C and a hypergravity level of (5 to 500) × g. 0.5 ～ 12h, forming prepolymer;

The solvent is removed at a temperature of 40 to 70 ° C, and then the temperature is raised to 80 to 160 ° C, and the reaction is performed for 0.5 to 5 hours to obtain a hyperbranched polyamide amine polymer.
The method according to claim 4, wherein a molar ratio of the polyamine monomer to the acrylate monomer is 1: (1 to 3.5).
The method according to claim 2 or 4, wherein the polyamine monomer comprises ethylenediamine, propylenediamine, succindiamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine Amine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, piperazine, N-aminoethyl One or more of piperazine, polyethylene polyamine, melamine; the acrylate monomers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate One or more of butyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate.
The preparation method according to claim 1, wherein when [IF] is

, Including the following steps:

Prepolymerization reaction: Polyol, polycarboxylic acid / polyacid anhydride and solvent are introduced into a hypergravity reactor, and the hypergravity level of the hypergravity reactor is (2 to 400) × g, and then a catalyst is added thereto. Under the protection of an inert gas, at a temperature of -10 to 140 ° C, the reaction is performed for 0.1 to 24 hours to prepolymerize to form a polymerized monomer;

Polymerization reaction: The temperature is increased to 20-250 ° C, and then the reaction system is evacuated, and the polymerization reaction is performed under vacuum conditions. The reaction time is 0.1-24 hours to obtain a dendritic or hyperbranched polymer.
The preparation method according to claim 7, characterized in that when [IF] is
At this time, the hypergravity level of the hypergravity reactor is (5 to 300) × g, the temperature of the prepolymerization reaction is -10 to 120 ° C, and the reaction time is 0.1 to 10h. The obtained dendritic or hyperbranched polymer is prepared It is a dendritic or hyperbranched polyester.
The method according to claim 8, wherein the polyhydric alcohol comprises glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, Tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol, bis (trimethylolpropane), bis (pentaerythritol), tris (hydroxymethyl) Base) isocyanurate, tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, glyceryl ricinoleate (castor oil), inositol, sugar, sugar alcohol One or more of them.
The preparation method according to claim 7, characterized in that when [IF] is

At this time, the hypergravity level of the hypergravity reactor is (2 to 200) × g, the temperature of the prepolymerization reaction is -10 to 120 ° C, and the reaction time is 0.1 to 10h. The obtained dendritic or hyperbranched polymer is prepared It is a dendritic or hyperbranched polyester amide or polyester amine.
The method according to claim 10, wherein the polyhydric alcohol is an amino alcohol having at least one amino group and at least two hydroxyl groups, and the amino alcohol includes diethanolamine, dipropanolamine, and diisopropanolamine. , 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, dibutanolamine, diisobutanolamine, bis (2-hydroxy-1- One or more of butyl) amine, bis (2-hydroxy-1-propyl) amine, and dicyclohexanolamine.
The preparation method according to claim 8 or 10, wherein a molar ratio of the added amount of the polyhydric alcohol to the polycarboxylic acid / polyacid anhydride is 15: (1 to 225); the polycarboxylic acid / Polybasic anhydride includes oxalic acid, citric acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, acetic anhydride, succinic anhydride, phthalic acid, isophthalic acid , Terephthalic acid, phthalic anhydride, metaphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ether tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, biphenyl tetra One or more of formic dianhydride and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride.
The preparation method according to claim 7, characterized in that when [IF] is
When the polyol is a polyether polyol, the hypergravity level of the hypergravity reactor is (10 to 400) × g, the temperature of the prepolymerization reaction is 20 to 140 ° C, and the reaction time is 1 to 24 hours; polymerization The reaction temperature is from 40 ° C to 250 ° C, and the reaction time is from 0.5 to 24 hours. A dendritic or hyperbranched polyether ester is prepared.
The preparation method according to claim 13, characterized in that the molar ratio of the polyether polyol to the polycarboxylic acid / polyacid anhydride is 1: (0.1 to 20); the polyether polyol includes a shrinkage Diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentylene glycol and polyhexanediol, polyglyceryl ether, trimethylolpropane polyether, polypentaerythritol, poly One or more of xylitol, polysorbate, and polysucrose; the polycarboxylic acid includes malonic acid; the polyanhydride includes trimellitic anhydride, pyromellitic anhydride, and diphenyl ether tetramethyl One or more of acid anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic dianhydride, and 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride.
A dendritic or hyperbranched polymer prepared by the preparation method according to any one of claims 1-5, 7-11, and 13-14.