CN111100292A - Preparation method of high molecular weight branched polyethyleneimine - Google Patents
Preparation method of high molecular weight branched polyethyleneimine Download PDFInfo
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- CN111100292A CN111100292A CN202010008056.7A CN202010008056A CN111100292A CN 111100292 A CN111100292 A CN 111100292A CN 202010008056 A CN202010008056 A CN 202010008056A CN 111100292 A CN111100292 A CN 111100292A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
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Abstract
The invention discloses a preparation method of high molecular weight branched polyethyleneimine. The low-temperature-resistant polyester resin is prepared by carrying out low-temperature polymerization on aliphatic polyamide with a branched structure, ethylene imine and a compound shown in a formula (I) in an aqueous solution. The high molecular weight branched polyethyleneimine prepared by the invention has a branched structure and high molecular weight, and is obtained by low-temperature polymerization. The high molecular weight branched polyethyleneimine prepared by the invention maintains the characteristics of polyethyleneimine, and introduces high reactivity of primary amine and secondary amine groups and lipophilicity of ethylene oxide and propylene oxide block polyoxyethylene ether chain segments.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of high molecular weight branched polyethyleneimine, which is suitable for the fields of papermaking, spinning, environmental protection and the like.
Background
The branched polyethyleneimine has good hydrophilic performance; simultaneously contains primary amine, secondary amine and tertiary amine groups, and can form adsorption with various surfaces; meanwhile, the primary amine and secondary amine groups can endow the polyethyleneimine with high reactivity. The polymerization of high molecular weight branched polyethylenimine disclosed in the prior art is relatively complicated in condition control and not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of high molecular weight branched polyethyleneimine, which has a branched structure and high molecular weight and is obtained by low-temperature polymerization.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of high molecular weight branched polyethyleneimine is prepared by carrying out low-temperature polymerization reaction on aliphatic polyamide with a branched structure, polyethyleneimine and a compound shown as a formula (I) in an aqueous solution;
the molar mass of the high molecular weight branched polyethyleneimine is Mw700000-; preferably, Mw＝1000000-2000000；
The structural formula of the compound of formula (I) is:
R-A-(EO)n-(PO)m-A-R (I)
wherein R is epoxy group, A is OCH2Or CH2EO is an ethylene oxide unit, PO is a propylene oxide unit, n is 1 to 60, and m is 1 to 50.
Further, in the above preparation method, the structural formula of the compound of formula (I) is:
wherein n is 1-60, and m is 1-50.
Further, the preparation method comprises the following steps: sequentially adding aliphatic polyamide with a branched structure, distilled water and a catalyst into a reaction kettle, starting stirring, heating the reaction system to 50-60 ℃, dropwise adding an ethylene imine aqueous solution into the reaction system by using a constant flow pump, controlling the dropwise adding time to be 3-4 hours, preserving heat for 1-1.5 hours at 50-60 ℃ after the dropwise adding is finished, then dropwise adding the compound shown in the formula (I) into the reaction system by using the constant flow pump until the viscosity of the obtained reactant is 300-500 mpa.s, preserving heat for 30-40 minutes at 50-60 ℃, and cooling to obtain the high molecular weight branched polyethylene imine.
Further, in the above production method, the amount of the ethyleneimine added is 5 to 20 times the number of moles of the amine groups in the aliphatic polyamide having a branched structure.
Further, in the above production method, the molar addition amount of the ethyleneimine is 5 to 10 times the molar number of the amine group in the aliphatic polyamide having a branched structure.
Further, in the above preparation method, the aliphatic polyamide with a branched structure is prepared by polycondensation of polyamine and a dibasic organic carboxylic acid, and the molar mass of the aliphatic polyamide with a branched structure is Mw 8000 ═ 5000-.
Further, in the above preparation method, the polyamine is one or a combination of two or more of triethanolamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Further, in the above preparation method, the organic dicarboxylic acid is one or a combination of two or more of maleic acid, adipic acid, glutaric acid, malonic acid and sebacic acid.
Further, in the above preparation method, the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid or acetic acid.
Further, in the above preparation method, the molar mass of the compound of formula (I) is Mw1500-3000, the epoxy capping rate is more than or equal to 95 percent, and n: m is 2:1-1: 2.
The invention has the beneficial effects that: the polyethyleneimine prepared by the invention has a branched structure, and simultaneously has high molecular weight and molar mass Mw700000-2000000, the hydrophobic chain segment of ethylene oxide and propylene oxide block polyether is introduced into the PEI chain segment with good hydrophilic effect, so that the application of polyethyleneimine in the oil field can be expanded. The method has simple preparation process and is easy to master.
Detailed Description
A preparation method of high molecular weight branched polyethyleneimine comprises the following steps: sequentially adding aliphatic polyamide with a branched structure, distilled water and a catalyst into a reaction kettle, starting stirring, heating the reaction system to 50-60 ℃, dropwise adding an ethylene imine aqueous solution into the reaction system by using a constant flow pump, controlling the dropwise adding time to be 3-4 hours, preserving heat for 1-1.5 hours at 50-60 ℃ after the dropwise adding is finished, then dropwise adding the compound shown in the formula (I) into the reaction system by using the constant flow pump until the viscosity of the obtained reactant is 300-500 mpa.s, preserving heat for 30-40 minutes at 50-60 ℃, and cooling to obtain the high molecular weight branched polyethylene imine.
The aliphatic polyamide with the branched structure is prepared by performing polycondensation reaction on polyamine and dibasic organic carboxylic acid, and the molar mass of the aliphatic polyamide with the branched structure is Mw (5000-. The polyamine is one or the combination of more than two of triethanolamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine. The dibasic organic carboxylic acid is one or the combination of more than two of maleic acid, adipic acid, glutaric acid, malonic acid and sebacic acid.
Preferably, the amount of the ethyleneimine added is 5 to 20 times the number of moles of the amine group in the aliphatic polyamide having a branched structure. More preferably, the molar addition amount of the ethyleneimine is 5 to 10 times the number of moles of the amine group in the aliphatic polyamide having a branched structure.
The structural formula of the compound of formula (I) is as follows:
R-A-(EO)n-(PO)m-A-R (I)
wherein R is epoxy group, A is OCH2Or CH2EO is an ethylene oxide unit, PO is a propylene oxide unit, n is 1 to 60, and m is 1 to 50.
Preferably, the compound of formula (I) has the structural formula:
wherein n is 1-60, and m is 1-50.
The compound of formula (I) has a molar mass Mw1500-3000, the epoxy capping rate is more than or equal to 95 percent, and n: m is 2:1-1: 2. Preferably, n: m ═ 2:1 to 1:1.
The molar mass of the high molecular weight branched polyethyleneimine is Mw700000-; preferably, Mw＝1000000-2000000。
The catalyst is concentrated sulfuric acid, concentrated hydrochloric acid or acetic acid.
Example 1
A process for the preparation of high molecular weight branched polyethylenimine (a1), comprising the steps of:
preparation of aliphatic polyamide-PA 1 with branched structure
Adding diethylenetriamine and deionized water into a reaction kettle according to the molar ratio of adipic acid to diethylenetriamine to deionized water of 1:1.1:3, adding adipic acid into the reaction kettle for 6 times, controlling the temperature of the reaction kettle not to exceed 70 ℃ in the process of adding adipic acid, starting heating and dehydrating after the addition is finished, controlling the reaction temperature to be 170-140 ℃, keeping the temperature for 2h after the dehydration is finished, cooling the reaction kettle to 130-140 ℃, starting slowly adding a certain amount of deionized water into the reaction kettle, stirring uniformly, and discharging to obtain an aliphatic polyamide aqueous solution with 60% of solid content and a branched structure, wherein the aliphatic polyamide aqueous solution is marked as PA 1.
Mw was 5000 by GPC (reverse osmosis gel chromatography).
(II) the compound of formula (I) is
Where n is 20, m is 10, Mw is 1600, and is denoted KF-15.
(III) preparation of high molecular weight branched polyethylenimine
Adding 800g (amino content is 0.3mol) PA1, 160g distilled water and 10g concentrated sulfuric acid into a reaction kettle, starting stirring, heating the reaction system to 50-60 ℃, dropwise adding 250g of 50 wt% ethylene imine aqueous solution (ethylene imine content is 3mol) into the reaction system by using a constant flow pump, controlling the dropwise adding time to be 3-4 hours, and keeping the temperature at 50-60 ℃ for 1 hour after the dropwise adding is finished. And then dripping a KF-15 aqueous solution with the concentration of 10 wt% into the reaction system by using a constant flow pump until the viscosity of reactants obtained in the reaction kettle reaches 300-500 mpa.s (25 ℃, rotational viscosity), preserving the temperature for 30 minutes at 50-60 ℃, cooling and discharging to obtain high molecular weight branched polyethyleneimine, which is recorded as A1.
(IV) detection
The weight-average molecular weight (Mw) of the high molecular weight branched polyethyleneimine A1 of the obtained product was 1000000g/moL as determined by GPC (reverse osmosis gel chromatography).
Example 2
A process for the preparation of high molecular weight branched polyethylenimine (a2), comprising the steps of:
preparation of aliphatic polyamide-PA 1 with branched structure
The preparation method is the same as that of example 1
(II) the compound of formula (I) is
Wherein n is 30, m is 30, Mw is 3000, and is marked as KF-30
(III) preparation of high molecular weight branched polyethylenimine
Adding 800g (amino content is 0.3mol) PA1, 160g distilled water and 10g concentrated sulfuric acid into a reaction kettle, starting stirring, heating the reaction system to 50-60 ℃, dropwise adding 250g of 50 wt% ethylene imine aqueous solution (ethylene imine content is 3mol) into the reaction system by using a constant flow pump, controlling the dropwise adding time to be 3-4 hours, and keeping the temperature at 50-60 ℃ for 1 hour after the dropwise adding is finished. And then dripping a KF-30 aqueous solution with the concentration of 10 wt% into the reaction system by using a constant flow pump until the viscosity of reactants obtained in the reaction kettle reaches 300-500 mpa.s (25 ℃, rotational viscosity), preserving the temperature for 30 minutes at 50-60 ℃, cooling and discharging to obtain high molecular weight branched polyethyleneimine, which is recorded as A2.
(IV) detection
The weight average molecular weight (Mw) of the resulting high molecular weight branched polyethyleneimine A2 was determined to be 1500000g/moL by GPC (reverse osmosis gel chromatography).
Example 3
A process for the preparation of high molecular weight branched polyethylenimine (a3), comprising the steps of:
preparation of aliphatic polyamide-PA 2 with branched structure
Putting triethylene tetramine and deionized water into a reaction kettle according to the molar ratio of adipic acid to triethylene tetramine to deionized water of 1:1.1:3, adding adipic acid into the reaction kettle for 6 times, controlling the temperature of the reaction kettle to be not more than 70 ℃ in the process of adding adipic acid, starting to raise the temperature and dehydrate after the addition is finished, controlling the reaction temperature to be 170-140 ℃, keeping the temperature for 2 hours after the dehydration is finished, cooling the reaction kettle to 130-140 ℃, starting to slowly add a certain amount of deionized water into the reaction kettle, stirring uniformly, discharging to obtain an aliphatic polyamide aqueous solution with a solid content of 60% and a branched structure, and marking as PA 2.
Mw was 8000 by GPC (reverse osmosis gel chromatography).
(II) Compounds of formula (I)
Where n is 20, m is 10, Mw is 1600, and is denoted KF-15.
(III) preparation of high molecular weight branched polyethylenimine
Adding 800g (amino content is 0.4mol) PA2, 160g distilled water and 10g concentrated sulfuric acid into a reaction kettle, starting stirring, heating the reaction system to 50-60 ℃, dropwise adding 360g of 50 wt% ethylene imine aqueous solution (ethylene imine content is 4mol) into the reaction system by using a constant flow pump, controlling the dropwise adding time to be 3-4 hours, and keeping the temperature at 50-60 ℃ for 1 hour after the dropwise adding is finished. And then dripping a KF-15 aqueous solution with the concentration of 10 wt% into the reaction system by using a constant flow pump until the viscosity of reactants obtained in the reaction kettle reaches 300-500 mpa.s (25 ℃, rotational viscosity), preserving the temperature for 30 minutes at 50-60 ℃, cooling and discharging to obtain high molecular weight branched polyethyleneimine, which is recorded as A3.
(IV) detection
The weight average molecular weight (Mw) of the resulting high molecular weight branched polyethyleneimine A2 was determined to be 750000g/moL by GPC (reverse osmosis gel chromatography).
Claims (10)
1. A preparation method of high molecular weight branched polyethyleneimine is characterized in that the high molecular weight branched polyethyleneimine is prepared by low-temperature polymerization reaction of aliphatic polyamide with a branched structure, the polyethyleneimine and a compound shown as a formula (I) in an aqueous solution;
the molar mass of the high molecular weight branched polyethyleneimine is Mw＝700000-2000000；
The structural formula of the compound of formula (I) is:
R-A-(EO)n-(PO)m-A-R (I)
wherein R is epoxy group, A is OCH2Or CH2EO is an ethylene oxide unit, PO is a propylene oxide unit,n＝1-60，m＝1-50。
2. the process of claim 1, wherein the compound of formula (I) has the formula:
wherein n is 1-60, and m is 1-50.
3. The method of claim 1 or 2, comprising the steps of: sequentially adding aliphatic polyamide with a branched structure, distilled water and a catalyst into a reaction kettle, starting stirring, heating the reaction system to 50-60 ℃, dropwise adding an ethylene imine aqueous solution into the reaction system by using a constant flow pump, controlling the dropwise adding time to be 3-4 hours, preserving heat at 50-60 ℃ for 1-1.5 hours after the dropwise adding is finished, then dropwise adding the compound shown in the formula (I) into the reaction system by using the constant flow pump until the viscosity of the obtained reactant is 300-500 mpa.s, preserving heat at 50-60 ℃ for 30-40 minutes, and cooling to obtain the high molecular weight branched polyethylene imine.
4. The process according to claim 3, wherein the amount of the ethyleneimine added is 5 to 20 times the number of moles of the amine groups in the aliphatic polyamide having a branched structure.
5. The process according to claim 4, wherein the molar amount of the ethyleneimine added is 5 to 10 times the molar amount of the amine group in the aliphatic polyamide having a branched structure.
6. The production method according to claim 3, wherein the aliphatic polyamide having a branched structure is obtained by polycondensation of a polyamine and a dibasic organic carboxylic acid, and the molar mass of the aliphatic polyamide having a branched structure is Mw 8000 ═ 5000-.
7. The method according to claim 6, wherein the polyamine is one or a combination of two or more of triethanolamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
8. The method according to claim 6, wherein the organic dicarboxylic acid is one or a combination of two or more of maleic acid, adipic acid, glutaric acid, malonic acid and sebacic acid.
9. The method according to claim 3, wherein the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid, or acetic acid.
10. The process according to claim 3, wherein the compound of formula (I) has a molar mass Mw1500-3000, the epoxy capping rate is more than or equal to 95 percent, and n: m is 2:1-1: 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111732733A (en) * | 2020-07-17 | 2020-10-02 | 辽宁科隆精细化工股份有限公司 | Polyethyleneimine and polyether double-modified polyamide dendrimer compound and preparation method and application thereof |
| CN112457591A (en) * | 2020-11-25 | 2021-03-09 | 江苏金发科技新材料有限公司 | Laser-weldable long glass fiber reinforced polypropylene composite material with good air tightness and preparation method thereof |
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Cited By (2)
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| CN112457591A (en) * | 2020-11-25 | 2021-03-09 | 江苏金发科技新材料有限公司 | Laser-weldable long glass fiber reinforced polypropylene composite material with good air tightness and preparation method thereof |
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Application publication date: 20200505 |