CN111732733B - Polyethyleneimine and polyether double-modified polyamide dendrimer compound and preparation method and application thereof - Google Patents
Polyethyleneimine and polyether double-modified polyamide dendrimer compound and preparation method and application thereof Download PDFInfo
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- CN111732733B CN111732733B CN202010691739.7A CN202010691739A CN111732733B CN 111732733 B CN111732733 B CN 111732733B CN 202010691739 A CN202010691739 A CN 202010691739A CN 111732733 B CN111732733 B CN 111732733B
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
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Abstract
The invention discloses an ethylene imine and polyether double-modified polyamide dendrimer compound and a preparation method and application thereof. The dendrimer compound is prepared from aliphatic polyamide, ethylene imine and allyl polyether through Michael addition reaction. According to the prepared ethyleneimine and polyether double-modified polyamide dendrimer compound, the ethyleneimine and polyether groups are introduced into the main chain and the side chain of the polyamide, so that the characteristics of the polyamide are retained, and the anchoring property of the ethyleneimine and the hydrophilicity of the polyether are improved. The polyamide dendrimers obtained by the method can be used as retention aids for papermaking.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of an ethyleneimine and polyether double-modified polyamide dendrimer compound, in particular to an additive suitable for papermaking raw materials, such as a retention aid used in the papermaking industry.
Background
The polyamide dendrimer can be used as a retention aid in the papermaking industry because the polyamide dendrimer has a branch structure and can absorb fillers such as calcium carbonate. However, polyamide is hydrophobic, requires emulsification when used, and causes secondary pollution to pulp.
Disclosure of Invention
The invention aims to provide a preparation method of an ethylene imine and polyether double-modified polyamide dendrimer compound. According to the polyethyleneimine and polyether double-modified polyamide dendrimer compound prepared by the method, the polyethyleneimine and polyether groups are introduced into the polyamide structure, so that the polyamide dendrimer has hydrophilicity, and emulsification is not required during use.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: an ethylene imine and polyether dual-modified polyamide dendrimer compound is prepared from aliphatic polyamide, ethylene imine and allyl polyether through Michael addition reaction in aqueous solution.
Further, the aliphatic polyamide is prepared from dihexyltriamine and a dicarboxylic acid through a polycondensation reaction.
Further, in the above-mentioned ethyleneimine and polyether double-modified polyamide dendrimer compound, the dibasic organic carboxylic acid is maleic acid, adipic acid, glutaric acid, malonic acid or sebacic acid.
Furthermore, in the above-mentioned polyimide and polyether double-modified polyamide dendrimer compound, the organic dicarboxylic acid is adipic acid.
Further, the above-mentioned ethyleneimine and polyether double-modified polyamide dendrimer compound, the allyl polyether has a structural formula shown in (I):
R-A-(EO)n-A-R (I)
wherein R is allyl or vinyl, A is-OCH2-or-CH2-EO is ethylene oxide units and n is 1-20.
Furthermore, in the above-mentioned polyimide and polyether double-modified polyamide dendrimer compound, R is vinyl, n is 8-14, and the allyl polyether has a structural formula shown in (ii);
a preparation method of an ethylene imine and polyether double-modified polyamide dendrimer compound comprises the following steps: adding aliphatic polyamide, distilled water and a catalyst into a reaction kettle in sequence, starting stirring, heating a reaction system to 80-90 ℃, 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 80-90 ℃ for 2 hours after the dropwise adding is finished, cooling the reaction system to 50-60 ℃, dropwise adding allyl polyether into the reaction system by using the constant flow pump, preserving heat at 50-60 ℃ for 30-40 minutes after the dropwise adding is finished, and cooling to obtain a target product.
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 catalyst is concentrated sulfuric acid.
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.
Further, in the above production method, the amount of ethyleneimine added is 5 to 10 times the molar number of amine groups in the aliphatic polyamide
The invention relates to an application of an ethylene imine and polyether dual-modified polyamide dendrimer compound as a retention aid in the paper industry.
The invention has the beneficial effects that: according to the prepared ethylene imine and polyether dual-modified polyamide, the ethylene imine and polyether units are introduced into the main chain and the branched chain of the polyamide while the characteristics of the polyamide are kept, so that the polyamide has a dendritic structure and has the anchoring property of the ethylene imine, the polyether is introduced into the polyamide, the molecular weight of the polyamide can be further improved, the polyamide has the hydrophilicity of the polyether, and the hydrophobicity of the polyamide is improved. The prepared polyethyleneimine and polyether dual-modified polyamide dendrimer has both a hydrophobic group and a hydrophilic group, has anchoring property and high reactivity, and can be used as a retention aid in the paper industry. The method has simple preparation process and is easy to master.
Detailed Description
A preparation method of an ethylene imine and polyether double-modified polyamide dendrimer compound comprises the following steps: adding aliphatic polyamide, distilled water and a catalyst into a reaction kettle in sequence, starting stirring, heating a reaction system to 80-90 ℃, 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 80-90 ℃ for 2 hours after the dropwise adding is finished, cooling the reaction system to 50-60 ℃, dropwise adding allyl polyether into the reaction system by using the constant flow pump, preserving heat at 50-60 ℃ for 30-40 minutes after the dropwise adding is finished, and cooling to obtain a target product.
In the preparation method, the aliphatic polyamide is prepared by condensation polymerization of dihexyltriamine and a dibasic organic carboxylic acid, and the molar mass of the aliphatic polyamide is Mw (5000-. The dibasic organic carboxylic acid is maleic acid, adipic acid, glutaric acid, malonic acid or sebacic acid. Preferably, the dibasic organic carboxylic acid is adipic acid.
In the above preparation method, the addition amount of the ethylene imine is 5 to 20 times of the mole number of the amine groups in the aliphatic polyamide. Preferably, the molar addition amount of the ethylene imine is 5 to 10 times the molar number of the amine groups in the aliphatic polyamide.
In the preparation method, the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid or acetic acid. Preferably, the catalyst is concentrated sulfuric acid.
In the above preparation method, the allyl polyether has a structural formula shown in (I):
R-A-(EO)n-A-R(I)
wherein R is allyl or vinyl, A is-OCH2-or-CH2-EO is ethylene oxide units and n is 1-20.
Preferably, R is vinyl, n is 8-14, and the allyl polyether has the formula shown in (ii):
example 1
Polyethyleneimine and polyether double-modified polyamide dendrimer compound-A1
The preparation method comprises the following steps
1. Preparation of aliphatic Polyamide having branched Structure-PA 1
Adding dihexyltriamine and deionized water into a reaction kettle according to the molar ratio of adipic acid to dihexyltriamine to deionized water of 1:1.1:3, wherein nitrogen protection is needed in the reaction process, adding adipic acid into the reaction kettle for 6 times at intervals of 30min every time, controlling the temperature of the reaction kettle not to exceed 70 ℃ in the process of adding adipic acid, and cooling by using circulating water if the temperature exceeds 70 ℃. And after the feeding is finished, heating for dehydration, controlling the reaction temperature at 170-140 ℃ for reaction for 8h, preserving the heat for 2h after the dehydration is finished, then cooling the reaction kettle to 130-140 ℃, slowly adding a certain amount of deionized water into the reaction kettle, uniformly stirring, discharging to obtain an aliphatic polyamide aqueous solution with the solid content of 60%, and recording as PA 1.
Mw was 8000 by GPC (reverse osmosis gel chromatography).
2. The structural formula of the polyether compound is as follows
Where n is 9 and Mw is 500, and is recorded as KLPG 5.
3. Preparation of ethyleneimine and polyether double-modified polyamide dendrimer compound
Adding 800g (amino content is 0.2mol) PA1, 160g distilled water and 10g concentrated sulfuric acid into a reaction kettle in sequence, starting stirring, heating the reaction system to 80-90 ℃, dropwise adding 160g of 50 wt% ethylene imine aqueous solution (ethylene imine content is 2mol) 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 80-90 ℃ for 2 hours after the dropwise adding is finished. And then cooling the reaction system to 50-60 ℃, dropwise adding 565g of 50 wt% KLPG5 aqueous solution into the reaction system by using a constant flow pump, preserving the temperature at 50-60 ℃ for 30 minutes after dropwise adding, cooling and discharging to obtain the polyethyleneimine and polyether double-modified polyamide dendrimer compound, which is marked as A1.
(II) detection
The weight average molecular weight (Mw) of the obtained product, namely the ethyleneimine and polyether double modified polyamide dendrimer compound A1 is 20000g/moL through GPC (reverse osmosis gel chromatography).
Example 2
Polyethyleneimine and polyether double-modified polyamide dendrimer compound-A2
The preparation method comprises the following steps:
1. preparation of aliphatic Polyamide having branched Structure-PA 1
The preparation method is the same as that of example 1
2. The structural formula of the polyether compound is as follows
Where n is 14 and Mw is 700, which is recorded as KLPG 7.
3. Preparation of ethyleneimine and polyether double-modified polyamide dendrimer compound
Adding 800g (amino content is 0.2mol) PA1, 160g distilled water and 10g concentrated sulfuric acid into a reaction kettle in sequence, starting stirring, heating the reaction system to 80-90 ℃, dropwise adding 160g of 50 wt% ethylene imine aqueous solution (ethylene imine content is 2mol) 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 80-90 ℃ for 2 hours after the dropwise adding is finished. And then cooling the reaction system to 50-60 ℃, dropwise adding 565g of 50 wt% KLPG7 aqueous solution into the reaction system by using a constant flow pump, preserving the temperature at 50-60 ℃ for 30 minutes after dropwise adding, cooling and discharging to obtain the polyethyleneimine and polyether double-modified polyamide dendrimer compound, which is marked as A2.
(II) detection
The weight average molecular weight (Mw) of the obtained product, namely the ethylene imine and polyether double modified polyamide dendrimer compound A2, is 40000g/moL according to GPC (reverse osmosis gel chromatography).
Example 3
Polyethyleneimine and polyether double-modified polyamide dendrimer compound-A3
The preparation method comprises the following steps:
1. preparation of aliphatic Polyamide having branched Structure-PA 1
The preparation method is the same as that of example 1
2. The structural formula of the polyether compound is as follows
Where n is 14 and Mw is 700, which is recorded as KLPG 7.
(III) preparing the ethyleneimine and polyether double-modified polyamide dendrimer compound
Adding 800g (amino content is 0.2mol) PA1, 160g distilled water and 10g concentrated sulfuric acid into a reaction kettle in sequence, starting stirring, heating the reaction system to 80-90 ℃, dropwise adding 160g of 50 wt% ethylene imine aqueous solution (ethylene imine content is 2mol) 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 80-90 ℃ for 2 hours after the dropwise adding is finished. And then cooling the reaction system to 50-60 ℃, dropwise adding 1130g of 50 wt% KLPG7 aqueous solution into the reaction system by using a constant flow pump, preserving the temperature at 50-60 ℃ for 30 minutes after dropwise adding, cooling and discharging to obtain the ethyleneimine and polyether double-modified polyamide dendrimer compound, which is recorded as A3.
(II) detection
The weight average molecular weight (Mw) of the obtained product, namely the ethylene imine and polyether double modified polyamide dendrimer compound A3, is 50000g/moL through GPC (reverse osmosis gel chromatography).
Example 4
The retention rates of the ethyleneimine and polyether double modified polyamide dendrimer compound A1-A3 prepared in examples 1-3 were measured by a dynamic drainage meter, and the results are shown in Table 1.
TABLE 1
| Polymers of the examples | Retention (%) |
| A1 | 88％ |
| A2 | 91％ |
| A3 | 90.5％ |
As can be seen from Table 1, the retention rate of the prepared ethyleneimine and polyether dual-modified polyamide dendrimer compound is 88-91%, and the compound can be used as an additive of papermaking raw materials, in particular as a retention aid in the papermaking industry.
Claims (3)
1. A preparation method of an ethylene imine and polyether double-modified polyamide dendrimer compound is characterized by comprising the following steps: sequentially adding aliphatic polyamide with a branched structure, distilled water and a catalyst into a reaction kettle, starting stirring, heating a reaction system to 80-90 ℃, 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 80-90 ℃ for 2 hours after the dropwise adding is finished, then cooling the reaction system to 50-60 ℃, dropwise adding allyl polyether into the reaction system by using the constant flow pump, preserving heat at 50-60 ℃ for 30-40 minutes after the dropwise adding is finished, and cooling to obtain a target product;
the preparation method of the aliphatic polyamide with the branched structure comprises the following steps: putting dihexyltriamine and deionized water into a reaction kettle according to a molar ratio of adipic acid to dihexyltriamine to deionized water =1:1.1:3, wherein nitrogen protection is required in the reaction process, adding adipic acid into the reaction kettle for 6 times at intervals of 30min every time, controlling the temperature of the reaction kettle to be not more than 70 ℃ in the process of adding adipic acid, cooling with circulating water if the temperature is more than 70 ℃, starting heating and dehydrating after the addition is finished, controlling the reaction temperature to be 170-200 ℃ for reaction for 8 hours, preserving heat for 2 hours after the dehydration is finished, then cooling the reaction kettle to 130-140 ℃, slowly adding a certain amount of deionized water into the reaction kettle, stirring uniformly, and discharging to obtain an aliphatic polyamide aqueous solution with a solid content of 60%;
the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid or acetic acid;
the allyl polyether has a structural formula shown as (II):
2. the process according to claim 1, wherein the amount of the ethyleneimine added is 5 to 20 times the number of moles of the amine groups in the aliphatic polyamide.
3. Use of an ethyleneimine and polyether double modified polyamide dendrimer compound prepared according to the method of claim 1 or 2 as a retention aid in the paper industry.
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| US4144123A (en) * | 1974-07-19 | 1979-03-13 | Basf Aktiengesellschaft | Incorporating a crosslinked polyamidoamine condensation product into paper-making pulp |
| DE19921507A1 (en) * | 1999-05-10 | 2000-11-16 | Basf Ag | Process for the fractionation of water-soluble or dispersible amino group-containing polymers with a broad molar mass distribution |
| AU2007254145B2 (en) * | 2006-05-18 | 2012-05-24 | Solenis Technologies Cayman, L.P. | Michael addition adducts as additives for paper and papermaking |
| CN101492900B (en) * | 2009-01-12 | 2010-12-01 | 山东轻工业学院 | Retention aid and filtering aid of cation dendroid macromolecule for papermaking, preparation and uses thereof |
| CN103127525B (en) * | 2013-02-27 | 2015-10-28 | 万礼 | A kind of dendrimers nanometer drug administration carrier targeting peptide-doxorubicin and method for making thereof |
| CN105735048A (en) * | 2015-12-15 | 2016-07-06 | 广东省造纸研究所 | High-permeability paper material and production process thereof |
| CN106543447B (en) * | 2016-10-23 | 2019-07-19 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of hyper-branched type high water-content crude oil demulsifier |
| CN111100292A (en) * | 2020-01-06 | 2020-05-05 | 辽宁科隆精细化工股份有限公司 | Preparation method of high molecular weight branched polyethyleneimine |
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