CN108384023B - Preparation and application of a hyperbranched animal protein foaming agent - Google Patents

Abstract

The invention relates to the technical field of foaming agents for foamed concrete, in particular to a preparation method and application of a hyperbranched animal protein foaming agent. In the present invention, succinic anhydride and diethanolamine are first used to synthesize AB ₂ monomers, and then trimethylolpropane is used as a core molecule to carry out a polycondensation reaction with AB ₂ monomers under the action of p-toluenesulfonic acid as a catalyst to synthesize terminal hydroxyl hyperbranched polymerization The product is then subjected to a condensation reaction with a traditional animal protein foaming agent to obtain a hyperbranched animal protein foaming agent. The self-made hyperbranched animal protein foaming agent was tested, and the results showed that the self-made hyperbranched animal protein foaming agent had obvious improvement in foaming height, foaming multiple and foam stabilization time.

Description

Preparation and application of a hyperbranched animal protein foaming agent

technical field

The invention relates to the technical field of foaming agents, in particular to a preparation method of a hyperbranched animal protein foaming agent, and also relates to the application of the hyperbranched animal protein foaming agent.

Background technique

With the implementation of relevant policies on building energy conservation in my country, the structure of building walls has undergone reforms. Among them, foamed concrete is more and more widely used in the field of construction due to its excellent properties such as light weight, heat preservation, heat insulation and sound insulation. Foamed concrete is usually prepared into foam by mechanically stirring an aqueous solution of a foaming agent, and then adding the foam into the building slurry. After mixing, pouring, molding and curing, it is a kind of "dense-cell" concrete with a large number of closed pores inside. . The key to producing foamed concrete is to formulate a foaming agent. At present, the most commonly used foaming agent is animal protein foaming agent, which has the advantages of excellent performance, easy availability of raw materials and environmental friendliness. It has the disadvantages of few functions, low output, unsatisfactory stability of the generated foam and poor foaming, so it is very important to study a new type of concrete foaming agent.

Hyperbranched polymers have been a hot research topic in recent decades. They have many advantages such as: high branching, three-dimensional network, low viscosity, a large number of active groups and relatively strong chemical activity, which make them special. performance. In addition, with the advantages of easy preparation and simple operation, this type of polymer is more and more popular.

In this paper, hyperbranched polymer was introduced into animal protein foaming agent to synthesize an animal protein foaming agent containing hyperbranched structure. The hyperbranched animal protein foaming agent has multiple hydrophilic groups and hydrophobic groups, which can significantly reduce the surface tension, improve the foam stabilization performance, and reduce the amount of bleeding and the settling distance.

SUMMARY OF THE INVENTION

In order to solve the problem of poor foam stability of the traditional animal protein foaming agent, the present invention provides a preparation method of a hyperbranched animal protein foaming agent with good foam stability.

The present invention is obtained through the following steps:

The hyperbranched polymer is added to the animal protein foaming agent, and p-toluenesulfonic acid is used as a catalyst to carry out a condensation reaction to obtain a hyperbranched animal protein foaming agent.

The hyperbranched polymer is obtained by reacting succinic anhydride and diethanolamine to obtain an AB ₂ type monomer, and using trimethylolpropane as a core molecule, and the AB ₂ type monomer is obtained by reacting with the core molecule.

For the hyperbranched polymer, the ratio of the core molecule trimethylolpropane to the AB ₂ -type monomer is: 1:3, 1:9, 1:21, 1:45 to obtain the first generation, the second generation, the first generation, and the first generation, respectively. The third and fourth generation hyperbranched polymers.

The hyperbranched polymer, AB ₂ type monomer is obtained by 1:1 reaction of succinic anhydride and diethanolamine.

The hyperbranched animal protein foaming agent was foamed using an air compression foaming machine during the test. During the test, the mixing ratio of the cement paste was cement:water=1:0.45.

The concrete synthesis of described hyperbranched animal protein foaming agent is as follows:

(1) Synthesis of AB type ₂ monomer

Weigh a certain amount of diethanolamine in a three-necked bottle, add an appropriate amount of DMAC to the three-necked bottle to mix, take a certain amount of succinic anhydride in a beaker with an appropriate amount of DMAC, and after the succinic anhydride is completely dissolved, transfer it to a In the constant pressure dropping funnel, it is assembled with the three-necked flask, the dropwise addition is completed in half an hour, and the reaction is carried out at room temperature for 8 hours to obtain the AB ₂ monomer. The reaction equation is as follows:

(2) Synthesis of hyperbranched polymers

A certain amount of toluene was added to the above system as a water-carrying agent, and a certain amount of trimethylolpropane was weighed as the core molecule. After all the core molecules were dissolved, the catalyst p-toluenesulfonic acid was added, a water separator was inserted, and an oil bath was added. The temperature was 140 °C, the reaction was carried out for 24 h, and the solvent was removed by distillation under reduced pressure to obtain the second-generation hyperbranched polymer. The reaction equation is as follows:

(3) Preparation of hyperbranched animal protein foaming agent

The hyperbranched polymer and the animal protein foaming agent are mixed, and p-toluenesulfonic acid is used as a catalyst to carry out a condensation reaction at 60° C. to obtain the hyperbranched animal protein foaming agent. The structure is as follows:

The basic properties of the animal protein foaming agent, such as: foaming ratio, foaming height, foam stabilization time, bleeding amount, and settling distance are based on the requirements of Q/MF 001-2006 "Animal Protein Cement Foaming Agent and Low Density Foaming Agent". Foamed concrete products" were tested, and its concentration was 1%.

Beneficial effects of the present invention:

The hyperbranched animal protein foaming agent synthesized by the invention has higher foaming ratio, foaming height and foam stabilization time, lower bleeding rate and settling distance, excellent performance, simple production process and good market. Prospects.

Detailed ways

The following is a more detailed statement of the specific implementation method of the present invention, which is intended to illustrate the concept and characteristics of the present invention, but not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.

The basic properties of the animal protein foaming agent, such as: foaming ratio, foaming height, foam stabilization time, bleeding amount, and settling distance are based on the requirements of Q/MF 001-2006 "Animal Protein Cement Foaming Agent and Low Density Foaming Agent". Foamed concrete products" were tested, and its concentration was 1%.

Implementation Example 1

(1) Weigh 18.90 g of diethanolamine into a three-necked flask, add 40 mL of DMAC to the three-necked flask to mix, and take 18.00 g of succinic anhydride in a beaker containing 40 mL of DMAC. All of them were transferred to a constant pressure dropping funnel, assembled with a three-necked flask, dropped in half an hour, and reacted at room temperature for 8 hours to obtain an AB ₂ monomer.

(2) 60 mL of water-carrying agent was added to the above system, and 8.04 g of trimethylolpropane was weighed as the core molecule. After all the core molecules were dissolved, the catalyst was added under the action of p-toluenesulfonic acid, and a water separator was inserted. , the oil bath temperature was 140 °C, the reaction was performed for 24 h, and the solvent was removed by distillation under reduced pressure to obtain the first-generation hyperbranched polymer.

(3) Add the first generation hyperbranched polymer and animal protein foaming agent into a three-necked flask, use p-toluenesulfonic acid as a catalyst, heat at 60°C, and react for 12 hours to obtain a hyperbranched animal protein foaming agent.

(4) Test the first-generation hyperbranched animal protein foaming agent according to Q/MF 001-2006 "Animal protein-based cement foaming agent and low-density foamed concrete products" to determine the foaming height and foaming multiple. , Steady foam time, the test results are shown in Table 1.

(5) The first generation of hyperbranched animal protein foaming agent is foamed by air compression type, and added to the cement paste with water:cement ratio of 0.45:1, according to JC/T 2199-2013 "foamed concrete Foaming agent" The foam concrete slurry was sampled and tested, and the test results are shown in Table 2.

Implementation Example 2

(1) Weigh 18.90 g of diethanolamine into a three-necked flask, add 40 mL of DMAC to the three-necked flask to mix, and take 18.00 g of succinic anhydride in a beaker containing 40 mL of DMAC. All of them were transferred to a constant pressure dropping funnel, assembled with a three-necked flask, dropped in half an hour, and reacted at room temperature for 8 hours to obtain AB ₂ monomers.

(2) 60 mL of water-carrying agent was added to the above system, and 2.68 g of trimethylolpropane was weighed as the core molecule. After all the core molecules were dissolved, the catalyst was added under the action of p-toluenesulfonic acid, and a water separator was inserted. , the temperature of the oil bath is 140 ℃, the reaction is carried out for 24 hours, and the solvent is removed by distillation under reduced pressure to obtain the second-generation hyperbranched polymer.

(3) Adding the second generation hyperbranched polymer and animal protein foaming agent into a three-necked flask, using p-toluenesulfonic acid as a catalyst, heating at 60°C, and reacting for 12 hours to obtain a hyperbranched animal protein foaming agent.

(4) Test the second-generation hyperbranched animal protein foaming agent in accordance with Q/MF 001-2006 "Animal protein-based cement foaming agent and low-density foamed concrete products" to determine its foaming height and foaming multiple. , Steady foam time, the test results are shown in Table 1.

(5) The second-generation hyperbranched animal protein foaming agent is foamed by air compression, and added to the cement paste with a water:cement ratio of 0.45:1, according to JC/T 2199-2013 "foamed concrete Foaming agent" The foam concrete slurry was sampled and tested, and the test results are shown in Table 2.

Implementation Example 3

(1) Weigh 22.08 g of diethanolamine in a three-necked flask, add 40 mL of DMAC to the three-necked flask to mix, and take 21.01 g of succinic anhydride in a beaker containing 40 mL of DMAC. All of them were transferred to a constant pressure dropping funnel, assembled with a three-necked flask, dropped in half an hour, and reacted at room temperature for 8 hours to obtain AB ₂ monomers.

(2) 60 mL of water-carrying agent was added to the above system, and 1.34 g of trimethylolpropane was weighed as the core molecule. After all the core molecules were dissolved, the catalyst was added under the action of p-toluenesulfonic acid, and a water separator was inserted. , the temperature of the oil bath is 140°C, the reaction is carried out for 24h, and the solvent is removed by distillation under reduced pressure to obtain the third-generation hyperbranched polymer.

(3) Add the third-generation hyperbranched polymer and animal protein foaming agent into a three-necked flask, use p-toluenesulfonic acid as a catalyst, heat at 60° C., and react for 12 hours to obtain a hyperbranched animal protein foaming agent.

(4) Test the third-generation hyperbranched animal protein foaming agent in accordance with Q/MF 001-2006 "Animal Protein Cement Foaming Agent and Low Density Foaming Concrete Products" to determine its foaming height and foaming ratio , Steady foam time, the test results are shown in Table 1.

(5) The third-generation hyperbranched animal protein foaming agent is foamed by air compression, and added to the cement paste with water:cement ratio of 0.45:1, according to JC/T 2199-2013 "foamed concrete Foaming agent" The foam concrete slurry was sampled and tested, and the test results are shown in Table 2.

Implementation Example 4

(1) Weigh 18.90 g of diethanolamine into a three-necked flask, add 40 mL of DMAC to the three-necked flask to mix, and take 18.00 g of succinic anhydride in a beaker containing 40 mL of DMAC. All of them were transferred to a constant pressure dropping funnel, assembled with a three-necked flask, dropped in half an hour, and reacted at room temperature for 8 hours to obtain AB ₂ monomers.

(2) 60 mL of water-carrying agent was added to the above system, and 0.54 g of trimethylolpropane was weighed as the core molecule. After all the core molecules were dissolved, the catalyst was added under the action of p-toluenesulfonic acid, and a water separator was inserted. , the oil bath temperature is 140 ℃, the reaction is carried out for 24 hours, and the solvent is removed by distillation under reduced pressure to obtain the fourth-generation hyperbranched polymer.

(3) Add the fourth generation hyperbranched polymer and animal protein foaming agent into a three-necked flask, use p-toluenesulfonic acid as a catalyst, heat at 60°C, and react for 12 hours to obtain a hyperbranched animal protein foaming agent.

(4) Test the fourth-generation hyperbranched animal protein foaming agent in accordance with Q/MF 001-2006 "Animal Protein-based Cement Foaming Agent and Low-density Foaming Concrete Products" to determine its foaming height and foaming multiple. , Steady foam time, the test results are shown in Table 1.

(5) The fourth-generation hyperbranched animal protein foaming agent is foamed by air compression, and added to the cement paste with a water:cement ratio of 0.45:1. According to JC/T 2199-2013 "foamed concrete Foaming agent" The foam concrete slurry was sampled and tested, and the test results are shown in Table 2.

Comparative example

(1) Test the commercially available animal protein foaming agent according to Q/MF 001-2006 "Animal Protein Cement Foaming Agent and Low Density Foaming Concrete Products", and measure its foaming height, foaming multiple and foam stabilization time , and the test results are shown in Table 1.

(2) The commercially available animal protein foaming agent is foamed with air compression type, and added to the cement slurry with water:cement ratio of 0.45:1. According to JC/T 2199-2013 "Foaming agent for foamed concrete" The concrete slurry was sampled and tested, and the test results are shown in Table 2.

Performance Testing

By comparing the performance of the embodiment and the comparative example, it can be seen that the self-made hyperbranched animal protein foaming agent has obvious improvement in foaming ratio and foam stability compared with the commercially available animal protein foaming agent.

By comparing the performance of the embodiment and the comparative example, it can be seen that the self-made hyperbranched animal protein foaming agent has obvious reduction in sedimentation distance and bleeding volume compared with the commercially available animal protein foaming agent.

The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the examples, and any other changes, modifications, combinations, substitutions, and simplifications made without departing from the spirit and principle of the present invention All should be equivalent alternatives, and all are included within the protection scope of the present invention.

Claims (1)

1. A hyperbranched animal protein foaming agent is characterized by being prepared by the following steps:

firstly, reacting succinic anhydride with diethanol amine to generate AB2 monomer;

using trimethylolpropane as a nuclear molecule to react with AB2 monomer at 140 ℃, and using p-toluenesulfonic acid as a catalyst to obtain a hydroxyl-terminated hyperbranched polymer;

and thirdly, carrying out condensation reaction on the hydroxyl-terminated hyperbranched polymer and the animal protein foaming agent under the action of p-toluenesulfonic acid as a catalyst to obtain the hyperbranched animal protein foaming agent.