CN101302731A - Preparation method of organosilicon modified paper moistening strength agent - Google Patents

Abstract

The invention discloses a preparation method of an organosilicon modified paper moistening strength agent. Firstly, a polyamide polyamine intermediate is synthesized by using a dibasic acid and a polyamine as raw materials. Take a certain amount of polyamide polyamine intermediate, epichlorohydrin and organosilane coupling agent, react at a certain temperature until a certain viscosity is reached, and add acid to terminate the reaction, and then the organosilicon modified paper humidifying agent can be obtained. The invention can reduce the consumption of epichlorohydrin and reduce the organic chlorine content in the discharge; the molecular weight of the cross-linked product is greatly increased, and the cross-linking active points of the molecular chain segments are increased. The retention rate of the invented product has been greatly improved, which can not only improve the wet strength of paper, but also increase the physical properties of paper such as folding endurance, tensile strength, and dry strength. If it is used for paper surface coating, it can also Greatly improve the surface water resistance of paper.

Description

Preparation method of organosilicon modified paper moistening strength agent

technical field

The invention belongs to the field of preparation technology of fine chemicals, and in particular relates to a preparation method of an organosilicon-modified paper moisturizing strength agent.

Background technique

Many paper products, especially industrial papers, require high wet strength. Polyamide polyamine epichlorohydrin (PAE), as the most widely used wet strength agent at present, has advantages that cannot be compared with traditional wet strength agents urea-formaldehyde resin (UF), modified melamine-formaldehyde resin (MF) and acrylamide polymers . It not only has good wet strength effect and repulpability, but also has no free formaldehyde in the production process, which is friendly to the ecological environment and human health. The existing PAE preparation method is usually prepared by reacting adipic acid and diethylenetriamine or triethylenetetramine under alkaline conditions to prepare polyamine, and then reacting with epichlorohydrin. Since this type of product has not been cross-linked and modified, its cross-linking degree and molecular weight are low, and its retention performance is poor. The wet strength effect of the paper is far from the production requirements, especially for some paper types that require high wet strength. It is still not ideal; at the same time, it will bring many adverse effects to papermaking, such as easy generation of air bubbles and flocculation in the slurry, poor uniformity of paper sheets, and low rigidity.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned shortcoming of prior art, provide a kind of preparation method that can have high retention performance in pulp, wet strength effect and environment-friendly organosilicon modified paper moistening strength agent.

In order to achieve the above-mentioned purpose, the technical solution adopted in the present invention is: add polyamine and dibasic acid into the drying reactor at a molar ratio of 0.7-1.5:1, heat to 140-200°C, and keep warm for 3-7 hours to make The polyamide polyamine in the reactor has a viscosity of 100-160mPa.s at 25°C, and deionized water is added to dilute the polyamide polyamine to a solid content of 50% to obtain a solution A of the intermediate of the moisturizing enhancer; After mixing solution A, epichlorohydrin and organosilane coupling agent uniformly in a mass ratio of 100:1-40:1-5, add deionized water to dilute the system to a solid content of 20%. ℃ for 1-6 hours, when the viscosity of the system reaches 20-60mPa.s at 25℃, stop heating, dilute with deionized water to a solid content of 10%-15%, adjust the pH of the system to 1-4 with acid, that is Silicone-modified polyamide polyamine epichlorohydrin can be obtained as a paper humidification strength agent.

The polyamine of the present invention adopts one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine or a mixture thereof in any proportion; the dibasic acid is succinic acid, adipic acid, fumaric acid, One of maleic acid, etc. or a mixture of one of them in any proportion; the acid is one of hydrochloric acid, glacial acetic acid, formic acid, sulfuric acid, nitric acid, or a mixture of one of them in any proportion; organic silane coupling The agent is methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, gamma -Mercaptopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ- Chloropropyltriethoxysilane, Triaminopropylmethyldimethoxysilane, Cyanoethylmethyldimethoxysilane, Methyltributylketoximosilane, Vinyltributylketoximosilane , one of γ-glycidyl etheroxypropyl trimethoxysilane or a mixture of one of them in any proportion.

In the preparation process of the present invention, no organic solvent is added, no free formaldehyde is released, and at the same time, the organic chlorine content of emanations can be reduced, which is friendly to the ecological environment and human health; and an organosilane coupling agent is introduced as a crosslinking agent to obtain a certain molecular weight of the product. The improvement of the modified polyamide polyamine epichlorohydrin has greatly improved the retention performance, and the paper can achieve the ideal wet strength effect at a lower dosage; at the same time, the introduction of the crosslinking agent increases the molecular segment The cross-linking activity of the polymer further enhances the affinity between the polymer and the fiber, and the strength of the interlaced chain structure formed around the fiber, so as to better limit the movement between the fiber and the fiber, and prevent the fiber from swelling and water absorption. Reduce the stretching and deformation of paper sheets, and greatly improve the wet strength of paper. In addition, the inventive product can not only improve the wet strength of paper, but also increase the physical properties of paper such as folding endurance, tensile strength, and dry strength. If it is used for paper surface coating, it can also greatly improve the paper's Surface water resistance.

Detailed ways

Example 1: Add polyamine diethylenetriamine and dibasic acid succinic acid into a drying reactor at a molar ratio of 1.0:1, heat to 200°C, and keep warm for 5 hours to make the polyamide polyamine in the reactor The viscosity of the product reaches 100mPa.s (the product viscosity is measured at 25°C and the polyamide polyamine has a solid content of 50%). Add deionized water to dilute the polyamide polyamine to a solid content of 50% to obtain humidification Solution A of strong agent intermediate; after mixing solution A, epichlorohydrin and organic silane coupling agent methyltrimethoxysilane in a mass ratio of 100:20:2, add deionized water to dilute the system to contain The solid content is 20%, react at 80°C for 1 hour, when the viscosity of the system reaches 20mPa.s (the product viscosity is measured at 25°C), stop heating, dilute with deionized water to a solid content of 15%, and adjust the system with hydrochloric acid When the pH reaches 1, the organosilicon-modified polyamide polyamine epichlorohydrin paper wetting strength agent can be obtained.

Example 2: Add polyamine triethylenetetramine and dibasic acid adipic acid into a drying reactor at a molar ratio of 0.8:1, heat to 180°C, and keep warm for 7 hours to make the polyamide polyamine in the reactor The viscosity of the product reaches 150mPa.s (the product viscosity is measured at 25°C and the polyamide polyamine has a solid content of 50%). Add deionized water to dilute the polyamide polyamine to a solid content of 50% to obtain humidification Solution A of strong agent intermediate; after mixing solution A, epichlorohydrin and organic silane coupling agent methyltriethoxysilane according to the mass ratio of 100:5:4, add deionized water to dilute the system to The solid content is 20%, react at 70°C for 3 hours, when the viscosity of the system reaches 30mPa.s (the product viscosity is measured at 25°C), stop heating, dilute with deionized water to a solid content of 12%, and use glacial acetic acid The pH of the system is adjusted to 3, and the silicone-modified polyamide polyamine epichlorohydrin paper humidifying agent can be obtained.

Example 3: Add the polyamine tetraethylenepentamine and the dibasic acid fumaric acid into the dry reactor at a molar ratio of 1.2:1, heat to 150°C, and keep the temperature for 3 hours to make the polyamide polyamine in the reactor The viscosity of the product reaches 130mPa.s (the product viscosity is measured at 25°C and the polyamide polyamine has a solid content of 50%). Add deionized water to dilute the polyamide polyamine to a solid content of 50% to obtain humidification Solution A of the strong agent intermediate; after mixing solution A, epichlorohydrin and organic silane coupling agent methyltriacetoxysilane in a mass ratio of 100:30:1, add deionized water to dilute the system to The solid content is 20%, react at 60°C for 5 hours, when the viscosity of the system reaches 40mPa.s (the product viscosity is measured at 25°C), stop heating, dilute with deionized water to a solid content of 10%, adjust with formic acid When the pH of the system reaches 2, the organosilicon-modified polyamide polyamine epichlorohydrin paper humidifying agent can be obtained.

Example 4: Add a mixture of polyamines diethylenetriamine and triethylenetetramine in any proportion and dibasic acid maleic acid in a molar ratio of 0.7:1 to a drying reactor, heat to 170°C, and keep warm React for 6 hours to make the viscosity of the polyamide polyamine in the reactor reach 160mPa.s (the product viscosity is at 25 ℃, polyamide polyamine solid content is measured under the condition of 50%), add deionized water, the polyamide polyamine Dilute to a solid content of 50% to obtain a solution A of the intermediate of the moisturizing enhancer; mix solution A, epichlorohydrin and organosilane coupling agent phenyltrimethoxysilane in a mass ratio of 100:1:3 After uniformity, add deionized water to dilute the system to a solid content of 20%, and react at 50°C for 6 hours. When the viscosity of the system reaches 50mPa.s (the product viscosity is measured at 25°C), stop heating and dilute with deionized water The solid content is 13%, and the pH of the system is adjusted to 4 with sulfuric acid to obtain the silicone-modified polyamide polyamine epichlorohydrin paper moisturizing strength agent.

Embodiment 5: Add the mixture of polyamine diethylenetriamine, triethylenetetramine and tetraethylenepentamine in any proportion with dibasic acid succinic acid and adipic acid in a molar ratio of 1.4:1 In the drying reactor, heat to 140°C, keep the heat for 4 hours to make the polyamide polyamine viscosity in the reactor reach 120mPa.s (the product viscosity is measured at 25°C and the polyamide polyamine solid content is 50%) , adding deionized water, diluting the polyamide polyamine to a solid content of 50%, to obtain a solution A of the intermediate of the moisturizing enhancer; After the base silane is mixed evenly according to the mass ratio of 100:25:5, add deionized water to dilute the system to a solid content of 20%, react at 55°C for 4 hours, and when the viscosity of the system reaches 60mPa.s (the product viscosity is at 25°C Measure under), stop heating, dilute with deionized water to a solid content of 11%, and adjust the pH of the system to 1 with nitric acid to obtain the silicone-modified polyamide polyamine epichlorohydrin paper wetting strength agent.

Example 6: A mixture of polyamines diethylenetriamine and tetraethylenepentamine in any proportion and a mixture of dibasic acids fumaric acid and maleic acid in any proportion is added to the drying reactor in a molar ratio of 0.9:1 In the process, heat to 160°C, heat preservation reaction for 3 hours so that the viscosity of the polyamide polyamine in the reactor reaches 140mPa.s (the viscosity of the product is measured at 25°C and the solid content of the polyamide polyamine is 50%), add Ionized water, dilute the polyamide polyamine to a solid content of 50%, to obtain the solution A of the intermediate of the moisturizing enhancer; mix the solution A, epichlorohydrin and organosilane coupling agent diphenyldimethoxysilane After mixing evenly according to the mass ratio of 100:10:1, add deionized water to dilute the system to a solid content of 20%, react at 65°C for 2 hours, and when the viscosity of the system reaches 35mPa.s (the product viscosity is measured at 25°C ), stop heating, dilute with deionized water to a solid content of 14%, adjust the pH of the system to 4 with a mixture of hydrochloric acid and glacial acetic acid in any proportion, and then obtain the organosilicon-modified polyamide polyamine epichlorohydrin paper Moisturizer.

Example 7: Add polyamine tetraethylenepentamine and dibasic acid adipic acid into a drying reactor at a molar ratio of 1.5:1, heat to 190°C, and keep warm for 7 hours to make the polyamide polyamine in the reactor The viscosity of the product reaches 110mPa.s (the product viscosity is measured at 25°C and the polyamide polyamine has a solid content of 50%). Add deionized water to dilute the polyamide polyamine to a solid content of 50% to obtain humidification Solution A of strong agent intermediate; mix solution A, epichlorohydrin and organosilane coupling agent γ-chloropropyl triethoxysilane and γ-chloropropyl triethoxysilane in any proportion by 100 : After the mass ratio of 40:5 is mixed evenly, add deionized water to dilute the system to a solid content of 20%, react at 75°C for 5 hours, and when the viscosity of the system reaches 55mPa.s (the product viscosity is measured at 25°C), Stop heating, dilute with deionized water to a solid content of 10%, adjust the pH of the system to 3 with a mixture of formic acid and sulfuric acid in any proportion, and obtain the humidification strength of silicone-modified polyamide polyamine epichlorohydrin paper. agent.

The invention can reduce the consumption of epichlorohydrin and reduce the organic chlorine content in the discharge; the molecular weight of the product cross-linked by the organosilicon coupling agent is greatly increased, and the cross-linking active points of the molecular chain segments are increased. The retention rate of this moisturizing strength agent is greatly improved. It can not only improve the wet strength of paper, but also increase the physical properties of paper such as folding endurance, tensile strength, and dry strength. For example, it can be used for paper surface coating. Cloth can also greatly improve the surface water resistance and surface strength of paper.

Claims (5)

1, the preparation method of organic silicon modified paper humidifying strength agent, it is characterized in that: 1) Add the polyamine and the dibasic acid into the drying reactor at a molar ratio of 0.7-1.5:1, heat to 140-200°C, and keep warm for 3-7 hours to make the polyamide polyamine in the reactor cool at 25°C When the viscosity reaches 100-160mPa.s, deionized water is added to dilute the polyamide polyamine to a solid content of 50% to obtain a solution A of the intermediate of the moisturizing enhancer; 2) After mixing the solution A, epichlorohydrin and organosilane coupling agent uniformly in a mass ratio of 100:1-40:1-5, add deionized water to dilute the system to a solid content of 20%. React at -80°C for 1-6 hours. When the viscosity of the system reaches 20-60mPa.s at 25°C, stop heating, dilute with deionized water to a solid content of 10%-15%, and adjust the pH of the system to 1-4 with acid , that is, silicone-modified polyamide polyamine epichlorohydrin paper wetting strength agent. 2. The preparation method of silicone modified paper moisturizing strength agent according to claim 1, characterized in that: the polyamine is one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine Or a mixture of more than one of them in any proportion. 3. The preparation method of silicone-modified paper moisturizing strength agent according to claim 1, characterized in that: the dibasic acid is succinic acid, adipic acid, fumaric acid, maleic acid One of them or a mixture of more than one of them in any proportion. 4. The preparation method of silicone modified paper moisturizing strength agent according to claim 1, characterized in that: the acid is one of hydrochloric acid, glacial acetic acid, formic acid, sulfuric acid, nitric acid or one of them Mixtures in any proportion. 5. The preparation method of silicone modified paper moisturizing strength agent according to claim 1, characterized in that: the organosilane coupling agent is methyltrimethoxysilane, methyltriethoxysilane, Methyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β-aminoethyl- γ-Aminopropyltrimethoxysilane, γ-Chloropropyltrimethoxysilane, γ-Chloropropyltriethoxysilane, γ-Chloropropyltriethoxysilane, Triaminopropylmethyldi One of methoxysilane, cyanoethylmethyldimethoxysilane, methyl tributylketoxime silane, vinyl tributylketoxime silane, γ-glycidyl etheroxypropyl trimethoxysilane or A mixture of one of them in any proportion.