CN104589444B - Alkaline silica sol color fixing agent and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of alkaline silica sol color fixing agent and preparation method thereof, alkaline silica sol color fixing agent is with tetraethyl orthosilicate, water, alcohol, catalyst and silane coupler as raw material, according to mol ratio be 1: 30～40: 20～30: 0.3～0.7: 0.001～0.01 mix after, prepared by solgel reaction；Its preparation method is: tetraethyl orthosilicate and alcoholic solvent is mixed, stirs, be made into solution A；Water is mixed homogeneously with catalyst, is made into B solution；Take 30wt%A solution in reactor, it is warming up to 30～60 DEG C, under agitation the solution A of B solution and residue 70wt% is added drop-wise in reactor, with 30～60 DEG C of condensing refluxes, after reaction 30min, drip silane coupler again, continue stirring reaction 0.5～3h, be aged 8～12h, complete the preparation of alkaline silica sol color fixing agent, there is safety and environmental protection, colour fixation strong, the advantage such as silica sol granule particle diameter is little, narrow distribution.

Description

Alkaline silica sol color fixing agent and preparation method thereof

technical field

The invention relates to the technical field of color-fixing agents, in particular to an alkaline silica sol color-fixing agent and a preparation method thereof.

Background technique

Wood reactive dyeing is a process in which reactive dye molecules are adsorbed and infiltrated in wood, and the reactive active groups in the reactive dye molecules are combined with wood by covalent bonds to fix them in the wood. It is a coloring treatment for plantation fast-growing wood. To produce a wood processing method whose color, texture and other physical and mechanical properties reach or exceed ideal precious tree species wood, increase the added value of plantation fast-growing wood, and realize efficient utilization of plantation fast-growing wood.

After wood is dyed with reactive dyes, although some reactive dyes are adsorbed on the surface of wood fibers but not chemically bonded to wood fibers, these reactive dyes that are not bonded to wood fibers may fade, making the color fixing rate and color fastness of wood, Especially the color fastness to rubbing and washing is poor. In order to solve the problems of poor color fastness to rubbing and color fastness to washing of reactive dyes on wood, it has become a common practice to use color fixing agents to improve the color fastness and color fastness of reactive dyes on wood. an effective way. Although the traditional color-fixing agent soda ash can improve the color fastness of wood, its strong alkalinity will hydrolyze 20-40% of reactive dyes, reducing the probability of reactive dyes reacting with wood fibers to form covalent bonds; Dyes are easily adsorbed on the surface of wood to form multi-layered associations, which hinder the further adsorption and diffusion of dye molecules, resulting in floating colors, which not only make the color fixation rate and color fastness not much improved, but also increase water consumption and Environmental pollution; at the same time, adding a large amount of soda ash makes the printing and dyeing wastewater contain a large amount of inorganic salts, which aggravates the difficulty of biological treatment of printing and dyeing wastewater. The color fastness of wood can also be improved by using more color-fixing agent Alkali Y in the cotton textile industry. However, due to the high formaldehyde content in Y, it seriously affects human health and causes environmental pollution.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, to provide an alkaline silica sol color-fixing agent that is safe and environmentally friendly, and can significantly improve the color-fixing effect of wood dyeing, and also provides a simple preparation process, easy operation, and reaction A method for preparing a controllable alkaline silica sol color-fixing agent with small silica sol particle size and narrow distribution.

In order to solve the above-mentioned technical problems, a kind of alkaline silica sol color-fixing agent is provided, the aforementioned alkaline silica sol color-fixing agent is raw material with orthosilicate ethyl ester, water, alcohol, catalyst and silane coupling agent, according to molar ratio: 1: 30-40: 20-30: 0.3-0.7: 0.001-0.01 are mixed and prepared by sol-gel reaction.

The aforementioned alkaline silica sol color-fixing agent, further, the viscosity of the aforementioned alkaline silica sol color-fixing agent is 25mPa·S～35mPa·S, the solid content is 10%～15%, and the average particle diameter of silica particles is 10nm ~20nm.

As a general technical conception, the present invention also provides the aforementioned preparation method of alkaline silica sol color fixing agent, comprising the following steps:

(1) Mix ethyl orthosilicate and alcohol solvent, stir evenly, and make A solution;

(2) water and catalyst are uniformly mixed to form B solution;

(3) Take 30wt% of the aforementioned A solution in the reactor, heat up to 30°C to 60°C, add the aforementioned B solution and the remaining 70wt% of the A solution to the reactor dropwise under stirring conditions, and heat the mixture at 30°C to 60°C Condensate and reflux, after reacting for 30 minutes, add the silane coupling agent dropwise, continue to stir and react for 0.5h-3h, and age for 8h-12h to complete the preparation of the alkaline silica sol color-fixing agent.

In the aforementioned preparation method, further, in step (3), the drop rate of solution B and the remaining 70 wt% of solution A is added to the reactor at a rate of 1 mL/min to 2 mL/min.

In the aforementioned preparation method, further, the stirring speed in step (3) is 400 rpm to 800 rpm.

In the aforementioned preparation method, further, the aforementioned alcohol solvent is a mixture of one or more of absolute ethanol, propanol, isopropanol, tert-butanol and n-butanol.

The aforementioned preparation method, further, the aforementioned silane coupling agent is γ-aminopropylethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxysilane, vinyltriethoxy A mixture of one or more of base silane and vinyl-(β-methoxyethoxy) silane.

In the aforementioned preparation method, further, the aforementioned catalyst is ammonia water. Preferably, the mass percent concentration of ammonia water is 25%-28%.

Compared with the prior art, the present invention has the advantages of:

(1) The alkaline silica sol color-fixing agent provided by the invention is a colloidal solution formed by the uniform diffusion of silica colloidal particles in water or other solvents, and the surface of silica particles contains a large amount of hydroxyl groups, which can improve wettability, and Due to its high reactivity, it is widely used as a post-treatment finishing agent in the textile industry. It can form a network particle film on the fiber surface to achieve the purpose of color fixation and wrinkle smoothing.

(2) The alkaline silica sol color-fixing agent of the present invention is a low-viscosity colloidal solution with good dispersibility, which can be fully immersed and filled into solid objects, especially porous substances, and make the surface smooth.

(3) The alkaline silica sol color-fixing agent of the present invention has good adhesion, and can form a firm film by drying. Not only the film-forming temperature is low, but once the film is formed, it will not dissolve in water and deteriorate.

(4) The preparation process of the alkaline silica sol color fixing agent provided by the present invention is simple, easy to operate, the reaction is controllable, the particle size of the silica sol is small, the particle size of the silica is generally 1-100nm, and the distribution is narrow.

(5) when alkaline silica sol color-fixing agent of the present invention is used for dyeing of wood reactive dyes, on the one hand wood after alkaline silica sol treatment, the gel particle on the wood fiber promotes more reactive dyes to absorb and dye; On the one hand, the tiny gel particles have a large specific surface area and high specific surface energy, and it is easy to form a layer of oxide film with a three-dimensional network structure on the surface of the wood. Effects of wood fastness to rubbing and color fastness to washing. When the alkaline silica sol color-fixing agent prepared by the present invention is used to replace the traditional color-fixing agent, there is no need to modify the traditional reactive dye dyeing equipment, the use of inorganic salts in the traditional process can be reduced or not used at all, and the pollution to the environment and the biological treatment of printing and dyeing wastewater can be reduced. The difficulty of achieving environmentally friendly low-salt wood reactive dyeing; and the alcohol solvent in the fixing agent can be recycled and reused to realize resource recycling and save production costs; at the same time, the sol- Gel particles impart water and moisture resistance to stained wood.

detailed description

The present invention will be further described below in conjunction with specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

All materials and instruments used in the following examples are commercially available.

Example 1:

The preparation method of alkaline silica sol of the present invention specifically comprises the following steps:

(1) Mix 21.2g tetraethyl orthosilicate and 92g absolute ethanol, stir evenly, and make A solution.

(2) 76g of distilled water and 7mL of concentrated ammonia water with a mass fraction of 28% were mixed to obtain solution B.

(3) Get 38g of A solution and put it into the reactor, heat up to 40°C at a heating rate of 2°C/min, start the stirrer in the reactor, and control the stirring speed at 500 rpm; Add solution B and the remaining solution A dropwise, condense and reflux at 40°C, react for 30 minutes, then add 0.1g of KH550 (γ-aminopropylethoxysilane) dropwise, continue to stir and react for 1.5 hours, and let it stand for aging After 12 hours, a milky white alkaline silica sol color fixing agent was obtained.

The alkali silica sol color-fixing agent has a viscosity of 25 mPa·S, a solid content of 12%, and an average particle diameter of silica particles in the alkaline silica sol color-fixing agent of 18.5 nm.

The above embodiment 1 is only a preferred embodiment of the present invention. In the present invention, the alkaline silica sol color fixing agent can also be raw materials with tetraethyl orthosilicate, water, alcohol, catalyst and silane coupling agent, according to the molar ratio It is prepared by sol-gel reaction after mixing at 1:30-40:20-30:0.3-0.7:0.001-0.01. Simultaneously, the condensing reflux temperature in the step (3) is 30 ℃～60 ℃; The A solution that B solution and remaining 70wt% are added dropwise in the reactor is 1mL/min～2mL/min; The stirring reaction time is 0.5h～3h, the stirring speed is 400rpm～800rpm/min, the aging time is 8h～12h; the mass percentage concentration of ammonia water is 25%～28%, and the prepared alkaline silica sol can be solidified The viscosity of the agent can be distributed in the range of 25mPa·S to 35mPa·S, the solid content can be distributed in the range of 10% to 15%, and the average particle diameter of the silica particles can be distributed in the range of 10nm to 20nm.

The silane coupling agent that embodiment 1 adopts is γ-aminopropylethoxysilane, and in the present invention, other silane coupling agents such as: N-(β-aminoethyl)-γ-aminopropyl dimethyl Oxysilane, vinyltriethoxysilane, vinyl-(β-methoxyethoxy)silane; or a mixture of two or more of these silane coupling agents can also play a role with γ-ammonia Propylethoxysilane has the same effect and achieves the same or similar technical effects.

Equally, the alcoholic solvent that embodiment 1 adopts is dehydrated alcohol, and in the present invention, other alcoholic solvents are as: two or two kinds in propanol, Virahol, tert-butanol, n-butanol or these alcoholic solvents The above mixture can also play the same role as absolute ethanol, and achieve the same or similar technical effects.

Example 2:

The alkaline silica sol color-fixing agent of embodiment 1 is compared with soda ash, investigates the color-fixing effect of reactive dyestuff to wood staining:

Respectively prepare reactive red X-3B dyeing solution, reactive red M-3BE dyeing solution, reactive blue X-BR dyeing solution, reactive blue M-2GE dyeing solution, reactive yellow X-R dyeing solution, reactive Yellow M-3RE dyeing solution; add 40g/L sodium sulfate to each dyeing solution, and dye poplar veneer (specification 100×50×2mm) for 3 hours at a bath ratio of 1:20 at a constant temperature of 80°C.

Experimental group: add 8wt% (mass ratio to dye liquor) of the alkaline silica sol color-fixing agent obtained in Example 1 to the above dye liquor, fix the color at a constant temperature of 60° C. for 80 minutes, soap wash, wash with water, and dry to obtain dyed wood.

Control group: add 20g/L soda ash color fixing agent to the above dye solution, fix the color at a constant temperature of 60°C for 80 minutes, soap wash, wash with water, and dry to obtain dyed wood.

Investigate the color fastness to soaping (tested according to GB/T3921-2008) and the color fastness to dry and wet rubbing (tested according to GB/T 3920-2008) of the dyed wood fixed by alkaline silica sol and soda ash The data and the results of the investigation are listed in Table 1.

Table 1: Comparison table of color fixing effect of alkaline silica sol color fixing agent and soda ash color fixing agent

As can be seen from the comparative results of table 1, the color fastness to soaping of the dyed wood that adopts the alkaline silica sol color fixing agent of the present invention to fix the color reaches 4.5 grades, the color fastness to dry rubbing reaches 4.5 grades, and the color fastness to wet rubbing reaches 4.5 grades. It reaches level 4, which is 0.5-1 level higher than the color fastness to soaping and wet and dry rubbing of stained wood obtained by using traditional soda ash as a color-fixing agent.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with the art, without departing from the spirit and technical solutions of the present invention, can use the methods and technical content disclosed above to make many possible changes and modifications to the technical solutions of the present invention, or modify them to be equivalent Variations of equivalent embodiments. Therefore, any simple modifications, equivalent replacements, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention, which do not deviate from the technical solutions of the present invention, still fall within the protection scope of the technical solutions of the present invention.

Claims (8)

1. an alkaline silica sol color-fixing agent, is characterized in that, described alkaline silica sol color-fixing agent is raw material with tetraethyl orthosilicate, water, alcohol, catalyst and silane coupling agent, is 1 according to mol ratio : 30～40: 20～30: 0.3～0.7: 0.001～0.01 After mixing, it is prepared by sol-gel reaction; the silane coupling agent is γ-aminopropylethoxysilane, N-(β -A mixture of one or more of aminoethyl)-γ-aminopropyldimethoxysilane, vinyltriethoxysilane and vinyl-(β-methoxyethoxy)silane. 2. The alkaline silica sol color-fixing agent according to claim 1, characterized in that, the viscosity of the alkaline silica sol color-fixing agent is 25mPa·s～35mPa·s, and the solid content is 10%～15%, The average particle diameter of the silicon dioxide particles is 10 nm to 20 nm. 3. a preparation method of alkaline silica sol color fixing agent described in claim 1 or 2, is characterized in that, comprises the following steps: (1) Mix ethyl orthosilicate and alcohol solvent, stir evenly, and make A solution; (2) Mix water and catalyst evenly to make solution B; (3) Put 30wt% of the A solution into the reactor, raise the temperature to 30°C-60°C, add the B solution and the remaining 70wt% of the A solution dropwise into the reactor under stirring conditions, and set the temperature at 30°C Condensate and reflux at ~60°C, react for 30 minutes, then add the silane coupling agent dropwise, continue to stir and react for 0.5h to 3h, and age for 8h to 12h to complete the preparation of the alkaline silica sol color fixing agent; the silane coupling agent is γ-aminopropylethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxysilane, vinyltriethoxysilane and vinyl-(β-methoxyethoxy base) a mixture of one or more silanes. 4. The preparation method according to claim 3, characterized in that, in the step (3), the dripping rate of the B solution and the remaining 70wt% of the A solution into the reactor is 1mL/min～2mL/min . 5 . The preparation method according to claim 3 , wherein the stirring speed in the step (3) is 400 rpm to 800 rpm. 6. according to the preparation method described in any one in claim 3 to 5, it is characterized in that, described alcohol solvent is one or more in dehydrated alcohol, propanol, Virahol, tert-butanol and n-butanol mixture of species. 7. according to the preparation method described in any one in claim 3 to 5, it is characterized in that, described catalyst is ammoniacal liquor. 8. The preparation method according to claim 7, characterized in that, the mass percent concentration of the ammonia water is 25%-28%.