阅读说明：本技术 一种无色变环保复合型阻燃剂、制备方法及其应用 (Colorless-change environment-friendly composite flame retardant, and preparation method and application thereof ) 是由 周晓珊 郭宇涵 于 2020-06-11 设计创作，主要内容包括：本发明公开了一种无色变环保复合型阻燃剂,属于功能助剂合成技术领域。所述复合型阻燃剂的组分包括反应型阻燃剂、含氮有机物、催化剂；所述反应型阻燃剂、含氮有机物、催化剂的质量比为50-150：5-30：1:15本发明还提供了一种无色变环保复合型阻燃剂制备方法及其应用。本发明提供的复合型阻燃剂有效使纯棉或纤维素织物做到无色变耐水洗无甲醛的情况下阻燃性依旧优良。(The invention discloses a colorless environment-friendly composite flame retardant, and belongs to the technical field of synthesis of functional auxiliaries. The composite flame retardant comprises the components of a reactive flame retardant, a nitrogenous organic matter and a catalyst; the mass ratio of the reactive flame retardant to the nitrogen-containing organic matter to the catalyst is 50-150: 5-30: the invention also provides a preparation method and application of the colorless environment-friendly composite flame retardant. The composite flame retardant provided by the invention effectively enables pure cotton or cellulose fabrics to have excellent flame retardance under the condition of no color change, washing resistance and no formaldehyde.)

1. A colorless environment-friendly composite flame retardant which is characterized in that,

the composite flame retardant comprises the components of a reactive flame retardant, a nitrogenous organic matter and a catalyst;

the mass ratio of the reactive flame retardant to the nitrogen-containing organic matter to the catalyst is 50-150: 5-30: 1 to 15; the reactive flame retardant is a nitrogen-containing hydroxymethyl propionamido flame retardant or a phosphorus acid/phosphite ester/dimethyl phosphite based flame retardant; the nitrogen-containing organic matter is dicyandiamide, urea, melamine, acrylamide, polyacrylamide or biuret; the catalyst is inorganic acid or ammonium salt containing phosphorus.

2. The colorless environment-friendly composite flame retardant according to claim 1, wherein the phosphorus-containing inorganic acid is phosphoric acid, phosphorous acid or hypophosphorous acid.

3. The colorless environment-friendly composite flame retardant according to claim 1, wherein the ammonium salt is ammonium chloride, ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate.

4. The preparation method of the colorless environment-friendly composite flame retardant as claimed in any one of claims 1 to 3, characterized by comprising the following steps:

respectively weighing a reaction type flame retardant, a nitrogen-containing organic matter and a catalyst according to the mass ratio, uniformly mixing, and carrying out liquefaction reaction at the temperature of 1-80 ℃ for 1-30min to obtain the composite flame retardant.

5. The application of the colorless environment-friendly composite flame retardant as defined in any one of claims 1-3 in a fabric flame-retardant finishing process.

6. The application of the colorless environment-friendly composite flame retardant in the fabric flame-retardant finishing process according to claim 5, characterized in that the application method of the composite flame retardant in the fabric flame-retardant finishing process specifically comprises the following steps:

preparing the composite flame retardant into flame retardant liquid with the concentration of 300-600g/L, and selecting fabric for later use;

soaking the selected fabric in the flame retardant liquid, and then rolling to obtain the padded fabric; wherein, the liquid carrying rate of the fabric after rolling is 50-200%;

and (3) baking the padded fabric at the temperature of 170-200 ℃ for 0.5-10min, cooling the fabric to room temperature, washing the fabric for 1-10min by using water at the temperature of 30-40 ℃, and drying the fabric to obtain the fabric treated by the composite flame retardant.

Technical Field

The invention belongs to the technical field of synthesis of functional additives, and particularly relates to a colorless environment-friendly composite flame retardant, a preparation method and application thereof.

Background

Cotton fiber (or cellulose) is one of the most important natural fibers, and because of its advantages of good mechanical properties, biodegradability, air permeability, good dyeability and hydrophilicity, cotton fiber fabrics are widely used in many fields in people's daily life. For example: bedding, upholstery (carpets, upholstery, cushions, etc.), clothing, and the like.

However, cotton fabrics produced from cotton fibers (or cellulose) are flammable fabrics, and the fire caused by the cotton fibers (or cellulose) seriously endangers the life and property safety of consumers. Therefore, the cotton fabric is accompanied with fire hazard when serving the daily life of consumers. In recent years, the research on flame retardant modification of pure cotton fabrics is increasing and the attention is paid to the pure cotton fabrics. The traditional flame retardant finishing agent for cotton fabrics is mainly halogen-containing flame retardant finishing agent and phosphorus flame retardant finishing agent. Although the halogen-containing flame retardant has good flame retardant effect, a large amount of smoke and toxic corrosive gas are generated in the combustion process, which may cause corrosion of circuit system switches and other metal objects and cause serious harm to human respiratory tracts and other organs, so the flame retardant is basically forbidden at present. In the prior art, the problems of no formaldehyde, no color change, water washing resistance and the like are difficult to simultaneously solve no formaldehyde, no color change, no water washing resistance and the like no matter the prophenylamine fumigation method or the CP resin method is adopted.

To achieve this, the durable cotton flame retardant used by those skilled in the art is PyrovatexCP, the main chemical component of which is N-hydroxymethyl-3- (dimethoxyphosphoryl) propionamide, which contains a reactive group N-CH₂OH can form covalent bond with cellulose by crosslinking at the temperature of more than 150 ℃, so that the fiber fabric has durable flame retardant property. Although the flame retardant has good flame retardant effect, the product is washable and has soft hand feeling, formaldehyde can be released, and the health of consumers is harmed; meanwhile, the phosphorus-nitrogen flame retardant is tetra-hydroxymethyl phosphoryl chloride (THPC), the flame retardant is subjected to flame retardant treatment by the most extensive Proban process, and the flame retardant treatment is finished by the procedures of padding, drying, ammonia fumigation, oxidation, alkali washing, water washing, drying and the like on the fabric, so that the flame retardant treated by the processThe fabric has soft hand feeling, little strength reduction and washing resistance, basically keeps the excellent performance of the cellulose fiber, but has very complex process and long production period and can release formaldehyde. In addition, Fyroltex HP newly developed in the United states is a phosphate flame retardant used for flame retarding of cotton fabrics, and although the Fyroltex HP is smokeless, has a good flame retarding effect and strong washing fastness, the Fyroltex HP can release formaldehyde.

Currently, for cotton fabrics, flame retardants that do not generate formaldehyde do not have durability, and flame retardants with durability release formaldehyde. Therefore, in order to produce the cotton fabric of GB-18401A infant clothing, the formaldehyde content of the cotton fabric is not more than 20ppm, and the development of the flame retardant which has durability, does not contain halogen and release formaldehyde, and has simple process and easy operation has important practical significance.

Aiming at the defects of the prior art, the invention provides a flame retardant which has durability, is halogen-free and formaldehyde-free and releases cotton fabrics, has simple process and is easy to operate, and a preparation method and application thereof.

Disclosure of Invention

Aiming at the technical problems, the invention provides a colorless-change environment-friendly composite flame retardant, a preparation method and application thereof, so that pure cotton or cellulose fabric has excellent flame retardance under the condition of colorless change, washing resistance and no formaldehyde.

The first purpose of the invention is to provide a colorless environment-friendly composite flame retardant, which comprises the components of a reactive flame retardant, a nitrogenous organic matter and a catalyst;

the mass ratio of the reactive flame retardant to the nitrogen-containing organic matter to the catalyst is 50-150: 5-30: 1-15

Wherein the reactive flame retardant is a nitrogen-containing hydroxymethyl propionamido flame retardant or a phosphorus acid/phosphite ester/dimethyl phosphite based flame retardant;

the nitrogen-containing organic matter is dicyandiamide, urea, melamine, acrylamide, polyacrylamide or biuret;

the catalyst is inorganic acid or ammonium salt containing phosphorus.

Preferably, the phosphorus-containing inorganic acid is phosphoric acid, phosphorous acid or hypophosphorous acid.

Preferably, the ammonium salt is ammonium chloride, ammonium phosphate, diammonium phosphate or ammonium dihydrogen phosphate.

The second purpose of the invention is to provide a preparation method of the colorless environment-friendly composite flame retardant, which comprises the following steps: respectively weighing a reaction type flame retardant, a nitrogen-containing organic matter and a catalyst according to the mass ratio, uniformly mixing, and carrying out liquefaction reaction at the temperature of 1-80 ℃ for 1-30min to obtain the composite flame retardant.

The third purpose of the invention is to provide an application of the colorless environment-friendly composite flame retardant, and the application method of the composite flame retardant in the fabric flame-retardant finishing process specifically comprises the following steps:

preparing the composite flame retardant into flame retardant liquid with the concentration of 300-600g/L, and selecting fabric for later use;

soaking the selected fabric in the flame retardant liquid, and then rolling to obtain the padded fabric; wherein, the liquid carrying rate of the fabric after rolling is 50-200%;

and (3) baking the padded fabric at the temperature of 170-200 ℃ for 0.5-10min, cooling the fabric to room temperature, washing the fabric for 1-10min by using water at the temperature of 30-40 ℃, and drying the fabric to obtain the fabric treated by the composite flame retardant.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides a colorless environment-friendly composite flame retardant which comprises the components of a reactive flame retardant, a nitrogen-containing organic matter and a catalyst, wherein the reactive flame retardant has flame retardance; the nitrogenous organic matter has the effects of protecting color, promoting the grafting reaction of the reactive flame retardant and the cellulose fiber to have washability, reducing and removing formaldehyde and having certain flame retardance; the catalyst plays a role in catalytic reaction and has certain flame retardance, so that the pure cotton (or cellulose) fabric has excellent flame retardance under the condition of no color change, water washing resistance and no formaldehyde.

After the fabric is treated by the flame retardant process, the composite flame retardant provided by the invention has excellent carbon length performance, excellent color difference grade performance and excellent formaldehyde content performance which is far lower than 20ppm of GB-18401 infant garment A standard, which shows that the colorless-to-washable formaldehyde-free flame retardant fabric can be obtained when the composite flame retardant provided by the invention is applied to the flame retardant finishing process of the fabric; mainly because of the nitrogen-containing hydroxymethyl propionamide group flame retardant or the reactive flame retardant containing phosphoric acid/phosphite ester/dimethyl phosphite ester flame retardant, in the baking process, under the participation of nitrogen-containing organic matters and the catalytic action of a catalyst, the flame retardant can be crosslinked with hydroxyl in fiber macromolecules through a crosslinking agent to form a covalent bond, and can be crosslinked with cellulose macromolecules, so that the formaldehyde content is slightly lower, and the flame retardant has the excellent performance of colorless change and water washing resistance.

Detailed Description

In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described with reference to the following specific examples, which are not intended to limit the present invention.

It should be noted that the experimental methods described in the following examples, application examples and comparative application examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.