Preparation and application of mechanochemical method biomass cake composite flame retardant

Abstract

The invention relates to the technical field of bio-based flame-retardant composite materials, in particular to a biomass cake composite flame retardant prepared based on a mechanochemical method and application of the biomass cake composite flame retardant. The bio-based composite, namely the target bio-based composite flame retardant, is prepared through a mechanochemical reaction on the basis of various components such as crude protein and amino acid contained in biomass cakes. The flame retardant can be directly used as a cotton fabric, a wood board, an ecological board, a shaving board, polyurethane and polyester flame retardant additive or can be directly prepared into a material for use.

Description

TECHNICAL FIELD

[0001] The present application relates to the preparation of bio-based flame retardant materials by mechanochemical method, and in particular to a kind of biomass cake compound flame retardant preparation and its application, belong to flame retardant material technical field. BACKGROUND

[0002] The world generally pays more and more attention to the product related to personal safety and health, with the progress of society, people's clothing, food, shelter has been greatly improved, but the fire safety problem is still a scientific and social problem to be solved. According to the national fire statistics analysis, fire often occurs in residential areas, and the death toll is as high as 79.9% of the total number of people, and the clothes, bedclothes, various board furniture, polyurethane foam insulation layer, curtain nylon materials in residential areas are extremely easy to cause fire, so the flame retardant treatment of the above materials is the key flame retardant field and direction that must be considered in the future.

[0003] Flame retardation is an important means to solve the problem of fire, and flame retardant is one of the important additives of high polymer materials, which can endow the material with flame retardancy, self-extinguishing and smoke suppression performance. Halogen-based flame retardant has been widely used, but due to the toxic gas and smoke generated during combustion, it is easy to cause secondary harm and has carcinogenic effect. Phosphorus-nitrogen flame retardant system is the most potential and expected to replace halogen-based flame retardant system, but phosphorus-nitrogen flame retardant still has the problems of low flame retardant efficiency, large pollution in preparation and dependence on chemical raw materials.

[0004] Biomass cake is an important biomass resource, which is a kind of plant waste rich in protein and minerals. Its rich nitrogen, phosphorus, sulfur and other elements make it a potential green and pollution-free flame retardant raw material. According to the flame retardant characteristics of phosphorus-nitrogen flame retardant material, the phosphorus-nitrogen flame retardant obtained by biomimetic modification of biomass cake can broaden the source and preparation of flame retardant and solve the problem of dependence on chemical raw materials. The present application provides a kind of mechanical force chemical method for preparing high-efficiency and environment-friendly biomass cake based phosphorus-nitrogen synergistic flame retardant and its application. SUMMARY

[0005] The present application is based on mechanochemical method, and biomass cake is used to prepare composite flame retardant.

[0006] The specific application content is: based on mechanochemical method, the preparation method of biomass cake composite flame retardant is: bio-based cake, modification reagent, catalyst, additive and solvent are placed in a certain proportion in a powder mill or a ball mill at one time or in batches, and mechanochemical reaction is carried out at a certain temperature to obtain biomass cake flame retardant slurry or powder, which is the target flame retardant.

[0007] The reaction mechanism is that the residual active amino, hydroxyl, carboxyl and the like in the biomass cake and meal react with the modified reagent containing phosphoric acid to form phosphoric amine, phosphoric ester and the like covalent bond after the reaction, and further react with the additive. The catalyst on one hand catalyzes the chemical reaction process of phosphoric amine, phosphoric ester and ammonium phosphate, ammonium carboxylate, and on the other hand can be coordinated and chelated with macromolecular crude protein, crude fiber and the like to be stable, and realize the synergistic flame-retardant effect in the system.

[0008] Further, the biomass cake and meal is a common renewable cake and meal resource rich in crude protein, and specifically can be rapeseed cake and meal, cottonseed cake and meal, oil tea seed cake and meal, soybean cake and meal, peanut cake and meal, sunflower seed cake and meal, sesame cake and meal, palm cake and meal, flaxseed cake and meal, and safflower seed meal.

[0009] Further, the modified reagent containing phosphoric acid is one or a mixture of several of phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphoric acid, aminotrimethylphosphonic acid, diethylenetriamine pentamethylenephosphonic acid, phytic acid, boric acid, boric acid ester, phosphoric acid ester, phosphonic acid ester, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride.

[0010] Further, the additive is ammonium phosphate, ammonium polyphosphate, urea, thiourea, guanidine, ammonia, methylamine aqueous solution, dicyandiamide, melamine and the like, single addition, mixed addition of several or no addition.

[0011] Further, the catalyst is aluminum trichloride, zinc sulfate, zinc chloride, copper sulfate, cuprous iodide, cuprous chloride, titanium tetrachloride and the like, single addition, mixed addition of several or no addition.

[0012] Further, the composite flame retardant is directly added as a composite flame retardant, or is configured into a solution for use, or is used as a flame-retardant material itself.

[0013] Further, the flame retardant of this type can be applied to cellulose fibers, various boards, polyurethane materials,

[0014] polyester materials, and nylon materials. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application is further described in detail below in combination with embodiments. In addition, it should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0016] The following disclosure provides different embodiments or application cases for realizing the content and application of the present application.

[0017] For simplicity of the disclosure of the present application, specific examples are described hereinafter. Of course, they are merely examples and the purpose is not to limit the present application. In addition, the present application provides various specific examples of processes and materials, but those of ordinary skill in the art can realize the application of other processes and / or the use of other materials.

[0018] In some embodiments of the present application, the biomass cake compound flame retardant prepared by mechanochemical method and its application are proposed. The raw materials are common agricultural and sideline product cake resources, especially rapeseed cake, cottonseed cake and other cake resources containing more anti-nutritional substances, which are the most preferred. Other biomass cake resources containing a large amount of crude protein can be modified and applied. The modification reagent is an acid or ester composed of phosphorus elements, such as phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphoric acid, amino trimethyl phosphine acid, diethylene triamine pentamethylene phosphine acid, phytic acid, boric acid, boric acid ester, phosphoric acid ester, phosphonic acid ester, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and other non-specific phosphoric acid, phytic acid, polyphosphoric acid, etc. In addition to containing crude protein, biomass cake also contains various amino acids, cellulose, crude fat and other substances. These substances contain many groups that can react with phosphorus elements, such as hydroxyl, carboxyl, thiol, amino, amide, etc. In the reaction, the nitrogen-containing substance is salted, especially the phosphorus-nitrogen synergistic flame retardant system. On the one hand, it can play a good gas phase flame retardant effect, and on the other hand, the catalysis and coordination enhancement of the catalyst can enhance the stability of the composition containing phosphoric acid and amino acid.

[0019] Example 1

[0020] Based on the mechanochemical method, rapeseed cake (20.0 g), phosphoric acid (12.0 g), urea (12.0 g), aluminum chloride (0.4 g) were placed in a ball mill at one time, and mechanochemical reaction was carried out at room temperature. The grinding time was set to 12 hours. After the reaction was completed, the target biomass cake flame retardant was obtained.

[0021] Example 2

[0022] Based on the mechanochemical method, cottonseed cake (20.0 g), polyphosphoric acid (12.0 g), ammonium phosphate (12.0 g), zinc chloride (0.5 g) were placed in a ball mill in batches, and mechanochemical reaction was carried out for 6h. After the reaction was completed, the target biomass cake flame retardant was obtained.

[0023] Example 3

[0024] Based on the mechanochemical method, oil tea seed cake (20.0 g), diethylene triamine pentamethylene phosphine acid (12.0 g), thiourea (12.0 g), copper sulfate (0.4 g) were placed in a ball mill at one time, and the reaction was completed after 12h, to obtain the target biomass cake flame retardant.

[0025] Example 4

[0026] Based on the mechanical force chemical method, soybean meal (20.0 g), phytic acid (18.0 g), ammonia water (18.0 g), zinc sulfate (0.7 g) were placed in the crusher at one time, and the mechanical force chemical reaction was carried out. After 9 h of reaction, the target biomass meal flame retardant was obtained.

[0027] Example 5

[0028] Based on the mechanical force chemical method, peanut meal (20.0 g), pyrophosphoric acid (10.0 g), methylamine aqueous solution (10.0 g), cuprous chloride (0.9 g) were placed in the ball mill in batches, and the mechanical force chemical reaction was carried out at a certain temperature and the grinding time was set. After the reaction was completed, the target biomass meal flame retardant slurry was obtained.

[0029] Example 6

[0030] Based on the mechanical force chemical method, sunflower meal (20.0 g), phosphorus pentachloride (10.0 g), melamine (10.0 g), cuprous iodide (0.2 g) were placed in the ball mill in batches, and the mechanical force chemical reaction was carried out for 15 h. After the reaction was completed, the target biomass meal flame retardant was obtained.

[0031] Example 7

[0032] Based on the mechanical force chemical method, sesame meal (20.0 g), amino-trimethyl phosphonic acid (12.0 g), ammonium polyphosphate (12.0 g), titanium tetrachloride (0.5 g) were mechanically force chemically reacted for 8 h. After the reaction was completed, the target biomass meal flame retardant was obtained.

[0033] Example 8

[0034] Based on the mechanical force chemical method, palm meal (20.0 g), phosphonate (12.0 g), dicyandiamide (12.0 g), copper sulfate (0.4 g) were placed in the ball mill at one time, and the mechanical force chemical reaction was carried out for 5 h. After the reaction was completed, the target biomass meal flame retardant was obtained.

[0035] Example 9

[0036] Based on the mechanical force chemical method, flaxseed meal (20.0 g), phosphorous acid (16.0 g), methylamine aqueous solution (16.0 g), aluminum chloride (0.3 g), deionized water as solvent were placed in the ball mill in batches, and the mechanical force chemical reaction was carried out for 6 h. After the reaction was completed, the target biomass meal flame retardant slurry was obtained.

[0037] Example 10

[0038] Based on the mechanical force chemical method, safflower meal (20.0 g), phosphate ester (15.0 g), guanidine (15.0 g), zinc chloride (0.4 g), and deionized water as a solvent were placed in a ball mill in batches, and mechanical force chemical reaction was carried out for 1 h. After the reaction was completed, the target biomass cake fire retardant was obtained.

[0039] In addition, the present inventors also refer to the foregoing examples, and other raw materials, process operations, and process conditions described in the specification are tested, and ideal results are obtained.

[0040] The above is an embodiment of the present application, which does not limit the present application in any form. Although the present application is disclosed with the preferred embodiment, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, which is equivalent to an equivalent embodiment, and belongs to the scope of the technical solution.

[0041] Evaluation of fire retardant

[0042] According to the experimental scheme of the present application, the fire retardant prepared according to the different amounts of the embodiments is applied to cotton fabric, wood board, ecological board, shaving board, polyurethane, and polyester fire retardant, and the effects are compared. The fire retardant coating is added in an amount of 50%-100%, and a 50mm*150mm sample is prepared. The vertical burning test (Vertical Burn Test, VBT) and limiting oxygen index (Limiting Oxygen Index, LOI) are carried out, and the specific fire retardant results are shown in the following table:

[0043] Example 1 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 52 32 38 36 37 Oxygen index (LOI, %) 32.1 29.8 37.2 33.5 36.9

[0044] Example 2 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 58 39 42 39 39 Oxygen index (LOI, %) 28.9 30.3 33.6 34.9 35.7

[0045] Example 3 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 59 33 38 35 41 Oxygen index (LOI, %) 29.8 38.2 41.8 34.7 36.5

[0046] Example 4 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 53 31 40 41 41 Oxygen index (LOI, %) 31.8 29.9 34.8 37.8 37.4

[0047] Example 5 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 58 39 42 33 45 Oxygen index (LOI, %) 33.7 34.1 42.9 35.6 36.3

[0048] Example 6 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 55 33 41 39 46 Oxygen index (LOI, %) 33.2 31.3 31.9 36.2 35.7

[0049] Example 7 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 58 31 37 41 37 Oxygen index (LOI, %) 30.9 35.8 36.1 36.8 35.1

[0050] Example 8 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 56 37 41 42 39 Oxygen index (LOI, %) 30.7 34.8 35.1 37.6 37.3

[0051] Example 9 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 57 34 39 45 39 Oxygen index (LOI, %) 32.7 35.1 35.2 34.6 37.5

[0052] Example 10 Cotton fabric Ecoboard Nylon Polyurethane Polyester Carbon length (mm) 58 37 38 44 40 Oxygen index (LOI, %) 30.1 35.8 34.7 36.2 36.6

[0053] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that the technical solutions described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalent ones. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a mechanical force chemical biomass cake meal composite flame retardant and its application method, characterized by: The biomass cake and meal composite flame retardant is composed of bio-based cake and meal and modified reagent as core components, catalyst, additive and solvent.

2. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The preparation method of the biomass cake and meal composite flame retardant is that bio-based cake and meal, modified reagent, catalyst, additive and solvent are placed in a pulverizer or a ball mill in a certain proportion at one time or in batches, and mechanical chemical reaction is carried out at a certain temperature to obtain biomass cake and meal flame retardant slurry or powder, which is the target flame retardant.

3. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The biomass cake and meal is rapeseed cake and meal, cottonseed cake and meal, oil tea seed cake and meal, soybean cake and meal, peanut cake and meal, sunflower seed cake and meal, sesame cake and meal, palm cake and meal, flaxseed cake and meal, and safflower seed meal.

4. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The modified reagent is one or a mixture of several of phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphoric acid, amino trimethyl phosphine acid, diethylene triamine penta-methyl phosphine acid, phytic acid, boric acid, boric acid ester, phosphoric acid ester, phosphonic acid ester, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride.

5. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The additive is single addition, mixed addition of several or no addition of ammonium phosphate, ammonium polyphosphate, urea, thiourea, guanidine, ammonia, methylamine aqueous solution, dicyandiamide, melamine, etc.

6. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The catalyst is single addition, mixed addition of several or no addition of aluminum trichloride, zinc sulfate, zinc chloride, copper sulfate, cuprous iodide, cuprous chloride, titanium tetrachloride, etc.

7. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The composite flame retardant is directly added for use, configured into a solution for use, or used as a flame retardant material itself.

8. A method for preparing and applying a mechanical force chemical method biomass cake meal composite flame retardant, characterized in that: The type of flame retardant can be applied to cellulose fibers, various types of boards, polyurethane materials, polyester materials, and nylon materials.