CN115785145A - Preparation method, product and application of alkylamine boric acid phosphoric acid modified meglumine flame retardant - Google Patents
Preparation method, product and application of alkylamine boric acid phosphoric acid modified meglumine flame retardant Download PDFInfo
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Abstract
The invention provides a preparation method, a product and application of an alkylamine boric acid phosphoric acid modified meglumine flame retardant. In the preparation method, the meglumine is used as a matrix, and phosphoric acid and boric acid are sequentially added to carry out esterification reaction with the meglumine, so that the flame retardant property of phosphorylated meglumine is improved; and urea and alkylamine are added to modify phosphorylated meglumine borate, and the hydrophobic acting force of alkylamine is utilized to improve the adhesion of the flame retardant to the surface of the fabric, so that the flame retardant can achieve better flame retardant performance with less consumption, and the consumption of the flame retardant is reduced. The cotton fabric is endowed with excellent flame retardance and flame retardance durability through durable flame retardant finishing. The preparation method is simple, the raw materials are low in price, the requirement on treatment equipment is low, the reproducibility is good, and the industrial production is facilitated.
Description
Technical Field
The invention belongs to the technical field of spinning, and particularly relates to a preparation method, a product and application of an alkylamine boric acid phosphoric acid modified meglumine flame retardant.
Background
The cotton fabric has the excellent characteristics of good hygroscopicity, skin-friendly softness, easy degradation and the like, and is always well received by consumers. Has wide application prospect in the fields of clothing, medical treatment, packaging, home furnishing and the like. However, cotton fabrics have an LOI of about 18 percent, are extremely easy to burn, and bring great hidden danger to the life safety and property of people. Therefore, it is necessary to develop a new flame retardant to perform flame retardant finishing and improve the flame retardant performance.
The flame retardant for cotton is divided into three major categories, organic, inorganic and organic-inorganic composite. The organic flame retardant has the following characteristics: (1) the using amount is low and the flame retardant property is excellent. And (2) covalent grafting is easy, and flame retardant durability is realized. With the improvement of environmental protection consciousness, the development of the environment-friendly biomass-based textile flame retardant is the key point of the current research.
Meglumine is derived from glucose, is an amino sugar, is often used in the fields of pharmacy, food, cosmetics and the like, and has the advantages of high safety and biodegradability. In addition, meglumine is easy to obtain, contains N element, has a plurality of hydroxyl functional groups for chemical modification, and is a good flame retardant modified matrix.
The esterification of phosphoric acid and a polyol is a popular method for preparing a flame retardant. The method can optimize the biomass polyol to meet the requirement of environmental protection, and can also utilize the active ammonium phosphate group to endow the cotton fabric with washing resistance. However, studies have shown that, in the synthesis process of the phosphate ester polyol, the phosphorylation efficiency is low, and the high-efficiency flame retardant property is difficult to achieve. Researchers have prepared sorbitol-based flame retardants in 66% yield using phosphoric acid and sorbitol.
In order to further improve the flame retardant effect of the phosphorus-nitrogen flame retardant, boron, phosphorus and nitrogen are adopted for synergistic flame retardance. The boron flame retardant mainly comprises inorganic borates such as zinc borate, borax, calcium metaborate, sodium metaborate and the like and a small amount of organic boric acid vinegar, and has the advantages of good thermal stability, low toxicity, smoke abatement, low toxicity, easily obtained raw materials and the like. Reports indicate that the boron flame retardant and the nitrogen flame retardant or the phosphorus flame retardant can achieve the effect of synergistic flame retardance when compounded. However, due to the water solubility of the flame retardant, a high concentration of flame retardant finishing liquor needs to be formulated to meet the flame retardant performance during finishing, and it is difficult to meet the requirement of high efficiency.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method, a product and application of an efficient and durable alkylamine boric acid phosphoric acid modified meglumine flame retardant. The preparation method is based on a boron-phosphorus-nitrogen synergistic flame retardant thought and a hydrophobic modification strategy, firstly phosphoric acid and boric acid are sequentially subjected to esterification reaction with hydroxyl on meglumine, and then urea and alkylamine are used for simultaneously modifying the esterified product, so that the flame retardant effect of the flame retardant is improved, the hydrophilicity of the flame retardant is reduced, the flame retardant efficiency is improved, and the use cost is reduced. The alkylamine boric acid phosphoric acid modified meglumine flame retardant prepared by the preparation method has the characteristics of excellent flame retardant property and flame retardant durability, high efficiency and durability, simple and convenient preparation method, low requirement on treatment equipment, good reproducibility and contribution to industrial production.
Hydrophobic modification of flame retardants is a good way of modification. Alkylamine is an amine containing a carbon chain, the longer the carbon chain, the less water soluble. The alkylamine and the phosphoric acid in the flame retardant are aminated, the water solubility of the flame retardant is reduced by utilizing the hydrophobicity of the alkylamine, the adhesion of the flame retardant to the surface of the fabric is improved by depending on the hydrophobic acting force, and the aim of high-efficiency flame retardance is fulfilled.
A preparation method of alkylamine boracic acid phosphoric acid modified meglumine flame retardant comprises the following steps:
(1) Reacting meglumine and phosphoric acid in a solvent to obtain a solution A;
(2) Adding boric acid into the solution A for reaction to obtain a solution B;
(3) And adding urea and alkylamine into the solution B for reaction, and obtaining the alkylamine boric acid phosphoric acid modified meglumine flame retardant after the reaction is finished.
The reaction process in the preparation method is as follows:
wherein, due to phosphorusThe efficiency of esterification of the acid is low, so that R is not all
n＝3～12。
Performing esterification reaction on phosphoric acid and partial hydroxyl on meglumine to prepare phosphorylated meglumine; after boric acid is added, the boric acid and all or part of hydroxyl groups on phosphorylated meglumine are subjected to esterification reaction to obtain the phosphorylated meglumine borate; then adding urea and alkylamine for reaction to prepare ammonium phosphate salt and/or alkyl amine phosphate salt, namely the alkylamine boric acid phosphoric acid modified meglumine flame retardant.
Preferably, the molar ratio of meglumine to phosphoric acid is 1: (3-10). Due to the low efficiency of the phosphoric acid esterification, the addition of excessive phosphoric acid can not improve the esterification rate, but increases the cost and side reactions. Therefore, as a further preference, the molar ratio of meglumine to phosphoric acid is 1:5.
preferably, the molar ratio of meglumine to boric acid is 1: (1-5). More preferably 1: (3-5). Still more preferably 1: (3.5-4.5).
Preferably, the molar ratio of phosphoric acid to urea is 1: (0.01-0.9). More preferably 1: (0.2-0.8). Still more preferably 1: (0.4-0.8).
Preferably, the number of moles of alkylamine added is twice the difference between the number of moles of phosphoric acid and the number of moles of urea. I.e. the number of moles of alkylamine = (n) Phosphoric acid -n Urea ) X 2; wherein n is a mole number.
Preferably, in the step (1), the reaction temperature of the meglumine and the phosphoric acid is 120-140 ℃, and the reaction time is 1-3 h. More preferably, the reaction temperature is 125-135 ℃ and the reaction time is 1.5-2 h.
Preferably, the solvent is one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and dichloromethane. Further preferred is an anhydrous N, N-Dimethylformamide (DMF) solution.
Preferably, in the step (2), the reaction temperature after adding the boric acid is 110 to 150 ℃, and the reaction time is 1 to 3 hours. More preferably, the reaction temperature is 110 to 140 ℃ and the reaction time is 1.5 to 2.5 hours. More preferably, the reaction temperature is 125 to 140 ℃.
Preferably, in the step (3), the reaction temperature after adding urea and alkylamine is 110 to 130 ℃, and the reaction time is 0.5 to 2 hours. More preferably, the reaction temperature is 115 to 125 ℃ and the reaction time is 0.5 to 1.5 hours.
Preferably, the alkylamine is one or more of n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, heptylamine, octylamine and dodecylamine. Further preferably one or two of n-propylamine, n-butylamine, and n-pentylamine. More preferably, it is one of n-propylamine and n-butylamine.
Preferably, in step (3), after the reaction is completed, the following post-treatment is performed:
washing the reaction product with ethanol for several times, removing unreacted raw materials, and drying at 60-80 ℃ to obtain the alkylamine boric acid phosphoric acid modified meglumine flame retardant.
An alkylamine boric acid phosphoric acid modified meglumine flame retardant which is prepared by any one of the preparation methods.
The invention also provides durable flame-retardant finishing liquid, which is an aqueous solution of the alkylamine boric acid phosphoric acid modified meglumine flame retardant and a catalyst dicyandiamide.
The durable flame-retardant finishing liquid is applied to the flame-retardant finishing of cotton fabrics, and the cotton fabrics subjected to the flame-retardant finishing have better flame retardance and flame-retardant durability and wide application prospect. When dicyandiamide is used as a catalyst, ammonium phosphate groups can be catalyzed to form phosphoric anhydride, the phosphoric anhydride and hydroxyl on cellulose are subjected to esterification reaction, and the flame retardant is covalently combined with the fiber, so that the flame retardant durability of finished fabrics can be effectively improved, and durable finishing is realized.
Preferably, the durable flame retardant finishing liquid is prepared as follows:
dissolving the alkylamine boric acid phosphoric acid modified meglumine flame retardant in water to prepare an aqueous solution, adding dicyandiamide into the prepared aqueous solution as a catalyst, and uniformly stirring to obtain the durable flame-retardant finishing liquid.
Preferably, in the durable flame-retardant finishing liquid, the concentration of the alkylamine boric acid phosphoric acid modified meglumine flame retardant is 10-200 g/L. More preferably 30 to 100g/L.
Preferably, the mass concentration of dicyandiamide in the durable flame-retardant finishing liquid is 4-10 wt%. More preferably 4 to 8wt%. More preferably 4 to 6wt%.
The durable flame-retardant finishing liquid is applied to durable flame-retardant finishing of cotton fabrics.
And specifically, soaking the cotton fabric into the durable flame-retardant finishing liquid for padding, taking out after padding is finished, drying, and baking to obtain the durable flame-retardant cotton fabric.
The cotton fabric finished by the durable flame-retardant finishing liquid has excellent flame retardance and flame-retardant durability.
In the flame-retardant finishing process:
preferably, the bath ratio of the cotton fabric to the durable flame-retardant finishing liquid is 1: (10 to 30).
Preferably, the dipping temperature is 40 to 80 ℃ and the dipping time is 10 to 50min. More preferably, the dipping temperature is 60 to 80 ℃ and the dipping time is 20 to 40min.
Preferably, the padding mode is two-dipping and two-rolling, and the rolling residual ratio is 90-100%.
Preferably, the drying temperature is 60-90 ℃, and the drying time is 4-6 min.
Preferably, the baking temperature is 150-180 ℃, and the baking time is 3-6 min.
Preferably, the padding and drying process is repeated 1 to 2 times before baking.
According to the preparation method, the flame retardant performance of phosphorylated meglumine is further improved through the esterification reaction of boric acid, the water solubility of the flame retardant is reduced by skillfully utilizing the ionic reaction of alkylamine and phosphoric acid, and the alkylamine boric acid phosphoric acid modified meglumine flame retardant is prepared. The flame retardant can achieve better flame retardant performance with less consumption, reduces the consumption of the flame retardant, and endows the cotton fabric with excellent flame retardance and flame retardant durability through durable flame retardant finishing.
The preparation method of the alkylamine boracic acid phosphoric acid modified meglumine flame retardant takes meglumine as a matrix, and phosphoric acid and boric acid are added in sequence to carry out esterification reaction with the meglumine, so that the flame retardant property of phosphorylated meglumine is improved; and urea and alkylamine are added to modify the phosphorylated meglumine borate, and the hydrophobic acting force of the alkylamine is utilized to improve the adhesion of the flame retardant to the surface of the fabric, so that the using amount of the flame retardant is reduced, and the prepared alkylamine phosphorylated meglumine borate flame retardant has excellent flame retardant performance and flame retardant durability.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method, urea and alkylamine are added simultaneously to react with the phosphorylated meglumine borate, and the amino group of the alkylamine can perform an ionic reaction with phosphoric acid in the phosphorylated meglumine borate, so that the water solubility of the flame retardant is reduced; the prepared flame retardant can endow the cotton fabric with high-efficiency flame retardant effect at low dosage; compared with the boracic acid phosphorylated meglumine modified by only urea, when the LOI of the cotton fabric finished by adopting the durable flame-retardant finishing liquid reaches over 36 percent, the concentration of the alkylamine boracic acid phosphoric acid modified meglumine flame retardant is only 75g/L, and the concentration of the boracic acid phosphorylated meglumine modified by only urea is 200g/L.
(2) The invention has the advantages of low price of raw materials, simple and convenient preparation method, mild reaction conditions, strong controllability, good reproducibility and wide application prospect.
(3) After the durable flame-retardant cotton fabric finished by the durable flame-retardant finishing liquid provided by the invention is washed for 30 times, the LOI can still reach more than 30 percent and is reduced by less than 25 percent, and the durable flame-retardant cotton fabric has excellent flame-retardant durability and meets the requirement of durable finishing.
Drawings
FIG. 1 shows the dissolution of different flame retardants when the flame retardants prepared from different alkylamines are formulated into finishing liquid with a concentration of 200g/L; wherein, the alkylamine is n-propylamine, n-butylamine, n-pentylamine, octylamine and dodecylamine in sequence from left to right.
Detailed Description
The technical scheme of the invention is further explained by combining with specific embodiments. It should be understood that these examples are only for illustrating the technical solutions of the present invention and are not intended to limit the scope of the present invention. After reading the teaching of the present invention, the skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1: selection of alkylamines
(1) 6 parts of 75mL of DMF was put in 6 flasks, respectively, and 0.05mol of meglumine and 0.25mol of phosphoric acid were added to 6 parts of DMF to react at 130 ℃ for 2 hours. And then 0.20mol of boric acid is added into the six flasks, and the reaction is continued for 2 hours at 130 ℃ to obtain the phosphorylated meglumine borate. Finally, 0.25mol of urea was added to one of the flasks, and 0.15mol of urea and 0.20mol of alkylamine (n-propylamine, n-butylamine, n-pentylamine, octylamine, and dodecylamine, respectively) were added to the remaining 5 flasks, respectively, and reacted at 120 ℃ for 1 hour. Washing the reaction product with ethanol for several times, and drying at 80 ℃ to obtain 6 alkylamine boric acid phosphoric acid modified meglumine flame retardants, which are marked as 1#, 2#, 3#, 4#, 5# and 6# flame retardants respectively.
(2) And respectively preparing each flame retardant in the 6 alkylamine boric acid phosphoric acid modified meglumine flame retardants into 25g/L, 50g/L, 75g/L, 100g/L and 200g/L aqueous solutions for later use. Adding 6wt% of dicyandiamide as a catalyst into the prepared aqueous solution to obtain 30 flame-retardant finishing liquids.
(3) And (2) correspondingly dipping 30 cotton fabrics in the prepared 30 flame-retardant finishing liquids one by one, wherein the dipping temperature is 70 ℃, the dipping time is 30min, and the bath ratio is 1:20, soaking and rolling twice, keeping the liquid carrying rate at 100%, baking at 80 ℃ for 3min, repeating the soaking, rolling and drying process once, and baking at 170 ℃ for 5min. 30 different flame-retardant cotton fabrics are obtained.
In order to find out the influence of the type of alkylamine and the concentration of the flame retardant on the flame retardant performance of the flame retardant, the limiting oxygen index (LOI, unit%) of 30 flame-retardant cotton fabrics prepared above were respectively tested (reference standard GB/T5454-1997 textile Combustion Performance test-oxygen index test), and the results are shown in Table 1.
TABLE 1 influence of different alkylamine types and flame retardant concentrations on LOI of flame retardant finished cotton fabric
As can be seen from Table 1, the addition of alkylamine to flame retardants # 2- # 4 effectively reduced the amount of flame retardant used as compared to flame retardant # 1 without alkylamine. The alkyl chain is hydrophobic, so that the water solubility of the flame retardant is reduced due to the introduction of the alkyl chain in the flame retardant, and the hydrophobic acting force of the flame retardant is enhanced, so that the flame retardant is more easily attached to a fabric in the finishing process, and a better flame retardant effect can be achieved at a lower concentration. Under the condition of the same flame retardant amount, the flame retardant (2 #) prepared from the n-propylamine has the best flame retardant property, the longer the alkyl chain is, the lower the flame retardant property is, and the flame retardant properties of the 5# (octylamine) flame retardant and the 6# (dodecylamine) flame retardant are poorer than that of the 1# flame retardant. This is probably because the alkyl chain has no flame retardant effect, but rather reduces the LOI of the cotton fabric due to its flammability, and the longer the alkyl chain, the less flame retardant elements are in the flame retardant, and the combination of factors results in the reduction of flame retardant properties.
FIG. 1 shows the dissolution of various flame retardants in a solution when different kinds of alkylamine boric acid phosphoric acid modified meglumine flame retardants are respectively prepared into flame-retardant finishing liquid with the concentration of 200g/L. As can be seen from FIG. 1, the longer the alkyl chain of the selected alkylamine is, the more hydrophobic the prepared flame retardant is, and the poorer the solubility is.
In order to examine the flame-retardant washfastness (flame-retardant durability) of the flame-retardant cotton fabric, a wash-fastness test was carried out on the flame-retardant cotton fabric finished with the flame-retardant finishing liquor having a concentration of 200g/L formulated with # 2 flame retardant (reference standard AATCC 61-2013 wash-fastness to water: accelerated method, which is equivalent to 5 washes in the home). The flame retardant durability of the flame retardant cotton fabric was evaluated by LOI values after 5, 10, 15, 20, 25, 30 home washes. The results are shown in Table 2.
TABLE 2 LOI Effect of different washing times on flame retardant Cotton fabrics
| Number of washes | LOI/％ |
| 5 | 39.2 |
| 10 | 38.1 |
| 15 | 37.2 |
| 20 | 35.9 |
| 25 | 34.5 |
| 30 | 33.4 |
As can be seen from Table 2, after 30 times of household washing, the LOI of the flame-retardant cotton fabric is still more than 30%, and the flame-retardant cotton fabric has excellent flame-retardant durability.
Comparing the No. 1, the No. 2 and the No. 3 flame retardants, it can be found that when the LOI of the cotton fabric reaches more than 36%, the concentration of the flame retardant required for preparing the flame-retardant finishing liquid by the No. 1 flame retardant without adding alkylamine is 200g/L, while the concentration of the flame retardant required for preparing the flame-retardant finishing liquid by the No. 2 and the No. 3 flame retardants is only 75g/L, so that the using amount is obviously reduced, the flame-retardant efficiency is effectively improved, and the cost is reduced.
Example 2: selection of reaction temperature of boric acid
(1) 5 parts of 75mL of DMF was put in five flasks, respectively, and 0.05mol of meglumine and 0.25mol of phosphoric acid were added to 5 parts of DMF to react at 130 ℃ for 2 hours. Subsequently, 0.2mol of boric acid was added to the 5 flasks and reacted at 110 ℃,120 ℃,130 ℃, 140 ℃ and 150 ℃ for 2 hours, respectively. Finally, 0.15mol of urea and 0.2mol of n-propylamine were added to the five flasks, respectively, and reacted at 120 ℃ for 1 hour. Washing the reaction product with ethanol for several times, and drying at 80 ℃ to obtain 5 alkylamine boric acid phosphoric acid modified meglumine flame retardants.
(2) And respectively preparing the 5 alkylamine boric acid phosphoric acid modified meglumine flame retardants into 75g/L aqueous solutions for later use. 6wt% of dicyandiamide is added into the prepared aqueous solution as a catalyst.
(3) And (3) correspondingly dipping 5 pieces of cotton fabrics in the prepared flame-retardant finishing liquid one by one, wherein the dipping temperature is 70 ℃, the dipping time is 30min, the bath ratio is 1. Obtaining 5 different flame-retardant cotton fabrics
The Limiting Oxygen Index (LOI) of the 5 flame-retardant cotton fabrics was tested and the results are shown in Table 2.
TABLE 3 influence of different reaction temperatures on the flame retardancy of flame retardant finished Cotton fabrics
| Boric acid reaction temperature/. Degree.C | LOI/％ |
| 110 | 33.4 |
| 120 | 34.8 |
| 130 | 36.9 |
| 140 | 36.8 |
| 150 | 36.7 |
Because the esterification reaction is a reversible reaction, water generated in the reaction system needs to be continuously taken away to promote the forward reaction, the reaction temperature cannot be too low, and the influence of the temperature on the LOI value is examined in the range of 110-150 ℃. As shown in Table 2, at a lower temperature, the reaction was incomplete, and as the reaction temperature increased, the LOI value increased and the degree of reaction increased; however, when the temperature is too high, the viscosity of the system is rapidly increased, which affects the subsequent reaction, and the system also has partial side reactions, which affect the LOI value, so that the temperature of 130 ℃ is preferably selected.
Example 3: selection of the amount of n-propylamine to be used (selection of the molar ratio of phosphoric acid to urea)
(1) 5 parts of 75mL of DMF was put in five flasks, respectively, and 0.05mol of meglumine and 0.25mol of phosphoric acid were added to 5 parts of DMF to react at 130 ℃ for 2 hours. Then, 0.2mol of boric acid was added to the 5 flasks and reacted at 130 ℃ for 2 hours. Finally, urea and n-propylamine (0.2 mol of urea and 0.1mol of n-propylamine, 0.15mol of urea and 0.2mol of n-propylamine, 0.1mol of urea and 0.3mol of n-propylamine, 0.05mol of urea and 0.4mol of n-propylamine, 0.5mol of n-propylamine) were added to the five flasks, respectively, and reacted at 120 ℃ for 1 hour. Washing the reaction product with ethanol for several times, and drying at 80 ℃ to obtain 5 alkylamine boric acid phosphoric acid modified meglumine flame retardants.
(2) And respectively preparing the 5 alkylamine boric acid phosphoric acid modified meglumine flame retardants into 75g/L aqueous solutions for later use. 6wt% of dicyandiamide is added into the prepared aqueous solution as a catalyst.
(3) And (3) correspondingly dipping 5 cotton fabrics in the prepared flame-retardant finishing liquid one by one, wherein the dipping temperature is 70 ℃, the dipping time is 30min, the bath ratio is 1.
The Limiting Oxygen Index (LOI) of 5 flame-retardant cotton fabrics was tested and the results are shown in Table 4.
TABLE 4 Effect of different amounts of n-propylamine on LOI of flame retardant finished Cotton Fabric
| Flame-retardant cotton fabric numbering | LOI/％ |
| A | 35.2 |
| B | 36.9 |
| C | 34.8 |
| D | 33.2 |
| E | 31.9 |
As can be seen from table 4, the flame retardant cotton fabric B (molar ratio of phosphoric acid to urea is 1. The LOI of the flame-retardant cotton fabric A (the molar ratio of phosphoric acid to urea is 1. While the flame retardant properties of the flame retardant cotton fabrics C, D and E (the molar ratio of phosphoric acid to urea is 1, 0.4, 1, 0.2 and no urea is used) are inferior to B, probably because the urea is used in a small amount or not used, the n-propylamine is used in a large amount, and the n-propylamine itself is not flame retardant and flammable, so the flame retardant properties of the prepared flame retardant are reduced.
Example 4: selection of the molar ratio of meglumine to boronic acid
(1) 6 parts of 75mL of DMF were placed in 6 flasks, respectively, and 0.05mol of meglumine and 0.25mol of phosphoric acid were added to 6 parts of DMF, followed by reaction at 130 ℃ for 2 hours. Then, boric acid (wherein the molar mass of the boric acid is 0mol, 0.05mol, 0.10mol, 0.15mol, 0.20mol or 0.25 mol) is added into the six flasks, and the reaction is continued for 2 hours at 130 ℃ to obtain the phosphorylated meglumine borate. Finally, 0.15mol of urea and 0.2mol of n-propylamine were added to the six flasks, respectively, and reacted at 120 ℃ for 1 hour. Washing the reaction product with ethanol for several times, and drying at 80 ℃ to obtain 6 alkylamine boric acid phosphoric acid modified meglumine flame retardants.
(2) The 6 alkylamine boric acid phosphoric acid modified meglumine flame retardants are respectively prepared into 75g/L aqueous solution for later use. 6wt% of dicyandiamide is added into 6 parts of the prepared aqueous solution respectively to serve as a catalyst, and 6 kinds of flame-retardant finishing liquid are obtained.
(3) Soaking 6 pieces of cotton fabrics in the prepared 6 flame-retardant finishing liquids in a one-to-one correspondence manner, wherein the soaking temperature is 70 ℃, the soaking time is 30min, and the bath ratio is 1:20, soaking and rolling twice, keeping the liquid carrying rate at 100%, baking at 80 ℃ for 3min, repeating the soaking, rolling and drying process once, and baking at 170 ℃ for 5min. 6 different flame-retardant cotton fabrics are obtained.
The resulting 6-medium cotton fabric was subjected to a Limiting Oxygen Index (LOI) test, and the results are shown in table 5.
TABLE 5 influence of different meglumine to boric acid molar ratios on the LOI of flame-retardant cotton fabrics
| Molar ratio of meglumine to boric acid | LOI/％ |
| 1:0 | 29.9 |
| 1:1 | 31.3 |
| 1:2 | 32.6 |
| 1:3 | 34.4 |
| 1:4 | 36.9 |
| 1:5 | 36.7 |
It can be seen from table 5 that the addition of boric acid can improve the flame retardant performance of the flame retardant, and as the amount of boric acid is increased, the LOI of the finished cotton fabric is increased, and when the molar ratio of meglumine to boric acid is 1: at 4, LOI reaches a maximum of 36.9%. When the boric acid is added too much (the molar ratio of the meglumine to the boric acid is 1:5), the degree of side reaction of the system is increased, and the LOI value is slightly reduced.
Claims (10)
1. The preparation method of the alkylamine boric acid phosphoric acid modified meglumine flame retardant is characterized by comprising the following steps of:
(1) Reacting meglumine with phosphoric acid in a solvent to obtain a solution A;
(2) Adding boric acid into the solution A for reaction to obtain a solution B;
(3) And adding urea and alkylamine into the solution B for reaction, and obtaining the alkylamine boric acid phosphoric acid modified meglumine flame retardant after the reaction is finished.
2. The method for preparing the alkylamine boronic acid phosphoric acid modified meglumine flame retardant of claim 1, wherein the molar ratio of meglumine to phosphoric acid is 1: (3-10);
the molar ratio of the meglumine to the boric acid is 1: (1-5).
3. The method of claim 1, wherein the molar ratio of phosphoric acid to urea is 1: (0.01 to 0.9);
the number of moles of alkylamine added is twice the difference between the number of moles of phosphoric acid and the number of moles of urea.
4. The preparation method of the alkylamine boronic acid phosphoric acid modified meglumine flame retardant of claim 1, wherein in the step (1), the reaction temperature of meglumine and phosphoric acid is 120-140 ℃, and the reaction time is 1-3 h;
the solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide and dichloromethane.
5. The method for preparing the alkylamine boronic acid phosphoric acid modified meglumine flame retardant of claim 1, wherein in the step (2), the reaction temperature after the addition of the boric acid is 110 to 150 ℃, and the reaction time is 1 to 3 hours.
6. The method for preparing the alkylamine boronic acid phosphoric acid modified meglumine flame retardant according to claim 1, wherein in the step (3), the reaction temperature after adding the urea and the alkylamine is 110 to 130 ℃, and the reaction time is 0.5 to 2 hours;
the alkylamine is one or more of n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, heptylamine, octylamine and dodecylamine.
7. An alkylamine boracic acid phosphoric acid modified meglumine flame retardant which is prepared by the preparation method of any one of claims 1 to 6.
8. A durable flame retardant finishing liquor characterized in that the durable flame retardant finishing liquor is an aqueous solution of alkylamine boracic acid phosphoric acid modified meglumine flame retardant and catalyst dicyandiamide described in claim 7.
9. The method for preparing the alkylamine boronic acid phosphoric acid modified meglumine flame retardant of claim 8, wherein the concentration of the alkylamine boronic acid phosphoric acid modified meglumine flame retardant in the durable flame-retardant finishing liquid is 10 to 200g/L;
the mass concentration of the dicyandiamide is 4-10 wt%.
10. Use of a durable flame retardant finishing liquor according to claim 8 or 9 in durable flame retardant finishing of cotton fabrics.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211386163.9A CN115785145A (en) | 2022-11-07 | 2022-11-07 | Preparation method, product and application of alkylamine boric acid phosphoric acid modified meglumine flame retardant |
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| CN202211386163.9A CN115785145A (en) | 2022-11-07 | 2022-11-07 | Preparation method, product and application of alkylamine boric acid phosphoric acid modified meglumine flame retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118240497A (en) * | 2024-04-03 | 2024-06-25 | 皇冠新材料科技股份有限公司 | Flame-retardant water-based pressure-sensitive adhesive protective film and processing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118240497A (en) * | 2024-04-03 | 2024-06-25 | 皇冠新材料科技股份有限公司 | Flame-retardant water-based pressure-sensitive adhesive protective film and processing method thereof |
| CN118240497B (en) * | 2024-04-03 | 2024-08-30 | 皇冠新材料科技股份有限公司 | Flame-retardant water-based pressure-sensitive adhesive protective film and processing method thereof |
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