CN111116903A - Silicon-containing polycarbonyl urea flame retardant and preparation method thereof - Google Patents
Silicon-containing polycarbonyl urea flame retardant and preparation method thereof Download PDFInfo
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- CN111116903A CN111116903A CN201911413704.0A CN201911413704A CN111116903A CN 111116903 A CN111116903 A CN 111116903A CN 201911413704 A CN201911413704 A CN 201911413704A CN 111116903 A CN111116903 A CN 111116903A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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Abstract
The invention provides a silicon-containing polycarbonyl urea flame retardant and a preparation method thereof, wherein the silicon-containing polycarbonyl urea is prepared by a two-step method: firstly, methyl carbamate is used as a reaction monomer to prepare the polycarbonyl urea, and then the terminal amino group of the polycarbonyl urea reacts with the epoxy group of a silane coupling agent KH-560 to obtain the silicon-containing polycarbonyl urea. The molecular chain of the silicon-containing polycarbonyl urea flame retardant has high-density amido bonds, the end group contains flame-retardant silicon elements, and the flame retardant is efficient, non-toxic and low-cost.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to a silicon-containing polycarbonyl urea flame retardant and a preparation method thereof.
Background
The intumescent flame retardant has the advantages of good flame retardant effect, low smoke and low toxicity, and meets the requirement of environmental protection, so the intumescent flame retardant is a focus and hot spot of research of a new generation of flame retardant at present. The char-forming agent is an important component of the intumescent flame retardant, and the char-forming amount, char-forming density, char-forming strength and the like of the intumescent flame retardant applied to the polymer have a direct relationship with the char-forming agent, which can also directly influence the flame-retardant effect of the intumescent flame retardant on the polymer. The molecules of the traditional carbon forming agent contain a large amount of hydroxyl groups, so that the application of the polymer material is influenced due to small molecular weight, poor thermal stability and poor water resistance. The currently researched novel macromolecule carbon forming agent greatly makes up the defects of the traditional carbon forming agent in the aspects of molecular weight, thermal stability, molecular structure, group reaction activity and the like.
The novel macromolecular charring agent mainly comprises triazine charring agents, hyperbranched charring agents, phenolic resin charring agents and polyamide charring agents, the former three macromolecular charring agents are widely researched at present, the polyamide charring agents are mainly polyamide-6 and aromatic polyamide, and the other types of polyamides are less in application as charring agents, especially polyamides with high-density amido bonds.
Disclosure of Invention
The invention aims to provide a silicon-containing polycarbonyl urea flame retardant and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a silicon-containing polycarbonyl urea flame retardant having the structural formula:
in the formula (I), the compound is shown in the specification,
n is an average polymerization degree, and n is 10 to 1000.
The invention also provides a preparation method of the silicon-containing polycarbonyl urea flame retardant, which comprises the following steps:
s1, mixing methyl carbamate, urea, a catalyst and a solvent, and heating the mixed solution to completely dissolve the methyl carbamate and the urea, wherein the mixed solution is colorless transparent liquid;
s2, continuously heating the mixed solution, and reacting until the mixed solution turns from colorless transparent liquid to turbid and then turns into milky liquid;
s3, after continuously reacting for 8-12 hours, adding a silane coupling agent KH-560 into the mixed solution, dropwise adding an alkaline solution, adjusting the pH value to 10-11, and continuously reacting;
and S4, washing the reaction precipitate at the bottom of the mixed solution with water, washing with alcohol, filtering and drying to obtain a white powder product.
Further, in S1, the mass ratio of the methyl carbamate to the urea is 20-50: 1; the mixed solution is heated to 20-80 ℃.
Further, in S1, the catalyst includes alkali metal salts, carbonates, and organic acid salts of alcohols.
Further, in S1, the catalyst is an alkali metal salt of an alcohol, including sodium methoxide or potassium methoxide; the dosage of the catalyst is 0.1-5% of the mass of the methyl carbamate.
Further, in S2, the mixed solution is continuously heated to 100-160 ℃.
Further, in S3, after continuing the reaction for 10 hours, the silane coupling agent KH-560 was added to the mixture, and a sodium hydroxide solution was added dropwise to adjust the pH to 11, and the reaction was continued.
Further, in S4, washing the reaction precipitate at the bottom of the mixed solution with deionized water and ethanol, and drying the reaction precipitate for 3-12 hours at 80-120 ℃ under normal pressure or vacuum. Preferably, drying is carried out under vacuum at 110 ℃ for 6 hours.
In the present invention, the chemical reaction equation of the polycarbonyl urea is shown in formula (1).
The chemical reaction equation of the silicon-containing polycarbonyl urea is shown as a formula (2).
The flame retardant containing silicon polycarbonyl urea and the preparation method thereof have the beneficial effects that:
1. the preparation method of the silicon-containing polycarbonyl urea flame retardant has simple process, and the needed raw materials of methyl carbamate and urea have wide sources. The whole preparation process is not used, no toxic substance is generated, the environment is not polluted, instruments and equipment are not corroded, and the green synthesis process is realized.
2. According to the invention, methyl carbamate is used as a reaction monomer to prepare the polycarbonyl urea, and then the terminal amino group of the polycarbonyl urea is reacted with the epoxy group of a silane coupling agent KH-560 to obtain the silicon-containing polycarbonyl urea, wherein the molecular chain of the silicon-containing polycarbonyl urea has high-density amido bonds, the main chain of the silicon-containing polycarbonyl urea is the same as that of polyamide-1, and the terminal group of the silicon-containing polycarbonyl urea contains a flame retardant element silicon, so that the silicon-containing polycarbonyl urea is a high-efficiency, non-toxic and.
3. The silicon-containing polycarbonyl urea flame retardant prepared by the invention has the characteristics of adjustable thermal stability, capability of being compounded and modified with different polymers, and wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an IR spectrum of KH-560, polycarbonyl urea, silicon-containing polycarbonyl urea of example 6 of the present invention;
FIG. 2 is a graph of the experimental thermogravimetry of KH-560, polycarbonyl urea, KH-560/polycarbonyl urea fitted with the thermogravimetry curve, silicon-containing polycarbonyl urea of example 6 of the present invention;
FIG. 3 is a water contact angle of a polycarbonyl urea, silicon-containing polycarbonyl urea, in example 6 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a more typical embodiment of the present invention, there is provided a method for preparing a silicon-containing polycarbonyl urea flame retardant, comprising the steps of:
s1, adding methyl carbamate, urea, a catalyst and a solvent into a three-necked bottle, mixing, and heating the mixed solution to completely dissolve the methyl carbamate and the urea, wherein the mixed solution is colorless transparent liquid;
s2, continuously heating the mixed liquid, connecting a condensation pipe and a tail pipe to recover the solvent, reacting under stirring until the mixed liquid in the three-necked bottle turns turbid from colorless transparent liquid and then turns into milky liquid;
s3, after continuously reacting for 8-12 hours, adding a silane coupling agent KH-560 into a three-necked flask, dropwise adding an alkaline solution, adjusting the pH value to 10-11, and continuously reacting;
s4, turning off a power supply and condensed water after the reaction is finished, and taking out the three-necked bottle; and washing the reaction precipitate at the bottom of the mixed solution with water, washing with alcohol, filtering and drying to obtain a white powder product.
The technical solution of the present invention is further explained below with reference to several embodiments and corresponding drawings. In the following examples, the purity of the reagents used, including methyl carbamate, urea, catalyst, etc., was analytical.
Example 1
75g of methyl carbamate, 1.5g of urea, 1.35g of sodium methoxide and 100ml of methanol are added into a three-necked flask, and the temperature is raised to 60 ℃ to dissolve the methyl carbamate, the urea and the sodium methoxide to obtain colorless transparent liquid. After further heating to 140 ℃ and reaction for about 20 minutes, the colorless transparent liquid in the three-necked flask became cloudy and then turned into a milky white liquid. After 8 hours of reaction, 5.9g of silane coupling agent KH-560 is added, a certain amount of sodium hydroxide solution is dripped, the pH value is adjusted to 10, and the reaction is continued for 3 hours. And (3) after the reaction is finished, turning off the power supply, taking out the product after the three-necked bottle is cooled to room temperature, and carrying out water washing, alcohol washing, filtering and suction filtration on the product, and then carrying out vacuum drying for 6 hours at 110 ℃ to obtain a white powder product.
Example 2
75g of methyl carbamate, 3g of urea, 2.7g of sodium methoxide and 100ml of methanol are added into a three-necked flask, and the temperature is raised to 60 ℃ to dissolve the methyl carbamate, the urea and the sodium methoxide to obtain colorless transparent liquid. After further heating to 140 ℃ and reaction for about 20 minutes, the colorless transparent liquid in the three-necked flask became cloudy and then turned into a milky white liquid. After 10 hours of reaction, 5.9g of silane coupling agent KH-560 is added, a certain amount of sodium hydroxide solution is dripped, the pH value is adjusted to 10, and the reaction is continued for 3 hours. And (3) after the reaction is finished, turning off the power supply, taking out the product after the three-necked bottle is cooled to room temperature, and carrying out water washing, alcohol washing, filtering and suction filtration on the product, and then carrying out vacuum drying for 6 hours at 110 ℃ to obtain a white powder product.
Example 3
75g of methyl carbamate, 3g of urea, 1.35g of sodium methoxide and 100ml of methanol are added into a three-necked flask, and the temperature is raised to 60 ℃ to dissolve the methyl carbamate, the urea and the sodium methoxide to obtain colorless transparent liquid. After further heating to 150 ℃ and reaction for about 20 minutes, the colorless transparent liquid in the three-necked flask became cloudy and then turned into a milky white liquid. After 10 hours of reaction, 5.9g of silane coupling agent KH-560 is added, a certain amount of sodium hydroxide solution is added dropwise, the pH value is adjusted to 11, and the reaction is continued for 3 hours. And (3) after the reaction is finished, turning off the power supply, taking out the product after the three-necked bottle is cooled to room temperature, and carrying out water washing, alcohol washing, filtering and suction filtration on the product, and then carrying out vacuum drying for 6 hours at 110 ℃ to obtain a white powder product.
Example 4
75g of methyl carbamate, 1.5g of urea, 2.7g of sodium methoxide and 100ml of methanol are added into a three-necked flask, and the temperature is raised to 60 ℃ to dissolve the methyl carbamate, the urea and the sodium methoxide to obtain colorless transparent liquid. After further heating to 150 ℃ and reaction for about 20 minutes, the colorless transparent liquid in the three-necked flask became cloudy and then turned into a milky white liquid. After 12 hours of reaction, 5.9g of silane coupling agent KH-560 is added, a certain amount of sodium hydroxide solution is added dropwise, the pH value is adjusted to 11, and the reaction is continued for 3 hours. And (3) after the reaction is finished, turning off the power supply, taking out the product after the three-necked bottle is cooled to room temperature, and carrying out water washing, alcohol washing, filtering and suction filtration on the product, and then carrying out vacuum drying for 6 hours at 110 ℃ to obtain a white powder product.
Example 5
75g of methyl carbamate, 1.5g of urea, 2.7g of sodium methoxide and 100ml of methanol are added into a three-necked flask, and the temperature is raised to 60 ℃ to dissolve the methyl carbamate, the urea and the sodium methoxide to obtain colorless transparent liquid. After further heating to 160 ℃ and reaction for about 20 minutes, the colorless transparent liquid in the three-necked flask became cloudy and then turned into a milky white liquid. After 12 hours of reaction, 5.9g of silane coupling agent KH-560 is added, a certain amount of sodium hydroxide solution is dripped, the pH value is adjusted to 10, and the reaction is continued for 3 hours. And (3) after the reaction is finished, turning off the power supply, taking out the product after the three-necked bottle is cooled to room temperature, and carrying out water washing, alcohol washing, filtering and suction filtration on the product, and then carrying out vacuum drying for 6 hours at 110 ℃ to obtain a white powder product.
Example 6
75g of methyl carbamate, 1.5g of urea, 4.05g of sodium methoxide and 100ml of methanol are added into a three-necked flask, and the temperature is raised to 60 ℃ to dissolve the methyl carbamate, the urea and the sodium methoxide to obtain colorless transparent liquid. After further heating to 160 ℃ and reaction for about 20 minutes, the colorless transparent liquid in the three-necked flask became cloudy and then turned into a milky white liquid. After 10 hours of reaction, 5.9g of silane coupling agent KH-560 is added, a certain amount of sodium hydroxide solution is added dropwise, the pH value is adjusted to 11, and the reaction is continued for 3 hours. And (3) after the reaction is finished, turning off the power supply, taking out the product after the three-necked bottle is cooled to room temperature, and carrying out water washing, alcohol washing, filtering and suction filtration on the product, and then carrying out vacuum drying for 6 hours at 110 ℃ to obtain a white powder product.
The properties of the white powder product obtained in example 6 were characterized. FIG. 1 is an IR spectrum of KH-560, polycarbonyl urea (PCU), silicon-containing polycarbonyl urea (Si-PCU) in example 6; FIG. 2 is a graph of experimental thermogravimetry of KH-560, polycarbonyl urea (PCU), KH-560/polycarbonyl urea (KH-560+ PCU) fitted with thermogravimetry curve, silicon-containing polycarbonyl urea (Si-PCU) in example 6 of the present invention; FIG. 3 is a water contact angle of polycarbonyl urea (PCU) and silicon-containing polycarbonyl urea (Si-PCU) in example 6 of the present invention.
As can be seen from FIGS. 1-3, the silicon-containing polycarbonylureas have good thermal stability and lipophilicity.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A silicon-containing polycarbonyl urea flame retardant characterized by: the structural formula of the silicon-containing polycarbonyl urea flame retardant is as follows:
in the formula (I), the compound is shown in the specification,
n is an average polymerization degree, and n is 10 to 1000.
2. The method of preparing a silicon-containing polycarbonyl urea flame retardant of claim 1, wherein: the method comprises the following steps:
s1, mixing methyl carbamate, urea, a catalyst and a solvent, and heating the mixed solution to completely dissolve the methyl carbamate and the urea, wherein the mixed solution is colorless transparent liquid;
s2, continuously heating the mixed solution, and reacting until the mixed solution turns from colorless transparent liquid to turbid and then turns into milky liquid;
s3, after continuously reacting for 8-12 hours, adding a silane coupling agent KH-560 into the mixed solution, dropwise adding an alkaline solution, adjusting the pH value to 10-11, and continuously reacting;
and S4, washing the reaction precipitate at the bottom of the mixed solution with water, washing with alcohol, filtering and drying to obtain a white powder product.
3. The method of claim 2, wherein: in S1, the mass ratio of the methyl carbamate to the urea is 20-50: 1; the mixed solution is heated to 20-80 ℃.
4. The production method according to claim 2 or 3, characterized in that: in S1, the catalyst includes alkali metal salts, carbonates, and organic acid salts of alcohols.
5. The method of claim 4, wherein: in S1, the catalyst is alkali metal salt of alcohol, including sodium methoxide or potassium methoxide; the dosage of the catalyst is 0.1-5% of the mass of the methyl carbamate.
6. The method of claim 2, wherein: in S2, the mixed solution is continuously heated to 100-160 ℃.
7. The method of claim 2, wherein: in S3, after the reaction is continued for 10 hours, the silane coupling agent KH-560 is added to the mixed solution, and a sodium hydroxide solution is added dropwise to adjust the pH to 11, and the reaction is continued.
8. The method of claim 2, wherein: and S4, washing the reaction precipitate at the bottom of the mixed solution with deionized water and ethanol, and drying for 3-12 hours at 80-120 ℃ under normal pressure or vacuum.
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Citations (4)
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|---|---|---|---|---|
| CN103254101A (en) * | 2013-04-03 | 2013-08-21 | 中北大学 | Method and equipment for preparation of methyl carbamate |
| CN104262930A (en) * | 2014-10-13 | 2015-01-07 | 四川大学 | Polycarbonate composition of sulfur and nitrogen contained organic silicon flame retardant and preparation method |
| CN105176074A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nano hybridized flame-retardant polyamide 6 and preparation method thereof |
| CN110114381A (en) * | 2016-09-12 | 2019-08-09 | 树脂材料集团公司 | Blend and coating containing polyphenol alcoxylates |
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- 2019-12-31 CN CN201911413704.0A patent/CN111116903A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254101A (en) * | 2013-04-03 | 2013-08-21 | 中北大学 | Method and equipment for preparation of methyl carbamate |
| CN104262930A (en) * | 2014-10-13 | 2015-01-07 | 四川大学 | Polycarbonate composition of sulfur and nitrogen contained organic silicon flame retardant and preparation method |
| CN105176074A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nano hybridized flame-retardant polyamide 6 and preparation method thereof |
| CN110114381A (en) * | 2016-09-12 | 2019-08-09 | 树脂材料集团公司 | Blend and coating containing polyphenol alcoxylates |
Non-Patent Citations (1)
| Title |
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| YING REN等: ""Synthesis of silicic poly carbonyl urea and its flame-retardant effect on polypropylene for char forming"", 《JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY》 * |
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Application publication date: 20200508 |