CN114890960A - Preparation method and application of hydroxyl modified melamine - Google Patents
Preparation method and application of hydroxyl modified melamine Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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Abstract
The invention discloses a preparation method of hydroxyl modified melamine, which comprises the steps of adding melamine into a reactor with a reflux device, adding deionized water, stirring uniformly, heating to 60-100 ℃, then dropwise adding hydroxyl-containing halohydrocarbon, dropwise adding an alkaline aqueous solution until the pH value is not changed when a reaction solution becomes clear, continuing stirring for reaction for 1-3 hours, cooling, standing, removing solids after solid-liquid separation, removing a solvent from a filtrate, and drying to obtain the hydroxyl modified melamine. Compared with the prior art, the method avoids using harmful raw materials such as formaldehyde and the like in the preparation process, byproducts are nontoxic and harmless inorganic salts, and the method is simple to operate, mild in reaction conditions, low in requirement on equipment and suitable for industrial production; the prepared modified melamine has high activity, can be compounded with other polyols and completely reacted, can be used as a reactive flame retardant, and the polyurethane material prepared by adopting the modified melamine has excellent flame retardance and mechanical property.
Description
Technical Field
The invention relates to a preparation method and application of hydroxyl modified melamine, belonging to the technical field of polyurethane materials.
Background
Polyurethane (PU) materials are developed from the 30 s of the 20 th century, become the sixth most synthetic materials in the world at present, have excellent physical properties, are resistant to chemical corrosion, have strong adhesive force with various materials, and are widely applied to the fields of coatings, adhesives, fibers, synthetic leather, refrigeration equipment, building heat preservation and insulation materials and the like. However, polyurethane, one of the organic high molecular polymers, has been troubling the flammability problem of its related products, and the fire extinguishing work is very difficult due to the high heat release rate during the combustion process and the large amount of toxic smoke generated. In order to solve the problem, researchers have conducted a lot of research work, and adding flame retardants to polyurethane materials is an effective way.
Flame retardants are generally classified into physical addition type flame retardants and chemical reaction type flame retardants. The physical addition type flame retardant is prepared by adding inorganic substances (such as aluminum hydroxide, antimony oxide and the like) or organic substances (organic halides, organic phosphide, organic nitrogen-containing compounds and the like) into a polyurethane material by a mechanical mixing method to ensure that the polyurethane material has flame retardant performance, but the method is easy to reduce the performance of the polyurethane material and easily generates a dialysis migration phenomenon to reduce the flame retardant performance; halogen, phosphorus and nitrogen atoms are introduced into polyether polyol molecules to form a chemical reaction type flame retardant which can be chemically embedded into polyurethane molecules to form flame retardant polyurethane hard bubbles, so that the physical properties of the obtained polyurethane material cannot be reduced, and the phenomenon of dialysis and migration cannot occur. However, halogen-containing flame retardants form hydrogen halides during combustion, and are highly toxic and costly. The melamine is one of important series in the halogen-free flame retardant, has obvious effect on improving the flame retardant property of polyurethane, and has the characteristics of low smoke, no corrosion, low toxicity, stable property, low price and the like, so that the melamine flame retardant can be widely applied to the flame retardant field of polyurethane.
The Chinese patent with publication number CN 102229746A discloses a flame-retardant polyurethane composite material and a preparation method thereof, wherein firstly, flame-retardant polyol is prepared, then the flame-retardant polyol is mixed with a co-mixing type flame retardant to form a mixed system, polyisocyanate is added into the mixed system, and the flame-retardant polyurethane composite material is obtained after reaction, wherein the co-mixing type flame retardant is one or more of ammonium polyphosphate, melamine cyanurate, polysiloxane, graphene, carbon nano tubes, kaolin and montmorillonite. Although melamine is used as a flame retardant, the application of melamine still belongs to physical mixing, so that the performance of the polyurethane material is easily reduced, and the flame retardant performance is reduced due to the dialysis and migration phenomena; the Chinese patent with publication number CN111116893A discloses a synthesis method of flame-retardant melamine-phenolic aldehyde hard bubble polyether polyol, which comprises the steps of firstly reacting melamine with formaldehyde to obtain a melamine-phenolic resin copolymer, continuously introducing propylene oxide to react until the reaction is finished in the presence of a catalyst dimethylethanolamine at the temperature of 90-105 ℃ and the pressure of 0.05-0.30 MPa to obtain the flame-retardant hard bubble polyether polyol, wherein a large amount of phenol and formaldehyde are used in the reaction, and the reaction is not environment-friendly; the Chinese patent with publication number CN 111117209A discloses a preparation method of a polyurethane flame-retardant antistatic composite material, graphene oxide is reduced by melamine through the reaction of the graphene oxide and the melamine in an aqueous solution, and a novel antistatic flame retardant is generated by a one-step method. The Shuguang et al researches the synthesis of flame-retardant melamine hard bubble polyether polyol (polyurethane industry, 2017, 32 and 28), melamine and propylene oxide are used as raw materials, and the flame-retardant melamine polyether polyol is obtained by heating reaction in a high-pressure reaction kettle.
In conclusion, in the research and invention of melamine as a flame retardant, most melamine monomers are used as the flame retardant, and basically belong to a physical additive type; in the use of few chemical reaction type flame retardants, either a large amount of phenol and formaldehyde are used as raw materials or reaction equipment and conditions such as high temperature and high pressure are used, which are unfavorable for environmental protection and safety.
Disclosure of Invention
The invention aims to solve the problems that melamine is directly used as an additive in the prior art and a large amount of phenol, formaldehyde and other harmful chemical reagents are used in the reaction of modifying melamine, and provides a preparation method of hydroxyl modified melamine.
Technical scheme
The method firstly reacts melamine with hydroxyl-containing halohydrocarbon to prepare hydroxyl-modified melamine, and the modified melamine has the characteristics of high activity, capability of being compounded with other polyols and complete reaction; and then uniformly mixing the hydroxyl modified melamine with the isocyanate modified attapulgite and the like, adding metered isocyanate into a mixing system, and mechanically stirring for reaction for a period of time to obtain the flame retardant polyurethane material. The specific scheme is as follows:
a preparation method of hydroxyl modified melamine comprises the following steps: adding melamine into a reactor with a reflux device, adding deionized water, heating to 60-100 ℃ after uniformly stirring, then dropwise adding halogenated hydrocarbon containing hydroxyl, dropwise adding an alkaline aqueous solution when the reaction solution becomes clear, tracking and detecting the pH value until the pH value does not change, continuously stirring and reacting for 1-3 h, then cooling, standing, removing solids after solid-liquid separation to obtain a filtrate, removing the solvent from the filtrate, and drying to obtain the hydroxyl modified melamine.
Further, the halogenated hydrocarbon containing hydroxyl is selected from one or more of bromoethanol, chloroethanol, 3-bromo-1-propanol, 3-chloro-1-propanol, 2-bromo-1-propanol, 2-chloro-1-propanol, 4-bromo-1-butanol, 4-chloro-1-butanol, 3-bromo-1-butanol, 3-chloro-1-butanol, 2-bromo-1-butanol, 2-chloro-1-butanol or chlorotert-butanol in any proportion.
Further, the molar ratio of the melamine to the hydroxyl-containing halogenated hydrocarbon is 1: 2-6.
Further, the alkaline aqueous solution is NaOH, KOH or NH 3 ·H 2 O、K 2 CO 3 Or Na 2 CO 3 An aqueous solution of (a).
The hydroxyl modified melamine is used for preparing flame-retardant polyurethane materials. The application method comprises the following steps:
mixing the hydroxyl modified melamine with a micromolecular chain extension cross-linking agent, polyether polyol, isocyanate modified attapulgite and an auxiliary agent, mechanically stirring for 8-12 min at the speed of 1200-2000 r/min, pouring into a mould after vacuum defoaming, and curing at room temperature to obtain a flame retardant polyurethane material;
the using amount of the micromolecule chain extension cross-linking agent accounts for 1-2% of the weight of the flame-retardant polyurethane material; the using amount of the polyether polyol accounts for 35-45% of the weight of the flame-retardant polyurethane material; the auxiliary agent is one or more of a catalyst, an antioxidant, an ultraviolet absorbent, a mildew preventive, a defoaming agent or a vulcanizing agent, and the amount of the auxiliary agent accounts for 2-5% of the weight of the flame-retardant polyurethane material;
the hydroxyl modified melamine accounts for 5-30% of the weight of the flame-retardant polyurethane material.
The amount of the isocyanate accounts for 30-50% of the weight of the flame-retardant polyurethane material; the amount of the isocyanate modified attapulgite accounts for 5-10% of the weight of the flame retardant polyurethane material.
The micromolecule chain-extending cross-linking agent is one or the combination of more than two of 1, 4-butanediol, ethylene glycol, diethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol or trimethylolpropane.
The polyether polyol is one or the combination of more than two of PPG2000, PPG3000, PEG2000, PEG3000, N-206, YG-84 or polytetrahydrofuran glycol (PTMG).
The isocyanate is one or the combination of more than two of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI) and hydrogenated diphenylmethane diisocyanate (H12 MDI).
The preparation method of the isocyanate modified attapulgite refers to the Chinese invention patent with the publication number of CN 106560235A.
The catalyst is any one of dibutyltin dilaurate, dibutyltin acetate or dibutyltin bis (dodecyl sulfur); the vulcanizing agent is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), 3, 5-dimethylthiotoluenediamine (DMTDA) or a combination thereof.
The invention has the beneficial effects that:
(1) the method takes the melamine and the halohydrocarbon as reaction raw materials, obtains the hydroxyl modified melamine through simple substitution reaction, has simple operation, mild reaction condition and low requirement on equipment, and is suitable for industrial production; in the preparation process, harmful raw materials such as formaldehyde and the like are avoided, the molecular utilization rate of the raw materials is high, most of the raw materials are converted into products, and byproducts are inorganic salts which are nontoxic and harmless to the environment, so that the preparation method conforms to the concept of green chemistry.
(2) The hydroxyl modified melamine with different structures is designed by utilizing the molecular theory and prepared, and the modified melamine has the characteristics of high activity, capability of being compounded with other polyols and complete reaction, and can be used as a reactive flame retardant.
(3) According to the invention, the added hydroxyl modified melamine and isocyanate modified attapulgite are used as a reactive flame retardant, and through in-situ polycondensation with the polyurethane prepolymer, the melamine and the attapulgite are uniformly dispersed in the polyurethane prepolymer in a chemical bonding form to prepare the structural melamine/polyurethane composite material. The use of the reactive flame retardant changes the additive flame retardant adopted in the traditional polyurethane material, uses the reactive flame retardant, increases the stability and other mechanical properties of the material, and reduces the production cost by adopting the reactive flame retardant.
Drawings
FIG. 1 is an infrared spectrum of a hydroxyl-modified melamine prepared in example 1;
FIG. 2 is an infrared spectrum of a hydroxyl modified melamine prepared in example 2.
Detailed Description
The technical solutions of the present invention are further described below with reference to the accompanying drawings and specific embodiments, which should not be construed as limiting the technical solutions.
Example 1
A preparation method of hydroxyl modified melamine comprises the following steps: adding melamine (5.04g, 40mmol) into a three-neck flask with a reflux device, adding 120mL of deionized water, stirring uniformly, heating to 82 ℃, starting to dropwise add bromoethanol (15.0g, 120mmol) to obtain a reaction solution, and dropwise adding K when the reaction solution becomes clear 2 CO 3 (16.56g,120mmol) of aqueous solution, tracking and detecting the pH value until the pH value is not changed, continuing stirring for reacting for 3 hours, then cooling, standing, filtering to remove solids to obtain filtrate, removing the solvent from the filtrate, and drying to obtain 7.28g of hydroxyl modified melamine.
The infrared spectrum of the hydroxyl-modified melamine obtained in example 1 is shown in FIG. 1, and the product was analyzed to contain the hydroxyl-modified melamine.
Example 2
A preparation method of hydroxyl modified melamine comprises the following steps: adding melamine (5.04g, 40mmol) into a three-neck flask with a reflux device, adding 50mL of deionized water, stirring uniformly, heating to 70 ℃, then dropwise adding chloroethanol (6.40g,80mmol) to obtain a reaction solution, and waiting for the reaction solution to reactWhen the solution became clear, Na was added dropwise 2 CO 3 And (3) tracking and detecting the pH value of the aqueous solution (8.49g,80mmol) until the pH value is not changed, continuously stirring for reacting for 2 hours, cooling, standing, filtering to remove solids to obtain filtrate, removing the solvent from the filtrate, and drying to obtain 6.84g of hydroxyl modified melamine.
The infrared spectrum of the hydroxyl modified melamine obtained in example 2 is shown in fig. 2, and the product contains hydroxyl modified melamine by analysis.
Example 3
The hydroxyl-modified melamine prepared in example 1 was used to prepare a flame retardant polyurethane material:
taking 15g of hydroxyl modified melamine, 8g of 1, 4-butanediol and 200035g of PPG into a three-neck flask, adding 0.4g of dibutyltin dilaurate serving as a catalyst, 2640.4 g of antioxidant BHT, 0.2g of N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine (UV-1) serving as an ultraviolet absorbent, 0.4g of attapulgite modified by a mildew preventive, 0.4g of an organic silicon defoamer and 0.4g of 3, 5-dimethylthiotoluenediamine serving as a vulcanizing agent, vacuum dehydrating the mixture at 105 ℃ for 2 hours, adding 5g of isocyanate modified attapulgite (prepared by adopting the method of example 1 in the Chinese invention patent with the publication number of CN 106560235A) and 40g of diphenylmethane diisocyanate (MDI), uniformly mixing, preheating the mixture by using high microwave fire for 2 minutes, mechanically stirring the mixture for 10 minutes at the rotating speed of 2000r/min, and then discharging the mixture, and (3) defoaming in a vacuum drying oven at 50 ℃ for 20min, taking out, pouring into a mold preheated to 70 ℃, and curing and molding at room temperature to obtain the flame-retardant polyurethane.
Example 4
The hydroxyl-modified melamine prepared in example 1 was used to prepare a flame retardant polyurethane material: the hydroxyl-modified melamine had a mass of 20g and the rest was the same as in example 3.
Example 5
The hydroxyl-modified melamine prepared in example 1 was used to prepare a flame retardant polyurethane material: the hydroxyl-modified melamine had a mass of 25g and was the same as in example 3.
Example 6
The hydroxyl-modified melamine prepared in example 1 was used to prepare a flame retardant polyurethane material: the hydroxyl-modified melamine had a mass of 30g and the rest was the same as in example 3.
Comparative example 1
Unmodified melamine was used to prepare flame retardant polyurethane materials: adding 8g of 1, 4-butanediol and 200035g of PPG into a three-neck flask, adding 0.4g of dibutyltin dilaurate serving as a catalyst, 2640.4 g of antioxidant BHT, 0.2g of ultraviolet absorbent N- (ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine (UV-1), 0.4g of mildew preventive modified attapulgite, 0.4g of organic silicon defoamer, 0.4g of vulcanizing agent 3, 5-dimethylthiotoluenediamine and 30g of melamine, vacuum dehydrating the melamine at 105 ℃ for 2h, adding 40g of diphenylmethane diisocyanate (MDI), uniformly mixing, preheating by microwave and high fire for 2min, mechanically stirring at the rotating speed of 2000r/min for 10min, discharging, defoaming in a vacuum drying box at 50 ℃ for 20min, taking out, pouring into a mold preheated to 70 ℃, and curing and molding at room temperature to obtain the flame retardant polyurethane.
And (3) performance testing:
the flame retardant performance and the mechanical property of the flame retardant polyurethane materials prepared in the embodiments 3-6 and the comparative example 1 are tested, the flame retardant performance is characterized by a limiting oxygen index, the oxygen index is determined according to GB/T2406.2-2009, the sample size is (80-150) mm × 10mm × 10mm, the instrument is JF-3, Beijing Zhonghang times instrument and equipment Limited company; hardness was measured using an LX-a rubber hardness tester (Shunno instruments, Inc., Tianjin). The flame retardant polyurethane material prepared in examples 3 to 6 has the following relevant properties:
TABLE 1 relevant Properties of the polyurethane materials
As can be seen from the test data in Table 1, the modified melamine flame retardant has good flame retardant property. The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of hydroxyl modified melamine is characterized by adding melamine into a reactor with a reflux device, adding deionized water, uniformly stirring, heating to 60-100 ℃, then dropwise adding hydroxyl-containing halohydrocarbon, dropwise adding an alkaline aqueous solution and tracking and detecting the pH value when a reaction solution becomes clear until the pH value does not change, continuously stirring and reacting for 1-3 hours, cooling, standing, removing solids after solid-liquid separation to obtain a filtrate, removing a solvent from the filtrate, and drying to obtain the hydroxyl modified melamine.
2. The process for producing hydroxyl-modified melamine according to claim 1, wherein the hydroxyl-containing halogenated hydrocarbon is one or a combination of two or more selected from the group consisting of bromoethanol, chloroethanol, 3-bromo-1-propanol, 3-chloro-1-propanol, 2-bromo-1-propanol, 2-chloro-1-propanol, 4-bromo-1-butanol, 4-chloro-1-butanol, 3-bromo-1-butanol, 3-chloro-1-butanol, 2-bromo-1-butanol, 2-chloro-1-butanol and chlorobutanol in any ratio.
3. The method for producing a hydroxyl-modified melamine according to claim 1, wherein the molar ratio of the melamine to the hydroxyl-containing halogenated hydrocarbon is 1:2 to 6.
4. Process for the preparation of hydroxyl-modified melamine according to claim 1,2 or 3, characterized in that the aqueous alkaline solution is NaOH, KOH, NH 3 ·H 2 O、K 2 CO 3 Or Na 2 CO 3 An aqueous solution of (a).
5. Use of a hydroxyl-modified melamine according to claim 1 or 2 or 3 or 4 for the preparation of flame retardant polyurethane materials, characterized in that the application process comprises: mixing hydroxyl modified melamine with a micromolecular chain extension cross-linking agent, polyether polyol, isocyanate modified attapulgite and an auxiliary agent, mechanically stirring for 8-12 min at the speed of 1200-2000 r/min, pouring into a mould after vacuum defoaming, and curing at room temperature to obtain a flame retardant polyurethane material;
the using amount of the micromolecule chain extension cross-linking agent accounts for 1-2% of the weight of the flame-retardant polyurethane material; the using amount of the polyether polyol accounts for 35-45% of the weight of the flame-retardant polyurethane material; the auxiliary agent is one or more of a catalyst, an antioxidant, an ultraviolet absorbent, a mildew preventive, a defoaming agent or a vulcanizing agent, and the amount of the auxiliary agent accounts for 2-5% of the weight of the flame-retardant polyurethane material; the hydroxyl modified melamine accounts for 5-30% of the weight of the flame-retardant polyurethane material; the amount of the isocyanate accounts for 30-50% of the weight of the flame-retardant polyurethane material; the amount of the isocyanate modified attapulgite accounts for 5-10% of the weight of the flame retardant polyurethane material.
6. The use of claim 5, wherein the small molecule chain extending crosslinker is one or a combination of two or more of 1, 4-butanediol, ethylene glycol, diethylene glycol, tetraethylene glycol, 1, 2-propanediol, 1, 3-butanediol, or trimethylolpropane.
7. The use of claim 5, wherein the polyether polyol is one or a combination of two or more of PPG2000, PPG3000, PEG2000, PEG3000, N-206, YG-84, or polytetrahydrofuran diol.
8. The use of claim 5 or 6 or 7, wherein the isocyanate is one or a combination of two or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or hydrogenated diphenylmethane diisocyanate.
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