CN114989105B - Pollution-free method for synthesizing superfine melamine hypophosphite and flame-retardant method thereof - Google Patents
Pollution-free method for synthesizing superfine melamine hypophosphite and flame-retardant method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 69
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 62
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 41
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title abstract description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000003292 glue Substances 0.000 claims abstract description 19
- 150000004645 aluminates Chemical class 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 23
- -1 oxygen isopropyl aluminate Chemical class 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 6
- 239000003607 modifier Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical class [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Chemical class 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
Abstract
The invention provides a pollution-free method for synthesizing superfine melamine hypophosphite and a flame-retardant method thereof, which comprises the following steps: s1: adding hypophosphorous acid and melamine into a kneader for stirring reaction, and controlling the reaction temperature to be 60-85 ℃; s2: after 1-2h of reaction, KH570 and KH171 which have functional groups and can be crosslinked with acrylic glue are added in the reaction process, and aluminate coupling agent containing metal ions is added; s3: stirring and reacting for 1-2h, drying and discharging. The process can greatly reduce water consumption, does not generate a large amount of wastewater, and greatly reduces reaction process steps; meanwhile, the product controls the granularity of the product through reaction, and a surface modifier is added in the drying process or the reaction process to change the problem of easy cluster of synthetic powder, and the surface modifier has specific reactivity and self-film forming capability with acrylic glue and metal ion doping contained in the acrylic glue, so that the glue has the capability of inhibiting smoke. And the method has higher synthesis efficiency compared with the traditional method.
Description
Technical Field
The invention particularly relates to a pollution-free method for synthesizing superfine melamine hypophosphite and a flame-retardant method thereof.
Background
Since the 80 s of the 20 th century, flame retardants have become the second largest synthetic material use aid next to plasticizers. With the development of economy, people have greatly improved environmental protection and safety awareness, and have more attention to ecological environment and life value. Conventional halogen-based flame retardants are used in large amounts for the production of flame retardant materials due to their high flame retardant efficiency. However, the halogen flame-retardant products are limited in application because they generate a large amount of smoke and toxic corrosive gas during combustion, which prevent rescue and personnel evacuation, resulting in secondary disasters. The halogen-free flame retardant is widely applied due to the environment-friendly characteristics of low smoke, low toxicity and the like. The use of high-efficiency, low-smoke, non-toxic or low-toxicity halogen-free flame retardants will become a necessary trend in the development of future flame retardant materials. In the present inorganic series of aluminum hydroxide, magnesium hydroxide, zinc borate, etc., organic phosphorus nitrogen silicon series such as ammonium polyphosphate, melamine polyphosphate, aluminum hypophosphite, diethyl aluminum hypophosphite, melamine cyanurate, DOPO, etc. are widely used. But they all have problems such as low flame retardant efficiency or high temperature and high pressure required for the synthesis process, etc. Compared with other phosphorus-nitrogen flame retardants, the melamine hypophosphite is pollution-free and efficient, contains an air source and free radicals, has the capability of consuming oxygen, has excellent tissue combustion capability and has excellent flame retardant effect. CN101570518A discloses a synthesis method of melamine hypophosphite: the aqueous phase synthesis method is adopted, and the molar ratio is 1: adding melamine and hypophosphorous acid of 0.5-3 into water, stirring and reacting for 2 hours at the temperature of 0-100 ℃ at the stirring speed of 300r/min, and then carrying out suction filtration and washing on the reaction product, and drying for 3 hours at the temperature of 150 ℃. The yield is about 85%, and a part of application research is performed. Chen Saijun and Zhou Junhong in the text of preparation and characterization of Melamine and phosphite, 50% concentration hypophosphorous acid is added into a round bottom flask for dilution by 5 times, melamine is added at 80 ℃ until the PH is not changed, and then the product is obtained through reaction, filtration, washing and drying, and the performance and the morphology of the product are characterized.
The synthesis process of the phosphorus-nitrogen flame retardant is complex, high temperature and high pressure are generally required, and the synthesis process of the existing melamine salt, such as melamine hydrobromide, is simple, but halogen elements exist; the melamine polyphosphate needs high temperature for synthesis, the melamine cyanurate also needs high temperature and consumes a large amount of water, the valence of phosphorus element in the existing melamine series flame retardant is basically pentavalent, and the oxygen consumption of the flame retardant in the flame retardant process is far lower than that of normal-valence phosphorus in melamine hypophosphite. The existing melamine hypophosphite synthesis technology mainly comprises the steps of reaction in a reaction kettle, high water demand, filtration, washing, drying and other processes, and the process is complicated. The yield is low, and only 85%; the yield is low, the method is not suitable for industrial production, and the resource environment-friendly society construction is not facilitated; and the particle size is larger, which limits the application range.
In summary, a pollution-free method for synthesizing superfine melamine hypophosphite has been proposed to solve the above problems.
Disclosure of Invention
The invention aims to provide a pollution-free method for synthesizing superfine melamine hypophosphite and a flame-retardant method thereof, which can well solve the problems.
In order to meet the requirements, the invention adopts the following technical scheme: the method for synthesizing the superfine melamine hypophosphite without pollution and the flame-retardant method thereof are provided, and the method for synthesizing the superfine melamine hypophosphite without pollution and the flame-retardant method thereof comprise the following steps:
s1: adding hypophosphorous acid and melamine into a kneader for stirring reaction, and controlling the reaction temperature to be 60-85 ℃;
s2: after 1-2h of reaction, KH570 and KH171 which have functional groups and can be crosslinked with acrylic glue are added in the reaction process, and aluminate coupling agent containing metal ions is added;
s3: stirring and reacting for 1-2h, drying and discharging.
The pollution-free method for synthesizing the superfine melamine hypophosphite and the flame-retardant method thereof have the following advantages:
the process can greatly reduce water consumption, does not generate a large amount of wastewater, and greatly reduces reaction process steps; meanwhile, the product controls the granularity of the product through reaction, and a surface modifier is added in the drying process or the reaction process to change the problem of easy cluster of synthetic powder, and the surface modifier has specific reactivity and self-film forming capability with acrylic glue and metal ion doping contained in the acrylic glue, so that the glue has the capability of inhibiting smoke.
Drawings
The accompanying drawings, where like reference numerals refer to identical or similar parts throughout the several views and which are included to provide a further understanding of the present application, are included to illustrate and explain illustrative examples of the present application and do not constitute a limitation on the present application. In the drawings:
fig. 1 schematically shows a flow diagram of a method for pollution-free synthesis of ultra-fine melamine hypophosphite according to one embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and specific embodiments.
In the following description, references to "one embodiment," "an embodiment," "one example," "an example," etc., indicate that the embodiment or example so described may include a particular feature, structure, characteristic, property, element, or limitation, but every embodiment or example does not necessarily include the particular feature, structure, characteristic, property, element, or limitation. In addition, repeated use of the phrase "according to an embodiment of the present application" does not necessarily refer to the same embodiment, although it may.
Certain features have been left out of the following description for simplicity, which are well known to those skilled in the art.
According to one embodiment of the present application, there is provided a method for synthesizing superfine melamine hypophosphite without pollution and a flame retardant method thereof, as shown in fig. 1, comprising the steps of:
s1: adding hypophosphorous acid and melamine into a kneader for stirring reaction, and controlling the reaction temperature to be 60-85 ℃;
s2: after 1-2h of reaction, KH570 and KH171 which have functional groups and can be crosslinked with acrylic glue are added in the reaction process, and aluminate coupling agent containing metal ions is added;
s3: stirring and reacting for 1-2h, drying and discharging.
According to one embodiment of the application, the molar ratio of the hypophosphorous acid to the melamine in the step S1 of the pollution-free method for synthesizing the superfine melamine hypophosphite and the flame retardant method thereof is 1:1-1:1.02.
According to one embodiment of the present application, the hypophosphorous acid in the step S1 of the method for synthesizing superfine melamine hypophosphite and the flame retardant method thereof is 50% of the original concentration of hypophosphorous acid.
According to one embodiment of the application, the method for synthesizing the superfine melamine hypophosphite without pollution and the flame retardant method thereof further comprise the following steps between the step S1 and the step S2: water accounting for 35% -50% of the total feeding amount is supplemented twice, the interval between the two times is 0.5h, and the proportion of the water is 1:0.3 to 1.
According to one embodiment of the application, in the step S1 of the pollution-free method for synthesizing superfine melamine hypophosphite and the flame retardant method thereof, the reaction temperature is monitored, and meanwhile, the materials are slowly fed to avoid the excessive reaction temperature.
According to one embodiment of the present application, the aluminate coupling agent in the method for synthesizing superfine melamine hypophosphite and the flame retardant method thereof is distearoyl oxyisopropyl aluminate.
According to one embodiment of the present application, the ratio of KH570 to KH171 and the aluminate coupling agent with metal ion is 1.5-2:1:0.5 in the method for synthesizing superfine melamine hypophosphite and the flame retardant method thereof.
According to one embodiment of the present application, the addition sequence of the aluminate coupling agent, KH171, KH570 in the step S2 of the method for synthesizing superfine melamine hypophosphite without pollution and the flame retardant method thereof is sequentially aluminate coupling agent, KH171, KH570.
According to one embodiment of the application, the method for synthesizing the superfine melamine hypophosphite without pollution and the flame retardant method thereof are characterized in that in the step S2 of the method for synthesizing the superfine melamine hypophosphite, the three components of the aluminate coupling agent, KH171 and KH570 are hydrolyzed and then are rapidly mixed, and then are added into reactants for stirring reaction.
According to one embodiment of the present application, the drying in the step S3 of the method for synthesizing ultrafine melamine hypophosphite without pollution and the flame retardant method thereof may be performed by using a kneader for negative pressure drying at 100-120 ℃ or vacuum bipyramid drying at 100-120 ℃ for 1-2 hours.
Example 1:
setting the oil bath temperature of the kneader at 120 ℃, adding 1.26kg of melamine and 0.903kg of water when the temperature of the kneader is 80 ℃, adding 1.32kg of hypophosphorous acid solution with the concentration of 50% in the stirring process, stirring and reacting for 15min, setting the material temperature at 75 ℃, adding 0.387kg of water after timing and reacting for 0.5h, and continuously stirring and reacting for 1h. Then 0.5% distearoyl oxyisopropyl aluminate, 1% KH171 and 1.5% KH570 are added, and after stirring for 1h, the mixture is dried for 1.5h under negative pressure at 105 ℃ by controlling the temperature of the kneader, and then discharged. The output of the material is 1.86kg, the yield is 96.9%, and the fluidity of the material is good.
Example 2:
setting the oil bath temperature of the kneader at 120 ℃, adding 1.28kg of melamine and 0.912kg of water when the temperature of the kneader is 80 ℃, adding 1.32kg of hypophosphorous acid solution with the concentration of 50% in the stirring process, stirring and reacting for 16min, setting the material temperature at 75 ℃, adding 0.390kg of water after timing and reacting for 0.5h, and continuously stirring and reacting for 1h. The reaction was stirred for 1h. Then 0.5% distearoyl oxyisopropyl aluminate, 1% KH171 and 1.5% KH570 are added, and after stirring for 1h, the mixture is dried for 1.5h under negative pressure at 105 ℃ by controlling the temperature of the kneader, and then discharged. The output of the material is 1.87kg, the yield is 97.7%, and the fluidity of the material is good.
Example 3:
setting the oil bath temperature of the kneader at 80 ℃, adding 1.26kg of melamine when the temperature of the kneader is 60 ℃, slowly adding 1.32kg of hypophosphorous acid solution with the concentration of 50% in the stirring process, stirring and reacting for 5min, and stirring and reacting for 2h at the material temperature of 75 ℃. Then adding 0.5% distearoyl oxyisopropyl aluminate, 1% KH171 and 1.5% KH570 which are hydrolyzed respectively, and drying at 110 ℃ for 1 hour under negative pressure by a kneader, and discharging. The output of the material is 1.885kg, the yield is 98.2%, and the fluidity of the material is good.
Example 4:
setting the oil bath temperature of the kneader at 80 ℃, adding 1.26kg of melamine when the temperature of the kneader is 60 ℃, slowly adding 1.32kg of hypophosphorous acid solution with the concentration of 50% in the stirring process, stirring and reacting for 5min, and stirring and reacting for 2h at the material temperature of 75 ℃. Then adding 0.8% distearoyl oxygen isopropyl aluminate, 1.6% KH171 and 2.4% KH570 which are hydrolyzed respectively, drying at 110 ℃ for 1 hour under negative pressure by a kneader, and discharging. The output of the material is 1.87kg, the yield is 97.4%, and the fluidity of the material is good.
Example 5:
setting the oil bath temperature of the kneader at 120 ℃, adding 1.26kg of melamine and 0.903kg of water when the temperature of the kneader is 80 ℃, adding 1.32kg of hypophosphorous acid solution with the concentration of 50% in the stirring process, stirring and reacting for 15min, setting the material temperature at 75 ℃, adding 0.387kg of water after timing and reacting for 0.5h, and continuously stirring and reacting for 1h. Then 0.5% distearoyl oxyisopropyl aluminate, 1% KH171 and 1.5% KH570 are added, and after stirring for 1h, the mixture is dried for 1h under negative pressure at 105 ℃ by controlling a double cone, and then discharged. The output of the stirred reaction is 1.88kg, the output is 98.0%, and the fluidity of the discharged material is good.
Example 6:
setting the oil bath temperature of the kneader at 80 ℃, adding 1.26kg of melamine when the temperature of the kneader is 60 ℃, slowly adding 1.32kg of hypophosphorous acid solution with the concentration of 50% in the stirring process, stirring and reacting for 5min, and stirring and reacting for 2h at the material temperature of 75 ℃. Then adding 0.5% distearoyl oxyisopropyl aluminate, 1% KH171 and 1.5% KH570 which are hydrolyzed respectively and then mixed, and discharging after drying for 1h at the temperature of double cones of 100 ℃. The output of the material is 1.87kg, the yield is 97.4%, and the fluidity of the material is good.
Comparative example 1: (numbering experiment 7) refer to CN101570518A example 1: experiment 126g melamine and 132g hypophosphorous acid (l mol) with a concentration of 50% were taken, hypophosphorous acid and 1000ml water were added to a 2000ml beaker, placed in a 25℃water bath, stirred at 300r/min with a constant speed electric stirrer, and the melamine was added in portions and reacted for 2 hours. The reaction product was filtered off with suction and washed with a suitable amount of water, and dried in a vacuum oven at 150℃for 3 hours with a weighing of melamine hypophosphite MHP yield of 145g, 75.5% yield.
Comparative example 2: (number experiment 8) 126g of melamine and 132g of 50% strength hypophosphorous acid (l mol) were taken, hypophosphorous acid and 1000m of water were added to a 2000ml beaker, placed in a 50℃water bath, stirred at 300r/min with a constant speed electric stirrer, and melamine was added in portions and reacted for 2 hours. The reaction product was filtered off with suction and washed with a suitable amount of water, and dried in a vacuum oven at 150 degrees celsius for 3 hours weighing melamine hypophosphite MHP yield 155g with a reaction yield of 80.7%.
Comparative example 3: (modified comparative experiment, numbered experiment 9) 126g of melamine and 132g of hypophosphorous acid (l mol) having a concentration of 50% were taken, hypophosphorous acid and 1000m of water were added to a 2000ml beaker, placed in a water bath at 80℃and stirred at a speed of 300r/min with a constant speed electric stirrer, and melamine was added in portions and reacted for 2 hours. The reaction product was filtered off with suction and washed with a suitable amount of water, dried in a vacuum oven at 150℃for 3 hours and weighed to give 179g of melamine hypophosphite MHP with a reaction yield of 93.2%.
Product application examples:
10g of the products of examples 5 and 6 and the product of comparative example 9 are respectively taken and respectively compounded with 10g of ammonium polyphosphate, added into 80g of oily acrylic glue, added with 1g of glue curing agent, stirred, coated on cotton paper with the thickness of 15cm multiplied by 20cm, subjected to UL94 vertical burning test after drying and curing at 100 ℃ and subjected to initial bonding capability and lasting bonding capability test.
The particle sizes of the examples and the comparative examples were measured by using a BT-9300H laser particle size analyzer (solvent ethanol, ultrasonic for 1 min) of Dandong Baite instruments, the nitrogen content of the product was measured by using a Kjeldahl nitrogen analyzer (HGK-50) of Shanghai nuclear crown instruments by Kjeldahl nitrogen method, the hypophosphite content in the product and the hypophosphite content in the water-soluble substance thereof were measured by referring to an aluminum hypophosphite line standard HG-T-4833-2015, the fluidity was measured, and the time(s) after 500g hourglass was measured, the specific cases are shown in the following table:
| numbering device | Yield rate | Numbering device | Yield rate | |
| 1 | 96.9 | 6 | 97.4 | |
| 2 | 97.7 | 7 | 75.5 | |
| 3 | 98.2 | 8 | 80.7 | |
| 4 | 97.4 | 9 | 93.2 | |
| 5 | 98.0 |
Comparison experiments were applied:
by comparing examples 1-6 with comparative examples 1-3 (experiment 7/8/9), the invention has the advantages that the synthesis yield of the melamine hypophosphite synthesized by the technical scheme is high and is more than or approximately 97%, which is far superior to other synthesis processes, especially the yield of the melamine hypophosphite synthesized by the comparative examples under the low-temperature condition; and the melamine residue of the comparative examples 1 and 2 is too much, the reaction is incomplete, the purity of the product is not high, and the unreacted hypophosphorous acid is seriously lost through the filtration scheme; and other synthetic schemes use huge amounts of water, the ratio to the synthetic product is about 10:1.92, and also requires wash water, whereas our inventive solution product has a water to product ratio of 0.91:1.92, and also producing 1 ton of the product, the water consumption of the product is only 9% of that of other schemes or no additional water is added, and only the reaction temperature needs to be controlled. The technical scheme has huge process water saving amount, and the scheme of adding the water into the water twice improves the heat and water utilization efficiency; the product has small particle size and has smaller influence on the mechanical properties of various products when in use; the product of the technical scheme has good fluidity after drying, is easy to screen, does not need ball milling in the actual use process, saves energy sources, has a certain active group on the surface of part of the product, is beneficial to improving the compatibility with part of base materials, and can be seen by application of a comparison experiment that the flame retardance of the product of the technical scheme is superior to that of the products of other technical schemes, the addition amount of 25 percent can reach V0, but the initial bonding capacity and the lasting bonding capacity of the product are far better than those of the products of the external sample technical scheme.
According to the embodiment of the application, the product has good flame retardant effect when being applied to acrylic glue flame retardance, the addition amount is low, the influence on the bonding capability of materials is small, and the initial bonding capability and the lasting bonding capability of the glue can be improved by the modified product. The process firstly uses distearoyl oxygen isopropyl aluminate to stir and mix with the product, so that the inorganic part of the distearoyl oxygen isopropyl aluminate and the surface hydroxyl of the powder have full bonding effect; then adding KH570 and KH171 to hydrolyze and dehydrate to form silanol groups, reacting with powder hydroxyl groups, and forming a layer of methacryloxy chemical groups with chemical active groups and carbon-carbon double bonds with crosslinking activity and organic long chain groups containing aluminum ions on the surface of the powder. In the stirring reaction and drying process, methacryloxy groups are easy to attack by nucleophilic reagents, and are crosslinked with self or double bonds on the surface of the generated powder to form a coating layer, and aluminate organic groups and aluminum ions are inserted in the coating layer. The far excessive KH570 keeps a large amount of unreacted active groups, when the unreacted active groups are applied to the acrylic glue, the unreacted active groups can react with methyl methacrylate and similar structures in the acrylic glue, the initial and lasting bonding capacity of the glue is improved, the melamine hypophosphite with a large amount of organic groups on the surface improves the water resistance and the compatibility with the acrylic glue, and metal aluminum ions improve the smoke suppression performance of the acrylic glue
The foregoing examples are merely representative of several embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, which are within the scope of the invention. The scope of the invention should therefore be pointed out with reference to the appended claims.
Claims (8)
1. A method for synthesizing superfine melamine hypophosphite without pollution, which is characterized by comprising the following steps:
s1: adding hypophosphorous acid and melamine into a kneader for stirring reaction, and controlling the reaction temperature to be 60-85 ℃;
s2: after reacting for 1-2 hours, adding KH570 and KH171 which have functional groups and can be crosslinked with acrylic glue and distearoyl oxyisopropyl aluminate in the reaction process;
s3: stirring for reaction for 1-2 hours, drying and discharging;
the steps S1 and S2 also include the following steps: water accounting for 35% -50% of total feeding amount is supplemented twice, the interval between the two times is 0.5h, and the proportion of water is 1:0.3 to 1.
2. The method for pollution-free synthesis of superfine melamine hypophosphite according to claim 1, characterized in that: and in the step S1, the molar ratio of the hypophosphorous acid to the melamine is 1:1-1:1.02.
3. The method for pollution-free synthesis of superfine melamine hypophosphite according to claim 1, characterized in that: the hypophosphorous acid in the step S1 is the hypophosphorous acid with the original concentration of 50%.
4. The method for pollution-free synthesis of ultra-fine melamine hypophosphite according to claim 1, characterized in that: in the step S1, the reaction temperature is required to be monitored, and meanwhile, the material is slowly fed to avoid overhigh reaction temperature.
5. The method for pollution-free synthesis of superfine melamine hypophosphite according to claim 1, characterized in that: the mass ratio of KH570 to KH171 to distearoyl oxyisopropyl aluminate is 1.5-2:1:0.5.
6. The method for pollution-free synthesis of superfine melamine hypophosphite according to claim 1, characterized in that: the addition sequence of distearoyl oxygen isopropyl aluminate, KH171 and KH570 in the step S2 is sequentially aluminate coupling agent, KH171 and KH570.
7. The method for pollution-free synthesis of superfine melamine hypophosphite according to claim 1, characterized in that: in the step S2, the three distearoyl oxygen isopropyl aluminate, KH171 and KH570 are hydrolyzed and then are quickly mixed, and then are added into reactants for stirring reaction.
8. The method for pollution-free synthesis of superfine melamine hypophosphite according to claim 1, characterized in that: and (3) drying in the step (S3) by adopting a kneader at 100-120 ℃ for 1-2 hours under negative pressure or adopting vacuum double cone drying at 100-120 ℃ for 1-2 hours.
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