CN117089079A - Preparation method of melamine polyphosphate containing carboxyl functional groups - Google Patents
Preparation method of melamine polyphosphate containing carboxyl functional groups Download PDFInfo
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- CN117089079A CN117089079A CN202311341535.0A CN202311341535A CN117089079A CN 117089079 A CN117089079 A CN 117089079A CN 202311341535 A CN202311341535 A CN 202311341535A CN 117089079 A CN117089079 A CN 117089079A
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- acid
- melamine
- functional groups
- melamine polyphosphate
- containing carboxyl
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 45
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 35
- 229920000388 Polyphosphate Polymers 0.000 title claims abstract description 26
- 239000001205 polyphosphate Substances 0.000 title claims abstract description 26
- 235000011176 polyphosphates Nutrition 0.000 title claims abstract description 26
- 125000000524 functional group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 9
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of new high molecular polymer materials, in particular to a preparation method of melamine polyphosphate containing carboxyl functional groups, which comprises the following steps: firstly, adding melamine, a carboxylic acid compound and a solvent into a reaction container, and reacting for 1-3 hours to obtain an amino unsaturated salt of the carboxylic acid melamine; adding phosphoric acid into the carboxylic acid melamine amino unsaturated salt for reaction, and filtering and drying to obtain carboxyl block melamine phosphate; and (3) carrying out dehydration condensation reaction on the carboxyl block melamine phosphate for 1-3 hours under the conditions that the temperature is 260-350 ℃, the pressure is 0.1-0.5 MPa and the nitrogen protection is carried out, so as to obtain the carboxyl embedded melamine polyphosphate. The preparation method of the melamine polyphosphate containing carboxyl functional groups solves the problem of poor compatibility between the melamine polyphosphate and resin in the prior art.
Description
Technical Field
The invention relates to the technical field of new high molecular polymer materials, in particular to a preparation method of melamine polyphosphate containing carboxyl functional groups.
Background
Along with the wide application of flame retardant materials and the importance of people on environmental protection, the development of environment-friendly flame retardants is also attracting more attention, and as a representative of halogen-free environment-friendly flame retardants, melamine polyphosphate (MPP) is also becoming a hot spot for research and development of people, and the flame retardants can be almost used for all plastics, and are particularly suitable for flame retardance of engineering plastics with higher processing temperature, such as glass fiber reinforced nylon, polyester and other high polymer materials.
However, the poor compatibility of the MPP and the resin in the prior art can affect the mechanical properties of the resin, especially the high processing temperature resin groups, such as polyamide PA6, PA66, polyester PBT, PET and the like, and after the MPP is added into the resin, the impact strength, tensile strength and the like of the receptor such as the resin can be rapidly reduced, so that the performance requirements of engineering plastics can not be met.
Disclosure of Invention
The invention aims to provide a preparation method of melamine polyphosphate containing carboxyl functional groups, which solves the problem of poor compatibility of melamine polyphosphate and resin in the prior art.
In order to achieve the above object, the present invention provides a method for preparing melamine polyphosphate containing carboxyl functional groups, comprising the steps of:
s1, adding melamine, a carboxylic acid compound and a solvent into a reaction container, and reacting for 1-3 hours to obtain an amino unsaturated salt of the carboxylic acid melamine, wherein the reaction equation is as follows:
；
s2, adding phosphoric acid into the carboxylic acid melamine amino unsaturated salt for reaction, filtering and drying to obtain carboxyl block melamine phosphate, wherein the reaction equation is as follows:
；
s3, carrying out dehydration condensation reaction on carboxyl block melamine phosphate for 1-3 hours under the conditions that the temperature is 260-350 ℃, the pressure is 0.1-0.5 MPa and the nitrogen protection is adopted, so as to obtain carboxyl embedded melamine polyphosphate, wherein the reaction equation is as follows:
；
preferably, the addition amount of melamine is 30-50% by mass, the addition amount of carboxylic acid compound is 5-30% by mass, and the addition amount of phosphoric acid is 10-50% by mass.
Preferably, the solvent in the step S1 is one of water, alcohol, benzene, toluene, xylene and trimethylbenzene.
Preferably, the reaction temperature in the step S1 is 50-80 ℃ and the reaction pressure is normal.
Preferably, the carboxylic acid compound in step S1 is one of monocarboxylic acid, dicarboxylic acid, and polycarboxylic acid.
Preferably, the monocarboxylic acid is one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, lauric acid and stearic acid.
Preferably, the dicarboxylic acid is one of oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, terephthalic acid, phthalic acid, isophthalic acid.
Preferably, the polycarboxylic acid is one of trimesic acid, pyromellitic acid, and pyromellitic acid.
Preferably, in the step S2, the reaction temperature is 50-90 ℃, the reaction time is 1-3 hours, and the reaction pressure is normal pressure.
The invention has the beneficial effects that:
the invention adopts a stepwise reaction mode, utilizes the mechanism of polymer embedded reaction, embeds small molecular substances with carboxyl functional groups into melamine phosphate to form heterozygous melamine phosphate, namely carboxyl embedded melamine phosphate heterozygous salt, and then carries out polymerization reaction to generate melamine polyphosphate containing carboxyl groups. Because the amino groups of the melamine and the acid radical structures of the phosphoric acid are uniform and symmetrical, when the melamine reacts with the phosphoric acid, the opportunities of any acid radical and any amino group reaction are the same, so that the formed melamine phosphate is of a crosslinked network structure, the melamine phosphate has higher stability, carboxyl groups are used for embedded modification on the network structure, the compatibility of the melamine phosphate and the resin is improved according to the principle of similar compatibility, and the influence of the melamine on the mechanical properties of the resin is further reduced.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
The present invention will be further described with reference to examples in which various chemicals and reagents are commercially available unless otherwise specified. The invention will be further described with reference to examples. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The above-mentioned features of the invention or the features mentioned in the specific examples can be combined in any desired manner, and these specific examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
126g of melamine and 1500g of deionized water are weighed, added into a 2000ml three-neck flask with a stirring and condensing reflux device, stirred and heated to 50 ℃, 130g of heptanoic acid is weighed and added into a 500ml balance dropping funnel, the balance dropping funnel is connected with the three-neck flask, the heptanoic acid is added into the melamine at a constant speed, the dripping is completed for about 30 minutes, and the stirring reaction is continued for 3 hours, so that the carboxylic acid melamine amino unsaturated salt is obtained. 70g of 85% phosphoric acid is weighed and added into a 500ml balance dropping funnel, the mixture is slowly dropped for about 30 minutes, the solution temperature is kept to 60 ℃, and the carboxyl block melamine phosphate is obtained after 4 hours of reaction. The carboxyl block melamine phosphate is filtered and dried to obtain 310g of white powdery product. And (3) loading the product into a rotary reactor with stirring, introducing nitrogen for sealing protection, controlling the pressure of the reactor to be between 0.1 and 0.5MPa under the protection of a pressure limiting valve, heating to 260 ℃, and reacting for 8 hours to obtain 290g of target product heptanoic acid group modified melamine polyphosphate. The yield of the product was about 97.3%.
Example 2
126g of melamine and 1500g of deionized water are weighed, added into a 2000ml three-neck flask with a stirring and condensing reflux device, stirred and heated to 50 ℃, 88g of butyric acid is weighed and added into a 500ml balance dropping funnel, the balance dropping funnel is connected with the three-neck flask, the butyric acid is added into the melamine at a constant speed, the dropping is completed for about 30 minutes, and the stirring reaction is continued for 3 hours, so as to obtain the amino unsaturated salt of the carboxylic acid melamine. 70g of 85% phosphoric acid is weighed and added into a 500ml balance dropping funnel, the mixture is slowly dropped for about 30 minutes, the solution temperature is kept to 60 ℃, and the carboxyl block melamine phosphate is obtained after 4 hours of reaction. The carboxyl block melamine phosphate is filtered and dried to obtain 270g of white powdery product with the product yield of 99%. And (3) loading the product into a rotary reactor with stirring, introducing nitrogen for sealing protection, controlling the pressure of the reactor to be between 0 and 0.5MPa under the protection of a pressure limiting valve, heating to 290 ℃, and reacting for 4 hours to obtain 250g of target product butyrate-based modified melamine polyphosphate, wherein the product yield is about 96.9%.
Example 3
Weighing 126g of melamine, 83g of terephthalic acid and 1500g of deionized water, adding the mixture into a 2000ml three-neck flask with a stirring and condensing reflux device, stirring and heating to 50 ℃, and continuing stirring and reacting for 3 hours to obtain the amino unsaturated salt of the melamine carboxylate. 70g of 85% phosphoric acid is weighed and added into a 500ml balance dropping funnel, the mixture is slowly dropped for about 30 minutes, the solution temperature is kept to 60 ℃, and the carboxyl block melamine phosphate is obtained after 4 hours of reaction. The carboxyl block melamine phosphate is filtered and dried to obtain 265g of white powdery product with the product yield of 98.7 percent. And (3) loading the product into a rotary reactor with stirring, introducing nitrogen for sealing protection, controlling the pressure of the reactor to be between 0 and 0.5MPa under the protection of a pressure limiting valve, heating to 310 ℃, and reacting for 2 hours to obtain 249g of target product terephthalic acid modified melamine polyphosphate, wherein the product yield is about 98.4%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (9)
1. A process for the preparation of melamine polyphosphate containing carboxyl functionality, comprising the steps of:
s1, adding melamine, a carboxylic acid compound and a solvent into a reaction container, and reacting for 1-3 hours to obtain an amino unsaturated salt of the carboxylic acid melamine;
s2, adding phosphoric acid into the carboxylic acid melamine amino unsaturated salt for reaction, and filtering and drying to obtain carboxyl block melamine phosphate;
s3, carrying out dehydration condensation reaction on carboxyl block melamine phosphate for 1-3 hours under the conditions that the temperature is 260-350 ℃, the pressure is 0.1-0.5 MPa and the nitrogen protection is adopted, so as to obtain carboxyl embedded melamine polyphosphate.
2. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 1, wherein the method comprises the following steps: the addition amount of melamine is 30-50% by mass, the addition amount of carboxylic acid compound is 5-30% by mass, and the addition amount of phosphoric acid is 10-50% by mass.
3. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 1, wherein the method comprises the following steps: in the step S1, the solvent is one of water, alcohol, benzene, toluene, dimethylbenzene and trimethylbenzene.
4. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 1, wherein the method comprises the following steps: in the step S1, the reaction temperature is 50-80 ℃ and the reaction pressure is normal.
5. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 1, wherein the method comprises the following steps: the carboxylic acid compound in the step S1 is one of monocarboxylic acid, dicarboxylic acid and polycarboxylic acid.
6. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 5, wherein the method comprises the following steps: the monocarboxylic acid is one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, lauric acid and stearic acid.
7. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 5, wherein the method comprises the following steps: the dicarboxylic acid is one of oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, terephthalic acid, phthalic acid and isophthalic acid.
8. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 5, wherein the method comprises the following steps: the polycarboxylic acid is one of trimesic acid, pyromellitic acid and pyromellitic acid.
9. The method for preparing melamine polyphosphate containing carboxyl functional groups according to claim 1, wherein the method comprises the following steps: in the step S2, the reaction temperature is 50-90 ℃, the reaction time is 1-3 hours, and the reaction pressure is normal pressure.
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|---|---|---|---|---|
| ES224890A1 (en) * | 1954-11-09 | 1956-02-01 | Albright & Wilson | Bromine containing nitrilo methylol-phosphorus polymers |
| US20070049753A1 (en) * | 2005-08-30 | 2007-03-01 | Chang Chun Plastics Co., Ltd. | Method for preparing amino phosphate compounds |
| CN102030848A (en) * | 2010-11-10 | 2011-04-27 | 苏州科技学院 | Macromolecular flame retardant and preparation method thereof |
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