CN117089079B - Preparation method of melamine polyphosphate - Google Patents

Preparation method of melamine polyphosphate Download PDF

Info

Publication number
CN117089079B
CN117089079B CN202311341535.0A CN202311341535A CN117089079B CN 117089079 B CN117089079 B CN 117089079B CN 202311341535 A CN202311341535 A CN 202311341535A CN 117089079 B CN117089079 B CN 117089079B
Authority
CN
China
Prior art keywords
acid
melamine
reaction
melamine polyphosphate
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311341535.0A
Other languages
Chinese (zh)
Other versions
CN117089079A (en
Inventor
廖洪书
刘旭东
张俊文
易孔旭
易胜莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Chengdu Fulailong Technology Co ltd
Original Assignee
Sichuan Chengdu Fulailong Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Chengdu Fulailong Technology Co ltd filed Critical Sichuan Chengdu Fulailong Technology Co ltd
Priority to CN202311341535.0A priority Critical patent/CN117089079B/en
Publication of CN117089079A publication Critical patent/CN117089079A/en
Application granted granted Critical
Publication of CN117089079B publication Critical patent/CN117089079B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00Macromolecular 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
    • C08G79/02Macromolecular 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
    • C08G79/04Phosphorus linked to oxygen or to oxygen and carbon

Abstract

The invention relates to the technical field of new high molecular polymer materials, in particular to a preparation method of melamine polyphosphate, 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 melamine amino unsaturated salt; adding phosphoric acid into the melamine amino unsaturated salt for reaction, filtering and drying to obtain block melamine phosphate; and (3) carrying out dehydration condensation reaction on the 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 embedded melamine polyphosphate. The preparation method of the melamine polyphosphate solves the problem of poor compatibility between the melamine polyphosphate and resin in the prior art.

Description

Preparation method of melamine polyphosphate
Technical Field
The invention relates to the technical field of new high-molecular polymer materials, in particular to a preparation method of melamine polyphosphate.
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, 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, 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 melamine amino unsaturated salt, wherein the reaction equation is as follows:
s2, adding phosphoric acid into the melamine amino unsaturated salt for reaction, filtering and drying to obtain block melamine phosphate, wherein the reaction equation is as follows:
s3, carrying out dehydration condensation reaction on the 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 the embedded melamine polyphosphate, wherein the reaction equation is as follows:
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 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 polycarboxylic 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 stirring reaction is continued for 3 hours, so that the 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 temperature of the solution is kept to 60 ℃, and the reaction is carried out for 4 hours to obtain the block melamine phosphate. The blocked melamine phosphate was dried by suction filtration to give 310g of the product as a white powder. 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 stirring reaction is continued for 3 hours, so that the 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 temperature of the solution is kept to 60 ℃, and the reaction is carried out for 4 hours to obtain the block melamine phosphate. The 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 melamine amino unsaturated salt. 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 temperature of the solution is kept to 60 ℃, and the reaction is carried out for 4 hours to obtain the block melamine phosphate. The blocked melamine phosphate was suction filtered and dried to give 265g of a white powdery product with a product yield of 98.7%. 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 (8)

1. A method for preparing melamine polyphosphate, 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 melamine amino unsaturated salt;
s2, adding phosphoric acid into the melamine amino unsaturated salt for reaction, and filtering and drying to obtain block melamine phosphate;
s3, carrying out dehydration condensation reaction on the 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 embedded melamine polyphosphate;
the addition amount of melamine is 30-50% by mass percent, the addition amount of carboxylic acid compound is 5-30% by mass percent, and the addition amount of phosphoric acid is 10-50% by mass percent, wherein the sum of the addition amounts of melamine, carboxylic acid compound and phosphoric acid is 100%.
2. The method for preparing melamine polyphosphate according to claim 1, wherein: in the step S1, the solvent is one of water, alcohol, benzene, toluene, dimethylbenzene and trimethylbenzene.
3. The method for preparing melamine polyphosphate according to claim 1, wherein: in the step S1, the reaction temperature is 50-80 ℃ and the reaction pressure is normal.
4. The method for preparing melamine polyphosphate according to claim 1, wherein: the carboxylic acid compound in step S1 is one of monocarboxylic acid and polycarboxylic acid.
5. The method for preparing melamine polyphosphate according to claim 4, wherein: 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.
6. The method for preparing melamine polyphosphate according to claim 4, wherein: the polycarboxylic acid is one of oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, terephthalic acid, phthalic acid and isophthalic acid.
7. The method for preparing melamine polyphosphate according to claim 4, wherein: the polycarboxylic acid is one of trimesic acid, pyromellitic acid and pyromellitic acid.
8. The method for preparing melamine polyphosphate according to claim 1, wherein: in the step S2, the reaction temperature is 50-90 ℃, the reaction time is 1-3 hours, and the reaction pressure is normal pressure.
CN202311341535.0A 2023-10-17 2023-10-17 Preparation method of melamine polyphosphate Active CN117089079B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311341535.0A CN117089079B (en) 2023-10-17 2023-10-17 Preparation method of melamine polyphosphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311341535.0A CN117089079B (en) 2023-10-17 2023-10-17 Preparation method of melamine polyphosphate

Publications (2)

Publication Number Publication Date
CN117089079A CN117089079A (en) 2023-11-21
CN117089079B true CN117089079B (en) 2023-12-26

Family

ID=88780594

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311341535.0A Active CN117089079B (en) 2023-10-17 2023-10-17 Preparation method of melamine polyphosphate

Country Status (1)

Country Link
CN (1) CN117089079B (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES224890A1 (en) * 1954-11-09 1956-02-01 Albright & Wilson Bromine containing nitrilo methylol-phosphorus polymers
CN102030848A (en) * 2010-11-10 2011-04-27 苏州科技学院 Macromolecular flame retardant and preparation method thereof
CN102127230A (en) * 2010-01-19 2011-07-20 中化蓝天集团有限公司 New process for preparing modified melamine polyphosphate
CN102321245A (en) * 2011-07-10 2012-01-18 东华大学 Benzoguanamine propyloic phenyl phosphinic acid condensation compound and preparation method
CN102417596A (en) * 2011-10-19 2012-04-18 浙江大学宁波理工学院 Phosphate ester polymer intumescent flame retardant and preparation method thereof
CN102604111A (en) * 2012-01-16 2012-07-25 苏州科技学院 Novel preparation method of polymeric phosphate ester flame retardant containing active hydroxyl
DE102012204642A1 (en) * 2012-03-22 2013-09-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Phosphorus-containing unsaturated polyesters, polyester resins and possibly fiber-reinforced components thereof
CN105504292A (en) * 2015-12-24 2016-04-20 瓮福(集团)有限责任公司 Preparation method of MPOP
CN107459492A (en) * 2017-07-26 2017-12-12 东华大学 A kind of organically-modified melamine polyphosphate and preparation method thereof
CN108148011A (en) * 2018-01-18 2018-06-12 湖南工学院 High melamine polyphosphate of a kind of thermal stability and preparation method thereof
CN112538094A (en) * 2020-12-15 2021-03-23 江苏长能节能新材料科技有限公司 Melamine alkyl phosphate and preparation method and application thereof
CN113580293A (en) * 2021-07-27 2021-11-02 菏泽奕普新材料有限公司 High-dispersion modified melamine polyphosphate flame retardant and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI307704B (en) * 2005-08-30 2009-03-21 Chang Chun Plastics Co Ltd Method for preparing amino phosphate
DE102009055434A1 (en) * 2009-12-31 2011-07-07 Chemische Fabrik Budenheim KG, 55257 Flame retardant composition for thermoplastic molding compositions

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES224890A1 (en) * 1954-11-09 1956-02-01 Albright & Wilson Bromine containing nitrilo methylol-phosphorus polymers
CN102127230A (en) * 2010-01-19 2011-07-20 中化蓝天集团有限公司 New process for preparing modified melamine polyphosphate
CN102030848A (en) * 2010-11-10 2011-04-27 苏州科技学院 Macromolecular flame retardant and preparation method thereof
CN102321245A (en) * 2011-07-10 2012-01-18 东华大学 Benzoguanamine propyloic phenyl phosphinic acid condensation compound and preparation method
CN102417596A (en) * 2011-10-19 2012-04-18 浙江大学宁波理工学院 Phosphate ester polymer intumescent flame retardant and preparation method thereof
CN102604111A (en) * 2012-01-16 2012-07-25 苏州科技学院 Novel preparation method of polymeric phosphate ester flame retardant containing active hydroxyl
DE102012204642A1 (en) * 2012-03-22 2013-09-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Phosphorus-containing unsaturated polyesters, polyester resins and possibly fiber-reinforced components thereof
CN105504292A (en) * 2015-12-24 2016-04-20 瓮福(集团)有限责任公司 Preparation method of MPOP
CN107459492A (en) * 2017-07-26 2017-12-12 东华大学 A kind of organically-modified melamine polyphosphate and preparation method thereof
CN108148011A (en) * 2018-01-18 2018-06-12 湖南工学院 High melamine polyphosphate of a kind of thermal stability and preparation method thereof
CN112538094A (en) * 2020-12-15 2021-03-23 江苏长能节能新材料科技有限公司 Melamine alkyl phosphate and preparation method and application thereof
CN113580293A (en) * 2021-07-27 2021-11-02 菏泽奕普新材料有限公司 High-dispersion modified melamine polyphosphate flame retardant and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Melamine Cyanurate, Halogen and Phosphorus Free Flame Retardant ";Stern Gila, et al.;《INTERNATIONAL JOURNAL OF POLYMERIC MATERIALS AND POLYMERIC BIOMATERIALS》;第25卷(第3-4期);255-268 *
"三聚氰胺聚磷酸盐阻燃剂的合成与表征";张泽江,等;《应用化学》;第20卷(第11期);1035-1038 *
"磷酸三聚氰胺硼酸盐阻燃剂的合成";赵爱明,等;《山东化工》;第38卷(第12期);1-6 *
"磷酸三聚氰胺聚丙烯酸盐膨胀型阻燃剂的制备及性能研究";董延茂,等;《塑料科技》;第40卷(第7期);90-94 *

Also Published As

Publication number Publication date
CN117089079A (en) 2023-11-21

Similar Documents

Publication Publication Date Title
JP6210066B2 (en) Fiber reinforced polyamide resin material
JP2019203129A (en) Method for manufacturing thermoplastic material made from semi-crystalline polyamide
WO2013088932A1 (en) Molded article
US8680199B2 (en) Reinforced polyamide composition
JP6130400B2 (en) Method for preparing halogen-free flame retardant polyamide composition
CN109438976B (en) Copolymerized nylon product and preparation method thereof
CN107523049A (en) A kind of graphene macromolecule composite heat-conducting plastics and preparation method
CN117089079B (en) Preparation method of melamine polyphosphate
Gao et al. Synthesis and characterization of poly (hexamethylene terephthalate/hexamethylene oxamide) alternating copolyamide (alt‐PA6T/62)
CN110229343A (en) A kind of polylactic acid-metal organic frame composite material and preparation method
CN109705342A (en) A kind of color inhibition polyamide and its raw materials for production and production method
CN113429782B (en) Transparent polyamide resin and preparation method thereof
CN113831732B (en) Low-water-absorption high-toughness high-temperature nylon composite material and preparation method thereof
CN104479122A (en) Stable-color fatty-aromatic copolyester and preparation method thereof
JP5272511B2 (en) Method for producing polybutylene terephthalate
CN117069948B (en) Preparation method of melamine polyphosphate containing aldehyde functional group
CN114437521A (en) Processing technology of degradable composite packaging film based on PBAT
CN116218037A (en) Epoxy plastic package material of modified silicon dioxide grafted epoxy resin and preparation method thereof
CN115612095A (en) High-temperature-resistant semi-aromatic copolyamide and preparation method, composition and molded product thereof
CN108129626B (en) Polymeric carbodiimide compound and preparation method thereof
CN1350008A (en) Modified polyvinyl acetate emulsion
JP5751604B2 (en) Method for producing polybutylene terephthalate resin
CN109206817A (en) A kind of composite plastic and preparation method thereof
JP2019011478A (en) Halogen-free flame-retardant polyamide composition and method of preparing the same, and application thereof
JP2010100668A (en) Preparation of polybutylene terephthalate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant