CN108559041B - Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof - Google Patents

Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof Download PDF

Info

Publication number
CN108559041B
CN108559041B CN201711482748.XA CN201711482748A CN108559041B CN 108559041 B CN108559041 B CN 108559041B CN 201711482748 A CN201711482748 A CN 201711482748A CN 108559041 B CN108559041 B CN 108559041B
Authority
CN
China
Prior art keywords
flame retardant
spherical
free flame
phosphorus
halogen
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
CN201711482748.XA
Other languages
Chinese (zh)
Other versions
CN108559041A (en
Inventor
周俊文
马文石
吴力
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.)
South China Institute of Collaborative Innovation
Original Assignee
South China Institute of Collaborative Innovation
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 South China Institute of Collaborative Innovation filed Critical South China Institute of Collaborative Innovation
Priority to CN201711482748.XA priority Critical patent/CN108559041B/en
Publication of CN108559041A publication Critical patent/CN108559041A/en
Application granted granted Critical
Publication of CN108559041B publication Critical patent/CN108559041B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention belongs to the technical field of flame retardants, and discloses a spherical phosphorus-nitrogen synergistic flame retardant and a preparation method thereof. The method comprises the following steps: mixing 65-95 parts by weight of water, 1-11 parts by weight of melamine and 1-30 parts by weight of formaldehyde aqueous solution, adding an alkaline compound to adjust the pH to 8-12, heating to 50-140 ℃, and carrying out heat preservation reaction for 1-8 hours; adding 0.5-5 parts by weight of a compound containing phosphoric acid groups, continuing to react for 2-6 hours, and performing subsequent treatment to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant is spherical, has good fluidity and is convenient to process; meanwhile, the nitrogen and phosphorus synergistic flame retardant effect is realized, so that the flame retardant has excellent flame retardance; the flame retardant has stable structure; the compatibility with the polymer is better.

Description

Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a spherical phosphorus-nitrogen synergistic halogen-free flame retardant and a preparation method thereof.
Background
The development of high molecular materials brings great convenience and benefits to human life, but simultaneously becomes a potential fire source, and in order to reduce fire and harm caused by fire, the industry is vigorously researching and developing new flame retardants and flame retardant materials. There are many kinds of flame retardants, and there are halogen and halogen-free flame retardants according to the presence or absence of halogen. The application of halogen flame retardants, especially bromine flame retardants, is continuously limited due to the environmental safety hazard problem in the combustion process. The halogen-free flame retardant has the advantages of high efficiency, environmental protection and the like, wherein the phosphorus-nitrogen flame retardant is a halogen-free flame retardant which develops rapidly in recent years. Phosphorus-nitrogen flame retardant belongs to intumescent flame retardant, which takes phosphorus and nitrogen as main active components, does not contain halogen, has little smoke during combustion, does not generate toxic gases such as hydrogen halide and the like, and has the function of molten drop prevention. Although the phosphorus-containing flame retardant has the advantages, the phosphorus-containing flame retardant has poor compatibility with certain high molecular materials, and the flame retardant can migrate from the polymer product to the surface to be lost along with the increase of the service time, so that the expected flame retardant effect cannot be achieved. Meanwhile, the common phosphorus-containing flame retardant is decomposed by heating at high temperature to generate a small molecular compound, so that the requirement of processing thermoplastic and thermosetting plastics at high temperature is difficult to meet.
In order to overcome the above disadvantages, chinese patent CN03116283.0 and US4639331 use melamine-formaldehyde or phenol-formaldehyde resin as a capsule material to coat ammonium polyphosphate, etc., while european patent EP0542373a1 uses amino resin as a capsule material to coat ammonium polyphosphate, etc. However, the material obtained by the method has unstable combination between the flame retardant and the coating material, is easy to be partially broken by external force in the processing process, and finally cannot achieve the expected flame retardant effect.
The spherical phosphorus-containing flame retardant with stable performance is formed by a chemical synthesis mode, and the flame retardant effect is better due to a synergistic action mechanism of phosphorus and nitrogen; meanwhile, due to the spherical shape and good fluidity of the flame retardant, the lubricity and the compatibility of the flame retardant in the high polymer material are improved, so that the addition proportion of the flame retardant in the high polymer material is improved, and the flame retardant is favorable for achieving a better flame retardant effect.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a spherical phosphorus-nitrogen synergistic halogen-free flame retardant and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a spherical phosphorus-nitrogen synergistic halogen-free flame retardant comprises the following steps:
mixing 65-95 parts by weight of water, 1-11 parts by weight of melamine and 1-30 parts by weight of formaldehyde aqueous solution, adding an alkaline compound to adjust the pH to 8-12, heating to 50-140 ℃, and carrying out heat preservation reaction for 1-8 hours; adding 0.5-5 parts by weight of a compound containing phosphoric acid groups, continuing to react for 2-6 hours, and performing subsequent treatment to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant.
The mass concentration of the formaldehyde aqueous solution is 20-40%, and preferably 38%; the temperature of the continuous reaction is 50-140 ℃; the subsequent treatment comprises cooling and filtering the reaction product, washing with deionized water and drying.
The alkaline compound is more than one of sodium hydroxide, potassium hydroxide, ammonia water and triethylamine.
The compound containing the phosphoric acid group is more than one of phosphoric acid, methyl phosphonic acid, ethyl phosphoric acid and phenyl phosphonic acid.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the halogen-free flame retardant is spherical, and the spherical halogen-free flame retardant with different particle sizes can be obtained by adjusting the proportion of the raw materials and water, so that the obtained spherical flame retardant has good fluidity and is convenient to process; meanwhile, the nitrogen and phosphorus synergistic flame retardant effect is realized, so that the flame retardant has excellent flame retardance; according to the invention, through the reaction of melamine and formaldehyde, a nitrogen-containing prepolymer is obtained, then a compound containing a phosphoric acid group is reacted with the nitrogen-containing prepolymer, nitrogen and phosphorus are fixed in a product through a chemical bond, and the flame retardant has a stable structure; the flame retardant has good compatibility with polymers, particularly polymers containing polar groups.
Drawings
FIG. 1 is an SEM image of a spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in example 1;
FIG. 2 is an SEM image of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in example 3.
Detailed Description
The present invention will be described in further detail below with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Adding 88g of deionized water, 3.6g of melamine and 7.2g of formaldehyde aqueous solution (38% by mass) into a reactor, adding sodium hydroxide to adjust the pH value to 9, stirring (the stirring speed is 600rpm), heating to 65 ℃, and carrying out heat preservation reaction for 2 hours; adding 0.7g of phosphoric acid, continuing to react for 4 hours, cooling and filtering the reaction product, washing by using deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure. FIG. 1 is an SEM image of a spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in example 1.
Example 2
Adding 74g of deionized water, 8.1g of melamine and 15.9g of formaldehyde aqueous solution (the mass percentage is 38%) into a reactor, adding ammonia water to adjust the pH value to 10, stirring (the stirring speed is 600rpm), heating to 85 ℃, and carrying out heat preservation reaction for 1.5 hours; adding 2.0g of ethyl phosphoric acid, continuing to react for 4 hours, cooling and filtering the reaction product, washing by using deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure.
Example 3
Adding 74g of deionized water, 8.1g of melamine and 15.9g of formaldehyde aqueous solution (the mass percentage is 38%) into a reactor, adding ammonia water to adjust the pH value to 9, stirring (the stirring speed is 600rpm), heating to 65 ℃, and carrying out heat preservation reaction for 3 hours; adding 2.0g of phenylphosphoric acid, continuing to react for 4 hours, cooling and filtering the reaction product, washing by deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure. FIG. 2 is an SEM image of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in example 3.
Example 4
Adding 70g of deionized water, 5.7g of melamine and 22.3g of formaldehyde aqueous solution (the mass percentage is 38%) into a reactor, adding ammonia water to adjust the pH value to 10, stirring (the stirring speed is 600rpm), heating to 85 ℃, and carrying out heat preservation reaction for 1.5 h; adding 1.6g of methylphosphonic acid, continuing to react for 4h, cooling and filtering the reaction product, washing by deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure.
Example 5
Adding 65g of deionized water, 5.7g of melamine and 27.3g of formaldehyde aqueous solution (the mass percentage is 38%) into a reactor, adding ammonia water to adjust the pH value to 10, stirring (the stirring speed is 600rpm), heating to 85 ℃, and carrying out heat preservation reaction for 1.5 h; adding 2g of phosphoric acid, continuing to react for 4 hours, cooling and filtering the reaction product, washing by using deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure.
Example 6
Adding 75g of deionized water, 5.7g of melamine and 17.3g of formaldehyde aqueous solution (38% by mass) into a reactor, adding sodium hydroxide to adjust the pH value to 12, stirring (the stirring speed is 600rpm), heating to 140 ℃, and carrying out heat preservation reaction for 1.5 hours; adding 2g of phosphoric acid, continuing to react for 4 hours, cooling and filtering the reaction product, washing by using deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure.
Example 7
Adding 75g of deionized water, 5.7g of melamine and 17.3g of formaldehyde aqueous solution (38% by mass) into a reactor, adding sodium hydroxide to adjust the pH value to 12, stirring (the stirring speed is 600rpm), heating to 55 ℃, and carrying out heat preservation reaction for 6 hours; adding 2g of methyl phosphoric acid, continuing to react for 4 hours, cooling and filtering the reaction product, washing by using deionized water, and drying (the drying temperature is 50 ℃) to obtain the spherical phosphorus-nitrogen synergistic halogen-free flame retardant. The halogen-free flame retardant of the embodiment is a spherical halogen-free flame retardant, and has good fluidity and stable structure.
Test for flame retardancy
The flame retardant performance of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in the example 1, the example 3 and the example 5 is tested: according to 100 parts by weight of polyurethane, 20% of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in example 1, example 3 and example 5 (20% of the weight of the polyurethane) is added respectively, and vertical combustion experiments are carried out on the spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in example 1, example 3 and example 5 respectively, and the three can reach the UL-94 standard V-0 grade.
The spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared in the embodiment 1, the embodiment 3 and the embodiment 5 has good compatibility with polyurethane.

Claims (5)

1. A preparation method of a spherical phosphorus-nitrogen synergistic halogen-free flame retardant is characterized by comprising the following steps: the method comprises the following steps:
mixing 65-95 parts by weight of water, 1-11 parts by weight of melamine and 1-30 parts by weight of formaldehyde aqueous solution, adding an alkaline compound to adjust the pH to 8-12, heating to 50-140 ℃, and carrying out heat preservation reaction for 1-8 hours; adding 0.5-5 parts by weight of a compound containing phosphoric acid groups, continuing to react for 2-6 hours, and performing subsequent treatment to obtain a spherical phosphorus-nitrogen synergistic halogen-free flame retardant;
the temperature of the continuous reaction is 50-140 ℃;
the mass concentration of the formaldehyde aqueous solution is 20-40%.
2. The preparation method of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant according to claim 1, characterized in that: the compound containing the phosphoric acid group is more than one of phosphoric acid, methyl phosphonic acid, ethyl phosphoric acid and phenyl phosphonic acid.
3. The preparation method of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant according to claim 1, characterized in that: the alkaline compound is more than one of sodium hydroxide, potassium hydroxide, ammonia water and triethylamine.
4. The preparation method of the spherical phosphorus-nitrogen synergistic halogen-free flame retardant according to claim 1, characterized in that: the subsequent treatment comprises cooling and filtering the reaction product, washing with deionized water and drying.
5. The spherical phosphorus-nitrogen synergistic halogen-free flame retardant prepared by the preparation method of any one of claims 1 to 4.
CN201711482748.XA 2017-12-29 2017-12-29 Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof Active CN108559041B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711482748.XA CN108559041B (en) 2017-12-29 2017-12-29 Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711482748.XA CN108559041B (en) 2017-12-29 2017-12-29 Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108559041A CN108559041A (en) 2018-09-21
CN108559041B true CN108559041B (en) 2020-03-24

Family

ID=63529636

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711482748.XA Active CN108559041B (en) 2017-12-29 2017-12-29 Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108559041B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4195139A (en) * 1977-06-08 1980-03-25 Imperial Chemical Industries Limited Fire retardant composition comprising a melamine-aldehyde-phosphate condensate
CN102827399A (en) * 2012-09-06 2012-12-19 四川大学 Phosphorus and nitrogen fire retardant and preparation method thereof
CN103588992A (en) * 2013-11-06 2014-02-19 四川大学 In-situ polymerized double-layer-wrapped modified ammonium polyphosphate, and preparation method and application thereof
CN105086455A (en) * 2015-01-15 2015-11-25 淄博孚恩化工科技有限公司 Preparation method of compound microcapsule-coated ammonium polyphosphate master batch

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4195139A (en) * 1977-06-08 1980-03-25 Imperial Chemical Industries Limited Fire retardant composition comprising a melamine-aldehyde-phosphate condensate
CN102827399A (en) * 2012-09-06 2012-12-19 四川大学 Phosphorus and nitrogen fire retardant and preparation method thereof
CN103588992A (en) * 2013-11-06 2014-02-19 四川大学 In-situ polymerized double-layer-wrapped modified ammonium polyphosphate, and preparation method and application thereof
CN105086455A (en) * 2015-01-15 2015-11-25 淄博孚恩化工科技有限公司 Preparation method of compound microcapsule-coated ammonium polyphosphate master batch

Also Published As

Publication number Publication date
CN108559041A (en) 2018-09-21

Similar Documents

Publication Publication Date Title
CN101812186B (en) Microencapsulation expansion type flame retardant and application in epoxy resin composite material thereof
WO2019100592A1 (en) Halogen-free flame retardant compound system for glass fiber reinforced nylon and application thereof in halogen-free flame retardant glass fiber reinforced nylon material
CN104093727B (en) Diphosphinic acid and the mixture of dialkyl phosphinic acid, Its Preparation Method And Use
WO2019100929A1 (en) Phosphor aluminium compound-based halogen-free flame retardant compound system and application thereof in glass fiber reinforced engineering plastic
TWI788386B (en) Flame-retardant polyamide compositions with a high glow wire ignition temperature and use thereof
CN111116987B (en) Method for synthesizing fine-grained aluminum hypophosphite composite flame retardant
CN105482160A (en) Preparation method and application for grafted modified ammonium polyphosphate with ultralow water sliding property and hydrolysis resistance
CN103910907A (en) Method for modifying melamine pyrophosphate fire retardant by grafting oxidized graphene
CN109181295A (en) Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic and alkyl phosphite
CN107312199B (en) A kind of hypo-aluminum orthophosphate Hybrid fire retardant and preparation method thereof
CN108997612A (en) Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic phosphorous acid metal salt
CN104497041A (en) Melamine aminotrimethylene phosphonate and preparation method thereof
TW201912771A (en) Synergistic flame retardant combinations for polymer compositions and the use thereof
CN112876736A (en) Dialkyl phosphinic acid-aluminum phosphite composite salt, preparation method and application thereof
CN106398192A (en) Low-separation red phosphorus flame-retardant polyamide material and preparation method thereof
CN108559041B (en) Spherical phosphorus-nitrogen synergistic flame retardant and preparation method thereof
CN105492520B (en) The fire retardant and its manufacturing method prepared by amide derivatives
CN109251526A (en) Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using alkyl phosphite
CN112457526B (en) Melon ring inclusion-based low-smoke antimony-free flame retardant and application thereof
CN108794804B (en) The halogen-free flame-retardant system and its application of dialkyl dithio hypophosphites and nitrogenous compound collaboration
CN106433040A (en) Low-precipitation red phosphorus flame-retardant terylene material and preparation method thereof
CN108948423B (en) The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite
CN111635559A (en) Organic phosphide flame retardant and preparation method and application thereof
CN108794805A (en) Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of organic phosphite and nitrogenous compound collaboration and its application
JP2006110965A (en) Fire retardancy imparting liquid material for wood, and its manufacturing method

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