CN106349175B - Inorganic hybridization melamine methylol phosphate and preparation method thereof - Google Patents
Inorganic hybridization melamine methylol phosphate and preparation method thereof Download PDFInfo
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- CN106349175B CN106349175B CN201610620404.XA CN201610620404A CN106349175B CN 106349175 B CN106349175 B CN 106349175B CN 201610620404 A CN201610620404 A CN 201610620404A CN 106349175 B CN106349175 B CN 106349175B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/64—Condensation products of melamine with aldehydes; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/10—Organic materials containing nitrogen
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization melamine methylol phosphate and preparation method thereof.It mainly comprises the steps that (1) hydroxymethylation, melamine, formaldehyde and water is added into reaction kettle, methylol reaction is carried out under the conditions of weak alkaline medium, obtains melamine methylol；(2) hydridization is reacted, and is reacted with inorganic hybridization compound；(3) salt-forming reaction；(4) cold filtration is cooled to 40 DEG C of following crystallization filterings, obtains inorganic hybridization melamine methylol phosphate.Inorganic hybridization melamine methylol phosphate made from the method through the invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the melamine methylol phosphate ultimately generated introduces the heat-resistant fireproofs element such as boron, molybdenum, antimony, to improve the high temperature resistance and flame retardant property of melamine.
Description
Technical field
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization methylol melamine
Amine phosphate with and preparation method thereof.
Background technique
With the extensive use and fast development of engineering plastics, to the performance of material, more stringent requirements are proposed, is keeping
Under the premise of strong mechanical performance, flame retardant property, electric property are also had higher requirement, so grinding engineering plastics are flame-retardant modified
The thoroughly evaluating of comprehensive performance is increasingly valued by people in studying carefully.The common fire retardant of engineering plastics mainly has halogen system resistance
Fire agent, phosphorus-nitrogen containing flame retardant, inorganic fire retardants.Wherein halogenated flame retardant additive amount is small, and flame retarding efficiency is high, but can generate when burning
Poison gas.Inorganic fire retardants thermal stability is good, non-volatile, nontoxic, but additive amount is big, can reduce the mechanical property of material.For
Overcome above-mentioned deficiency, thus developing the high halogen-free flame retardants of comprehensive cost performance is flame-retardant modified one of the developing direction of material.
The widely used phosphorus nitrogen synergistic fire retardant of current melamine polyphosphate, but since it is monomer molecule three
The deficiencies of salt of poly cyanamid, melamine easily distils evolution when being presented with high temperature, and heat-resisting quantity is poor, thus how to melamine
Quadrafos is further improved, to overcome its deficiency to have market in urgent need.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides a kind of inorganic hybridization melamine methylols
Phosphate and preparation method thereof under the conditions of weak alkaline medium, carries out hydroxyl first with formaldehyde and water heating using melamine as raw material
Glycosylation reaction, then reacted with inorganic hybridization compound, inorganic hybridization melamine methylol is generated, phosphoric acid progress is added
Reaction, ultimately generates inorganic hybridization melamine methylol phosphate, flame retardant property and high temperature resistance with higher.
The technical solution adopted in the present invention is as follows:
Inorganic hybridization melamine methylol phosphate, it is characterised in that: molecular structure is as follows:
X in the molecular structure is inorganic hybridization element, including one of B or Sb.
The inorganic hybridization melamine methylol method for production of phosphate salt, it is characterised in that: mainly include following
Step:
By melamine, formaldehyde and water, under the conditions of weak alkaline medium, heating carries out hydroxymethylation and generates methylol
Melamine；
The melamine methylol of generation is reacted 0.5~2 under conditions of 100~110 DEG C with inorganic hybridization compound
Hour, hydridization reaction is completed, and is added phosphoric acid and is carried out reaction 1~2 hour, is cooled to 40 DEG C of following crystallization filterings, is obtained inorganic
Hydridization melamine methylol phosphate.
The inorganic hybridization melamine methylol method for production of phosphate salt, it is characterised in that: mainly include following
Step:
(1) hydroxymethylation
Melamine, formaldehyde and water are added into reaction kettle, adding alkali to adjust pH is 8.0~9.0, in 35~65 DEG C of condition
Under, 30~120min of heat preservation carries out methylol reaction, obtains melamine methylol resin；
(2) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 0.5~2 hour, hydridization
Reaction is completed；
(3) salt-forming reaction
Phosphoric acid is at the uniform velocity added into reaction kettle, it is 1~2 hour that the time, which is added, is at the uniform velocity stirred after adding 10~30 minutes；
(4) cold filtration
40 DEG C of following crystallization filterings are cooled to, inorganic hybridization melamine methylol phosphate is obtained.
The inorganic hybridization melamine methylol method for production of phosphate salt, it is characterised in that: in the step (2)
Inorganic hybridization compound are as follows: Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, antimony oxide,
One of antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The inorganic hybridization melamine methylol method for production of phosphate salt, it is characterised in that: in the step (1)
Adjusting alkali used in pH is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, and mass concentration is 25~35%.
The inorganic hybridization reaction principle of the invention patent:
The principle reacted can be crosslinked with boron, molybdenum, antimony element using the methylol contained on compound, realize this hair
The hydridization reaction process of bright patent eliminates reactive group because enclosing methylol, and the temperature in reaction process can be substantially
Degree is improved to 110 DEG C, and boron, molybdenum, antimony ignition-proof element are introduced on molecular structure, so that the stability of product, flame retardant property
It is substantially improved with high temperature resistance.
Above-mentioned technical proposal of the invention compared with prior art, has the advantage that
1, it is reacted by methylolated melamine resin with the hybrid cross-linked of inorganic hybridization compound, so that most throughout one's life
At inorganic hybridization melamine methylol phosphate introduce the heat-resistant fireproofs element such as boron, antimony, molybdenum, to improve trimerization
The high temperature resistance and flame retardant property of cyanamide, compared with the melamine before non-hydridization, high temperature resistance improves 50 DEG C or more,
Flame retardant property improves at least 20%.
2, it is fire-retardant to overcome the introducing of melamine molecule structure for the phosphatic preparation of the inorganic hybridization melamine methylol
The technical problem of element solves the skills such as outer influence and flame retardant effect of the addition fire retardant to product physical mechanical property be undesirable
Art problem.
Specific embodiment
The present invention will be described in detail combined with specific embodiments below, but the invention is not limited to specific embodiments.
Embodiment 1
The phosphatic preparation of boron hydridization melamine methylol
Molecular structural formula:
Raw material proportioning:
(1) hydroxymethylation
Melamine, formaldehyde and water is added into reaction kettle according to the above ratio, it is 8.0 that adding sodium hydroxide, which adjusts pH, 35
Under conditions of DEG C, 60 revs/min of revolving speed, heat preservation 120min carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Four water, eight Boratex and water are added into reaction kettle, is warming up to 100 DEG C and reacts 2 hours, hydridization reaction is completed；
(3) salt-forming reaction
Phosphoric acid is at the uniform velocity added into reaction kettle, it is 1 hour that the time, which is added, is at the uniform velocity stirred after adding 30 minutes；
(4) cold filtration
40 DEG C of following crystallization filterings are cooled to, boron hydridization melamine methylol phosphate is obtained.
Embodiment 2
The phosphatic preparation of stilba melamine methylol
Molecular structural formula:
Raw material proportioning:
(1) hydroxymethylation
Melamine, formaldehyde and water is added into reaction kettle according to the above ratio, adding potassium hydroxide to adjust pH is 9.0,65
Under conditions of DEG C, 80 revs/min of revolving speed, heat preservation 30min carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Antimony oxide and water are added into reaction kettle, is warming up to 110 DEG C and reacts 0.5 hour, hydridization reaction is completed；
(3) salt-forming reaction
Phosphoric acid is at the uniform velocity added into reaction kettle, it is 2 hours that the time, which is added, is at the uniform velocity stirred after adding 10 minutes；
(4) cold filtration
40 DEG C of following crystallization filterings are cooled to, stilba melamine methylol phosphate is obtained.
Embodiment 3
The phosphatic preparation of molybdenum hydridization melamine methylol
Molecular structural formula:
Raw material proportioning:
(1) hydroxymethylation
Melamine, formaldehyde and water is added into reaction kettle according to the above ratio, adding sodium bicarbonate to adjust pH is 8.5,50
Under conditions of DEG C, 70 revs/min of revolving speed, heat preservation 80min carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1 hour, hydridization reaction is completed；
(3) salt-forming reaction
Phosphoric acid is at the uniform velocity added into reaction kettle, it is 1.5 hours that the time, which is added, is at the uniform velocity stirred after adding 20 minutes；
(4) cold filtration
40 DEG C of following crystallization filterings are cooled to, molybdenum hydridization melamine methylol phosphate is obtained.
Claims (3)
1. inorganic hybridization melamine methylol method for production of phosphate salt, it is characterised in that: mainly comprise the steps that
(1) hydroxymethylation
Melamine, formaldehyde and water are added into reaction kettle, adding alkali to adjust pH is 8.0~9.0, under conditions of 35~65 DEG C,
It keeps the temperature 30~120min and carries out methylol reaction, obtain melamine methylol resin；
(2) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 0.5~2 hour, hydridization reaction
It completes；
(3) salt-forming reaction
Phosphoric acid is at the uniform velocity added into reaction kettle, it is 1~2 hour that the time, which is added, is at the uniform velocity stirred after adding 10~30 minutes；
(4) cold filtration
40 DEG C of following crystallization filterings are cooled to, inorganic hybridization melamine methylol phosphate is obtained；
Inorganic hybridization compound in the step (2) are as follows: Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight boron
In sour sodium, antimony oxide, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate
It is a kind of.
2. inorganic hybridization melamine methylol method for production of phosphate salt according to claim 1, it is characterised in that: institute
Stating and adjusting alkali used in pH in step (1) is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration
It is 25~35%.
3. inorganic hybridization melamine methylol phosphate obtained by any one of -2 methods, feature exist according to claim 1
In: molecular structure is as follows:
X in the molecular structure is inorganic hybridization element, is selected from one of B or Sb.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712749A (en) * | 2009-11-19 | 2010-05-26 | 中国科学院广州化学研究所 | Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof |
| CN103319673A (en) * | 2013-05-30 | 2013-09-25 | 山东圣泉化工股份有限公司 | Modification method of melamine formaldehyde resin |
| CN104530340A (en) * | 2014-12-22 | 2015-04-22 | 沙县宏盛塑料有限公司 | Method for preparing boron modified melamine formaldehyde resin |
| CN104592138A (en) * | 2015-01-08 | 2015-05-06 | 重庆大学 | Method of increasing hydroxymethyl content of hexahydroxymethyl melamine |
| CN105199096A (en) * | 2015-11-11 | 2015-12-30 | 江苏钟山化工有限公司 | Preparation and application of nitrogen and phosphorus structured flame-retardant polyether polyol |
| CN105814014A (en) * | 2013-12-02 | 2016-07-27 | 英派尔科技开发有限公司 | Novel gemini surfactants and use thereof |
-
2016
- 2016-08-01 CN CN201610620404.XA patent/CN106349175B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712749A (en) * | 2009-11-19 | 2010-05-26 | 中国科学院广州化学研究所 | Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof |
| CN103319673A (en) * | 2013-05-30 | 2013-09-25 | 山东圣泉化工股份有限公司 | Modification method of melamine formaldehyde resin |
| CN105814014A (en) * | 2013-12-02 | 2016-07-27 | 英派尔科技开发有限公司 | Novel gemini surfactants and use thereof |
| CN104530340A (en) * | 2014-12-22 | 2015-04-22 | 沙县宏盛塑料有限公司 | Method for preparing boron modified melamine formaldehyde resin |
| CN104592138A (en) * | 2015-01-08 | 2015-05-06 | 重庆大学 | Method of increasing hydroxymethyl content of hexahydroxymethyl melamine |
| CN105199096A (en) * | 2015-11-11 | 2015-12-30 | 江苏钟山化工有限公司 | Preparation and application of nitrogen and phosphorus structured flame-retardant polyether polyol |
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