CN104370966B - A kind of metallo-organic compound and preparation method thereof - Google Patents
A kind of metallo-organic compound and preparation method thereof Download PDFInfo
- Publication number
- CN104370966B CN104370966B CN201410523309.9A CN201410523309A CN104370966B CN 104370966 B CN104370966 B CN 104370966B CN 201410523309 A CN201410523309 A CN 201410523309A CN 104370966 B CN104370966 B CN 104370966B
- Authority
- CN
- China
- Prior art keywords
- dopo
- metal
- organic compound
- ball milling
- preparation
- 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.)
- Expired - Fee Related
Links
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of metallo-organic compound and preparation method thereof, the compound is based on organic fire-retardant DOPO, react with the activated metal after ball milling under uniform temperature and ambient atmosphere conditions, synthesize a kind of metallo-organic compound fire retardant, belong to the synthesis technical field of material science fire retardant.The structural formula of the compound is：Wherein, M is metal, preferred Mg, Al or Be.The compound has higher heat decomposition temperature and lower hygroscopicity, can apply in fire-retardant or harsh to the moisture absorption requirement material of the higher polymer of decomposition temperature；After introducing metal, due to P elements and the fire-retardant synergy of metallic element, its anti-flammability is further enhanced；The preparation process is carried out under melting condition, and metal powder used first passes through ball milling activation, sieves, and reactivity is big, is not required to introduce catalyst etc., prepares and last handling process is simple.
Description
Technical field
The present invention relates to a kind of metal organic compound and preparation method thereof, the compound is based on organic fire-retardant DOPO,
React with the activated metal after ball milling under uniform temperature and ambient atmosphere conditions, synthesize a kind of metal organic compound
Fire retardant, belongs to the synthesis technical field of material science fire retardant.
Background technology
Miscellaneous phenanthrene -10- the oxides (DOPO) of the miscellaneous -10- phosphines of 9,10- dihydro-9-oxies are a kind of with higher antioxidant and good
Resistance to water environmental protection organic phosphorus flame retardant, synthesized by Saito first within 1972, but its heat decomposition temperature be relative
It is relatively low, start to decompose at 194 DEG C, therefore also limit the range of application of DOPO.Active O=P-H keys in its structure to thiazolinyl,
Epoxy radicals and carbonyl have very high addition activity.DOPO can generate a series of with the addition reaction such as organic acid, aldehydes, quinones
Phosphonium flame retardant, and it is applied to various high scores such as linear polyester, epoxy resin, polyamide, BMI, polyurethane
Sub- material it is fire-retardant, in recent years DOPO and its derivative because its Halogen, it is smokeless, nontoxic, do not migrate, and anti-flammability is persistently, state
The inside and outside research to this based flame retardant is relatively broad.
The content of the invention
Present invention aim to address DOPO heat endurances are low to apply the problems such as limiting to down to which, a kind of metal of proposition-have
Machine compound and preparation method thereof, it is 414 DEG C that the technology of the present invention is obtained the heat decomposition temperature of compound.First metal is incorporated into
In DOPO structures, in the case where imposing a condition, the activated metal powder after active O=P-H groups in DOPO and ball milling is according to 1:2
There is substitution reaction in mol ratio, successfully synthesize a kind of novel metal-organic compound.Compare DOPO and its with organic acid, aldehyde
Phosphorus-containing compound obtained by the additions such as class, present invention gained material have higher heat decomposition temperature and lower hygroscopicity.
The present invention adopts metal ball-milling technology, is introduced in DOPO structures first, be exposed to metal in air due to
Surface coating has oxide layer, it is difficult to react, metal ball milling is activated by the technology first, in making activated metal powder and DOPO
Active O=P-H radical reactions, successfully synthesize a kind of novel metal-organic compound, compared with the derivative of other DOPO,
The compound has higher heat decomposition temperature and lower hygroscopicity, can apply to the resistance of the higher polymer of decomposition temperature
In combustion or the material harsh to moisture absorption requirement.
The purpose of the present invention is achieved through the following technical solutions.
A kind of metal organic compound of the present invention, the structural formula of the compound is：
Wherein, M is metal, preferred Mg, Al or Be.
A kind of preparation method of metal organic compound of the present invention, step is：
(1) by metal powder ball milling 30min, 200 mesh sieves are crossed standby；Ball-milling technology is：Ratio of grinding media to material 10:1, in 1200r/min
Rotating speed under ball milling 48s, ball milling 12s under the rotating speed of 800r/min, this is a circulation, the circulation of ball milling 30；
(2) DOPO is added in glass container, is stirred, nitrogen atmosphere, heating melts DOPO；
Described heating adopts oil bath heating, and heating-up temperature is 160 DEG C, and mechanical agitation 1h melts DOPO；
(3) after DOPO is melted completely, the metal powder that step (1) is obtained is poured into into rapidly the glass in step (2) and is held
In device, 12-15h is reacted, in course of reaction, material is in gradually canescence in glass container, is stirred as thick；
(4), after reaction terminates, adjustment oil bath temperature is 110 DEG C；
(5) after system is down to the temperature of step (4), certain volume toluene is added in glass container, in nitrogen atmosphere
Lower stirring 1h；
(6) suction filtration, filter cake is placed in 110 DEG C of vacuum drying ovens and is dried 12h, obtains product, and the yield of product is 90%-
92.9%.
The structural formula of above-mentioned DOPO is：In raw material, metal with the mol ratio of DOPO is：n
(magnesium powder)/n (DOPO)=1/2, n (beryllium powder)/n (DOPO)=1/2, n (aluminium powder)/n (DOPO)=1/3, on this basis DOPO
Excessive 10%；In step (5), reactant quality (g)/solvent volume (mL) is：1/5.
Beneficial effect
The derivative of DOPO and other DOPO is compared, the compound has higher heat decomposition temperature and lower moisture absorption
Property, can apply in fire-retardant or harsh to the moisture absorption requirement material of the higher polymer of decomposition temperature；Introduce metal it
Afterwards, due to P elements and the fire-retardant synergy of metallic element, its anti-flammability is further enhanced；The preparation process is in melting
Under the conditions of carry out, and metal powder used first passes through ball milling activation, sieves, and reactivity is big, is not required to introduce catalyst etc., prepare and
Last handling process is simple.
Specific embodiment
The present invention is elaborated with reference to embodiment.
Embodiment 1
By metal magnesium powder ball milling 30min, 200 mesh sieves excessively are standby, and ball-milling technology is：Ratio of grinding media to material 10:1,1200r/min's
Ball milling 12s under the rotating speed of ball milling 48s under rotating speed, 800r/min, this is circulated for one, 30 circulations of ball milling.Attachment means, including
Stirring, heating, reflux condensation mode and nitrogen atmosphere.Take 11gDOPO in 250ml there-necked flasks, in a nitrogen atmosphere, control oil
Bath temperature is 160 DEG C, and mechanical agitation 1h melts DOPO, then weighs 0.55g activating powders and pours rapidly the flask into, reaction
15h, in course of reaction, in flask, material is in gradually canescence, is stirred as thick.After reaction terminates, adjustment oil bath temperature is
110 DEG C, after its it is near it is temperature required after, 50ml toluene is added in there-necked flask, 1h is stirred in a nitrogen atmosphere, suction filtration, very
110 DEG C of empty baking oven is dried 12h.Obtain product 9.8g, yield 92.9%.
Above-mentioned reaction equation is：
Embodiment 2
The metallic beryllium sphere of powder is ground into 30min, 200 mesh sieves excessively are standby, and ball-milling technology is：Ratio of grinding media to material 10:1,1200r/min's
Ball milling 12s under the rotating speed of ball milling 48s under rotating speed, 800r/min, this is circulated for one, 30 circulations of ball milling.Take 27.4gDOPO in
In 250ml there-necked flasks, stopper is covered, lead to nitrogen, begun to warm up when whole device is in nitrogen atmosphere, while start stirring
Mix, oil bath temperature is controlled for 160 DEG C, mechanical agitation 1h melts DOPO, then weigh 0.55g activation beryllium powder and pour rapidly the burning into
Bottle, reacts 12h, and in course of reaction, in flask, material is in gradually canescence, is stirred as thick.After reaction terminates, oil bath is adjusted
Temperature be 110 DEG C, after its it is near it is temperature required after, in there-necked flask add 50ml toluene, stir 1h in a nitrogen atmosphere, take out
Filter, 110 DEG C of vacuum drying oven are dried 12h.Obtain product 24.68g, yield 92.0%.
Above-mentioned reaction equation is：
Embodiment 3
By metallic aluminium powder ball milling 30min, 200 mesh sieves excessively are standby, and ball-milling technology is：Ratio of grinding media to material 10:1,1200r/min's
Ball milling 12s under the rotating speed of ball milling 48s under rotating speed, 800r/min, this is circulated for one, 30 circulations of ball milling.Take 14.2gDOPO in
In 250ml there-necked flasks, stopper is covered, lead to nitrogen, begun to warm up when whole device is in nitrogen atmosphere, while start stirring
Mix, oil bath temperature is controlled for 160 DEG C, mechanical agitation 1h melts DOPO, then weigh 0.55g activation aluminium powders and pour rapidly the burning into
Bottle, reacts 15h, and in course of reaction, in flask, material is in gradually canescence, is stirred as thick.After reaction terminates, oil bath is adjusted
Temperature be 110 DEG C, after its it is near it is temperature required after, in there-necked flask add 50ml toluene, stir 1h in a nitrogen atmosphere, take out
Filter, 110 DEG C of vacuum drying oven are dried 12h.Obtain product 12.32g, yield 90.0%.
Above-mentioned reaction equation is：
Claims (6)
1. a kind of metal organic compound, it is characterised in that：The structural formula of the compound is：
Wherein, M is Mg or Be.
2. the preparation method of the metal organic compound described in a kind of claim 1, it is characterised in that step is：
(1) by metal powder ball milling, then sieving for standby；
(2) DOPO is added in glass container, is stirred, nitrogen atmosphere, heating melts DOPO；
(3) after DOPO is melted completely, the metal powder that step (1) is obtained is poured in the glass container in step (2), is reacted
12-15h；
(4), after reaction terminates, adjustment oil bath temperature is 110 DEG C；
(5) after system is down to 110 DEG C, toluene is added in glass container, stirs 1h in a nitrogen atmosphere；
(6) suction filtration, filter cake is placed in 110 DEG C of vacuum drying ovens and is dried 12h, obtains product, and the yield of product is 90%-
92.9%.
3. the preparation method of metal organic compound according to claim 2, it is characterised in that：Ball milling work in step (1)
Skill is：Ratio of grinding media to material 10:1, the ball milling 48s under the rotating speed of 1200r/min, ball milling 12s under the rotating speed of 800r/min, this is followed for one
Ring, 30 circulations of ball milling.
4. the preparation method of metal organic compound according to claim 2, it is characterised in that：Described in step (2)
Heating adopts oil bath heating, and heating-up temperature is 160 DEG C, mechanical agitation 1h.
5. the preparation method of metal organic compound according to claim 2, it is characterised in that：Metal powder in step (1)
For magnesium powder or beryllium powder when, metal with the mol ratio of DOPO is：N (magnesium powder)/n (DOPO)=1/2, n (beryllium powder)/n (DOPO)=1/
2, DOPO excessive 10% on this basis.
6. the preparation method of metal organic compound according to claim 2, it is characterised in that：In step (5), glass holds
Reactant quality in device with volume of toluene ratio is：1g/5mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410523309.9A CN104370966B (en) | 2014-10-07 | 2014-10-07 | A kind of metallo-organic compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410523309.9A CN104370966B (en) | 2014-10-07 | 2014-10-07 | A kind of metallo-organic compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104370966A CN104370966A (en) | 2015-02-25 |
| CN104370966B true CN104370966B (en) | 2017-03-29 |
Family
ID=52550192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410523309.9A Expired - Fee Related CN104370966B (en) | 2014-10-07 | 2014-10-07 | A kind of metallo-organic compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104370966B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591150B (en) * | 2019-07-29 | 2021-05-07 | 浙江大学宁波理工学院 | Cerium-phosphorus complex flame retardant, cerium-phosphorus complex flame-retardant polycarbonate composite material and preparation methods of cerium-phosphorus complex flame retardant and cerium-phosphorus complex flame-retardant polycarbonate composite material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63135396A (en) * | 1986-11-26 | 1988-06-07 | Nippon Ester Co Ltd | Novel organic phosphorus compound |
| DE10360771A1 (en) * | 2003-12-23 | 2005-07-28 | Oxeno Olefinchemie Gmbh | Process for the preparation of trivalent organophosphorus compounds |
| CN101445520B (en) * | 2007-11-26 | 2011-03-30 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
| CN101560226B (en) * | 2008-04-18 | 2013-01-09 | 长春人造树脂厂股份有限公司 | Novel phosphorus series compound as well as preparation method and application thereof |
| CN102153586B (en) * | 2011-01-25 | 2013-11-06 | 浙江大学宁波理工学院 | Compounds containing phosphorus, nitrogen and transition metal elements, and preparation method thereof |
| CN102351904B (en) * | 2011-08-03 | 2014-04-16 | 广东华南精细化工研究院有限公司 | Phosphate rare earth salt with cagelike structure, synthesis method and application thereof |
-
2014
- 2014-10-07 CN CN201410523309.9A patent/CN104370966B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104370966A (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103613573B (en) | Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids | |
| CN109400957A (en) | A kind of alkaloid phosphate flame retardants and preparation method thereof | |
| CN111100303A (en) | Preparation method and application of organic phosphine grafted hollow metal organic framework material | |
| CN103289125B (en) | Phosphorus-nitrogen-silicon containing organic and inorganic hybrid fire retardant and preparation method thereof and formed polymer | |
| CN106928490B (en) | A kind of inorganic-organic hybridization nano compound, preparation method and its flame-proof polylactic acid with the fire-retardant synergistic effect of chain extension- | |
| CN109400649B (en) | Preparation of single-component intumescent flame retardant and application of single-component intumescent flame retardant in flame-retardant epoxy resin | |
| CN104370966B (en) | A kind of metallo-organic compound and preparation method thereof | |
| CN102417612B (en) | Preparation method for in-situ modified expansion type fire retardant | |
| CN110422859A (en) | A kind of preparation method of torispherical diamide ammonium crystal | |
| Janeta et al. | Synthesis, characterization and thermal properties of T8 type amido-POSS with p-halophenyl end-group | |
| CN104588046B (en) | Method for preparing BiOCl by using choline chloride/urea low-melting-point eutectic solvent as burning agent | |
| CN107033182B (en) | A kind of preparation method of Dibutyltin oxide | |
| CN106699551A (en) | Method for synthesizing antioxygen 1076 | |
| Zhan et al. | Synthesis and characterisation of polymeric materials consisting of {Fe2 (CO) 5}-unit and their relevance to the diiron sub-unit of [FeFe]-hydrogenase | |
| CN113376208A (en) | Application of molybdenum in improving reaction performance of boron-containing energetic material | |
| CN107188854A (en) | A kind of synthesis technique for improving carbendazim quality | |
| US9085466B2 (en) | Method for producing precipitated calcium carbonate using fowl egg shells | |
| CN106397832A (en) | Spiro-thiobicyclophosphate halogen-free flame retardant and preparation method thereof | |
| CN116751228A (en) | Bio-based phosphorus-containing diol, preparation method thereof and bio-based flame-retardant polyurethane | |
| CN108285465A (en) | Metal-organic framework material, preparation method, modification metal-organic framework material and preparation method thereof | |
| Xiaolong et al. | Montmorillonite-supported Copper (I) for catalyzing N-Arylation of nitrogen heterocycles | |
| CN106179452B (en) | A kind of preparation method of porous nitrogenous charcoal load palladium catalysis material | |
| CN106543120A (en) | Compound trimellitic anhydride N-butyl and its synthetic method | |
| CN113429629A (en) | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin | |
| CN109970703A (en) | The preparation method and application of 1,3- heterocyclic substituted aromatic ketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170329 Termination date: 20201007 |