CN104927061B - A kind of high molecular weight flame retardant of the keys of N containing P, preparation and its application in PLA - Google Patents
A kind of high molecular weight flame retardant of the keys of N containing P, preparation and its application in PLA Download PDFInfo
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Abstract
The invention discloses a kind of high molecular weight flame retardant of the keys of N containing P, preparation and its application in PLA, belong to field of fire-proof technology.High molecular weight flame retardant of the present invention is synthesized by double (4 Aminobenzoate) polycondensations of dichloro-phenyl phosphate and 1,3 propane diols.The high molecular weight flame retardant is degradable simultaneously containing ignition-proof elements such as phosphorus, nitrogen, and relative molecular mass height is difficult migration, the crystallinity of PLA can effectively be improved, its flame-retardant polylactic acid material technique is simple, good flame retardation effect, without halogen, the harm and pollution level to human body and environment are low.
Description
Technical field
The invention belongs to field of fire-proof technology, and in particular to the high molecular weight flame retardant of key containing P-N a kind of, prepare and its poly-
Application in lactic acid.
Background technology
In recent years, the product application from polymer such as the polyolefin of oil product is quite varied, but its product is used
Solid pollutant afterwards is not disposable, easily pollutes environment, takes a large amount of land resources.Therefore, the polymerization with degradability
The use of Tetramune is of increased attention.PLA is a kind of Green Polymer thermoplasticity fat synthesized by lactic acid
Adoption ester, can be degradable into carbon dioxide and water by the microorganism in nature after its product use, nontoxic, non-stimulated.Separately
Outside, PLA has good mechanical performance, thermoplasticity, biocompatibility, and transparency is good, intensity is high, absorbability is good.Cause
This, has wide application in fields such as electronic apparatus, automobile, agriculture and forestry, medical, food industry and packagings, still, gathers breast
Fiber, membrane material and sheet material that acid makes etc. has inflammability, and its limited oxygen index is 20%, limits PLA in some fields
Application and development.So, the fire-retardant research of poly-lactic acid material is very significant.
In conventional fire retardant, although can cause serious broken to environment after the height burning of halogenated flame retardant flame retarding efficiency
It is bad, thus be gradually eliminated.In all kinds of halogen-free flame retardants, phosphorus flame retardant is a kind of wide fire retardant of application, and it is not
Only have the advantages that low cigarette, low toxicity, non-corrosiveness gas are produced, moreover it is possible to overcome the high addition of inorganic combustion inhibitor to Material Physics machine
The negative influence that tool performance is brought.Compared with the fire retardant containing only phosphorus, while phosphorous, nitrogen fire retardant has lower poison
Property and more preferable heat endurance, and phosphorus, nitrogen have the effect of cooperative flame retardant.(the Jiang Ming visits etc., fire retardant three such as Jiang Ming visits
The synthesis of (diphenylphosphoric acid) isocyanuric acid ester and its application plastics industries .2014,42 (12) in polyurethane:103-
106) three (diphenylphosphoric acid) isocyanuric acid ester (P-THEIC) fire retardants have been synthesized and have been applied it in polyurethane, research knot
Fruit shows that P-THEIC has higher processing temperature, and when its addition is 20wt%, the oxygen of resistance combustion polyurethane foam refers to
Number can bring up to 26%, and can pass through UL-94V-0 grades of tests.Wang Huiya (Wang Huiya, new one pack system phosphorus nitrogen expanding fire retardant
Synthesis chemical research .2010,21 (1):32-35.) closed using neopentyl glycol, POCl3, benzimidizole derivatives as raw material
Into a kind of new one pack system phosphorus nitrogen expanding fire retardant, research finds that the heat endurance and charring rate of the fire retardant are higher, can have
Effect ground improves the molten drop phenomenon of polyolefin to prevent spreading for fire.Phosphorous, nitrogen the fire retardant of most of reports is low
Molecular weight, there is easily migration, poor compatibility.In recent years, the fire retardant of some aggretion types is also reported successively, Hu Yuan
Deng (Hu Yuan et al.A effective flame retardant for epoxy resins based on poly
(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate).Materials
Chemistry and Physics,2011,125(3):536-541.) report has synthesized a kind of dihydroxy benzenes of poly- DOPO substitutions
Base pentaerythrite diphosphate (PFR), is added in epoxy resin, when addition is 10wt% with regard to that can make epoxy resin
LOI values bring up to 30.2% and have passed through UL94V0 grades of test.High molecular weight flame retardant is not volatile and migrates, can be for a long time
Fire resistance is maintained, and the compatibility of most high molecular weight flame retardants and polymeric matrix is preferable, is not susceptible to be separated to protect
Its mechanical strength is demonstrate,proved, therefore, the synthesis of high molecular weight flame retardant also becomes the focus of a research in recent years.
The content of the invention
It is an object of the invention to provide a kind of high molecular weight flame retardant of key containing P-N, preparation and its application in PLA,
It is intended to overcome the deficiencies in the prior art, the fire resistance needed for material can not only be met, moreover it is possible to improves the crystallinity of PLA
Can, and be free of halogen, small toxicity, be difficult migration, flame retarding efficiency height, the harm and pollution level to human body and environment are low.
Realize that the object of the invention technical solution is：
A kind of high molecular weight flame retardant of key containing P-N, the fire retardant has following structure：
Wherein n=10-100.
Above-mentioned high molecular weight flame retardant, is prepared by following steps：
(1) 1,3-PD double (PABA esters) being dissolved in solvent and triethylamine mixing, lead to nitrogen and protect
Shield, is heated to reflux temperature, is added dropwise dropwise after dichloro-phenyl phosphate solution, completion of dropping, and reaction is kept at a reflux temperature；
(2) after reaction terminates, solvent is evaporated off in vacuum distillation, and residue is dissolved in dimethyl sulfoxide, is filtered to remove triethylamine hydrochloric acid
Salt, filtrate is poured into and white precipitate is separated out in a large amount of precipitating reagents, filtering, is cleaned with ethanol repeatedly, is dried to obtain the high score of the key containing P-N
Sub- fire retardant.
In step (1), the mol ratio of dichloro-phenyl phosphate and triethylamine is 1:2, the double (PABAs of 1,3-PD
Ester) with the mol ratio of dichloro-phenyl phosphate it is 1:1.
In step (1), dichloro-phenyl phosphate completion of dropping in 20-30min；Reflux time is 6-12h, preferably
8h。
In step (1), solvent uses lower boiling chloroform or tetrahydrofuran.
In step (2), precipitating reagent is any one in water, ethanol and methanol.
A kind of application of the high molecular weight flame retardant of key containing P-N in PLA, described application is by PLA and high score
Sub- fire retardant mixing, the area's temperature of Bing mono- is 175 ± 1 DEG C, and 2nd area are 176 ± 1 DEG C, and 3rd area are 177 ± 1 DEG C, 4th area are 177 ±
Under conditions of 1 DEG C, flame-retardant polylactic acid material is obtained through conical double screw extruder extrusion, wherein, PLA and high molecular fire retardant
The mass ratio of agent is (85~97)：(3~15).
The present invention compared with prior art, has the following advantages that：
(1) high molecular weight flame retardant of the key containing P-N is due to containing multiple phenyl ring, therefore with excellent flame retardant effect, on a small quantity
Fire retardant just can effectively improve the anti-flammability of PLA.
(2)-C (=O)-O and-CH are contained in the high molecular weight flame retardant main chain of the key containing P-N2CH2CH2- soft segment is waited, be
A kind of high T with certain crystallinitygFire retardant, the crystallinity of PLA can be effectively improved as a kind of nucleator.
(3) high molecular weight flame retardant of the key containing P-N has high molecular weight, therefore is difficult to migrate from material, reduces small point
Harm and the reduction of flame retarding efficiency that son amount fire retardant migration is caused to environment；Added it is also possible to reduce fire retardant to material
Expect the infringement of mechanical property.
(4) high molecular weight flame retardant and its flame-retardant polylactic acid material of the key containing P-N are free of halogen, and toxicity is low, no unwanted combustion
Product is produced.
Brief description of the drawings
The infrared spectrum of the high molecular weight flame retardant of the key containing P-N in Fig. 1 present invention.
The high molecular weight flame retardant of the key containing P-N in Fig. 2 present invention1HNMR schemes.
Embodiment
The following examples can make those skilled in the art that the present invention is more fully understood.
(1), the high molecular weight flame retardant preparation method of the key containing P-N of the invention is as follows：
Embodiment 1:1.60g 1,3- propane diols double (PABA esters) and 1.01g triethylamines are dissolved in 25mL through dry
In the chloroform of drying prescription processing；The chloroformic solution of 1,3- propane diols double (PABA esters) and triethylamine is moved into reactor
In, lead to nitrogen protection, lead to condensed water, stirring is heated to reflux temperature.Weigh 1.05g dichloro-phenyl phosphates and be dissolved in 5mL drying chlorine
It is imitative, dichloro-phenyl phosphate chloroformic solution is added dropwise dropwise into reactor, reaction 8h is kept after completion of dropping at a reflux temperature；Instead
After should terminating, rotary evaporation removes chloroform, and residue is dissolved in dimethyl sulfoxide, is filtered to remove triethylamine hydrochloride, in the bar of stirring
Filtrate is poured under part white precipitate is separated out in a large amount of ethanol, filtered, washed with ethanol three times, be dried to obtain the high score of the key containing P-N
Sub- fire retardant.Its infrared spectrum and1HNMR figures are shown in Fig. 1 and Fig. 2 respectively.
FTIR (KBr tablettings, cm-1):3140 (- NH-), 1715 (C=O), 1605,1511,1494 (phenyl ring double bond), 1205
(P=O), 1098 (P-O-Ph), 1020 (P-N)；
1H NMR (500MHz, d-DMSO):δ:6.5-7.8 (phenyl ring, 13H), 4.5 (- C (O)-O-CH2-C,4H),2.1(C-
CH2-C,2H),Mn=5555, Mw=7054.
(2), the high molecular weight flame retardant flame-retardant polylactic acid material of the key containing P-N of the invention, by mass percentage for (85~
97)：PLA is mixed and extruded with the high molecular weight flame retardant of the key containing P-N and obtained by the ratio of (3~15).In order to more fully understand
And implementation, describe the high molecular weight flame retardant flame-proof polylactic acid of the key containing P-N of the present invention in detail with reference to comparative example and embodiment
The preparation process of material.
Comparative example：40g PLA pellets are weighed, are 175 DEG C of an area, 176 DEG C of 2nd area, 177 DEG C of 3rd area, four in extrusion temperature
Under conditions of 177 DEG C of area, conical double screw extruder is added, pure PLA particle is made in extruded, cooling, granulation.By GB/
T2406-1993 standard test methods are determined, and its limited oxygen index is that the crystallinity in 20%, cooling procedure is 0%.
Embodiment 2：38.8g PLA pellets are weighed, the high molecular weight flame retardant of 1.2g keys containing P-N is one in extrusion temperature
Under conditions of 175 DEG C of area, 176 DEG C of 2nd area, 177 DEG C of 3rd area, 177 DEG C of 4th area, conical double screw extruder is added, it is extruded, cold
But the high molecular weight flame retardant flame-retardant polylactic acid material of the key containing P-N is made.Determined by GB/T2406-1993 standard test methods, its
Limited oxygen index is 31.5%, and the crystallinity in cooling procedure is 46.0%.
Embodiment 3：38g PLA pellets are weighed, the high molecular weight flame retardant of 2g keys containing P-N is an area 175 in extrusion temperature
DEG C, 176 DEG C of 2nd area, 177 DEG C of 3rd area, under conditions of 177 DEG C of 4th area, add conical double screw extruder, extruded, cooling is made
The high molecular weight flame retardant flame-retardant polylactic acid material of the key containing P-N.Determined by GB/T2406-1993 standard test methods, its limit oxygen
Index is 33.0%, and the crystallinity in cooling procedure is 42.6%.
Embodiment 4：36g PLA pellets are weighed, the high molecular weight flame retardant of 4g keys containing P-N is an area 175 in extrusion temperature
DEG C, 176 DEG C of 2nd area, 177 DEG C of 3rd area, under conditions of 177 DEG C of 4th area, add conical double screw extruder, extruded, cooling is made
The high molecular weight flame retardant flame-retardant polylactic acid material of the key containing P-N.Determined by GB/T2406-1993 standard test methods, its limit oxygen
Index is 32.5%, and the crystallinity in cooling procedure is 37.4%.
Embodiment 5：34g PLA pellets are weighed, the high molecular weight flame retardant of 6g keys containing P-N is an area 175 in extrusion temperature
DEG C, 176 DEG C of 2nd area, 177 DEG C of 3rd area, under conditions of 177 DEG C of 4th area, add conical double screw extruder, extruded, cooling is made
The high molecular weight flame retardant flame-retardant polylactic acid material of the key containing P-N.Determined by GB/T2406-1993 standard test methods, its limit oxygen
Index is 29.0%, and the crystallinity in cooling procedure is 36.8%.
Claims (7)
1. the high molecular weight flame retardant of a kind of key containing P-N, it is characterised in that the fire retardant has following structure：
Wherein n=10-100.
2. the preparation method of the high molecular weight flame retardant of the key as claimed in claim 1 containing P-N, it is characterised in that including following step
Suddenly：
(1) 1,3-PD double (PABA esters) being dissolved in solvent and triethylamine mixing, lead to nitrogen protection, plus
Heat is added dropwise after dichloro-phenyl phosphate solution, completion of dropping dropwise to reflux temperature, and reaction is kept at a reflux temperature；
(2) after reaction terminates, solvent is evaporated off in vacuum distillation, and residue is dissolved in dimethyl sulfoxide, is filtered to remove triethylamine hydrochloride, filter
Liquid pours into and white precipitate is separated out in a large amount of precipitating reagents, filtering, is cleaned with ethanol repeatedly, is dried to obtain the macromolecule resistance of the key containing P-N
Fire agent.
3. the preparation method of the high molecular weight flame retardant of the key as claimed in claim 2 containing P-N, it is characterised in that in step (1),
The mol ratio of dichloro-phenyl phosphate and triethylamine is 1:2,1,3-PD double (PABA ester) and dichloro-phenyl phosphates
Mol ratio be 1:1.
4. the preparation method of the high molecular weight flame retardant of the key as claimed in claim 2 containing P-N, it is characterised in that in step (1),
Dichloro-phenyl phosphate completion of dropping in 20-30min；Reflux time is 6-12h.
5. the preparation method of the high molecular weight flame retardant of the key as claimed in claim 2 containing P-N, it is characterised in that in step (1),
Solvent uses chloroform or tetrahydrofuran.
6. the preparation method of the high molecular weight flame retardant of the key as claimed in claim 2 containing P-N, it is characterised in that in step (2),
Precipitating reagent is any one in water, ethanol and methanol.
7. application of the high molecular weight flame retardant of the key as claimed in claim 1 containing P-N in PLA, it is characterised in that described
Application be to mix PLA and high molecular weight flame retardant, the area's temperature of Bing mono- is 175 ± 1 DEG C, and 2nd area are 176 ± 1 DEG C, 3rd area
For 177 ± 1 DEG C, 4th area are that under conditions of 177 ± 1 DEG C, flame-retardant polylactic acid material is obtained through conical double screw extruder extrusion, its
In, the mass ratio of PLA and high molecular weight flame retardant is (85~97)：(3~15).
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| CN201510364975.7A CN104927061B (en) | 2015-06-26 | 2015-06-26 | A kind of high molecular weight flame retardant of the keys of N containing P, preparation and its application in PLA |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801625A (en) * | 1987-08-27 | 1989-01-31 | Akzo America Inc. | Bicyclic phosphate ether, ester, and carbonate intumescent flame retardant compositions |
| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN104592297A (en) * | 2015-01-28 | 2015-05-06 | 中国科学技术大学 | Flame-retardant glycol containing phenyl phosphate-based symmetrical structure and preparation method thereof |
-
2015
- 2015-06-26 CN CN201510364975.7A patent/CN104927061B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801625A (en) * | 1987-08-27 | 1989-01-31 | Akzo America Inc. | Bicyclic phosphate ether, ester, and carbonate intumescent flame retardant compositions |
| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN104592297A (en) * | 2015-01-28 | 2015-05-06 | 中国科学技术大学 | Flame-retardant glycol containing phenyl phosphate-based symmetrical structure and preparation method thereof |
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