CN106700084B - Bis-phenol acidic group fire retardant of polyphosphate of the structure containing DOPO and preparation method thereof - Google Patents
Bis-phenol acidic group fire retardant of polyphosphate of the structure containing DOPO and preparation method thereof Download PDFInfo
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- CN106700084B CN106700084B CN201611232869.4A CN201611232869A CN106700084B CN 106700084 B CN106700084 B CN 106700084B CN 201611232869 A CN201611232869 A CN 201611232869A CN 106700084 B CN106700084 B CN 106700084B
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- 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
- C08G79/00—Macromolecular 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
- C08G79/02—Macromolecular 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
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A kind of bis-phenol acidic group fire retardant of polyphosphate of the structure containing DOPO and preparation method thereof, the polyphosphate phosphorus content of preparation is high, its additive amount, which is less than 12wt%, can reach preferable flame retardant effect, be a kind of efficient environment-friendly flame retardant agent far below the dosage of traditional phosphorus flame retardant；And fire retardant of the invention is compared to condensed phase fire-retardant group, and its heat resistance of DOPO of the invention is more excellent, usually in gas phase can play fire retardation, also has preferable flame retardant effect to epoxy；The present invention causes PLA to degrade in process in view of the phosphate group of end, therefore phosphate group is within the encirclement of two phenyl ring by the present invention, and the mechanical property extent of the destruction of such final material will substantially reduce；Shown in the general structure of the fire retardant such as following formula (I), it is phenyl either phenoxy group that wherein n, which is 3~20, R base:
Description
Technical field
The present invention relates to a kind of polyphosphate and preparation method thereof, this kind of polyphosphate can be used as efficient fire retardant and answer
For flame retardant area, it is specifically related to a kind of bis-phenol acidic group fire retardant of polyphosphate and preparation method thereof of structure containing DOPO.
Background technique
Currently, very active to the basic research of fire proofing and application and development both at home and abroad.With gas phase it is fire-retardant based on halogen
Be flame-retardant system, although having preferable flame retardant effect, release toxic, corrosive gas in burning, to the mankind and
There is great hidden danger for environment, are gradually limited or are forbidden to use.Compared with halogenated flame retardant, with absorb heat it is fire-retardant based on
Inorganic based flame retardant and condensed phase it is fire-retardant based on expansion type flame retardant be that current scientific circles and industry generally acknowledge that environmental protection is " green
Color " fire retardant, but the based flame retardant generally requires higher additive amount (inorganic usually no less than 40wt%, containing Phosphorus many
In 30wt%) just material can be made to reach expected flame retardant effect, flame retarding efficiency is lower, also results in the mechanical property of material and adds
Work performance is by biggish destruction；Meanwhile thermal stability is poor, decomposition temperature is low, causes fire-retardant high polymer processing and recycling aspect
Difficulty.Therefore, low content, processing stability height, more efficient environmental protection fire retarding agent are researched and developed, flame retardant area in recent years is become
One of primary study target.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of the prior art, provides the mechanical property that a kind of additive amount is low, will not influence material
And processing performance, and thermal stability is good, the bis-phenol acidic group fire retardant of polyphosphate of the high structure containing DOPO of decomposition temperature.
In order to solve the above-mentioned technical problem, a kind of the technical solution adopted by the present invention are as follows: bis-phenol acidic group of the structure containing DOPO
Fire retardant of polyphosphate, shown in the general structure of the fire retardant such as following formula (I):
It is phenyl either phenoxy group that wherein n, which is 3~20, R base,.
The present invention also provides a kind of preparation methods of the bis-phenol acidic group fire retardant of polyphosphate of structure containing DOPO, specific to walk
It suddenly include: the double of (1) preparation miscellaneous -10- phospho hetero phenanthrene -10- methylol -10- oxide (ODOPM) structure of dihydro-9-oxy containing 9,10-
Phenol acid-based monomers (II)；(2) polyphosphate (I) is prepared by polymerization reaction；Specific synthetic route is shown below:
The preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the above-mentioned structure containing DOPO of the present invention, in synthetic route (1)
Monomer (II) preparation method, specific steps include:
(1.1) by diphenolic acid and the miscellaneous -10- phospho hetero phenanthrene -10- methylol -10- oxide (ODOPM) of 9,10- dihydro-9-oxy
It is dissolved in N,N-dimethylformamide (DMF)；Then catalyst being added, under nitrogen protection heating reflux reaction, reaction terminates,
Except solvent obtains solid crude product；
(1.2) the impurity removal in solid crude product is obtained into structural formula intermediate product as shown in formula (II).
The diphenolic acid of step (1.1) of the present invention and the molar ratio of ODOPM are 1:0.7~1.0, and diphenolic acid is dense in DMF
Degree is 0.1~0.3g/mL；Catalyst is the concentrated sulfuric acid (98.3wt%), the additional amount of catalyst be diphenolic acid quality 10~
20%；Back flow reaction 20~40 hours.
The method of a large amount of boiling water boilings of solid crude product in step (1.2) of the present invention removes impurity diphenolic acid and ODOPM
(because DPA and ODOPM is soluble in boiling water, and product is insoluble), and using thin-layered chromatography tracking until not having in water
Until reactant.
The preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the above-mentioned structure containing DOPO of the present invention, in synthetic route (2)
Polyphosphate (I) preparation method, specifically includes the following steps:
(2.1) structural formula intermediate product as shown in formula (II) is dissolved in ethyl acetate and obtains solution；
(2.2) solution of step (2.1) is heated under nitrogen protection, phenyl phosphonyl chloride (diphenylphosphoryl is then added
Dichloro) or phenyl phosphate ester or phenyl phosphonyl chloride and phenyl phosphate ester blend, react be added after a period of time it is dry
Triethylamine, then heating reflux reaction obtains crude product；
(2.3) by gained filtration of crude product, the solid product polyphosphate for removing impurity, being dried to obtain structural formula (I).
According to the difference of reactant in step (2.2), the polyphosphate of structural formula (I), specific is respectively containing following
The mixture structure of formula III or formula IV or formula III and formula IV:
Step (2.1) the structural formula of the present invention concentration of intermediate product in ethyl acetate as shown in formula (II) be 0.1~
0.3g/mL。
Step (2.2) solution of the present invention is heated to 20~50 DEG C, structural formula intermediate product and phenyl as shown in formula (II)
Phosphonyl dichloride with phenyl phosphate ester or the molar ratio of blend constituted with both phenyl phosphonyl chloride and phenyl phosphate ester is
1.3~1:1.
Step (2.2) reaction a period of time of the present invention is 10-40 minutes, and the molar ratio of triethylamine and diphenolic acid is 2:1, is added
Hot back flow reaction 3~5 hours.
The advantages of the present invention:
1. the present invention is by Molecular Design, the polyphosphate phosphorus content of preparation is high, and additive amount is less than 12wt%
It can reach preferable flame retardant effect, be a kind of efficient environment-friendly flame retardant agent far below the dosage of traditional phosphorus flame retardant；And
And fire retardant of the invention, compared to condensed phase fire-retardant group (such as PEPA), its heat resistance of DOPO of the invention is more excellent
It is different, usually in gas phase can play fire retardation, also there is preferable flame retardant effect to epoxy；The present invention is in view of end
Phosphate group causes PLA to degrade in process, therefore phosphate group is within the encirclement of two phenyl ring by the present invention, this
The mechanical property extent of the destruction of sample final material will substantially reduce.
2. using the platform compound diphenolic acid (DPA) from biomass resource in the structure synthesis of fire retardant of the invention
As reaction raw materials, therefore there is certain advantage in terms of the sustainable development of flame retardant area, and traditional polyphosphate resistance
The typically no this point advantage of agent is fired, is mostly the petroleum chemicals from non-renewable resources used.
3. the preparation method of fire retardant of the present invention is simple, monomer (II) is prepared first with ODOPM and diphenolic acid reaction；
Efficient polyphosphate (I) can be obtained by polymerization reaction with phenyl phosphonyl chloride or phenyl phosphate ester or both blend again,
It is a kind of polymer, is different from small molecule, flame retardant property is more beneficial, fire retardant structure design is increasingly complex；Wherein it polymerize
The molar ratio of monomer (II) and phosphoryl chloride phosphorus oxychloride is greater than 1 in reaction, it is meant that has a large amount of phenolic hydroxyl group to block in final product, in this way
Just will be greatly reduced fire retardant causes mechanical performance to be destroyed the degradation of polylactic acid matrix.
4. the molecular weight of its synthesis of efficient fire retardant of polyphosphate according to the present invention is big, molecule medial end portions OH group
It is more, hydrogen bond action can be formed with polylactic acid molecule, binding force is larger, so should not migrate；One section is put in hot water or water
Time still has strong water resistance, overcomes the deficiencies of conventional flame retardant easily deliquesces, is easy to migrate, have Halogen, water resistance it is strong,
The advantages that not easy to migrate, good with matrix compatibility.
Detailed description of the invention
Fig. 1 is structural formula according to the present invention intermediate product as shown in formula (II)1H NMR and FTIR spectrogram.
Fig. 2 is polyphosphate according to the present invention (III)1H NMR spectra.
Fig. 3 is the infrared spectrum of polyphosphate according to the present invention (III).
Specific embodiment:
Example is given below, and invention is further explained, but the embodiment invented is without being limited thereto.It is used
Experimental raw unless otherwise instructed, can be obtained easily in commercial company.
Embodiment 1:
Diphenolic acid (DPA is added in 250mL there-necked flask；4,4- bis- (4- hydroxy phenyl) valeric acids, CAS 126-00-1)
Miscellaneous -10- phospho hetero phenanthrene -10- methylol -10- oxide (ODOPM) 24.6g of 28.6g, 9,10- dihydro-9-oxy, concentrated sulfuric acid 5g,
DMF100mL.Logical nitrogen protection, back flow reaction 40 hours under mechanical stirring.Period divides 5 azeotropic for steaming part DMF and water
Then object adds the DMF of respective volume, finally obtain the clear solution of yellow.Revolving removes solvent, obtains crude product.
Crude product is added in 100 DEG C of deionized water and removes impurity.It is tracked using thin-layer chromatography until not having in upper water
Until having diphenolic acid, then product is filtered, is dried in vacuo 10 hours in 80 DEG C of degree.Obtain monomer (II).(its1H NMR and
FTIR spectrogram is shown in attached drawing 1)
The synthesis of polyphosphate (III): being added monomer (II) 25.7g, ethyl acetate 120mL in the there-necked flask of 250mL,
Logical nitrogen rushes 10 minutes.Slowly it is warming up to 40 DEG C.It is disposably slowly added to diphenylphosphoryl dichloro 8.77g, reacts 20 minutes, then
Triethylamine 10g is added.It is heated slowly to flow back in 30 minutes.Reaction 4 hours.Yellow solid is obtained, the solid being obtained by filtration
Crude product washs 2 × 100mL with ethyl acetate, washes 2 × 100mL.Gained is deposited in 80 DEG C and is dried in vacuo 10 hours.Obtain tangerine
The polyphosphate (III) of yellow solid.(1H NMR is shown in that attached drawing 2, FTIR curve are shown in attached drawing 3)
It is added in polylactic acid with the polyphosphate (III) by the additive amount of mass fraction 3%, 6%, 9%, test result is such as
Shown in the following table 1:
Content and flame retardant property of the polyphosphate of 1 the present embodiment of table in polylactic acid
Note: fire retardant adds the anti-dissolved drip of people, and significantly (after lighting batten, the speed that molten drop does not generate or molten drop falls is very slow
Slowly, illustrate of the invention)
Embodiment 2:
Miscellaneous -10- phospho hetero phenanthrene -10- the methylol-of diphenolic acid 28.6g, 9,10- dihydro-9-oxy is added in 250mL there-necked flask
10- oxide (ODOPM) 22g, the concentrated sulfuric acid 5.5g, DMF100mL lead to nitrogen protection, back flow reaction 35 hours under mechanical stirring.
Period divides 7 azeotropic mixtures for steaming part DMF and water, then adds the DMF of respective volume, finally obtains the transparent molten of yellow
Liquid.Revolving removes solvent, obtains crude product.
Crude product is added in 100 DEG C of deionized water and is refined.It is tracked using thin-layer chromatography until not having in upper water
Until having diphenolic acid, then product is filtered, is dried in vacuo 10 hours in 80 DEG C of degree.Obtain monomer (II).
The synthesis of polyphosphate (IV): being added monomer (II) 25.7g, ethyl acetate 110mL in the there-necked flask of 250mL,
Logical nitrogen rushes 10 minutes.Slowly it is warming up to 40 DEG C.It is disposably slowly added to PhosphorodichloridicAcid Acid Phenyl Ester 9g, reacts 10 minutes, then
Triethylamine 10g is added.It is heated slowly to flow back in 30 minutes, react 4 hours.Light yellow solid is obtained, the solid that will be obtained
Filtration of crude product washs 2 × 100mL with ethyl acetate, washes 2 × 100mL.It is dried in vacuo 10 hours at 80 DEG C.It obtains pale yellow
The polyphosphate (IV) of color solid.
It is added in polylactic acid with the polyphosphate (IV) by the additive amount of mass fraction 4wt%, 8wt%, 12wt%, test
As a result as shown in table 2 below:
Content and flame retardant property of the polyphosphate of 2 the present embodiment of table in polylactic acid
From Fig. 1 structural formula according to the present invention intermediate product as shown in formula (II)1H NMR and FTIR spectrogram can
Know, the structural formula that the embodiment of the present invention obtains really intermediate product as shown in formula (II).
From Fig. 2 polyphosphate (III)1The infrared spectrum of H NMR spectra and Fig. 3 polyphosphate (III) is it is found that of the invention
Target product is really synthesized.
In addition, additive amount is less than through the foregoing embodiment it is found that polyphosphate phosphorus content prepared by the present invention is high
12wt% can reach preferable flame retardant effect, be a kind of efficient environmentally protective far below the dosage of traditional phosphorus flame retardant
Fire retardant；The deficiencies of easily deliquescing present invention overcomes conventional flame retardant, is easy to migrate, with Halogen, water resistance is strong, is not easy to move
The advantages that moving, be good with matrix compatibility.
Claims (9)
1. a kind of bis-phenol acidic group fire retardant of polyphosphate of structure containing DOPO, it is characterised in that: the general structure of the fire retardant is such as
Shown in lower formula (I):
It is phenyl either phenoxy group that wherein n, which is 3~20, R base,；
The specific preparation step of the fire retardant includes: (1) preparation miscellaneous -10- phospho hetero phenanthrene -10- methylol-of dihydro-9-oxy containing 9,10-
The bis-phenol acid-based monomers (II) of 10- oxide structure；(2) polyphosphate (I) is prepared by polymerization reaction；
Specific synthetic route is shown below:
(1)
(2)。
2. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 1 containing DOPO, feature
It is,
The specific preparation step of the fire retardant includes: (1) preparation miscellaneous -10- phospho hetero phenanthrene -10- methylol-of dihydro-9-oxy containing 9,10-
The bis-phenol acid-based monomers (II) of 10- oxide structure；(2) polyphosphate (I) is prepared by polymerization reaction；
Specific synthetic route is shown below:
(1)
(2)；
Wherein, the specific preparation step of the monomer (II) in step (1) includes:
(1.1) diphenolic acid and the miscellaneous -10- phospho hetero phenanthrene -10- methylol -10- oxide of 9,10- dihydro-9-oxy are dissolved in N, N- diformazan
In base formamide；Then catalyst is added, under nitrogen protection heating reflux reaction, reaction terminates, and produces except solvent obtains solids crude
Object；
(1.2) the impurity removal in solid crude product is obtained into structural formula intermediate product as shown in formula (II).
3. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 2 containing DOPO, feature
It is, the diphenolic acid and 9 of step (1.1), mole of the miscellaneous -10- phospho hetero phenanthrene -10- methylol -10- oxide of 10- dihydro-9-oxy
Than for 1:0.7~1.0, concentration of the diphenolic acid in n,N-Dimethylformamide is 0.1~0.3g/mL；Catalyst is
The concentrated sulfuric acid of 98.3wt%, the additional amount of catalyst are the 10~20% of diphenolic acid quality；Back flow reaction 20~40 hours.
4. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 3 containing DOPO, feature
It is, the method for a large amount of boiling water boilings of the solid crude product in step (1.2) removes impurity diphenolic acid and 9,10- dihydro-9-oxy
Miscellaneous -10- phospho hetero phenanthrene -10- methylol -10- oxide, and using thin-layered chromatography tracking until there is no reactant in water.
5. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 1 containing DOPO, feature
It is, the preparation method of the polyphosphate (I) in synthetic route (2), comprising the following steps:
(2.1) structural formula intermediate product as shown in formula (II) is dissolved in ethyl acetate and obtains solution；
(2.2) solution of step (2.1) is heated under nitrogen protection, be then added phenyl phosphonyl chloride or phenyl phosphate ester or
The blend of phenyl phosphonyl chloride and phenyl phosphate ester is added dry triethylamine after reacting a period of time, is then heated to reflux
Reaction obtains crude product；
(2.3) by gained filtration of crude product, the solid product polyphosphate for removing impurity, being dried to obtain structural formula (I).
6. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 5 containing DOPO, feature
It is, the polyphosphate in step (2.2), specific structure is respectively to contain following formula (III) or formula (IV) or formula (III) and formula
(IV) mixture structure:
7. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 5 containing DOPO, feature
It is, the structural formula concentration of intermediate product in ethyl acetate as shown in formula (II) is 0.1~0.3g/mL in step (2.1).
8. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 5 containing DOPO, feature
Be, step (2.2) solution is heated to 20~50 DEG C, structural formula intermediate product as shown in formula (II) and phenyl phosphonyl chloride or
It is 1.3~1:1 with phenyl phosphate ester or the molar ratio of the blend constituted with both phenyl phosphonyl chloride and phenyl phosphate ester.
9. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate of the structure according to claim 5 containing DOPO, feature
It is, step (2.2) reaction a period of time is 10-40 minutes, and the molar ratio of triethylamine and diphenolic acid is 2:1, is heated to reflux anti-
It answers 3~5 hours.
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| CN110423443B (en) * | 2019-08-20 | 2021-06-29 | 湖南工业大学 | Biomass-based high-toughness flame-retardant plate |
| CN110922636B (en) * | 2019-11-01 | 2021-06-25 | 浙江大学宁波理工学院 | Bisphenol acid-based phosphorus-nitrogen flame retardant and preparation method and application thereof |
| CN110903512B (en) * | 2019-11-21 | 2021-12-17 | 浙江大学宁波理工学院 | Efficient halogen-free phosphorus gas-phase flame retardant and high polymer material containing same |
| CN113234228B (en) * | 2021-05-31 | 2022-05-27 | 浙大宁波理工学院 | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328269A (en) * | 2008-07-20 | 2008-12-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| CN104311818A (en) * | 2014-10-28 | 2015-01-28 | 沈阳化工大学 | Novel phosphorus and nitrogen containing polymeric flame retardant and preparation method thereof |
| CN105838389A (en) * | 2016-04-13 | 2016-08-10 | 浙江大学宁波理工学院 | High-efficiency polyphosphate ester fire retardant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328269A (en) * | 2008-07-20 | 2008-12-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| CN104311818A (en) * | 2014-10-28 | 2015-01-28 | 沈阳化工大学 | Novel phosphorus and nitrogen containing polymeric flame retardant and preparation method thereof |
| CN105838389A (en) * | 2016-04-13 | 2016-08-10 | 浙江大学宁波理工学院 | High-efficiency polyphosphate ester fire retardant and preparation method thereof |
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