CN106700084A - Diphenolic acid-based polyphosphate ester flame retardant containing DOPO structure and preparation method of flame retardant - Google Patents
Diphenolic acid-based polyphosphate ester flame retardant containing DOPO structure and preparation method of flame retardant Download PDFInfo
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- CN106700084A CN106700084A CN201611232869.4A CN201611232869A CN106700084A CN 106700084 A CN106700084 A CN 106700084A CN 201611232869 A CN201611232869 A CN 201611232869A CN 106700084 A CN106700084 A CN 106700084A
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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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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention provides a diphenolic acid-based polyphosphate ester flame retardant containing a DOPO structure and a preparation method of the flame retardant. The prepared polyphosphate ester is high in phosphorus content, a good flame retarding effect can be achieved when the adding amount of the flame retardant is lower than 12 wt%, the using amount is far less than that of a traditional phosphorous flame retardant, and the efficient, green and environment-friendly flame retardant is obtained. The flame retardant has the advantages that compared with a condensed phase flame retardant group, the DOPO structure is more excellent in heat resistance, can play a flame retarding role in a gas phase and has a good flame retarding effect on epoxy; by considering that PLA is degraded in the processing process due to the end phosphate ester group, the phosphate ester group is enclosed by two benzene ring, and therefore the final mechanical property destruction degree of the material is greatly decreased; the structural general formula of the flame retardant is shown as the formula (I) in the description, wherein n is 3-20, and the R group is a phenyl group or phenoxy group.
Description
Technical field
The present invention relates to a kind of polyphosphate and preparation method thereof, this kind of polyphosphate can be answered as efficient fire retardant
For flame retardant area, a kind of bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures and preparation method thereof is specifically related to.
Background technology
At present, the basic research and application and development both at home and abroad to fire proofing are very active.With gas phase it is fire-retardant based on halogen
Be flame-retardant system, although with preferable flame retardant effect, but poisonous, corrosive gas discharged in burning, to the mankind and
Environment has great hidden danger, is progressively limited or prohibitted the use of.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 industrial quarters generally acknowledge that environmental protection is " green
Color " fire retardant, but the based flame retardant generally requires addition higher (inorganic generally no less than 40wt%, containing Phosphorus many
In 30wt%) material is reached expected flame retardant effect, flame retarding efficiency is relatively low, also results in the mechanical property of material and adds
Work performance is subject to larger destruction；Meanwhile, heat endurance is poor, decomposition temperature is low, causes fire-retardant high polymer processing and recovery aspect
Difficulty.Therefore, research and development low content, processing stability environmental protection fire retarding agent high, more efficient, as flame retardant area in recent years
One of primary study target.
The content of the invention
Above-mentioned deficiency of the present invention for prior art, there is provided a kind of addition is low, do not interfere with the mechanical property of material
And processing characteristics, and the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures that heat endurance is good, decomposition temperature is high.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of bis-phenol acidic group containing DOPO structures
Fire retardant of polyphosphate, shown in the general structure such as following formula (I) of the fire retardant：
Wherein n is that 3~20, R bases are phenyl or phenoxy group.
The present invention also provides a kind of preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures, specific step
Suddenly include：(1) the double of miscellaneous -10- phospho hetero phenanthrenes -10- methylols -10- oxides (ODOPM) structure of dihydro-9-oxy containing 9,10- are prepared
Phenol acid-based monomers (II)；(2) polyphosphate (I) is prepared by polymerisation；Specific synthetic route is shown below：
The preparation method of the above-mentioned bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures 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 phenanthrenes -10- methylols -10- oxides (ODOPM) of 9,10- dihydro-9-oxies
It is dissolved in N,N-dimethylformamide (DMF)；Catalyst is subsequently adding, under nitrogen protection heating reflux reaction, reaction terminates,
Except solvent obtains solid crude product；
(1.2) Impurity removal in solid crude product is obtained into intermediate product of the structural formula as shown in formula (II).
The diphenolic acid of step (1.1) of the present invention and the mol ratio of ODOPM are 1：0.7~1.0, diphenolic acid is dense in DMF
It is 0.1~0.3g/mL to spend；Catalyst is the concentrated sulfuric acid (98.3wt%), the addition of catalyst for diphenolic acid quality 10~
20%；Back flow reaction 20~40 hours.
Solid crude product in step (1.2) of the present invention removes impurity diphenolic acid and ODOPM with the method for a large amount of boiling water boilings
(because DPA and ODOPM is soluble in boiling water, and product is insoluble), and using thin-layered chromatography tracking until not having in water
Untill reactant.
The preparation method of the above-mentioned bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures of the present invention, in synthetic route (2)
Polyphosphate (I) preparation method, specifically include following steps：
(2.1) intermediate product by structural formula 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, is subsequently adding phenyl phosphonyl chloride (diphenylphosphoryl
Dichloro) or phenyl phosphate ester or phenyl phosphonyl chloride and the blend of phenyl phosphate ester, added after reaction for a period of time dry
Triethylamine, then heating reflux reaction obtain 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) is specific to be respectively containing following
The mixture structure of formula III or formula IV or formula III and formula IV：
Concentration of intermediate product of step (2.1) structural formula of the present invention as shown in formula (II) in ethyl acetate be 0.1~
0.3g/mL。
Step (2.2) solution of the present invention is heated to 20~50 DEG C, intermediate product and phenyl of the structural formula as shown in formula (II)
Phosphonyl dichloride or the mol ratio of blend constituted with phenyl phosphate ester or with both phenyl phosphonyl chloride and phenyl phosphate ester are
1.3~1:1.
Step (2.2) reaction a period of time of the present invention is 10-40 minutes, and the mol ratio of triethylamine and diphenolic acid is 2:1, plus
Hot back flow reaction 3~5 hours.
The advantages of the present invention：
1., by Molecular Design, the polyphosphate phosphorus content of preparation is high, and its addition is less than 12wt% for the present invention
Preferable flame retardant effect is can reach, is a kind of efficient environment-friendly flame retardant agent far below the consumption 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, generally can just play fire retardation in gas phase, to epoxy also have preferable flame retardant effect；The present invention is in view of end
Phosphate group causes PLA to degrade in process, therefore be in phosphate group within two encirclements of phenyl ring by the present invention, this
The mechanical property destructiveness of sample final material will be substantially reduced.
2. platform compound diphenolic acid (DPA) from biomass resource is employed 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 combustion typically no this point advantage of agent, is the petroleum chemicals from non-renewable resources for using mostly.
3. the preparation method of fire retardant of the present invention is simple, and monomer (II) is prepared first with ODOPM and bis-phenol acid reaction；
Efficient polyphosphate (I) can be obtained by polymerisation with phenyl phosphonyl chloride or phenyl phosphate ester or the two blend again,
It is a kind of polymer, is different from small molecule, fire resistance is more beneficial, fire retardant structure design is increasingly complex；Wherein it is polymerized
Monomer (II) is more than 1 with the mol ratio of phosphoryl chloride phosphorus oxychloride in reaction, it is meant that have substantial amounts of phenolic hydroxyl group to block in final product, so
Degraded of the fire retardant to PLA matrix will be substantially reduced causes mechanical performance to be destroyed.
4. the molecular weight of its synthesis of efficient fire retardant of polyphosphate involved in the present invention is big, molecule medial end portions OH groups
It is many, hydrogen bond action can be formed with polylactic acid molecule, adhesion is larger, so should not migrate；One section is put in hot water or water
Time still has strong water resistance, overcomes the easy deliquescence of conventional flame retardant, the easily deficiency such as migration, with Halogen, water resistance it is strong,
The advantages of being difficult migration and good matrix compatibility.
Brief description of the drawings
Fig. 1 is the intermediate product of structural formula involved in the present invention as shown in formula (II)1H NMR and FTIR spectrograms.
Fig. 2 is polyphosphate (III) involved in the present invention1H NMR spectras.
Fig. 3 is the infrared spectrum of polyphosphate (III) involved in the present invention.
Specific embodiment：
Example is given below to be further described the present invention, but the implementation method not limited to this invented.Used
Experimental raw unless otherwise instructed, can be obtained easily in commercial company.
Embodiment 1：
Diphenolic acid (DPA is added in 250mL there-necked flasks；4,4- bis- (4- hydroxy phenyls) valeric acids, CAS 126-00-1)
Miscellaneous -10- phospho hetero phenanthrenes -10- methylols -10- oxides (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 agitation.Period, the azeotropic for points for 5 times steaming part DMF and water
Thing, then adds the DMF of respective volume, finally gives the clear solution of yellow.Revolving removes solvent, obtains crude product.
Impurity is removed in the deionized water that crude product is added 100 DEG C.Using thin-layer chromatography tracking until not having in upper water
Untill having diphenolic acid, then product is filtered, be vacuum dried 10 hours in 80 DEG C of degree.Obtain monomer (II).(its1H NMR and
FTIR spectrograms are shown in accompanying drawing 1)
The synthesis of polyphosphate (III)：Monomer (II) 25.7g, ethyl acetate 120mL are added in the there-necked flask of 250mL,
Logical nitrogen is rushed 10 minutes.Slowly it is warmed up to 40 DEG C.It is disposable to be slowly added to diphenylphosphoryl dichloro 8.77g, react 20 minutes, then
Add triethylamine 10g.Backflow was heated slowly in 30 minutes.Reaction 4 hours.Yellow solid is obtained, the solid being filtrated to get
Crude product washs 2 × 100mL with ethyl acetate, washes 2 × 100mL.Gained is deposited in 80 DEG C and is vacuum dried 10 hours.Obtain tangerine
The polyphosphate (III) of yellow solid.(1H NMR are shown in accompanying drawing 2, and FTIR curves are shown in accompanying drawing 3)
In addition addition PLA with the polyphosphate (III) by mass fraction 3%, 6%, 9%, test result is such as
Shown in table 1 below：
Content and fire resistance of the polyphosphate of the present embodiment of table 1 in PLA
Note：Fire retardant adds the anti-dissolved drip of people, and significantly (after lighting batten, the speed that molten drop is not produced or molten drop falls is delayed very much
Slowly, illustrate of the invention)
Embodiment 2：
Added in 250mL there-necked flasks diphenolic acid 28.6g, 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrenes -10- methylols -
10- oxides (ODOPM) 22g, the concentrated sulfuric acid 5.5g, DMF100mL, lead to nitrogen protection, back flow reaction 35 hours under mechanical agitation.
Period divides 7 azeotropic mixtures for steaming part DMF and water, then adds the DMF of respective volume, finally gives the transparent molten of yellow
Liquid.Revolving removes solvent, obtains crude product.
Refined in the deionized water that crude product is added 100 DEG C.Using thin-layer chromatography tracking until not having in upper water
Untill having diphenolic acid, then product is filtered, be vacuum dried 10 hours in 80 DEG C of degree.Obtain monomer (II).
The synthesis of polyphosphate (IV)：Monomer (II) 25.7g, ethyl acetate 110mL are added in the there-necked flask of 250mL,
Logical nitrogen is rushed 10 minutes.Slowly it is warmed up to 40 DEG C.It is disposable to be slowly added to PhosphorodichloridicAcid Acid Phenyl Ester 9g, react 10 minutes, then
Add triethylamine 10g.Backflow was heated slowly in 30 minutes, is reacted 4 hours.Light yellow solid is obtained, the solid that will be obtained
Filtration of crude product, 2 × 100mL is washed with ethyl acetate, washes 2 × 100mL.It is vacuum dried 10 hours at 80 DEG C.Obtain pale yellow
The polyphosphate (IV) of color solid.
In addition addition PLA with the polyphosphate (IV) by mass fraction 4wt%, 8wt%, 12wt%, test
Result is as shown in table 2 below：
Content and fire resistance of the polyphosphate of the present embodiment of table 2 in PLA
From the intermediate product of structural formula Fig. 1 involved in the present invention as shown in formula (II)1H NMR and FTIR spectrograms can
Know, intermediate product of the structural formula that embodiments of the invention are obtained really as shown in formula (II).
From Fig. 2 polyphosphates (III)1The infrared spectrum of H NMR spectras and Fig. 3 polyphosphates (III) understands, of the invention
Really target product is synthesized.
Additionally, by above-described embodiment, polyphosphate phosphorus content prepared by the present invention is high, and its addition is less than
12wt% is that can reach preferable flame retardant effect, is a kind of efficient environmental protection far below the consumption of traditional phosphorus flame retardant
Fire retardant；Present invention overcomes the easy deliquescence of conventional flame retardant, the easily deficiency such as migration, with Halogen, water resistance is strong, be difficult to move
The advantages of shifting and matrix compatibility are good.
Claims (10)
1. a kind of bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures, it is characterised in that：The general structure of the fire retardant is such as
Shown in lower formula (I)：
Wherein n is that 3~20, R bases are phenyl or phenoxy group.
2. a kind of preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures described in claim 1, its feature
It is that specific step includes：(1) miscellaneous -10- phospho hetero phenanthrenes -10- methylols -10- oxide knots of dihydro-9-oxy containing 9,10- are prepared
The bis-phenol acid-based monomers (II) of structure；(2) polyphosphate (I) is prepared by polymerisation；Specific synthetic route is shown below：
(1)
(2)
3. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 2, its feature
It is that the preparation method of the monomer (II) in synthetic route (1), specific steps include:
(1.1) diphenolic acid and the miscellaneous -10- phospho hetero phenanthrenes -10- methylols -10- oxides (ODOPM) of 9,10- dihydro-9-oxies are dissolved in
In N,N-dimethylformamide (DMF)；Catalyst is subsequently adding, under nitrogen protection heating reflux reaction, reaction terminates, except molten
Agent obtains solid crude product；
(1.2) Impurity removal in solid crude product is obtained into intermediate product of the structural formula as shown in formula (II).
4. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 3, its feature
It is that the diphenolic acid of step (1.1) and the mol ratio of ODOPM are 1：0.7~1.0, concentration of the diphenolic acid in DMF be 0.1~
0.3g/mL；Catalyst is the concentrated sulfuric acid (98.3wt%), and the addition of catalyst is the 10~20% of diphenolic acid quality；Backflow is anti-
Answer 20~40 hours.
5. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 3, its feature
It is that the solid crude product in step (1.2) removes impurity diphenolic acid and ODOPM with the method for a large amount of boiling water boilings, and using thin
Layer chromatography is tracked untill not having reactant in water.
6. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 2, its feature
It is that the preparation method of the polyphosphate (I) in synthetic route (2) is comprised the following steps：
(2.1) intermediate product by structural formula 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 subsequently adding phenyl phosphonyl chloride or phenyl phosphate ester or
Phenyl phosphonyl chloride and the blend of phenyl phosphate ester, dry triethylamine is added after reaction for 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).
7. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 6, its feature
It is, the polyphosphate in step (2.2) that specific structure is respectively and contains following formula (III) or formula (IV) or formula (III) and formula
(IV) mixture structure：
8. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 6, its feature
It is that concentration of intermediate product of the structural formula as shown in formula (II) in ethyl acetate is 0.1~0.3g/mL in step (2.1).
9. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 6, its feature
Be that step (2.2) solution is heated to 20~50 DEG C, intermediate product of the structural formula as shown in formula (II) and phenyl phosphonyl chloride or
The mol ratio of the blend constituted with phenyl phosphate ester or with both phenyl phosphonyl chloride and phenyl phosphate ester is 1.3~1:1.
10. the preparation method of the bis-phenol acidic group fire retardant of polyphosphate containing DOPO structures according to claim 6, its feature
It is that step (2.2) reaction a period of time is 10-40 minutes, the mol ratio of triethylamine and diphenolic acid is 2:1, it is heated to reflux anti-
Answer 3~5 hours.
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| CN110423443A (en) * | 2019-08-20 | 2019-11-08 | 湖南工业大学 | A kind of biomass-based tough flame-proof sheet material of height |
| CN110903512A (en) * | 2019-11-21 | 2020-03-24 | 浙江大学宁波理工学院 | Efficient halogen-free phosphorus gas-phase flame retardant and high polymer material containing same |
| CN110922636A (en) * | 2019-11-01 | 2020-03-27 | 浙江大学宁波理工学院 | Bisphenol acid-based phosphorus-nitrogen flame retardant and preparation method and application thereof |
| CN113234228A (en) * | 2021-05-31 | 2021-08-10 | 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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| 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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| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110423443A (en) * | 2019-08-20 | 2019-11-08 | 湖南工业大学 | A kind of biomass-based tough flame-proof sheet material of height |
| CN110423443B (en) * | 2019-08-20 | 2021-06-29 | 湖南工业大学 | Biomass-based high-toughness flame-retardant plate |
| CN110922636A (en) * | 2019-11-01 | 2020-03-27 | 浙江大学宁波理工学院 | Bisphenol acid-based phosphorus-nitrogen flame retardant and preparation method and application thereof |
| 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 |
| CN110903512A (en) * | 2019-11-21 | 2020-03-24 | 浙江大学宁波理工学院 | Efficient halogen-free phosphorus gas-phase flame retardant and high polymer material containing same |
| 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 |
| CN113234228A (en) * | 2021-05-31 | 2021-08-10 | 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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