CN106967002A - A kind of ternary benzoxazine intermediate, preparation method and its polymer - Google Patents
A kind of ternary benzoxazine intermediate, preparation method and its polymer Download PDFInfo
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- CN106967002A CN106967002A CN201710224441.3A CN201710224441A CN106967002A CN 106967002 A CN106967002 A CN 106967002A CN 201710224441 A CN201710224441 A CN 201710224441A CN 106967002 A CN106967002 A CN 106967002A
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- ternary
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- benzoxazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
Abstract
The present invention relates to a kind of ternary benzoxazine intermediate, preparation method and its polymer, the preparation method comprises the following steps：1) paraformaldehyde, unary primary amine and reaction dissolvent, 0~10 DEG C of stirring reaction are added into reactor；The unary primary amine is at least one of aromatic amine, fatty amine, aliphatic cyclic amine；2) compound of formula II is continuously added, 60~90 DEG C of reactions are warming up to, reaction dissolvent is removed, obtains residue；3) residue is dissolved in dissolution solvent, and be poured onto in alkali lye, separate out solid, filtered, washing obtains ternary benzoxazine intermediate.The preparation method production cost is low, and the ternary benzoxazine intermediate processability of preparation is good, solidifies obtained resin excellent combination property.
Description
Technical field
The present invention relates to high-performance thermosetting resin making technique field, and in particular in the middle of a kind of ternary benzoxazine
Body, preparation method and its polymer.
Background technology
Benzoxazine be a class by phenolic compound, aminated compounds and aldehyde compound through condensation reaction synthesize it is hexa-atomic
Heterocyclic compound, initially finds that the ring-opening polymerisation under heating or catalyst action generates nitrogenous and class in Mannich reactions
Like the network structure of phenolic resin.Benzoxazine colophony is as a kind of new phenolic resin, and it not only has traditional phenolic aldehyde tree
The hot property of fat, mechanical property, electric property, and shrinkage factor is small during curing molding, no small molecule release, water absorption rate is low, stable
Property it is good, glass transition temperature is high, in addition raw material monomer wide material sources, and MOLECULE DESIGN flexibly, thus is received significant attention.
The A of Chinese invention patent CN 104356084 are to reactant aminated compounds, formalin and single phenol or dihydric phenol
A small amount of solvent is added in class compound, block as benzoxazine intermediate is formed in cooling after temperature reaction, and claims this method
Suspending agent is replaced with a small amount of solvent, the advantage of suspension reaction method, frit reaction method and solvent reaction method is combined, be prepared by this method
Benzoxazine intermediate it is not purified i.e. directly use, impurity is inevitably contained in product, solidfied material certainly will be influenceed
Performance, especially hot property and processing characteristics, after the bisphenol A-type benzoxazine intermediate solidification according to said method prepared disclosed in it
Weightless 15% corresponding temperature is only 356 DEG C, and heat resistance is unsatisfactory.
The A of Chinese invention patent CN 101220153 are using monoamine, phosphorous dihydric phenol and formaldehyde as reaction raw materials, in benzo
Phosphorus-containing compound is introduced in oxazine intermediate, phosphor-containing flame-proof benzoxazine intermediate has been synthesized, it is cured to obtain phosphor-containing flame-proof
Property benzoxazine colophony.This method replaces traditional bis-phenol as reaction raw materials by the use of phosphorous dihydric phenol, and cost is higher；Solidify
To resin in nitrogen and air weightless 5% corresponding temperature be respectively 287 DEG C, 293 DEG C, heat resistance is not excellent,
800 DEG C of carbon yield is 47% in nitrogen, and limited oxygen index is 37.9.The plexiglasization for how improving benzoxazine colophony turns
Temperature (Tg), hot property, mechanical property and fire resistance, as this area technical problem urgently to be resolved hurrily.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of ternary benzoxazine intermediate, preparation side
Method and its polymer, the ternary benzoxazine intermediate processability are good, solidify obtained polymer excellent combination property.
The present invention solves the technical scheme that is provided of above-mentioned technical problem, a kind of ternary benzoxazine intermediate, structure
Formula is as follows：
Wherein, R1~R6It is each independently selected from hydrogen or C1~C4Alkyl；R is selected from aromatic group, aliphatic group or fat
Ring race group.
Further, the aromatic group be preferably phenyl, o-methyl-phenyl, an aminomethyl phenyl, p-methylphenyl or
Ethynyl phenyl；The aliphatic group is preferably pi-allyl；The alicyclic group is preferably cyclohexyl.
The present invention also provides a kind of preparation method of ternary benzoxazine intermediate, comprises the following steps：
1) paraformaldehyde, unary primary amine and reaction dissolvent, 0~10 DEG C of stirring reaction are added into reactor；The unitary
Primary amine is at least one of aromatic amine, fatty amine, aliphatic cyclic amine；
2) compound of formula II is continuously added, 60~90 DEG C of reactions are warming up to, reaction dissolvent is removed, obtains residue；
Wherein, R1~R6It is each independently selected from hydrogen or C1~C4Alkyl, and phenolic hydroxyl group ortho position can not be alkyl simultaneously；
3) residue is dissolved in dissolution solvent, and be poured onto in alkali lye, separate out solid, filtered, washing obtains ternary
Benzoxazine intermediate.
Involved reaction equation is as follows：
Wherein, R1~R6As described above；RNH2For unary primary amine；(CH2O)nFor paraformaldehyde.
In above-mentioned technical proposal, from ternary phenolic compound (compound of formula II) as initiation material, to end-product three
Alkyl soft segment is introduced in first benzoxazine intermediate (type I compound), while increasing benzoxazine structure in unimolecule
Quantity, so as to reduce the fusing point of intermediate and add the degree of cross linking of benzoxazine colophony, can significantly widen process window
With raising plexiglas transition temperature (Tg), hot property, mechanical property and fire resistance.
The step 1) and 2) in reaction for lucifuge reaction.Because unary primary amine is shown in that light is perishable, therefore lucifuge should be taken anti-
Should, the generation of accessory substance is reduced, while improving yield.
It is preferred that, the step 1) in the lucifuge reaction time be 10~60min.
It is preferred that, the step 2) in the lucifuge reaction time be 2~10h.The removing reaction dissolvent is using revolving.
The step 1) in paraformaldehyde and unary primary amine by the mol ratio of aldehyde radical and amino be 2:0.6~1.2 feeds intake.
The step 2) Chinese style II compound and unary primary amine by mol ratio be 1:2.5~3.3 feed intake.
The step 2) in R1~R6It is hydrogen.The compound of formula II is preferably 1,1,1- tri- (4- hydroxy phenyls) ethane
(THPE)。
The step 1) in aromatic amine be preferably：Aniline, o-toluidine, m-toluidine, open-chain crown ether, an acetylene
Base aniline；Fatty amine is preferably：Allyl amine；Aliphatic cyclic amine is preferably：Cyclohexylamine.
Further preferably, the step 1) in unary primary amine be aniline.
The step 1) in reaction dissolvent in dioxane, toluene, butanone, acetone, ethanol, methanol, ethyl acetate
At least one；The step 3) in dissolution solvent be selected from DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N- methyl pyrroles
At least one of pyrrolidone.
The step 3) in alkali lye be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and bicarbonate
One kind in potassium.
It is preferred that, the step 3) in alkali lye concentration be 0.1~1mol/L.
The present invention also provides a kind of ternary benzoxazine polymer, heated solid by above-mentioned ternary benzoxazine intermediate
Change and be made.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) ternary benzoxazine intermediate prepared by the present invention adds the quantity of benzoxazine structure in unimolecule, from
And increase curing reaction reflecting point and resin's crosslinkage, resin Tg, hot property, mechanical property, fire resistance can be significantly improved
And carbon yield.
(2) ternary benzoxazine intermediate prepared by the present invention introduces alkyl soft segment, reduces its fusing point, significantly widens
Process window, has widened the optimum range of processing, has been more beneficial for machine-shaping significantly, and curing exotherm effect occurrence scope compared with
Greatly, heat release is not concentrated, advantageously reduce the internal stress of material, improve the strength of materials.
(3) reaction condition of the present invention is gentle, and step is few, and solvent recoverable, cost is low, and accessory substance is few, and yield is reachable
87%, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the structural formula of ternary benzoxazine intermediate；
Fig. 2 is the FTIR spectrograms of ternary benzoxazine intermediate prepared by embodiment 1；
Fig. 3 is the DSC spectrograms of ternary benzoxazine intermediate prepared by embodiment 1；
Fig. 4 is the cured obtained polymer TGA spectrograms of ternary benzoxazine intermediate prepared by embodiment 1.
Embodiment
With reference to specific embodiment and accompanying drawing, the invention will be further described.
The structural formula of ternary benzoxazine intermediate is as shown in Figure 1.
Embodiment 1
18.00g (0.60mol, is calculated by formaldehyde monomers, similarly hereinafter) paraformaldehyde, 27.90g are sequentially added into reactor
30.60g (0.10mol) formula II is added after (0.30mol) aniline and 200mL butanone, 5 DEG C of lucifuge stirring reaction 30min1Compound
(R1~R6It is hydrogen, specially THPE), 75 DEG C of lucifuge reaction 6h are warming up to, reaction dissolvent butanone, plus 150mL N, N- bis- is removed
Methyl vinyl amine solvent residue hypsokinesis separates out solid down in 2000mL 0.5mol/L sodium hydroxide solutions, filters, washing,
60 DEG C of vacuum drying 8h obtain ternary benzoxazine intermediate powder-product, yield 89%.
Formula II1Compound (THPE) structural formula is as follows：
FTIR spectrum test is carried out for the ternary benzoxazine intermediate prepared by embodiment 1, as a result such as Fig. 2
It is shown, 947cm-1Locate signal Wei oxazine ring characteristic peaks；1030cm-1And 1230cm-1Locate signal Fen Bie Wei oxazine rings C-O-C it is symmetrical
With asymmetric stretching vibration peak；1500cm-1、1600cm-1Place's signal is phenyl ring skeletal vibration peak.
Ternary benzoxazine intermediate powder is placed in aluminum rectangular die, the gradient increased temperature in Muffle furnace, be segmented
Solidification obtains ternary benzoxazine polymer, and program curing is：140 DEG C/1h, 160 DEG C/1h, 180 DEG C/2h, 200 DEG C/1h, 220
DEG C/3h, 240 DEG C/2h, obtain ternary benzoxazine polymer.
Embodiment 2~14
The process of embodiment 1 is repeated, changes reaction condition, obtains result listed by table 1：
The reaction condition and yield of the embodiment 2~23 of table 1
Note：3rd is classified as THPE and RNH2Mol ratio；4th is classified as the mol ratio of aldehyde radical and amino；6th is classified as stage i
Temperature：0~10 DEG C, time：10~60min；7th is classified as phase il temperature：60~90 DEG C, time：2~10h.
The preparation-obtained ternary benzoxazine intermediate powder of embodiment 2~14 is placed in aluminum rectangular die respectively
Interior, the gradient increased temperature in Muffle furnace is stage curing to obtain ternary benzoxazine polymer, and program curing is：140 DEG C/1h, 160
DEG C/1h, 180 DEG C/2h, 200 DEG C/1h, 220 DEG C/3h, 240 DEG C/2h, obtain ternary benzoxazine polymer.
Embodiment 15
18.00g (0.60mol) paraformaldehyde, 27.90g (0.30mol) aniline and 200mL are sequentially added into reactor
34.80g (0.10mol) formula II is added after butanone, 0 DEG C of lucifuge stirring reaction 60min2Compound, is warming up to 75 DEG C of lucifuge reactions
6h, removes reaction dissolvent butanone, plus 150mL DMAs dissolve residue hypsokinesis down to 1500mL 1mol/L carbon
In acid sodium solution, solid is separated out, is filtered, washing, 60 DEG C of vacuum drying 8h obtain ternary benzoxazine intermediate powder-product, yield
88%.
Formula II2Structural formula of compound is as follows：
Benzoxazine intermediate powder is placed in aluminum rectangular die, the gradient increased temperature in Muffle furnace is stage curing
Ternary benzoxazine polymer is obtained, program curing is：140 DEG C/1h, 160 DEG C/1h, 180 DEG C/2h, 200 DEG C/1h, 220 DEG C/
3h, obtains ternary benzoxazine polymer by 240 DEG C/2h.
Embodiment 16
18.00g (0.60mol) paraformaldehyde, 27.90g (0.30mol) aniline and 250mL are sequentially added into reactor
43.20g (0.10mol) formula II is added after ethyl acetate, 0 DEG C of lucifuge stirring reaction 60min3Compound, is warming up to 80 DEG C of lucifuges
5h is reacted, reaction dissolvent ethyl acetate is removed, plus 200mL DMFs dissolve residue hypsokinesis down to 2000mL
In 0.5mol/L sodium hydroxide solutions, solid is separated out, is filtered, washing, 60 DEG C of vacuum drying 8h obtain ternary benzoxazine intermediate
Powder-product, yield 87%.
Formula II3Structural formula of compound is as follows：
Benzoxazine intermediate powder is placed in aluminum rectangular die, the gradient increased temperature in Muffle furnace is stage curing
Ternary benzoxazine polymer is obtained, program curing is：140 DEG C/1h, 160 DEG C/1h, 180 DEG C/2h, 200 DEG C/1h, 220 DEG C/
3h, obtains ternary benzoxazine polymer by 240 DEG C/2h.
Comparative example 1
18.00g (0.60mol) paraformaldehyde, 27.90g (0.30mol) aniline and 200mL are sequentially added into reactor
34.20g (0.15mol) bisphenol-A is added after butanone, 5 DEG C of lucifuge stirring reaction 30min, 75 DEG C of lucifuge reaction 6h is warming up to, removes
Reaction dissolvent butanone, plus 150mL DMAs dissolve residue hypsokinesis down to 2000mL 0.5mol/L hydroxides
In sodium solution, solid is separated out, is filtered, washing, 60 DEG C of vacuum drying 8h obtain bisphenol A-type benzoxazine intermediate powder-product, produce
Rate 86%.
Benzoxazine intermediate powder is placed in aluminum rectangular die, the gradient increased temperature in Muffle furnace is stage curing
Polymer is obtained, program curing is：140 DEG C/1h, 160 DEG C/1h, 180 DEG C/2h, 200 DEG C/1h, 220 DEG C/3h, 240 DEG C/2h,
Obtain bisphenol A-type benzoxazine polymer.
Performance test
1st, differential scanning calorimetry test is carried out for the ternary benzoxazine intermediate prepared by embodiment 1,10 and 15, its
The middle result of embodiment 1 is as shown in figure 3, specific data are as shown in table 2.
Table 2, ternary benzoxazine intermediate DSC data
Understood according to table 2, as little as 65 DEG C of the fusing point of ternary benzoxazine intermediate, ring-opening polymerisation initial temperature in embodiment 1
For 152 DEG C, process window is 87 DEG C, and the optimum range of processing has been widened significantly, is more beneficial for machine-shaping, and curing exotherm is imitated
Should occur in the range of 138 DEG C, heat release is not concentrated, advantageously reduce the internal stress of material, improve the strength of materials.
As little as 63 DEG C of the fusing point of ternary benzoxazine intermediate in embodiment 10, ring-opening polymerisation initial temperature is 156 DEG C, plus
Work window is 93 DEG C, and curing exotherm effect occurs in the range of 131 DEG C.
As little as 61 DEG C of the fusing point of ternary benzoxazine intermediate in embodiment 15, ring-opening polymerisation initial temperature is 151 DEG C, plus
Work window is 90 DEG C, and curing exotherm effect occurs in the range of 128 DEG C.
2nd, thermal weight loss test, the wherein result of embodiment 1 are carried out for the polymer in embodiment 1,10,15 and comparative example 1
As shown in Figure 4.Specific data (Tg, hot property and limited oxygen index) are as shown in table 3.
The Tg for the benzoxazine polymer that table 3, embodiment are prepared with comparative example, hot property are compared with limited oxygen index
Understood according to table 3, Tg, heat (oxygen) stability, carbon yield and the fire resistance of the polymer in embodiment 1,10 and 15
It is superior to comparative example 1.Compared to bisphenol A-type binary benzoxazine intermediate and its polymer in comparative example 1, ternary in embodiment
Benzoxazine intermediate adds the quantity of benzoxazine structure in unimolecule, so as to increase curing reaction reflecting point and resin friendship
Connection degree, can significantly improve polymer Tg, heat (oxygen) stability, carbon yield and fire resistance.
Claims (10)
1. a kind of ternary benzoxazine intermediate, it is characterised in that structural formula is as follows：
Wherein, R1~R6It is each independently selected from hydrogen or C1~C4Alkyl；R is selected from aromatic group, aliphatic group or alicyclic
Group.
2. a kind of preparation method of ternary benzoxazine intermediate, it is characterised in that comprise the following steps：
1) paraformaldehyde, unary primary amine and reaction dissolvent, 0~10 DEG C of stirring reaction are added into reactor；The unary primary amine
For at least one of aromatic amine, fatty amine, aliphatic cyclic amine；
2) compound of formula II is continuously added, 60~90 DEG C of reactions are warming up to, reaction dissolvent is removed, obtains residue；
Wherein, R1~R6It is each independently selected from hydrogen or C1~C4Alkyl, and phenolic hydroxyl group ortho position can not be alkyl simultaneously；
3) residue is dissolved in dissolution solvent, and be poured onto in alkali lye, separate out solid, filtered, washing obtains ternary benzo
Oxazine intermediate.
3. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 1) and
2) reaction is lucifuge reaction in.
4. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 1) in
Paraformaldehyde is 2 by the mol ratio of aldehyde radical and amino with unary primary amine:0.6~1.2 feeds intake.
5. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 2) in
The compound of formula II is 1 by mol ratio with unary primary amine:2.5~3.3 feed intake.
6. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 2) in
R1~R6It is hydrogen.
7. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 1) in
Unary primary amine is aniline.
8. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 1) in
Reaction dissolvent is selected from least one of dioxane, toluene, butanone, acetone, ethanol, methanol, ethyl acetate；The step 3)
Middle dissolution solvent is selected from least one of DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, 1-METHYLPYRROLIDONE.
9. the preparation method of ternary benzoxazine intermediate according to claim 2, it is characterised in that the step 3) in
The one kind of alkali lye in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate and saleratus.
10. a kind of ternary benzoxazine polymer, it is characterised in that as the ternary benzoxazine intermediate described in claim 1
Heated solidification is made.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678880A (en) * | 2019-01-08 | 2019-04-26 | 江苏大学 | A kind of trifunctional benzoxazine monomer and preparation method thereof based on resveratrol |
| CN111019073A (en) * | 2019-12-20 | 2020-04-17 | 上海电动工具研究所（集团）有限公司 | Preparation method of toughened and modified dual-curing benzoxazine resin |
| CN112707932A (en) * | 2020-12-30 | 2021-04-27 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016109399A1 (en) * | 2014-12-29 | 2016-07-07 | Cytec Industries Inc. | Benzoxazines and compositions containing the same |
| CN106062036A (en) * | 2013-12-20 | 2016-10-26 | 塞特工业公司 | Multifunctional benzoxazines and composite materials incorporating the same |
-
2017
- 2017-04-07 CN CN201710224441.3A patent/CN106967002A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106062036A (en) * | 2013-12-20 | 2016-10-26 | 塞特工业公司 | Multifunctional benzoxazines and composite materials incorporating the same |
| WO2016109399A1 (en) * | 2014-12-29 | 2016-07-07 | Cytec Industries Inc. | Benzoxazines and compositions containing the same |
Non-Patent Citations (1)
| Title |
|---|
| CHING HSUAN LIN，等: "Synthesis and Properties of Flame-Retardant Benzoxazines by Three Approaches", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678880A (en) * | 2019-01-08 | 2019-04-26 | 江苏大学 | A kind of trifunctional benzoxazine monomer and preparation method thereof based on resveratrol |
| CN109678880B (en) * | 2019-01-08 | 2021-05-25 | 江苏大学 | Tri-functional benzoxazine monomer based on resveratrol and preparation method thereof |
| CN111019073A (en) * | 2019-12-20 | 2020-04-17 | 上海电动工具研究所（集团）有限公司 | Preparation method of toughened and modified dual-curing benzoxazine resin |
| CN112707932A (en) * | 2020-12-30 | 2021-04-27 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
| CN112707932B (en) * | 2020-12-30 | 2021-12-28 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
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