CN110183831A - Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material - Google Patents

Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material Download PDF

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CN110183831A
CN110183831A CN201910431900.4A CN201910431900A CN110183831A CN 110183831 A CN110183831 A CN 110183831A CN 201910431900 A CN201910431900 A CN 201910431900A CN 110183831 A CN110183831 A CN 110183831A
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unsaturated polyester
polyester resin
metal organic
composite flame
parts
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喻源
陈忠伟
张庆武
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Nanjing Tech University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605Binary compounds of nitrogen with carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008Supramolecular polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/28Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/08Ingredients agglomerated by treatment with a binding agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame retardant material. The composite flame-retardant material mainly comprises the following raw materials in parts by weight: 96-100 parts of unsaturated polyester, 10-20 parts of melamine, 5 parts of terephthalic acid, 2 parts of ferric chloride hexahydrate and 2 parts of initiator. And (3) fully mixing a proper amount of metal organic framework modified graphite carbon nitride, an initiator and unsaturated polyester resin, and then curing and molding to obtain the product. The invention has the advantages that: (1) the metal organic framework modified graphite carbon nitride can be successfully synthesized only by a hydrothermal method, and has the advantages of simple synthesis route, low raw material cost and mild reaction conditions; (2) the compatibility of the provided composite flame-retardant material between graphite carbon nitride and unsaturated polyester is poor; (3) the composite flame retardant material has low addition amount of the flame retardant and small influence on mechanical properties. And no toxic gas is generated during combustion, thereby being green and environment-friendly. (4) Compared with pure unsaturated polyester resin, the provided composite flame retardant material has better flame retardant property and thermal stability.

Description

A kind of metal organic frame modification graphitic nitralloy carbon/compound resistance of unsaturated polyester resin Combustible material preparation method and applications
Technical field
The invention belongs to carbon material hydridization flame-retardant high-molecular technical fields, and in particular to a kind of metal organic frame modification nitrogen Change carbon/unsaturated polyester resin composite flame-proof material preparation method and applications.
Background technique
Unsaturated polyester resin is using most extensively because of its at low cost, easy processing, excellent corrosion resistance and electrical property One of thermosetting resin.However, unsaturated polyester resin and its composite material can generate a large amount of smog in burning, especially When halogen flame is used as additive, toxic gas, such as hydrogen chloride, hydrogen bromide and carbon monoxide can be supervened.Therefore, In order to expand the application range of unsaturated polyester resin, it is desirable that people develop environmental protection and efficient unsaturated polyester resin flame-retardant is multiple Condensation material.
Recently, two-dimension nano materials cause extensive concern in the preparation and application of ignition resistant polymeric composite. Wherein, graphitic nitralloy carbon has excellent thermal stability and photostability.Also, graphitic nitralloy carbon synthetic route is convenient, raw material It is at low cost.But the compatibility of graphitic nitralloy carbon and unsaturated polyester resin is poor.On the other hand, metal organic framework itself Porous structure can promote the thermal stability of polymer composites.Therefore, it is organic to develop a kind of novel metal by the present invention Backbone modification graphitic nitralloy carbon fire proofing, and unsaturated polyester resin composite flame-proof material is prepared, improve unsaturated polyester (UP) tree The flame retardant property and thermal stability of resin composite material.
Patent CN101386669A discloses a kind of reaction-type flame-retarding unsaturated polyester resin composite material, but synthetic route Raw material that are complicated and needing are excessive.It is fire-retardant unsaturated poly- that CN101544815A and CN103524975A discloses two kinds of Compositional types Ester resin composite materials, but two patent additive amounts are all excessive.Metal organic frame modification graphitic nitralloy carbon provided by the invention/ Unsaturated polyester (UP) composite flame-proof material synthetic route is simpler, and fire retardant additive amount is low.
Summary of the invention
In order to solve deficiency in the prior art, the object of the present invention is to provide a kind of metal organic frames to modify graphite nitrogen Change carbon/unsaturated polyester resin composite flame-proof material and preparation method thereof.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of metal organic frame modification graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material, the unsaturation Polyester resin composite flame-proof material is mainly composed of the following raw materials by weight: 96~100 parts of unsaturated polyester (UP), melamine 10~ 20 parts, 5 parts of terephthalic acid (TPA), 2 parts of ferric chloride hexahydrate, 2 parts of initiator.
The initiator is benzoyl peroxide.
A kind of above-mentioned metal organic frame modification graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material preparation side Method mainly comprises the steps that
(1) it weighs melamine to be added in ceramic crucible with cover, and is calcined 4 hours at 550 DEG C using Muffle furnace, After natural cooling, using agate mortar by yellow product grind into powder, graphitic nitralloy carbon is obtained;
(2) terephthalic acid (TPA) is added in n,N-Dimethylformamide, stirring is sufficiently dissolved until terephthalic acid (TPA), is obtained To solution A;
(3) graphitic nitralloy carbon is added in solution A, stirs 5 minutes, obtains solution B;
(4) ferric chloride hexahydrate is added in solution B, stirs 30 minutes, obtains solution C;
(5) solution C is introduced into the steel autoclave of teflon lined, heats 12 hours, is cooled at 150 DEG C After room temperature, slurries are centrifuged to and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing, then dry in 80 DEG C of vacuum It is 12 hours dry in case, obtain particle A;
(6) particle A is annealed 2 hours in 350 DEG C of air, obtains metal organic frame modification graphitic nitralloy carbon;
(7) metal organic frame is modified into graphitic nitralloy carbon, initiator benzoyl peroxide is added to unsaturated polyester (UP) tree In rouge, stirs 20~60 minutes, obtain solution D after mixing;
(8) solution D is poured into Teflon mould, drying box is put into after injection molding, obtains belonging to organic after solidification demoulding Frame modifies graphitic nitralloy carbon/unsaturated polyester (UP) composite flame-proof material.
The step (1), (2), (3), (4) described stirring are magnetic agitation.
The revolving speed of the step (7) stirring is 500~700 revs/min.
The additive amount of the modified hydridization carbosphere in surface is the 4% of unsaturated polyester resin weight in the step (7);Cause The additive amount of agent is the 2% of unsaturated polyester resin weight.
Condition of cure described in the step (8) are as follows: constant temperature 60 minutes under the conditions of 80 DEG C, constant temperature 180 divides under the conditions of 110 DEG C Clock.
Compared with prior art, the present invention has the advantage that:
(1) metal organic frame modification graphitic nitralloy carbon provided by the invention only needs hydro-thermal method that can synthesize success, synthesizes Route is simple, reaction condition is mild.
(2) raw material needed for metal organic frame provided by the invention modification graphitic nitralloy carbon is few, and raw material sources extensively, It is low in cost, it is suitble to large-scale industrial production.
(3) metal organic frame provided by the invention modifies graphitic nitralloy carbon thermal stability with higher itself and at charcoal Performance can increase substantially the thermal stability of unsaturated polyester resin.
(4) metal organic frame provided by the invention modifies graphitic nitralloy carbon, for purer graphitic nitralloy carbon, improve with Compatibility between unsaturated polyester resin.
(5) metal organic frame provided by the invention modifies graphitic nitralloy carbon/unsaturated polyester (UP) flame retardant composite material, fire-retardant The additive amount of agent is low, smaller to Effect on Mechanical Properties.And toxic gas is not generated when burning, it is environmentally protective.
Detailed description of the invention
Fig. 1 is the FTIR spectrum figure of embodiment 1,2 and 3.
Fig. 2 is the X-ray diffractogram of embodiment 1,2 and 3.
Fig. 3 is thermogravimetric curve of the embodiment 1,2 and 3 in nitrogen atmosphere.
Fig. 4 be thermogravimetric (left side) of the unsaturated polyester resin composite material that provides of embodiment 4,5 and 6 in nitrogen atmosphere and Thermal weight loss rate curve (right side).
Fig. 5 is the total heat release figure that embodiment 4,5 and 6 provides.
Fig. 6 is that metal organic frame modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material preparation flow Figure.
Specific embodiment
The present invention is done below with reference to specific embodiment and more comprehensively, is meticulously described, but protection scope of the present invention It is not limited to embodiment in detail below.
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or Person can the product as made from well known method.
With reference to the accompanying drawings and examples, the technical solution used to invention is further elaborated.
Embodiment 1
The preparation of graphitic nitralloy carbon, specifically comprises the following steps:
10 parts of melamines are added in ceramic crucible with cover, and are calcined 4 hours at 550 DEG C using Muffle furnace, After natural cooling, using agate mortar by yellow product grind into powder, graphitic nitralloy carbon is obtained.
It will be seen from figure 1 that embodiment 1 is in 1200-1700cm-1Between have multiple characteristic peaks.Wherein, 1235, 1317 and 1407cm-1The characteristic peak at place is attributed to the stretching vibration of the connection unit of C-N (- C)-C or C-NH-C.In 1638 Hes 1458cm-1The characteristic peak at place is the stretching vibration of C-N and C=N in CN heterocycle.Furthermore it is possible to by 888 and 805cm-1The two of place A characteristic peak is that the exemplary bent of triazine ring is vibrated.In Fig. 2, there are two peaks at 27.4 and 13.9 ° in embodiment 1.Its In, the strong peak at 27.4 ° is the characteristic interlayer accumulation peak of aromatic systems, and the weak peak at 13.9 ° is related with interlayer accumulation. It may indicate that embodiment 1 is successfully prepared combined with Figure 1 and Figure 2,.
Show that embodiment 1 only has one thermal degradation stage in Fig. 3.As it can be seen from table 1 embodiment 1 can be with thermostabilization Until T0.1=638 DEG C (temperature of 10% weight loss), illustrate that embodiment 1 is heat-staple when temperature is lower than 600 DEG C.
Embodiment 2
The preparation of ferrous metal organic frame, specifically comprises the following steps:
(1) 5g terephthalic acid (TPA) is added in 100mL n,N-Dimethylformamide, magnetic agitation is until terephthaldehyde After completely dissolution, ferric chloride hexahydrate is added in above-mentioned solution for acid, is stirred 30 minutes, is obtained solution A.
(2) solution A is introduced into the steel autoclave of teflon lined, heats 12 hours, is cooled at 150 DEG C After room temperature, slurries are centrifuged to and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing, then dry in 80 DEG C of vacuum It is 12 hours dry in case, obtain particle A;
(3) particle A is annealed 2 hours in 350 DEG C of air, obtains ferrous metal organic frame.
It will be seen from figure 1 that observing six characteristic peaks at 1522,1382,1015,754 and 536cm-1 1625.Position In 1625,1522,1382 and 1015cm-1Vibration of the characteristic peak at place from carboxylate groups.754 and 536cm-1Characteristic peak The stretching vibration of the C-H bending vibration and Fe-O that are belonging respectively in terephthalic acid (TPA) ligand phenyl ring.The XRD diagram of Fig. 2 it can be found that There are multiple peaks in embodiment 2, these peaks are all the typical peaks of embodiment 2.It can be seen that embodiment 2 from Fig. 1 and Fig. 2 to prepare Success.
Embodiment 2 shows 3 main zero-g periods in Fig. 3.Due to the evaporation of solvent, the first stage occurs in 50- Between 150 DEG C.The decomposition of terephthalic acid (TPA) ligand leads to the second weight loss stage between 350-550 DEG C.Phase III Thermal degradation be 600 DEG C after form unbodied iron oxide.
Embodiment 3
Ferrous metal organic frame modifies the preparation of graphitic nitralloy carbon, specifically comprises the following steps:
(1) 5g terephthalic acid (TPA) and 0.6g graphitic nitralloy carbon are added in 100mL n,N-Dimethylformamide, magnetic force Stirring until terephthalic acid (TPA) after completely dissolution, ferric chloride hexahydrate is added in above-mentioned solution, magnetic force stir 30 points Clock obtains solution A;
(2) solution A is introduced into the steel autoclave of teflon lined, is heated 12 hours at 150 DEG C, is cooled to room Slurries are centrifuged and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing by Wen Hou, then in 80 DEG C of vacuum drying oven Middle drying 12 hours, obtains particle A;
(3) particle A is annealed 2 hours in 350 DEG C of air, obtains ferrous metal organic frame modification graphitic nitralloy carbon.
It is corresponding with embodiment 1 and embodiment 2 that embodiment 3 is located at the characteristic peak in Fig. 1 and Fig. 2, illustrates prepared by embodiment 3 Success.
Embodiment 3 mainly shows the weightlessness in two stages in Fig. 3.First stage occurs between 350-500 DEG C, this It is attributable to the decomposition of terephthalic acid (TPA) ligand.Then temperature, which increases, leads to the distillation of graphitic nitralloy carbon to occur second and lose The weight stage.Also, as it can be seen from table 1 the T of embodiment 30.1Than 1 low 175 DEG C of embodiment.Meanwhile compared with Example 1, real The residual quantity for applying example 3 increases 21.9wt%, shows the more thermostabilization than embodiment 1 of embodiment 3.
Embodiment 4
The preparation of pure unsaturated polyester resin, specifically comprises the following steps:
2g benzoyl peroxide is added in 98g unsaturated polyester resin, is stirred 60 minutes with 700 revs/min, observation After being completely dissolved to benzoyl peroxide, solution is poured into Teflon mould, 80 DEG C constant temperature 1 hour, 110 DEG C of constant temperature 3h, cooling and demolding after taking-up.
Thermogravimetric curve of the embodiment 4 under stream of nitrogen gas is as shown in figure 4, corresponding data are shown in Table 2.Embodiment 4 only shows A zero-g period out, T0.1And Tmax(the corresponding temperature of maximum heat weight loss rate) is respectively 339 and 430 DEG C, finally at 800 DEG C When only remain 10.6wt% carbon residue.Embodiment 4 total heat release be it is highest in embodiment 4,5 and 6, reach 131.9kW/m2, Illustrate that embodiment 4 discharges most heats in burning, i.e. the risk of embodiment 4 in a fire is just maximum.
Embodiment 5
The preparation of graphitic nitralloy carbon/unsaturated polyester resin composite material, specifically comprises the following steps:
4g graphitic nitralloy carbon is added in 94g unsaturated polyester resin, is stirred 20 minutes, is added with 700 revs/min 2g benzoyl peroxide continues stirring 40 minutes.Solution is poured into Teflon mould, 80 DEG C constant temperature 1 hour, 110 DEG C constant temperature 3h, cooling and demolding after taking-up.
Thermogravimetric curve of the embodiment 5 under stream of nitrogen gas is as shown in figure 4, corresponding data are shown in Table 2.Graphitic nitralloy carbon/no The T of saturated polyester resin composite material0.1、TmaxCarbon residue with 500 DEG C is all higher than embodiment 4.But since graphitic nitralloy carbon exists Temperature is higher than 600 DEG C and starts to distil, and graphitic nitralloy carbon/unsaturated polyester resin composite material is caused to be lower than in 800 DEG C of carbon residue Embodiment 4.The total heat release of embodiment 5 reduces 1.8kW/m for embodiment 42, illustrate the addition of graphitic nitralloy carbon The fire risk of unsaturated polyester resin can slightly be reduced.
Embodiment 6
Ferrous metal organic frame modify the preparation of carbonitride/unsaturated polyester resin flame-retardant composite material, specifically include as Lower step:
4g ferrous metal organic frame modification graphitic nitralloy carbon is added in 94g unsaturated polyester resin, with 700 revs/min Clock stirs 20 minutes, adds 2g benzoyl peroxide, continues stirring 40 minutes.Solution is poured into Teflon mould, 80 DEG C constant temperature 1 hour, 110 DEG C of constant temperature 3h, cooling and demolding after taking-up.
Thermogravimetric curve of the embodiment 6 under stream of nitrogen gas is as shown in figure 4, corresponding data are shown in Table 2.The T of embodiment 60.1With TmaxIt is reduced with the addition of ferrous metal organic frame modification carbonitride, but the carbon residue at 500 and 800 DEG C of embodiment 6 increases Add.This can illustrate that embodiment 6 is more stable than embodiment 4 and embodiment 5.The total heat of embodiment 6 is discharged relative to embodiment 4 With 5 for reduce 10.2% and 9.0%, illustrate ferrous metal organic frame modification carbonitride can reduce unsaturated polyester resin Fire risk improves the flame retardant property of unsaturated polyester resin.
The Thermogravimetric Data of above-described embodiment 1,2 and 3 in a nitrogen atmosphere is as shown in table 1:
Thermogravimetric Data under 1 embodiment of table, 1,2,3 nitrogen atmosphere
The thermogravimetric of unsaturated polyester resin flame-retardant composite material in a nitrogen atmosphere obtained by above-described embodiment 4,5 and 6 It is as shown in table 2 with total heat release data:

Claims (6)

1. a kind of metal organic frame modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material, which is characterized in that institute Unsaturated polyester resin composite flame-proof material is stated mainly to be composed of the following raw materials by weight: 96~100 parts of unsaturated polyester (UP), trimerization 10~20 parts of cyanamide, 5 parts of terephthalic acid (TPA), 2 parts of ferric chloride hexahydrate, 2 parts of initiator.
2. the modified hydridization carbosphere/unsaturated polyester (UP) flame retardant composite material in surface according to claim 1, feature exist In the initiator is benzoyl peroxide.
3. a kind of metal organic frame described in claim 1 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material The preparation method of material, which is characterized in that mainly comprise the steps that
(1) it weighs melamine to be added in ceramic crucible with cover, and is calcined 4 hours at 550 DEG C using Muffle furnace, in nature After cooling, using agate mortar by yellow product grind into powder, graphitic nitralloy carbon is obtained;
(2) terephthalic acid (TPA) is added in n,N-Dimethylformamide, stirring is sufficiently dissolved until terephthalic acid (TPA), is obtained molten Liquid A;
(3) graphitic nitralloy carbon is added in solution A, stirs 5 minutes, obtains solution B;
(4) ferric chloride hexahydrate is added in solution B, stirs 30 minutes, obtains solution C;
(5) solution C is introduced into the steel autoclave of teflon lined, heats 12 hours, is cooled to room temperature at 150 DEG C Afterwards, slurries are centrifuged to and are used respectively n,N-Dimethylformamide, ethyl alcohol and deionized water washing, then in 80 DEG C of vacuum drying oven It is 12 hours dry, obtain particle A;
(6) particle A is annealed 2 hours in 350 DEG C of air, obtains metal organic frame modification graphitic nitralloy carbon;
(7) metal organic frame modification graphitic nitralloy carbon, initiator benzoyl peroxide are added in unsaturated polyester resin, Stirring 20~60 minutes, obtains solution D after mixing;
(8) solution D is poured into Teflon mould, drying box is put into after injection molding, obtain belonging to organic frame after solidification demoulding Modify graphitic nitralloy carbon/unsaturated polyester (UP) composite flame-proof material.
4. metal organic frame according to claim 3 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material The preparation method of material, which is characterized in that step (1), (2), (3), (4) described stirring are magnetic agitation, step (7) described stirring Revolving speed be 500~700 revs/min.
5. metal organic frame according to claim 3 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material The preparation method of material, which is characterized in that the additive amount of metal organic frame modification graphitic nitralloy carbon is unsaturated poly- in step (7) The 4% of ester weight resin;The additive amount of initiator is the 2% of unsaturated polyester resin weight.
6. metal organic frame according to claim 3 modifies graphitic nitralloy carbon/unsaturated polyester resin composite flame-proof material The preparation method of material, which is characterized in that condition of cure described in step (8) are as follows: constant temperature 60 minutes under the conditions of 80 DEG C, 110 DEG C of items Constant temperature 180 minutes under part.
CN201910431900.4A 2019-05-21 2019-05-21 Preparation method and application of metal organic framework modified graphite carbon nitride/unsaturated polyester resin composite flame-retardant material Pending CN110183831A (en)

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Publication number Priority date Publication date Assignee Title
CN112239230A (en) * 2020-10-15 2021-01-19 北京理工大学 Hierarchical structure coating diaphragm for lithium-sulfur battery and preparation method thereof
CN112239230B (en) * 2020-10-15 2021-09-28 北京理工大学 Hierarchical structure coating diaphragm for lithium-sulfur battery and preparation method thereof

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Application publication date: 20190830