CN105968036A - Metal complex for catalysis of caprolactone polymerization - Google Patents
Metal complex for catalysis of caprolactone polymerization Download PDFInfo
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- CN105968036A CN105968036A CN201610186268.8A CN201610186268A CN105968036A CN 105968036 A CN105968036 A CN 105968036A CN 201610186268 A CN201610186268 A CN 201610186268A CN 105968036 A CN105968036 A CN 105968036A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
- C07C335/08—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C335/18—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a metal complex for efficient controllable ring opening of Epsilon-caprolactone, and specifically relates to thiourea metal salt. The metal complex is suitable for bulk polymerization and melt polymerization process of Epsilon-caprolactone and also suitable for slow controllable polymerization in a solution. The design of molecular weight of polycaprolactone is based on the ratio of a monomer to an initiator in the reaction system. The initiator is alcohol containing active hydroxyl terminal. The alcohol used as a co-initiator and the metal complex together have a synergistic effect on the catalysis system. The metal complex has rich selections of functional groups and is suitable for multiple polymerization conditions.
Description
Technical field
The present invention relates to organic chemistry catalytic field, particularly relate to the metallic catalyst of thiourea derivative coordination, definitely
Say the metal complex being to be catalyzed caprolactone polymerization.
Background technology
Under the big situation that, petroleum resources serious in environmental problem are short, biodegradable plastic has obtained paying close attention to widely.Its
In, polycaprolactone becomes the hot topic of research and development.Polycaprolactone is hydrophobicity, semi-crystalline polymer, and its degree of crystallinity is along with polymerization
Thing molecular mass declines, and polymer can be degraded under microbial action.The raw material of polycaprolactone industry is the biology that can regenerate
Material, end product of its degraded is the most all water and carbon dioxide, can with complete biodegradable, be most competitiveness can be biological
One of degradable material.
The synthesis of polyester in early days is the condensation reaction based on acids and alcohols, but the polymer being synthesized out with this
Structure may be straight chain, side chain or circulus, and molecular weight distribution is wide, and molecular weight is low and wayward, thus ultimately results in
The poor mechanical property of polymer.In recent years the study on the synthesis for polycaprolactone focus primarily upon exploitation coordination polymerization catalysts draw
Send out 6-caprolactone ring-opening polymerisation and prepare polycaprolactone.Compared with Direct Dehydration polycondensation method, the method for polyester is prepared in ring-opening polymerisation
Have the advantage that first, the molecular weight of polyester can accurately control, and molecular weight distribution is the narrowest;The second, Direct Dehydration contracting
Closing the molecular weight of polyesters that obtains low, its property can not meet some requirement in biomedicine, and anhydrous generation in ring-opening polymerisation, can
To synthesize the polymer of higher molecular weight;3rd, can gather by the modification of catalyst ligand being realized chiral monomer selectivity
Close.
At present, be applied to lactone coordination ring-opening polymerisation catalyst system mainly include stannous octoate, metallic aluminium, calcium, magnesium,
Zinc, titanium family complex and IIIB metal complex etc..Ring-opening polymerisation is prepared in the catalyst of polycaprolactone, the most pungent
Acid stannous, the alcohol of small-molecular-weight can control polymer molecular weight and molecular weight distribution as (being total to) initiator.But, above-mentioned urge
Agent system or activity is higher but molecular weight of product distribution width, or narrow molecular weight distribution but activity is low, be all difficult to take into account work
Property high the and feature of narrow molecular weight distribution.
Thiourea as hydrogen donor can activate the compound containing carbonyl, sulfoxide group and nitro
[Chem.Soc.Rev.2009,38,1,187 1198, Chem.Rev.2007,107,5,713 5743], is considered weak electrophilic examination
Agent, can activate the carbonyl of caprolactone monomer by the effect of hydrogen bond, this catalyst can effectively control molecular weight distribution and
Without metal residual in product, but such catalyst system needs to introduce basic group, the such as group such as imino group, guanidine radicals, acid
Although alkali is catalyzed beneficially reaction controlling altogether, but reactivity poor [Chem.Commun.2008, (1) 114 116].As can be seen here,
The catalyst of existing caprolactone ring-opening polymerisation can not be taken into account the feature that catalysis activity is narrower with molecular weight distribution.We are in research
Middle discovery, thiourea hydrogen bond system complexed metal activation energy largely promotes catalysis activity, and resulting polymer distribution is controlled.And
The invention provides a kind of thiourea metal complex catalysts, this catalyst have high catalytic activity and widely catalytic environment fit
Ying Xing, no matter the most described metal complex all embodies in polymerisation in bulk or polymerisation in solution is catalyzed by force activity, and product gathers
Caprolactone has the feature of Narrow Molecular Weight Distribution.So far, the metallic catalyst of this thiourea derivative coordination does not appear in the newspapers
Road.
Summary of the invention
In view of prior art exists above-mentioned technical problem, the invention provides a kind of metal being catalyzed 6-caprolactone polymerization
Coordination compound, this metal complex belongs to thiourea derivative metal complex, its can the ring-opening polymerisation of efficient catalytic 6-caprolactone,
There is high catalytic activity, and obtain the pla-pcl product that molecular weight distribution is narrower.Metal complex of the present invention have employed
Following technical scheme.
A kind of metal complex being catalyzed caprolactone polymerization, it is characterised in that: described metal complex is to have formula 1 structure
Compound:
Wherein, A, B are the most independent expression oxygen atom or sulphur atom;
X, y each stand alone as the integer of 18;
M is Sn, Mg, Ca or Zn.
Described metal complex, it is characterised in that after adding coinitiator, the activity increasing of catalysis caprolactone polymerization
By force.
Described metal complex, it is characterised in that described coinitiator is MeOH, EtOH,nPrOH、iPrOH、nBuOH
、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3In one or more.
The preparation method of described metal complex is: a certain amount of thiourea is dissolved in anhydrous acetonitrile, adds the denseest
Sulphuric acid, is slowly added dropwise trihydroxylic alcohol (such as 1,2,6-hexanetriols) at 50 DEG C, trihydroxylic alcohol consumption is 1.25 times of molar equivalents of thiourea, and three
Stir 20min after unit's alcohol dropping completely, be warming up to 80 DEG C of back flow reaction 12h, be cooled to room temperature, in addition sodium bicarbonate to PH
Property, to filter, after filtrate rotation is steamed, product separates (400 mesh, developing solvent is ethyl acetate/normal hexane=1/5) through silicagel column, collects
Polarity small component.Above-mentioned collection component being dissolved in oxolane, system noble gas is replaced 3 times, adds slaine or metal
Oxide (such as contains the Tin monoxide of water of crystallization), back flow reaction 8h, and negative pressure drains solvent, obtains powdery solid and is required
Thiourea slaine, stores stand-by under noble gas,.
A kind of metal complex being catalyzed caprolactone polymerization, it is characterised in that described metal complex is to have formula 2 structure
Compound:
Wherein, R1、R2、R3、R4Each represent C respectively1–C20Chain alkyl, C2–C10Cycloalkyl group, C2–C8Alkene
Alkyl, C2–C5Alkynes base,R5、R6Elect C independently of one another as1–C5Alkyl, C1–C5
Alkoxyl or hydrogen atom;M is Sn, Mg, Ca or Zn.
The preparation method of described metal complex is: a certain amount of thiourea is dissolved in anhydrous acetonitrile, adds the denseest
Sulphuric acid, is slowly added dropwise 3 at 50 DEG C, 5-dual-trifluoromethyl phenol, 3,5-dual-trifluoromethyl phenol consumptions are 2.5 times moles of thiourea
Equivalent, stirs 40min after 3,5-dual-trifluoromethyl phenol droppings completely, is warming up to 80 DEG C of back flow reaction 24h, is cooled to room temperature,
Add sodium bicarbonate neutral to PH, filter, after filtrate rotation is steamed, product through silicagel column separate (400 mesh, developing solvent be ethyl acetate/
Normal hexane=1/3), collect polarity small component.Above-mentioned collection component being dissolved in oxolane, system noble gas is replaced 3 times, adds
Entering slaine or metal-oxide (such as containing the Tin monoxide of water of crystallization), back flow reaction 8h, negative pressure is drained solvent, is obtained
Powdery solid is required thiourea slaine, stores stand-by under noble gas.
Described metal complex, it is characterised in that after adding coinitiator, the increased activity of catalysis cyclic ester polymerization.
Described metal complex, it is characterised in that described coinitiator is MeOH, EtOH,nPrOH、iPrOH、nBuOH
、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3In one or more.
The metal complex of catalysis caprolactone polymerization, is the compound with formula 1 structure:
Wherein, A, B elect oxygen atom or sulphur atom independently of one another as;X, y each stand alone as the integer of 18;M is Sn, Mg,
Ca or Zn.
The metal complex of described catalysis caprolactone polymerization, it can also is that the compound with formula 2 structure:
Wherein, R1、R2、R3、R4Elect C independently of one another as1–C20Chain alkyl, C2–C10Cycloalkyl group, C2–C8's
Alkylene, C2–C5Alkynes base,R5、R6Elect C independently of one another as1–C5Alkyl,
C1–C5Alkoxyl or hydrogen atom;M is Sn, Mg, Ca or Zn.
Above-mentioned metal complex, after adding coinitiator, the increased activity of catalysis 6-caprolactone polymerization.Described initiation altogether
Agent, for MeOH, EtOH,nPrOH、iPrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N
(CH2CH2OH)3In one or more.Above-mentioned alcohol and described metal complex mol ratio are for changing within a large range
As, (0.1 10): 1.The molecular weight of polymer can be controlled with coordination compound mol ratio by above-mentioned alcohol, in 0.1 ten thousand 20 ten thousand scopes
The most adjustable, molecular weight distribution between 1.01 1.20, active polymerization feature.
Described metal complex application in melt stability polymer (melt-stable polymer) production technology,
Also needing to additionally add stabilizer, described stabilizer is trialkyl phosphorous acid, and alkyl phosphorous acid, aromatic series phosphorous acid, space are subject to
Resistance cyclic nonaromatics, space be obstructed diphosphorous acid compound, hydroxy phenylpropionic acid, hvdroxvbenzvl compounds, benzyl alcohol,
One or more mixing in the amino-compound that is obstructed in alkylidene bisphenols, alkyl phenol, aminoacid, thioether, space, hydroquinone
Thing.
In the stable smelting process that described metal complex is applied, in addition it is also necessary to additionally add deicer, described deicer
For in clay, aluminium oxide, silica gel, zeolite, calcium chloride, calcium carbonate, sodium sulfate, calcium bicarbonate, sodium bicarbonate, potassium bicarbonate
Plant or several mixture.Be obstructed (alkyl, aryl, phenolic group) hydrazides, aromatic series or aliphatic can also be added in polymerization inhibitor
Amide mono hydroxyeicosatetraenoic acid or dihydroxy acid, cyclic amides, aliphatic or aromatic hydrazone aldehyde or dihydrazone aldehyde, diacyl-hydrazides derivant.
Described metal complex, except preparing polycaprolactone, it is also possible to make in organic solvent in polymerisation in bulk
Standby polycaprolactone, described organic solvent is benzene,toluene,xylene, DMF, chloroform, dichloromethane, second
One in nitrile, pyridine, dimethyl sulfoxide, 1,4-dioxane, furan, oxolane.Reaction mixture can be in another kind of polarity
Solvent separates out pressed powder.
Described metal complex catalyzed butyrolactone activity is relatively low, and can not be catalyzed the lactide with formula 3 structure, to 6~7 yuan
There is specificity in cyclic lactone monomer.Wherein, A, B are [(CR11R12)—]n, n is the integer of 2~6, A with B can identical also may be used
With difference;R11、R12Selected from H, there is 1~5 carbon atom alkyl, there is 1~5 carbon atom and taken by halogen atom or hydroxyl
The alkyl in generation;X is selected from O or NH.
Metal complex of the present invention has the advantages that
1, Gold Thiourea metal complex is used for the ring-opening polymerisation of caprolactone by the present invention first as catalyst;
2, metal complex of the present invention has high catalytic activity to 6-caprolactone;
3, the molecular weight of product narrow distribution that metal complex catalyzed 6-caprolactone monomer of the present invention is polymerized is used, and
Can be with Molecular regulator amount size, active polymerization feature.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
Should be appreciated that these describe simply as to further illustrate the features and advantages of the present invention rather than to the claims in the present invention
Limit.
Embodiment 1 10
Embodiment 1-10 have employed different metal complexs as catalyst, carries out body under identical reaction conditions
Polymerization.The 6-caprolactone being respectively 5.7g (50mmol) is respectively placed in 50mL flask, adds 0.2mmol metal complex,
0.1mmol benzyl alcohol.Oil bath heating at 120 DEG C.Isothermal reaction 1 hour, cooling, sample analysis, conversion ratio is surveyed with liquid chromatograph
, molecular weight records (polystyrene is as standard specimen) with GPC.The experimental result of embodiment 1-10 is shown in Table 1.
The monomer of the 6-caprolactone described in embodiment 1-10 is the product that in caprolactone production process, after rectification, purity is higher
Product.
From data, metal ion is unsuitable with hydrogen bond space length excessive or too small, and 4 carbochain distances are the most suitable.
Pink salt activity is better than other salt, and oxonium salt activity is better than sulfosalt, and in embodiment, catalyst activity is significantly stronger than traditional pungent
Acid stannous.
Bulk polymerization under table 1 different catalysts effect
Embodiment 11 15
In embodiment 11-15, the metal complex in employing above-described embodiment 3 is as catalyst, under condition of different temperatures
Carry out polymerisation in bulk.Respectively the 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flask, adds 0.2mmol embodiment 1
Middle metal complex, 0.1mmol benzyl alcohol.Oil bath heating at a temperature of 5 kinds, isothermal reaction 1 hour, cooling, sample analysis, convert
Rate records with liquid chromatograph, and molecular weight records (polystyrene is as standard specimen) with GPC.The experimental result of embodiment 11-15 is shown in Table 2.
The monomer of the 6-caprolactone described in embodiment 11-15 is the product that in caprolactone production process, after rectification, purity is higher
Product.Visible reaction temperature is high, is beneficial to react quickening, but molecular weight distribution is gradually increased, and 120 DEG C the most applicable.
Polymerization result under table 2 different temperatures
Embodiment 16 20
In embodiment 16-20, the metal complex in employing above-described embodiment 3 is as catalyst, at different catalysts consumption
Under the conditions of carry out polymerisation in bulk.Respectively the 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flask, adds in embodiment 2
5 batch quality of metal complex, 0.1mmol benzyl alcohol.Oil bath heating at 120 DEG C.Isothermal reaction 1 hour, cooling, sampling
Analyzing, conversion ratio records with liquid chromatograph, and molecular weight records (polystyrene is as standard specimen) with GPC.The experiment knot of embodiment 16-20
Fruit is shown in Table 3.Visible monomer ratio increases, and molecular weight increases, but conversion ratio reduces.
The monomer of the 6-caprolactone described in embodiment 16-20 is the product that in caprolactone production process, after rectification, purity is higher
Product.
The impact on aggregate rate of the table 3 metal complex different amounts
Embodiment 21 30
In embodiment 21-30, the metal complex in employing above-described embodiment 3 is as catalyst, at different organic solvents bar
Polymerisation in solution is carried out under part.Respectively the 6-caprolactone of 5.7g (50mmol) is respectively placed in 50mL flask, adds different organic molten
Agent 15mL.Add metal complex 0.5mmol in embodiment 1,0.5mmol benzyl alcohol.Room temperature isothermal reaction 4 hours, sampling point
Analysis, conversion ratio records with liquid chromatograph, and end-product pours precipitation white solid in ice methanol into, and molecular weight records (polyphenyl second with GPC
Alkene is standard specimen).The experimental result of embodiment 21-30 is shown in Table 4.Understand conventional organic solvent and may be applicable to system of the present invention, but
And it is unfavorable for quick large-scale production.
The monomer of the 6-caprolactone described in embodiment 21-30 is the product that in caprolactone production process, after rectification, purity is higher
Product.
Table 4: be polymerized situation in different organic solvents
Embodiment 31 34
Embodiment 31-34 uses the metal complex of above-described embodiment 3 as catalyst, is catalyzed 4 kinds of different cyclic esters and enters
Row polymerisation in bulk.Respectively by 4 kinds, the cyclic ester of 5g is respectively placed in 50mL flask, adds polymerization inhibitor in 1mg embodiment 3, at 120 DEG C
Oil bath is heated, and reacts 4 hours, cooling, the content of sample analysis cyclic ester.Cyclic ester conversion ratio (i.e. aggregate rate) is calculated with this, real
The experimental result executing example 31-34 is shown in Table 5, and thiourea slaine is relatively low to other cyclic esters in addition to valerolactone, lactide catalysis activity, can
Can be relevant to ring cyclosiloxane monomer tension force.
The polymerization of the different cyclic ester monomer of table 5
Claims (6)
1. the metal complex being catalyzed caprolactone polymerization, it is characterised in that: described metal complex has formula 1 structure
Compound:
Wherein, A, B represent oxygen atom or sulphur atom the most respectively;
X, y each stand alone as the integer of 18;
M is Sn, Mg, Ca or Zn.
Metal complex the most according to claim 1, it is characterised in that after adding coinitiator, catalysis caprolactone gathers
The increased activity closed.
Metal complex the most according to claim 2, it is characterised in that described coinitiator is MeOH, EtOH,nPrOH、iPrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3In one or more.
4. the metal complex being catalyzed caprolactone polymerization, it is characterised in that described metal complex has formula 2 structure
Compound:
Wherein, R1、R2、R3、R4Each represent C respectively1–C20Chain alkyl, C2–C10Cycloalkyl group, C2–C8Alkene
Base, C2–C5Alkynes base,
R5、R6Elect C independently of one another as1–C5Alkyl, C1–C5Alkoxyl or hydrogen atom;
M is Sn, Mg, Ca or Zn.
Metal complex the most according to claim 4, it is characterised in that after adding coinitiator, is catalyzed cyclic ester polymerization
Increased activity.
Metal complex the most according to claim 5, it is characterised in that described coinitiator is MeOH, EtOH,nPrOH、iPrOH、nBuOH、tBuOH、BnOH、Ph2CHOH、Ph3COH、Ph(CH2OH)3、N(CH2CH2OH)3In one or more.
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US11873381B2 (en) | 2018-02-19 | 2024-01-16 | Arkema Inc. | Accelerated peroxide-cured resin compositions having extended open times |
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JP7381479B2 (en) | 2018-02-19 | 2023-11-15 | アーケマ・インコーポレイテッド | Accelerator solutions useful in curing resins |
US11873381B2 (en) | 2018-02-19 | 2024-01-16 | Arkema Inc. | Accelerated peroxide-cured resin compositions having extended open times |
CN111741983B (en) * | 2018-02-19 | 2024-03-08 | 阿科玛股份有限公司 | Accelerator solutions useful for curing resins |
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