CN106631882A - Multi-ammonia dithio-formic acid sulfite derivative and preparation method and application thereof - Google Patents
Multi-ammonia dithio-formic acid sulfite derivative and preparation method and application thereof Download PDFInfo
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- CN106631882A CN106631882A CN201610846573.5A CN201610846573A CN106631882A CN 106631882 A CN106631882 A CN 106631882A CN 201610846573 A CN201610846573 A CN 201610846573A CN 106631882 A CN106631882 A CN 106631882A
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- 0 C*(*)N(C)C(S*)=S Chemical compound C*(*)N(C)C(S*)=S 0.000 description 2
- HVOYZOQVDYHUPF-UHFFFAOYSA-N CNCCN(C)C Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/40—Hydrazines having nitrogen atoms of hydrazine groups being quaternised
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
Abstract
The invention provides a multi-ammonia dithio-formic acid sulfite derivative which has a structure as shown in a formula (I). The invention further provides a method for preparing the derivative and application of the derivative as a reducing agent - chain transfer agent to the aspect of free radical polymerization reaction. A preparation method is simple, reaction conditions are mild, and the multi-ammonia dithio-formic acid sulfite derivative has very good application effects and application values in the free radical polymerization reaction triggered in an oxidation-reduction system.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of new many Ammonia dithiocarbonic acid sulfurous (sulphur) hydrochlorates spread out
It is biological, and preparation method thereof and as reducing agent-chain-transferring agent in terms of application.
Background technology
The chain-transferring agent commonly used in Raolical polymerizable includes alcohols (such as isopropanol), mercaptan, ethers, thioether, ketone
Class (such as acetone, MEK), lipid (such as MA, EA, DEM, DMC, DEC), halogen alkane (as chloroform, CFC-11, CFC-12,
HCFC-22, HCFC-123), aliphatic alkane (such as methyl cyclopentane, hexahydrotoluene etc.), also thio esters and xanthic acid
Esters etc..The characteristics of active free radical polymerization has controllable/living polymerization to most of monomer, is widely used in the structure of polymer
In design, at present existing active free radical polymerization includes nitroxide-mediated stable free-radical polymerization (NMP), ATRP
Method (ATRP) and reversible addion-fragmentation chain transfer radical polymerization (RAFT).
Reversible addion-fragmentation chain transfer radical polymerization is to introduce to have higher chain tra nsfer in traditional radical polymerization
Double sulfur esters of constant carry out controllable/living polymerization as chain-transferring agent, in the presence of initiator, obtain molecular weight
The polymer of controllable, molecular weight distribution very narrow (＜ 1.2).Double thioesters class chain-transferring agents can by the difference of the bonded groups of its C=S
It is divided into four classes：Dithioester class chain-transferring agent (C=S is bonded C), three thio esters of gallic acid chain-transferring agents (C=S is bonded S), xanthan
Esters of gallic acid chain-transferring agent (C=S is bonded O) and thiocarbamates chain-transferring agent (C=S is bonded N).
Using most chain-transferring agents it is alkyl sulfide alcohol compound in industrialized production, such as：TGA, mercaptopropionic acid
Deng, but alkyl hydrosulfide breath malodor, and chain transfer constant is generally larger, causes polymerisation early stage to consume fast, monomer conversion
It is difficult to effectively improve.
Till now existing many publications and literature research chain-transferring agent, are concentrated mainly on reversible addition-fracture chain and turn
In shifting, wherein research dithioester class, three thio esters of gallic acid, xanthic acid esters are in the majority.Zou Yousi etc. has carried out various of monomer
Active free radical polymerization and block copolymerization with double thioesters as chain-transferring agent, finds with PhC (S) SC (CH3)2Ph is chain-transferring agent
Effect than PhC (S) SCH (CH3) Ph is good.Yue Liying etc. have studied benzyl dithiobenzoate, dithiobenzoic acid benzene second
Bulk Polymerization of Styrene of the three kinds of RAFT reagents of base ester and dithiobenzoic acid isopropylbenzene base ester as chain-transferring agent.Hou Yueping is closed
Into important RAFT reagent dithiobenzoic acids, 4- cyanopentanoic acid dithiobenzoic acids, and explore optimum synthesising method.
Zhou Yingxue is prepared for 3 kinds of trithio ester type reversible addion-fragmentation chain transfer agent；Liu Zhongbin etc. has synthesized 3- (4- benzene first
Aminosulfonylphenyl methyl mercapto thiocarbonyl sulfenyl) propionic acid, as chain-transferring agent and light trigger, by allyl methacrylate
Emulsion polymerization be obtained reactivity polyallylmethacrylate, yield 91.5%；University Of Tianjin completes efficient RAFT chains and turns
Move agent S, S ' two (α, α '-methyl-α "-acetic acid) trithiocarbonate and its preparation；Mitsubishi Rayon Co., Ltd have studied new
The double sulfur esters of chain-transferring agent and the emulsion polymerization using the chain-transferring agent.
Xanthate synthetic method is simple, therefore it is also more as the people of chain-transferring agent to study xanthate.Xie little Li etc.
O- ethoxy-dithioformic acid ethyl propionates are synthesized.Sinopec Beijing Research Institute of Chemical Industry is in xanthate
Synthesize, and the comparison of application aspect research is comprehensive.
In addition, also have that other kinds of chain-transferring agent is studied, such as：Yang Fan etc. have studied chain-transferring agent laruyl alcohol to D, and L- is newborn
The impact of acid polymerization；Zhao Jue etc. have studied the preparation and application of the Macromolecular chain transfer agent containing iodine compound；Wang Wanlin etc. is studied
Sodium hydrogensulfite is used as application of the chain-transferring agent in polycarboxylate water-reducer synthesis；Chongqing Jian Jie Science and Technology Ltd.s are to winestone
Chain-transferring agent is made in acid, applies in terms of poly carboxylic acid series water reducer and is studied；Beijing University of Chemical Technology is to Organic Tellurium Compounds
Synthetic method and its application as chain-transferring agent in active free radical polymerization are studied；Li Ding have studied a kind of phosphorous
Compound is used as chain-transferring agent, and water reducer and preparation method thereof is synthesized under normal temperature condition；Shanghai Hua Yi companies are with Organic Selenium class
Compound is studied the controllability of radical polymerization as chain-transferring agent.
However, these chain-transferring agents not always make at aspects such as raw material, synthesis, technique, post processing, application or prices
People's satisfaction.
The content of the invention
For this purpose, the invention provides a kind of many Ammonia dithiocarbonic acid sulfite derivatives, tie with formula (I) Suo Shi
Structure,
Wherein, R1And R2It is respectively and independently selected from hydrogen bond, substituted or unsubstituted alkylidene, substituted or unsubstituted unsaturation
Alkylidene, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted sub- aralkyl, substituted or unsubstituted sub- virtue oxygen alkane
Base, substituted or unsubstituted aryl and substituted or unsubstituted inferior heteroaryl；
R3、R4、R5、R6And R7Be respectively and independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl,
Substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aralkenyl, replacement or unsubstituted
Aryloxyalkyl group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl-carboxylic acid, take
Generation or unsubstituted carboxylate alkyl, substituted or unsubstituted ester alkyl, substituted or unsubstituted amidoalkyl group, replacement or do not take
The ketone alkyl in generation and substituted or unsubstituted aldehyde alkyl；
L1 -、L2 -It is identical or different and represent arbitrary SO3 2-、HSO3 -、KSO3 -、NaSO3 -、NH4SO3- or R8-SO2 -, and its
In, R8Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aralkyl and replacement
Or unsubstituted aryl；
N, m are respectively and independently selected from the arbitrary integer more than or equal to 0.
Preferably, R1And R2It is respectively and independently selected from the straight-chain alkyl-sub of C1-6, the branched alkylidene of C1-6, the straight chain of C3-6
Alkylene group, the branched alkenylene of C3-6, these groups can be by halogen, hydroxyl, amino, nitro, cyano group, sulfonic group, C1-
At least one replacement in 4 alkyl, C1-4 alkoxyls, C1-4 Alkoximinos, C3-7 cycloalkyl；
The cycloalkylidene of C3-21, the arlydene of C6-18, these groups can by halogen, hydroxyl, amino, nitro, cyano group,
At least one replacement in sulfonic group, C1-4 alkyl；
Five yuan of inferior heteroaryls, hexa-atomic inferior heteroaryl, benzo-fused five yuan of inferior heteroaryls, benzo-fused hexa-atomic inferior heteroaryl,
These groups can be by halogen, C1-4 alkyl, C1-4 alkoxyls, C1-4 alkylthio groups, C1-4 haloalkyls, C1-4 haloalkoxies
Base, C1-4 halogenated alkylthios, C3-6 cycloalkyl, cyano group, hydroxyl, nitro, aryl, at least one replacement of aryloxy group；
R3-R7It is respectively and independently selected from the straight chained alkyl of C1-7, the branched alkyl of C1-7, the straight alkenyl of C3-7, C3-7's
Branched alkenyl, these groups can by halogen, C1-5 alkoxyls, C1-5 Alkoximinos, C3-7 cycloalkyl at least
One kind replaces；
The cycloalkyl of C3-7, these groups can be by halogen, hydroxyl, amino, nitro, cyano group, sulfonic group, C1-4 alkyl
At least one replacement；
Phenyl, naphthyl, anthryl, fluorenyl, quinary heteroaryl, six membered heteroaryl, benzo-fused quinary heteroaryl is benzo-fused
Six membered heteroaryl, the aralkyl of C9-14, C8-13 aryloxyalkyl groups, the aralkenyl of C7-14, these groups can be by halogen, C1-
4 alkyl, C1-4 alkoxyls, C1-4 alkylthio groups, C1-4 haloalkyls, C1-4 halogenated alkoxies, C1-4 halogenated alkylthios, C3-6 rings
At least one replacement in alkyl, cyano group, hydroxyl, nitro, aryl, aryloxy group；
C2-6 alkyl-carboxylic acids, C2-6 carboxylate alkyl, C2-6 ester alkyls, C2-6 amidoalkyl groups, C3-6 ketone alkyl, C2-6 aldehyde
Alkyl, these groups can be by least one in halogen, hydroxyl, amino, nitro, cyano group, sulfonic group, phenyl, C1-4 alkyl
Replace；
R8Selected from the straight chained alkyl of C1-6, the branched alkyl of C1-6, the straight alkenyl of C1-6, the branched alkenyl of C1-6
Base, these groups can be replaced by least one in halogen, hydroxyl, amino, nitro, cyano group, aryl；
The straight chain benzene alkyl of C1-6, the side chain benzene alkyl of C1-6, phenyl, these groups can by halogen, hydroxyl, amino,
At least one replacement in nitro, cyano group, aryl, C1-5 alkyl, the haloalkyl with 1 to 5 halogen atom；
N, m are respectively and independently selected from 0,1,2 or 3.
It is highly preferred that R1And R2It is respectively and independently selected from following structure：
R2、R4、R5、R6And R7It is respectively and independently selected from following structure：
R8Selected from following structure：
Preferably, many Ammonia dithiocarbonic acid sulfite derivatives are selected from following structural formula：
Present invention also offers a kind of method for preparing many Ammonia dithiocarbonic acid sulfite derivatives, including following step
Suddenly：
S1：With compound shown in formula (II) as raw material, with halides, sulfuric ester, carbonic ester or containing formaldehyde or poly first
The solution of the compound of aldehyde and active hydrogen is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains formula
(III) compound shown in；
S2：It is molten with the reaction containing carbon disulfide in the presence of diluent with compound shown in formula (III) as raw material
Agent is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains compound shown in formula (IV)；
S3：In the presence of diluent, by compound shown in formula (IV) and the reaction for including elemental sulfur or sulfur-containing compound
Solvent is reacted, and 0.5-3h is reacted within the temperature range of 0-100 DEG C, obtains compound shown in formula (I)；
Wherein, in S1-S3, the diluent is respectively and independently selected from water, DMSO, alcohol, ether, ketone, halogenated alkane, ester, acid amides
Or alkane；R in formula (II)-(IV)1、R2、R3、R4、R5、R6、R7It is defined as above with n, m.
Preferably, S1 is concretely comprised the following steps,
With compound shown in formula (II) as raw material, in the presence of diluent and alkali, with halides, sulfuric ester or carbonic ester
Reacted, 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtained compound shown in formula (III)；
Or, with compound shown in formula (II) as raw material, in the presence of diluent, with containing formaldehyde or paraformaldehyde and
The solution of the compound of active hydrogen is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains formula (III) institute
Show compound；
The compound of the active hydrogen is the compound containing active methylene group, amino or imino group.
Preferably, S2 is concretely comprised the following steps,
With compound shown in formula (III) as raw material, in the presence of diluent, with carbon disulfide and α, beta-unsaturated carbonyl
Compound is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains compound shown in formula (IV)；
Or, with compound shown in formula (III) as raw material, in the presence of diluent and alkali, in -10-100 DEG C of temperature
In the range of with carbon disulfide react 0.5-2h, then again within the temperature range of 30-100 DEG C with halides react 0.5-2h, obtain
To compound shown in formula (IV)；
Or, with compound shown in formula (III) as raw material, in the presence of diluent and alkali, in -10-100 DEG C of temperature
In the range of with carbon disulfide react 0.5-2h, then within the temperature range of 30-100 DEG C with thiol reactant 0.5-2h, obtain formula
(IV) compound shown in；
Or, with compound shown in formula (III) as raw material, in the presence of diluent and alkali, in -10-100 DEG C of temperature
In the range of with carbon disulfide, chloroform and MIBK or aldehyde reaction 0.5-2h, obtain compound shown in formula (IV).
Preferably, S3 is concretely comprised the following steps,
In the presence of diluent, compound shown in formula (IV) is reacted with sulfurous acid or sulphite, in 0-100
0.5-2h is reacted within the temperature range of DEG C, compound shown in formula (I) is obtained, the sulphite is selected from sodium hydrogensulfite, sulfurous
One kind in potassium hydrogen phthalate, ammonium bisulfite, R6_SO2H；
Or, in the presence of diluent, compound shown in formula (IV) is reacted with sulphite and strong acid, in 0-
0.5-2h is reacted within the temperature range of 100 DEG C, if there is two-phase or multinomial reaction, is carried out in the presence of a base, obtain formula (I) institute
Show compound, the one kind of the sulphite in sodium sulfite, sodium hydrogensulfite, potassium sulfite, ammonium sulfite is described strong
The one kind of acid in sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, p-methyl benzenesulfonic acid；
Or, in the presence of diluent, by compound and SO shown in formula (IV)2Reacted, in 0-100 DEG C of temperature model
Interior reaction 0.5-3h is enclosed, compound shown in formula (I) is obtained；
Or, in the presence of diluent, compound shown in formula (IV) is reacted with elemental sulfur and oxygen, in 0-100
0.5-3h is reacted within the temperature range of DEG C, is carried out in the presence of a base if necessary, obtain compound shown in formula (I).
Present invention also offers a kind of reproducibility-chain-transferring agent composition, including above-mentioned many Ammonia dithiocarbonic acid sulfurous
At least one in acid salt derivant.
Present invention also offers a kind of polycarboxylate water-reducer, is by filler and/or surface reactive material and above-mentioned
Arbitrary described many Ammonia dithiocarbonic acid sulfite derivatives mixing synthesis is obtained.
Preferably, many Ammonia dithiocarbonic acid sulfite derivatives that the present invention is provided, as reducing agent-chain-transferring agent
Application in Raolical polymerizable.
The present invention provide many Ammonia dithiocarbonic acid sulfite derivatives, oxidation-reduction system cause under from
There is extraordinary application effect and using value by base polymerisation, be a kind of outstanding reducing agent-chain-transferring agent.
Specific embodiment
In order that those skilled in the art more fully understand that technical scheme can be practiced, with reference to concrete
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Used reagent in following examples, it is involved in following examples if without specified otherwise, being conventional reagent
Method, if without specified otherwise, being known method.
A kind of many Ammonia dithiocarbonic acid sulfite derivatives, it is characterised in that with structure shown in formula (I),
Wherein, R1And R2It is respectively and independently selected from hydrogen bond, substituted or unsubstituted alkylidene, substituted or unsubstituted unsaturation
Alkylidene, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted sub- aralkyl, substituted or unsubstituted sub- virtue oxygen alkane
Base, substituted or unsubstituted aryl and substituted or unsubstituted heteroarylidene；
R3、R4、R5、R6And R7Be respectively and independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl,
Substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aralkenyl, replacement or unsubstituted
Aryloxyalkyl group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl-carboxylic acid, take
Generation or unsubstituted carboxylate alkyl, substituted or unsubstituted ester alkyl, substituted or unsubstituted amidoalkyl group, replacement or do not take
The ketone alkyl in generation and substituted or unsubstituted aldehyde alkyl；
L1 -、L2 -It is identical or different and represent arbitrary SO3 2-、HSO3 -、KSO3 -、NaSO3 -、NH4SO3 -Or R8-SO2 -, and its
In, R8Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aralkyl and replacement
Or unsubstituted aryl；
N, m are respectively and independently selected from the arbitrary integer more than or equal to 0.
Based on same inventive concept, present invention also offers the preparation method of the compound,
Specifically, its preparation method is divided into following three part：
S1：With compound shown in formula (II) as raw material, with halides, sulfuric ester, carbonic ester or containing formaldehyde or poly first
The solution of the compound of aldehyde and active hydrogen is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains formula
(III) compound shown in；
S2：It is molten with the reaction containing carbon disulfide in the presence of diluent with compound shown in formula (III) as raw material
Agent is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains compound shown in formula (IV)；
S3：In the presence of diluent, by compound shown in formula (IV) and the reaction for including elemental sulfur or sulfur-containing compound
Solvent is reacted, and 0.5-3h is reacted within the temperature range of 0-100 DEG C, obtains compound shown in formula (I)；
Wherein, in S1-S3, the diluent is respectively and independently selected from water, DMSO, alcohol, ether, ketone, halogenated alkane, ester, acid amides
Or alkane；R in formula (II)-(IV)1、R2、R3、R4、R5、R6、R7It is defined as above with n, m.
It should be noted that in formula (I), as m=0, it is not necessary to the step of S2, it is only necessary to S1 and S3 steps；When m ≠ 0
When, tri- steps of S1, S2 and S3 are required for.
Based on same inventive concept, present invention also offers compound and preparation method thereof in detail below.
Embodiment 1
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 1,
Synthesis technique flow process is as follows：
Specifically preparation method is：Under the conditions of ice-water bath, in the reaction bulb of 500ml, 80% hydrazine hydrate is sequentially added
15.6g, 30% dimethylamine agueous solution 75g and 150ml water, are added dropwise 15g paraformaldehydes and 200ml water are formed under stirring
Solution, time for adding takes around 1h, and completion of dropping carries out reaction 0.5h；
Ice-water bath is removed, continues to react 2h, form the colourless solution of transparent clarification；Sodium hydrogensulfite 104g is continuously added,
Reaction 2h, solid all dissolves, and stops reaction, and add water the solution for being configured to 20%, saves backup.
Embodiment 2
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 2,
Synthesis technique flow process is as follows：
Specifically preparation method is：Under the conditions of ice-water bath, in the reaction bulb of 500ml, 80% hydrazine hydrate is sequentially added
15.6g, diethyl malonate 80g and diluent ethanol 300ml, are added dropwise 15g paraformaldehydes under stirring, react 0.5h,
Ice-water bath is removed, continues to react 2-5h, form the colourless solution of transparent clarification；
Concentrated hydrochloric acid 50ml is subsequently adding, 2-5h is heated to reflux, diluent (ethanol) is sloughed；150ml water dissolves are added, is used
In 30% sodium hydroxide solution and pH be 5-6, have solid to separate out, filter；Solid is added to sodium hydrogensulfite 52g and water
In the solution that 200ml is formed, room temperature reaction 3h, solid all dissolves, and stops reaction, and add water the solution for being configured to 20%, preserves
It is standby.
Embodiment 3
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 3,
Synthesis technique flow process is as follows：
Specifically preparation method is：Under the conditions of ice-water bath, in the reaction bulb of 500ml, ethylenediamine 15g, 1H- are sequentially added
1,2,4- triazole 34.5g and 150ml water, is added dropwise the solution that 15g paraformaldehydes and 100ml water are formed, drop under stirring
Plus the time takes around 1h, completion of dropping is reacted 0.5h, removes ice-water bath, continues to react 2h, forms transparent, clarification colourless
Solution；
Sodium hydrogensulfite 104g is continuously added, 3h is reacted, solid all dissolves, and stops reaction, adds water and is configured to 20%
Solution, saves backup.
Embodiment 4
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 4,
Synthesis technique flow process is as follows：
Specifically preparation method is：Under the conditions of ice-water bath, in the reaction bulb of 500ml, ethylenediamine 15g, 1H- are sequentially added
1,2,4- triazole 34.5g and 150ml water, is added dropwise the solution that 15g paraformaldehydes and 100ml water are formed, drop under stirring
Plus the time takes around 1h, completion of dropping is reacted 0.5h, removes ice-water bath, continues to react 2h, forms transparent, clarification colourless
Solution；
Acrylic acid 7.4g is continuously added, carbon disulfide 7.6g is added dropwise, 1h is dripped off, react 3h；
Sodium hydrogensulfite 104g is added, 3h is reacted, solid all dissolves, and stops reaction, and add water the solution for being configured to 20%,
Save backup.
Embodiment 5
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 5,
Synthesis technique flow process is as follows：
Specifically preparation method is：Under the conditions of ice-water bath, in the reaction bulb of 500ml, diluent ethanol 50mL is added, then
15g ethylenediamines are added, under fast stirring, dimethyl suflfate 94.5g is added dropwise, 1.5-2h is dripped off, insulation reaction 2h；
20% NaOH solution 50g is added, carbon disulfide 19g is added dropwise, be stirred vigorously, without obvious phenomenon when just starting, ten
Start to become cloudy after a few minutes, react 3h, solution is changed into orange from yellow, add 29gClCH2COONa is dissolved in 50mL water and is formed
Solution, room temperature reaction 1.5h, solution is changed into crocus, is heated to reflux 2h from orange, cools down；
26g sodium hydrogensulfites are added, reaction 2h is stirred at room temperature, filtered, white or faint yellow solid adds water and is configured to 20%
Solution, save backup.
Embodiment 6
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 6,
Synthesis technique flow process is as follows：
Specifically preparation method is：Under the conditions of ice-water bath, in the reaction bulb of 500ml, ethanol 50mL is added, added
15g ethylenediamines, under fast stirring, are added dropwise chloroethanes 48.4g, and 2-3h is dripped off, insulation reaction 2h；
20% NaOH solution 50g is added, carbon disulfide 19g is added dropwise, be stirred vigorously, without obvious phenomenon when just starting, ten
Start to become cloudy after a few minutes, react 3h, solution is changed into orange from yellow, add 29gClCH2COONa is dissolved in 50mL water and is formed
Solution, room temperature reaction 1.5h, solution is changed into crocus, is heated to reflux 2h from orange, cools down；
26g sodium hydrogensulfites are added, reaction 2h is stirred at room temperature, filtered, white or faint yellow solid adds water and is configured to 20%
Solution, save backup.
Embodiment 7
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 7,
Synthesis technique flow process is as follows：
Specifically preparation method is：In 500mL there-necked flasks, 30mL deionized waters, ethylenediamine 15g, 10g NaOH are added,
After stirring and dissolving, after cooling；19g carbon disulfide is slowly added dropwise in ice-water bath, 1h is reacted, it is standby；In 500mL there-necked flasks
In, add 30.5g ethyl chloroacetates to be dissolved in 80mL ethanol, at ambient temperature, aforesaid liquid is instilled, time for adding is 1-
2h, solution yellowing, have precipitation generate, room temperature reaction 3h, add 26g sodium hydrogensulfites, react 3h, suction filtration, obtain it is white or
Faint yellow solid, add water the solution for being configured to 20%, saves backup.
Embodiment 8
The structural formula of many Ammonia dithiocarbonic acid sulfite derivatives is as follows, abbreviation compound 8,
Synthesis technique flow process is as follows：
Specifically preparation method is：In ice-water bath, in the there-necked flask of 500ml, sequentially add diethylenetriamine 10.3g, third
Olefin(e) acid 7.4g, NaOH 8g, 100mL deionized water, stir 0.5h, and it is molten that dropwise addition 7.6g carbon disulfide and 20mL DMF are formed
Liquid, insulated and stirred 2h, room temperature reaction 1h is subsequently adding sodium hydrogensulfite 31.2g, room temperature reaction 3h, becomes colorless or faint yellow
Clarification, clear solution, add water the solution for being configured to 20%, saves backup.
Based on same inventive concept, present invention also offers a kind of reproducibility-chain-transferring agent composition, including reality
Apply at least one in many Ammonia dithiocarbonic acid sulfite derivatives that a 1-8 is provided.This reproducibility-chain-transferring agent group
Compound can be applied in Raolical polymerizable as reducing agent-chain-transferring agent.
Based on same inventive concept, present invention also offers a kind of polycarboxylate water-reducer, is by filler and/or table
Face active material, and obtained in many Ammonia dithiocarbonic acid sulfite derivatives mixing synthesis of embodiment 1-8 offer.
Embodiment 9
Application of the compound that embodiment 1-8 is provided in the synthesis of cement water reducing agent and slump retaining agent
The preparation of water reducer
Prepare three mouthfuls of reaction bulbs of 8 500ml, 150g polymeric monomers (OXHP-702, isoamyl are added in each three mouthfuls of reaction bulb
Alkene end-blocking polyethylene glycol, molecular weight be 2400), deionized water 260g, stirring and dissolving is subsequently adding acrylic acid 18.48g, double
Oxygen water 1.5g, stirs 10min, the solution 8-40g that respectively prepared by dropwise addition above-described embodiment 1-8, stirring reaction 5-6h, and add water configuration
Into the water reducer mother liquor of 500g, save backup.
The preparation of slump retaining agent
Prepare three mouthfuls of reaction bulbs of 8 500ml, 370g polymeric monomers (OXAB-501, isobutyl are added in each three mouthfuls of reaction bulb
The polyethylene glycol of alkene end-blocking, molecular weight be 2700), deionized water 277g, stirring and dissolving is subsequently adding acrylic acid 24.2g, dioxygen
Water 2g, stirs 10min, and solution 8-40g prepared by above-described embodiment 1-8 is added dropwise respectively, and stirring reaction 5-6h adds water and is configured to
1000g solution, saves backup.
The 8 parts of water reducer mother liquors and 8 parts of slump retaining agents obtained to said method are numbered respectively, concrete as shown in table 1.
The number table of the water reducer mother liquor of table 1 and slump retaining agent
Net slurry experiment is carried out respectively to the water reducer mother liquor of above-mentioned 8 numberings, concrete preparation method is as follows：
Water intaking 87g, cement 300g, water reducer mother liquor 0.9g, in agitator for cement mortar (NJ-160B), stir slowly 120
Second, stop 15 seconds, stir soon 120 seconds, pour net slurry model into, model of taking away, after model of taking away, cement mortar will flow in the plane
One circular pattern, the concrete data of average diameter of the circular pattern surveyed after pulp flowage are as shown in table 2.
28 kinds of diminishing mother liquors of table starch experimental data only
As can be seen from Table 2, the net slurry of 8 kinds of water reducers test in the range of 270-310mm (national standard 180mm with
On), 8 kinds of water reducers are all a lot of beyond national standard, illustrate that 8 kinds of water reducers all have good net slurry water-reducing effect, diminishing effect
Fruit is strong and weak to be sequentially：JS-1 ＞ JS-3=JS-8 ＞ JS-4=JS-5 ＞ JS-2 ＞ JS-6 ＞ JS-7.
The slump retaining agent of water reducer mother liquor and 8 numberings to above-mentioned 8 numberings carries out respectively concrete flowability experiment, has
Preparation is as follows：
Cement 260kg, breeze 90kg, river sand 200kg, artificial sand 730kg, stone 930kg, water 165kg are taken, is configured in addition
Water reducer mother liquor 15g, the slump retaining agent 3g and 66g water of the offer of embodiment 9 provided with embodiment 9, in single horizontal axis forced action type coagulation
Stirring 2min in native mixer (HJW-30 types), in pouring slump cylinder into, model of taking away surveys the slump, the concrete data such as institute of table 3
Show.
The slump experimental data of the water reducer of table 3 and slump retaining agent
| Water reducer is numbered | JS-1 | JS-2 | JS-3 | JS-4 | JS-5 | JS-6 | JS-7 | JS-8 |
| Slump retaining agent is numbered | BT-1 | BT-2 | BT-3 | BT-4 | BT-5 | BT-6 | BT-7 | BT-8 |
| The slump (mm) | 270 | 260 | 265 | 270 | 260 | 250 | 250 | 255 |
| The slump (mm) after 1h | 268 | 255 | 255 | 265 | 258 | 247 | 246 | 253 |
As can be seen from Table 3, the concrete flowability of 8 kinds of water reducers tests the (national standard in the range of 250-270mm
180mm), the slump is not almost lost after 1 hour, and maximum loss is that JS-3 is 10mm (national standard 20mm), 8 kinds of water reducers
Also all exceed national standard in concrete use, illustrate that 8 kinds of water reducers all have good concrete water-reducing effect, coagulation
Native initial slump size order is：JS-1 ＞ JS-4 ＞ JS-3 ＞ JS-5=JS-2 ＞ JS-8 ＞ JS-6=JS-7, after 1 hour
Concrete slump loss size order is：JS-3 ＞ JS-4=JS-2 ＞ JS-7 ＞ JS-6 ＞ JS-1=JS-5=JS-8, mix
Solidifying soil using effect is fine or not to be sequentially：JS-1 ＞ JS-5 ＞ JS-8 ＞ JS-6 ＞ JS-7 ＞ JS-4 ＞ JS-2 ＞ JS-3.
Embodiment described above is only the preferred embodiment lifted to absolutely prove the present invention, and its protection domain is not limited
In this.Equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, in the protection of the present invention
Within the scope of, protection scope of the present invention is defined by claims.
Claims (10)
1. a kind of many Ammonia dithiocarbonic acid sulfite derivatives, it is characterised in that with structure shown in formula (I),
Wherein, R1And R2It is respectively and independently selected from hydrogen bond, substituted or unsubstituted alkylidene, substituted or unsubstituted unsaturated alkylene
Base, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted sub- aralkyl, substituted or unsubstituted sub- aryloxyalkyl group, take
Generation or unsubstituted aryl and substituted or unsubstituted heteroarylidene；
R3、R4、R5、R6And R7It is respectively and independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, replacement
Or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aralkenyl, substituted or unsubstituted virtue
Oxyalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl-carboxylic acid, replacement or
It is unsubstituted carboxylate alkyl, substituted or unsubstituted ester alkyl, substituted or unsubstituted amidoalkyl group, substituted or unsubstituted
Ketone alkyl and substituted or unsubstituted aldehyde alkyl；
L1 -、L2 -It is identical or different and represent arbitrary SO3 2-、HSO3 -、KSO3 -、NaSO3 -、NH4SO3 -Or R8-SO2 -, and wherein, R8
Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aralkyl and replacement or not
Substituted aryl；
N, m are respectively and independently selected from the arbitrary integer more than or equal to 0.
2. many Ammonia dithiocarbonic acid sulfite derivatives according to claim 1, it is characterised in that R1And R2Respectively
It is independently selected from following structure：
R3、R4、R5、R6And R7It is respectively and independently selected from following structure：
R8Selected from following structure：
-CH3 -CH2CH3
N, m are respectively and independently selected from 0,1,2 or 3.
3. many Ammonia dithiocarbonic acid sulfite derivatives according to claim 2, it is characterised in that many Ammonias
Dithiocarbonic acid sulfite derivative is selected from following structural formula：
4. a kind of preparation method of many Ammonia dithiocarbonic acid sulfite derivatives as claimed in claim 1, its feature exists
In comprising the steps：
S1：With compound shown in formula (II) as raw material, with halides, sulfuric ester, carbonic ester or containing formaldehyde or paraformaldehyde and
The solution of the compound of active hydrogen is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains formula (III) institute
Show compound；
S2：With compound shown in formula (III) as raw material, in the presence of diluent, enter with the reaction dissolvent containing carbon disulfide
Row reaction, reacts 0.5-2h within the temperature range of -10-100 DEG C, obtains compound shown in formula (IV)；
S3：In the presence of diluent, by compound shown in formula (IV) and the reaction dissolvent for including elemental sulfur or sulfur-containing compound
Reacted, 0.5-3h is reacted within the temperature range of 0-100 DEG C, obtained compound shown in formula (I)；
Wherein, in S1-S3, the diluent is respectively and independently selected from water, DMSO, alcohol, ether, ketone, halogenated alkane, ester, acid amides or alkane
Hydrocarbon；R in formula (II)-(IV)1、R2、R3、R4、R5、R6、R7Definition with n, m is with claim 1.
5. the preparation method of many Ammonia dithiocarbonic acid sulfite derivatives according to claim 4, it is characterised in that
S1's concretely comprises the following steps,
With compound shown in formula (II) as raw material, in the presence of diluent and alkali, carry out with halides, sulfuric ester or carbonic ester
Reaction, reacts 0.5-2h within the temperature range of -10-100 DEG C, obtains compound shown in formula (III)；
Or, with compound shown in formula (II) as raw material, in the presence of diluent, and containing formaldehyde or paraformaldehyde and vivaciously
The solution of the compound of hydrogen is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains formula (III) shownization
Compound；
The compound of the active hydrogen is the compound containing active methylene group, amino or imino group.
6. the preparation method of many Ammonia dithiocarbonic acid sulfite derivatives according to claim 4, it is characterised in that
S2's concretely comprises the following steps,
With compound shown in formula (III) as raw material, in the presence of diluent, with carbon disulfide and α, beta-unsaturated carbonyl is closed
Thing is reacted, and 0.5-2h is reacted within the temperature range of -10-100 DEG C, obtains compound shown in formula (IV)；
Or, with compound shown in formula (III) as raw material, in the presence of diluent and alkali, in -10-100 DEG C of temperature range
It is interior that 0.5-2h is reacted with carbon disulfide, then within the temperature range of 30-100 DEG C 0.5-2h is reacted with halides again, obtain formula
(IV) compound shown in；
Or, with compound shown in formula (III) as raw material, in the presence of diluent and alkali, in -10-100 DEG C of temperature range
It is interior to react 0.5-2h with carbon disulfide, then within the temperature range of 30-100 DEG C with thiol reactant 0.5-2h, obtain formula (IV) institute
Show compound；
Or, with compound shown in formula (III) as raw material, in the presence of diluent and alkali, in -10-100 DEG C of temperature range
Interior and carbon disulfide, chloroform and MIBK or aldehyde reaction 0.5-2h, obtain compound shown in formula (IV).
7. the preparation method of many Ammonia dithiocarbonic acid sulfite derivatives according to claim 4, it is characterised in that
S3's concretely comprises the following steps,
In the presence of diluent, compound shown in formula (IV) is reacted with sulfurous acid or sulphite, at 0-100 DEG C
Reaction 0.5-2h in temperature range, obtains compound shown in formula (I), and the sulphite is selected from sodium hydrogensulfite, bisulfite
Potassium, ammonium bisulfite, R8-SO2One kind in H；
Or, in the presence of diluent, compound shown in formula (IV) is reacted with sulphite and strong acid, at 0-100 DEG C
Within the temperature range of react 0.5-2h, if there is two-phase or multinomial reaction, carry out in the presence of a base, obtain formula (I) shownization
Compound, the one kind of the sulphite in sodium sulfite, sodium hydrogensulfite, potassium sulfite, ammonium sulfite, the strong acid choosing
One kind from sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, p-methyl benzenesulfonic acid；
Or, in the presence of diluent, by compound and SO shown in formula (IV)2Reacted, within the temperature range of 0-100 DEG C
Reaction 0.5-3h, obtains compound shown in formula (I)；
Or, in the presence of diluent, compound shown in formula (III) is reacted with elemental sulfur and oxygen, at 0-100 DEG C
Reaction 0.5-3h, is carried out in the presence of a base if necessary in temperature range, obtains compound shown in formula (I).
8. a kind of reproducibility-chain-transferring agent composition, it is characterised in that including many Ammonias described at least one claim 1
Dithiocarbonic acid sulfite derivative.
9. a kind of polycarboxylate water-reducer, it is characterised in that be and the claim 1 by filler and/or surface reactive material
Described many Ammonia dithiocarbonic acid sulfite derivatives mixing synthesis is obtained.
10. many Ammonia dithiocarbonic acid sulfite derivatives according to claim 1, it is characterised in that as reduction
Application of the agent-chain-transferring agent in Raolical polymerizable.
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| CN112794958A (en) * | 2021-01-21 | 2021-05-14 | 江苏奥莱特新材料股份有限公司 | Antibacterial polycarboxylate superplasticizer and preparation method thereof |
| CN114230788A (en) * | 2021-12-16 | 2022-03-25 | 中国石油大学(华东) | Novel multivalent polyanion oily sewage purifying agent and preparation method thereof |
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| CN103788253A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Chain transferring agent, its preparation method and its application |
| CN103819390A (en) * | 2013-11-25 | 2014-05-28 | 南京工业大学 | Synthesis method of RAFT chain transfer agent containing terminal hydroxyl |
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| WO2004037780A1 (en) * | 2002-10-23 | 2004-05-06 | Noveon Ip Holdings Corp. | S-(a, a’ -DISUBSTITUTED-a” -ACETIC ACID) SUBSTITUTED DITHIOCARBONATE DERIVATIVES FOR CONTROLLED RADICAL POLYMERIZATIONS, PROCESS AND POLYMERS MADE THEREFROM |
| CN103788253A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Chain transferring agent, its preparation method and its application |
| CN103819390A (en) * | 2013-11-25 | 2014-05-28 | 南京工业大学 | Synthesis method of RAFT chain transfer agent containing terminal hydroxyl |
Cited By (3)
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| CN112794958A (en) * | 2021-01-21 | 2021-05-14 | 江苏奥莱特新材料股份有限公司 | Antibacterial polycarboxylate superplasticizer and preparation method thereof |
| CN114230788A (en) * | 2021-12-16 | 2022-03-25 | 中国石油大学(华东) | Novel multivalent polyanion oily sewage purifying agent and preparation method thereof |
| CN114230788B (en) * | 2021-12-16 | 2023-08-29 | 中国石油大学(华东) | Multivalent polyanion oily sewage purifying agent and preparation method thereof |
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