CN109851695B - Chain transfer agent and preparation method and application thereof - Google Patents
Chain transfer agent and preparation method and application thereof Download PDFInfo
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- CN109851695B CN109851695B CN201910007098.6A CN201910007098A CN109851695B CN 109851695 B CN109851695 B CN 109851695B CN 201910007098 A CN201910007098 A CN 201910007098A CN 109851695 B CN109851695 B CN 109851695B
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- 239000012986 chain transfer agent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 26
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 23
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical group [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- -1 aluminium hydrogen sulphide Chemical compound 0.000 claims 1
- IXMXUFUUIFOUEW-UHFFFAOYSA-N barium;sulfane Chemical compound S.[Ba] IXMXUFUUIFOUEW-UHFFFAOYSA-N 0.000 claims 1
- LBVNUQQORDPZCR-UHFFFAOYSA-N calcium;sulfane Chemical compound S.[Ca] LBVNUQQORDPZCR-UHFFFAOYSA-N 0.000 claims 1
- UEAPXUBSQXHZRE-UHFFFAOYSA-N iron;sulfane Chemical compound S.[Fe] UEAPXUBSQXHZRE-UHFFFAOYSA-N 0.000 claims 1
- LXICEIPQWZZDRV-UHFFFAOYSA-N magnesium;sulfane Chemical compound [Mg].S LXICEIPQWZZDRV-UHFFFAOYSA-N 0.000 claims 1
- UNHKSXOTUHOTAB-UHFFFAOYSA-N sodium;sulfane Chemical compound [Na].S UNHKSXOTUHOTAB-UHFFFAOYSA-N 0.000 claims 1
- WFHQFPXTVRAZAL-UHFFFAOYSA-N sulfane;zinc Chemical compound S.[Zn] WFHQFPXTVRAZAL-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000012824 chemical production Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 6
- 239000002211 L-ascorbic acid Substances 0.000 description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 3
- 239000008030 superplasticizer Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AESSGCYWSBNEDM-UHFFFAOYSA-K aluminum sulfanide Chemical compound [Al+3].[SH-].[SH-].[SH-] AESSGCYWSBNEDM-UHFFFAOYSA-K 0.000 description 1
- IELPSGPHQCRVQW-UHFFFAOYSA-L barium(2+);sulfanide Chemical compound [SH-].[SH-].[Ba+2] IELPSGPHQCRVQW-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IOLHJDBDUPDVCP-UHFFFAOYSA-L iron(2+) sulfanide Chemical compound S[Fe]S IOLHJDBDUPDVCP-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OJXAKZMMWGESHM-UHFFFAOYSA-L magnesium sulfanide Chemical compound [Mg++].[SH-].[SH-] OJXAKZMMWGESHM-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- KEQKAMYELZXRRN-UHFFFAOYSA-L zinc;sulfanide Chemical compound [SH-].[SH-].[Zn+2] KEQKAMYELZXRRN-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a chain transfer agent, which comprises a compound shown as a general formula A: HS- (CH)2)2‑R1‑COO‑R2X, in the formula A, R1Is absent or selected from C1‑C10Alkylene and C6‑C10Arylene radical, R2Is selected from C1‑C10Alkylene and C6‑C10Arylene, X is selected from oxygen-containing groups, wherein C is1‑C10Alkylene and said C6‑C10Arylene being optionally selected from C1‑C6Alkyl, halogen, cyano and amino. The chain transfer agent provided by the invention has better chain transfer performance. The invention also provides a preparation method and application of the chain transfer agent. The raw materials selected by the invention are cheap and easily available, the production cost can be reduced, the reaction is carried out under the condition of normal temperature, the operation is simple, and the risk coefficient is small; meets the requirements of modern chemical production of green chemistry and green production.
Description
Technical Field
The invention belongs to the field of applied chemistry, and particularly relates to a chain transfer agent, and a preparation method and application thereof.
Background
Free radical polymerization has the advantages of wide monomer source, simple production process, various preparation methods, low industrial cost and the like, and becomes one of the most important reactions for synthesizing polymers. However, the conventional radical polymerization is a random process conforming to probability statistics, and the composition and structure of the synthetic polymer are difficult to control. Therefore, the synthesized chain transfer agent capable of adjusting the relative molecular mass of the polymer and controlling the relative molecular mass distribution of the polymer has good application prospect and practical value.
At present, β -mercaptopropionic acid is the most commonly used chain transfer agent in industry at home and abroad, and the patent CN1185432A introduces β -mercaptopropionic acid synthesized by the addition reaction of hydrogen sulfide and acrylic acid in the presence of a solid carrier containing basic functional groups, and because the reaction needs to be carried out under high pressure, the requirement on equipment is high, and because virulent hydrogen sulfide gas needs to be introduced for a long time, the operation risk coefficient is large, and industrialization is difficult to realize.
Patent CN100491346C describes a method for synthesizing β -mercaptopropionic acid from sodium hydroxide, sodium hydrosulfide, sodium polysulfide, acrylonitrile, hydrochloric acid, and zinc powder as raw materials, the sodium polysulfide catalyst used in the method needs to be prepared at present due to poor stability, and a large amount of thioether byproduct is generated in the production process due to the unstable factor of the sodium polysulfide, so that the solid waste pollution is serious.
Patent CN102229550A describes a method for synthesizing β -mercaptopropionic acid by using thiourea and acrylic acid as main raw materials, wherein the price of thiourea is high, and a plurality of byproducts such as sodium chloride, ammonia gas and barium sulfate exist in the reaction process, so that the recycling cost is high, and the product is difficult to be marketed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel chain transfer agent, a preparation method and application thereof aiming at the defects of the prior art. The chain transfer agent provided by the invention has better chain transfer performance. The raw materials selected by the preparation method are cheap and easily available, the production cost can be reduced, the reaction is carried out under the normal temperature condition, the operation is simple, and the risk coefficient is small; meets the modern chemical production requirements of green chemistry and green production.
To this end, in one aspect, the present invention provides a chain transfer agent comprising a compound of formula a:
HS-(CH2)2-R1-COO-R2-X
in the general formula A, R1Is absent or selected from C1-C10Alkylene and C6-C10Arylene radical, R2Is selected from C1-C10Alkylene and C6-C10Arylene, X is selected from oxygen-containing groups, wherein C is1-C10Alkylene and said C6-C10Arylene being optionally selected from C1-C6Alkyl, halogen, cyano and amino.
The inventors of the present application have found, in their studies, that a mercapto group located at one end of the above general formula a can function to transfer a radical during radical polymerization, while an oxygen-containing group contained in the above general formula a has a stabilizing function on the radical, and that an oxygen-containing group located at the other end of the above general formula a can improve the dispersing performance of the chain transfer agent. The three groups are matched with each other, so that the chain transfer agent disclosed by the application is beneficial to obtaining more excellent slump retaining performance in a free radical polymerization process.
According to some preferred embodiments of the invention, R1Is absent or selected from C1-C8Alkylene and C6-C10An arylene group; and/or R2Is selected from C1-C8Alkylene and C6-C10An arylene group; and/or X is selected from the group consisting of hydroxyl, carboxyl and aldehyde groups, preferably hydroxyl.
According to some preferred embodiments of the invention, R1Is absent or selected from C1-C6Alkylene and C6-C10An arylene group; and/or R2Is selected from C1-C6Alkylene and C6-C10An arylene group.
According to some preferred embodiments of the invention, R1Is absent or selected from C1-C6An alkylene group; and/or R2Is selected from C1-C6An alkylene group.
According to some preferred embodiments of the invention, the compound is represented by formula a 1: HS- (CH)2)m-COO-(CH2)n-OH, wherein m is an integer from 2 to 5 and n is an integer from 1 to 5, preferably said compound is HSCH2CH2COOCH2CH2OH。
According to the invention, when R1Is absent, R2Is C2When alkylene and X is hydroxy, i.e. the compound is HSCH2CH2COOCH2CH2When OH is used, the compound has higher conversion rate and better slump retaining performance.
Another aspect of the present invention provides a method for preparing the chain transfer agent, comprising the steps of:
reacting a compound represented by the general formula B: CH (CH)2＝CH-R1-COO-R2-X is added, preferably dropwise, to the aqueous solution containing the hydrogen sulfide, so as to react with the hydrogen sulfide to form the compound of the formula A,
in the general formula B, R1、R2And X has the meaning defined in formula A.
According to the invention, the compound of the formula B is preferably hydroxyethyl acrylate.
According to some preferred embodiments of the invention, the molar ratio of hydrogen sulfide to compound of formula B is (0.8-1.85):1, preferably (1-1.8): 1.
According to some preferred embodiments of the invention, the hydrosulfide is selected from one or more of ammonium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, calcium hydrosulfide, magnesium hydrosulfide, aluminum hydrosulfide, iron hydrosulfide, zinc hydrosulfide, barium hydrosulfide and ferrous hydrosulfide, preferably sodium hydrosulfide.
According to some preferred embodiments of the present invention, the compound of formula B is dissolved in a solvent, preferably water, and added to the aqueous solution containing the sulfur hydride.
According to some preferred embodiments of the invention, the reaction is carried out at 15 ℃ to 45 ℃; preferably, the reaction time is 1 to 3 hours, preferably 1.5 to 2.5 hours.
According to some preferred embodiments of the present invention, the concentration of hydrogen sulfide in the aqueous solution containing hydrogen sulfide is 20% to 40%, preferably 27% to 33%.
According to the invention, the compound of the formula B is added, preferably dropwise, to the aqueous solution containing the sulfur hydride with stirring, preferably stirring is continued for 1 to 3h, preferably 1.5 to 2.5h, after the addition or dropwise addition has been completed, and/or the stirring speed is 110-150 r/min.
In a further aspect the invention provides the use of a chain transfer agent as described or prepared according to the method in a free radical polymerisation reaction.
Compared with the prior art, the invention has the following advantages: the chain transfer agent provided by the invention can obtain higher conversion rate and better slump retaining performance. The raw materials selected by the reaction are cheap and easily available, so that the production cost can be reduced; the reaction is carried out under the condition of normal temperature, the operation is simple in the reaction process, the danger coefficient is small, and a good effect is achieved; the method has the advantages that no waste liquid is generated after the reaction, the raw materials and the products are nontoxic, the requirements of modern chemical production of green chemistry and green production are met, and the method has good technical effect and good social and economic benefits.
Drawings
FIG. 1 shows a schematic of the net slurry flow of the reaction products obtained in Experimental example 2 and comparative example 1.
FIG. 2 shows Gel Permeation Chromatography (GPC) of the reaction product obtained in Experimental example 2.
FIG. 3 shows GPC of the reaction product obtained in comparative example 1.
FIG. 4 shows GPC 702 on monomer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention easier to understand, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. The specific experimental methods not mentioned in the following examples are generally carried out according to conventional experimental methods.
In the present invention, the raw materials used in the examples are commercially available unless otherwise specified.
In the present invention, sodium hydrosulfide is purchased from Shanghai Michelin Biotechnology Ltd.
In the present invention, hydroxyethyl acrylate is purchased from Shanghai Huayi group construction, Inc.
In the present invention, the terminal alkylene polyoxyethylene polyoxypropylene ether (702) is available from Liaoning Oakc chemical Co.
In the invention, the normal temperature condition refers to 20 +/-5 ℃.
In the present invention, the net slurry fluidity of the reaction products in Experimental example 2 and comparative example 1 was measured according to GB 8077-2000.
The GPC of the reaction products in Experimental example 2 and comparative example 1 was measured using a PL-GPC50 instrument.
Example 1
At normal temperature, 7.2g of sodium hydrosulfide and 20g of water are added into a 100ml beaker and uniformly mixed, the sodium hydrosulfide is dissolved by stirring at 120r/min on a magnetic stirrer, and then 9.14g of hydroxyethyl acrylate is dropwise added into the beaker by a peristaltic pump for addition reaction, wherein the dropwise adding time is 10 min. And after the dropwise addition is finished, continuously stirring for 2 hours on a magnetic stirrer, and filtering to obtain the chain transfer agent A.
Example 2
At normal temperature, 7.2g of sodium hydrosulfide and 18.57g of water were added to a 100ml beaker and mixed uniformly, the sodium hydrosulfide was dissolved by stirring at 120r/min on a magnetic stirrer, and then 12.19g of hydroxyethyl acrylate was added dropwise to the beaker by a peristaltic pump for an addition reaction for 10 min. After the completion of the dropwise addition, the mixture was stirred for 2 hours on a magnetic stirrer and filtered to obtain a chain transfer agent B.
Example 3
At normal temperature, 7.2g of sodium hydrosulfide and 23.33g of water were added to a 100ml beaker and mixed uniformly, the sodium hydrosulfide was dissolved by stirring at 120r/min on a magnetic stirrer, and then 12.19g of hydroxyethyl acrylate was added dropwise to the beaker by a peristaltic pump for an addition reaction for 10 min. And stirring for 2 hours on a magnetic stirrer after the dropwise addition is finished, and filtering to obtain the chain transfer agent C.
Example 4
At normal temperature, 7.2g of sodium hydrosulfide and 18.57g of water were added to a 100ml beaker and mixed uniformly, the sodium hydrosulfide was dissolved by stirring at 120r/min on a magnetic stirrer, and then 12.19g of hydroxyethyl acrylate was added dropwise to the beaker by a peristaltic pump while 10g of water was added dropwise for an addition reaction for 10 min. And stirring for 2 hours on a magnetic stirrer after the dropwise addition is completed, and filtering to obtain a chain transfer agent D.
Example 5
At normal temperature, 7.2g of sodium hydrosulfide and 18.57g of water were added to a 100ml beaker and mixed uniformly, the sodium hydrosulfide was dissolved by stirring at 120r/min on a magnetic stirrer, and then 10.45g of hydroxyethyl acrylate was added dropwise to the beaker by a peristaltic pump for an addition reaction for 10 min. Then, the mixture was stirred for 2 hours on a magnetic stirrer and filtered to obtain a chain transfer agent E.
Experimental example 1
400g of terminal alkylene polyoxyethylene polyoxypropylene ether (702) and 300g of deionized water were mixed well and charged into a 1000ml three-necked flask. The temperature is normal temperature, the rotating speed of a stirring paddle is 120r/min, 2g of hydrogen peroxide is taken as an initiator, 36.5g of acrylic acid (the mass fraction is 70%), 1.96g of L-ascorbic acid and 43.5g of water are taken as a material A, 13g of chain transfer agent A and 71.54g of water are taken as a material B, and the materials are respectively dripped into a three-neck flask for 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour, after which the reaction was terminated by adding 237.775g of water. The solid content of the reaction product was 40%.
Experimental example 2
400g of terminal alkylene polyoxyethylene polyoxypropylene ether (702) and 300g of deionized water were mixed well and charged into a 1000ml three-necked flask. The temperature is normal temperature, the rotating speed of a stirring paddle is 120r/min, 2g of hydrogen peroxide is taken as an initiator, 36.5g of acrylic acid (the mass fraction is 70%), 1.96g of L-ascorbic acid and 43.5g of water are taken as a material A, 13g of chain transfer agent B and 71.54g of water are taken as a material B, and the materials are respectively dripped into a three-neck flask for 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour, after which the reaction was terminated by adding 237.775g of water. The solid content of the reaction product was 40%.
Experimental example 3
400g of terminal alkylene polyoxyethylene polyoxypropylene ether (702) and 300g of deionized water were mixed well and charged into a 1000ml three-necked flask. The temperature is normal temperature, the rotating speed of a stirring paddle is 120r/min, 2g of hydrogen peroxide is taken as an initiator, 36.5g of acrylic acid (the mass fraction is 70%), 1.96g of L-ascorbic acid and 43.5g of water are taken as a material A, 13g of chain transfer agent C and 71.54g of water are taken as a material B, and the materials are respectively dripped into a three-neck flask for 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour, after which the reaction was terminated by adding 237.775g of water. The solid content of the reaction product was 40%.
Experimental example 4
400g of terminal alkylene polyoxyethylene polyoxypropylene ether (702) and 300g of deionized water were mixed well and charged into a 1000ml three-necked flask. The temperature is normal temperature, the rotating speed of a stirring paddle is 120r/min, 2g of hydrogen peroxide is taken as an initiator, 36.5g of acrylic acid (the mass fraction is 70%), 1.96g of L-ascorbic acid and 43.5g of water are taken as a material A, 14.52g of chain transfer agent D and 71.54g of water are taken as a material B, and the materials are respectively dripped into a three-neck flask for 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour, after which the reaction was terminated by adding 240.055g of water. The solid content of the reaction product was 40%.
Experimental example 5
400g of terminal alkylene polyoxyethylene polyoxypropylene ether (702) and 300g of deionized water were mixed well and charged into a 1000ml three-necked flask. The temperature is normal temperature, the rotating speed of a stirring paddle is 120r/min, 2g of hydrogen peroxide is taken as an initiator, 36.5g of acrylic acid (the mass fraction is 70%), 1.96g of L-ascorbic acid and 43.5g of water are taken as a material A, 13g of chain transfer agent E and 71.54g of water are taken as a material B, and the materials are respectively dripped into a three-neck flask for 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour, after which the reaction was terminated by adding 237.775g of water. The solid content of the reaction product was 40%.
Comparative example 1
The polycarboxylate water reducer was prepared according to the method of the above experimental example 2, except that the chain transfer agent B was replaced by 3-mercaptopropionic acid, which is an industrial product obtained from shanghai alatin biochemical science and technology ltd, and 224.034g of water was supplemented after the reaction was completed, thereby ensuring that the solid content of the reaction product was 40%.
As can be seen from FIG. 1, compared with the polycarboxylic acid water reducing agent PC-1 synthesized by industrially producing 3-mercaptopropionic acid, the polycarboxylic acid water reducing agent PC-2 synthesized by using the chain transfer agent B has slightly larger initial fluidity and better slump retaining performance with the time.
As can be seen from FIGS. 2 and 3, the polycarboxylate water reducer PC-1 synthesized by industrial production of 3-mercaptopropionic acid and the polycarboxylate water reducer PC-2 synthesized by using the chain transfer agent B of the present application have narrow molecular weight distribution in GPC and both show "double peaks", that is, both high molecular weight and low molecular weight polymers exist, and the reference finds that in other high molecular fields such as plastics: the low molecular weight portion can increase the flowability of the polymeric material at processing temperatures; the high molecular weight fraction improves the performance of the material at the application temperature. But the second peak of the polycarboxylate superplasticizer PC-2 synthesized by using the chain transfer agent B is higher in strength than that of the polycarboxylate superplasticizer PC-1 synthesized by industrial 3-mercaptopropionic acid, and the polycarboxylate superplasticizer synthesized by using the chain transfer agent B is further verified to have better slump retaining performance.
As can be seen from FIGS. 2, 3 and 4, monomers are substantially absent from PC-1 and PC-2.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (19)
1. A chain transfer agent comprising a compound of formula a:
HS-(CH2)2-R1-COO-R2-X
in the general formula A, R1Is absent or selected from C1-C10Alkylene and C6-C10Arylene radical, R2Is selected from C1-C10Alkylene and C6-C10Arylene, X is selected from oxygen-containing groups, wherein C is1-C10Alkylene and said C6-C10Arylene being optionally selected from C1-C6Alkyl, halogen, cyano and amino.
2. The chain transfer agent of claim 1, wherein R is1Is absent or selected from C1-C8Alkylene and C6-C10An arylene group; and/or R2Is selected from C1-C8Alkylene and C6-C10An arylene group; and/or X is selected from hydroxyl, carboxyl and aldehyde groups.
3. The chain transfer agent of claim 2, wherein X is hydroxyl.
4. The chain transfer agent of any one of claims 1-3, wherein the compound is of formula A1: HS- (CH)2)m-COO-(CH2)n-OH, wherein m is an integer from 2 to 5 and n is an integer from 1 to 5.
5. The chain transfer agent of claim 4, wherein the compound is HSCH2CH2COOCH2CH2OH。
6. A method for preparing the chain transfer agent according to any one of claims 1 to 5, comprising the steps of:
reacting a compound represented by the general formula B: CH (CH)2＝CH-R1-COO-R2-X is added to an aqueous solution containing a hydrogen sulfide to react with the hydrogen sulfide to form a compound of formula A,
in the general formula B, R1、R2And X has the meaning defined in formula A.
7. The method of claim 6, wherein the compound of formula B: CH (CH)2＝CH-R1-COO-R2-X is added dropwise to an aqueous solution containing a sulfur hydride to react with the sulfur hydride to produce a compound represented by the general formula A.
8. The process according to claim 6 or 7, wherein the molar ratio of hydrogen sulfide to the compound of the formula B is (0.8-1.85): 1.
9. The process according to claim 8, wherein the molar ratio of hydrogensulfide to compound of formula B is (1-1.8): 1.
10. A process according to claim 6 or 7, wherein the hydrogen sulphide is selected from one or more of ammonium hydrogen sulphide, sodium hydrogen sulphide, potassium hydrogen sulphide, calcium hydrogen sulphide, magnesium hydrogen sulphide, aluminium hydrogen sulphide, iron hydrogen sulphide, zinc hydrogen sulphide, barium hydrogen sulphide and ferrous hydrogen sulphide.
11. The method of claim 10, wherein the hydrosulfide is sodium hydrosulfide.
12. The method according to claim 6 or 7, characterized in that the compound of formula B is dissolved in a solvent and added to the aqueous solution containing the sulfur hydride.
13. The method as set forth in claim 12, wherein said compound of formula B is dissolved in water and added to said aqueous solution containing the sulfur hydride.
14. The process according to claim 6 or 7, characterized in that the reaction is carried out at 15-45 ℃.
15. The method of claim 14, wherein the reaction time is 1-3 hours.
16. The process according to claim 15, wherein the reaction time is 1.5 to 2.5 hours.
17. The method according to claim 6 or 7, wherein the concentration of the hydrogen sulfide in the aqueous solution containing hydrogen sulfide is 20% to 40%.
18. The method as claimed in claim 15, wherein the concentration of hydrogen sulfide in the aqueous solution containing hydrogen sulfide is 27% to 33%.
19. Use of a chain transfer agent according to any one of claims 1 to 5 or prepared by a process according to any one of claims 6 to 18 in a free radical polymerisation reaction.
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