CN111848529A - Chain transfer agent with flame retardance and preparation method thereof - Google Patents
Chain transfer agent with flame retardance and preparation method thereof Download PDFInfo
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- CN111848529A CN111848529A CN202010637662.5A CN202010637662A CN111848529A CN 111848529 A CN111848529 A CN 111848529A CN 202010637662 A CN202010637662 A CN 202010637662A CN 111848529 A CN111848529 A CN 111848529A
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- chain transfer
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- benzylmercaptothiocarbonylpropanoic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
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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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
Abstract
The invention discloses a chain transfer agent with flame retardance and a preparation method thereof; the chain transfer agent with flame retardance is obtained by the steps of carrying out acyl chlorination reaction on 3-phenylmethylmercapto thiocarbonylpropionic acid and then carrying out condensation reaction on the 3-phenylmethylmercapto thiocarbonylpropionic acid and 1,3, 5-tri (2-hydroxyethyl) cyanuric acid; the synthesis process for preparing the chain transfer agent with flame retardance has the advantages of simple operation, no generation of toxic by-products, low synthesis raw material price, good flame retardance of the prepared chain transfer agent, and good wear resistance of the obtained chain transfer agent as a lubricating oil additive.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a chain transfer agent with flame retardance and a preparation method thereof.
Background
RAFT polymerization is based on the living propagation of a polymer chain by introducing a reversible chain transfer reaction through the cleavage of an S — C bond after the addition of a propagating radical to a double bond of a compound having an — S — C ═ S structure, and is called reversible addition-fragmentation chain transfer radical polymerization. The RAFT has the greatest advantage that the range of applicable monomers is wide, besides common monomers, protonic monomers such as acrylic acid, sodium p-vinylbenzene sulfonate, hydroxyethyl methacrylate, aminoethyl methacrylate and the like or acid and alkaline monomers can be smoothly polymerized, and the RAFT is very favorable for the polymerization reaction of alkene monomers containing special functional groups. Does not require the use of expensive reagents such as TEMPO and does not result in impurities or residual reagents such as transition metal ions in ATRP, bipyridine, etc. that are difficult to remove from the polymer product. The molecular weight distribution is narrow (generally below 1.3), the polymerization temperature is low, and the polymerization can be carried out at 60-70 ℃. The molecular design ability is strong, and the method can be used for preparing block, graft and star copolymers, mainly comprising dithioester and trithioester compounds.
Most of high polymer materials do not have flame retardance, such as polyethylene, polypropylene, polystyrene and the like, in order to enable the obtained polymer materials to have flame retardance, some flame retardants are usually added to enable the polymer materials to have flame retardance, on one hand, the added flame retardants may have poor compatibility and poor dispersibility with the polymer materials, and on the other hand, the problem that the flame retardants are easy to lose is solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the chain transfer agent with flame retardance, and the chain transfer agent with flame retardance has the advantages of simple synthesis process, no toxic by-product and low price of synthesis raw materials; the chain transfer agent has good flame retardant effect, and the obtained chain transfer agent has good wear resistance when being used as a lubricating oil additive.
The invention aims to provide a chain transfer agent with flame retardance.
Another object of the present invention is to provide a method for preparing the above chain transfer agent having flame retardancy.
The above purpose of the invention is realized by the following technical scheme:
a chain transfer agent having flame retardancy, which has the following structural formula (I):
wherein R is1、R2、R3Are respectively as
Or H.
The preparation method of the chain transfer agent with flame retardance comprises the following steps:
1. dissolving 3-benzylmercaptothiocarbonylpropanoic acid in dichloromethane, slowly dropwise adding thionyl chloride, reacting at 40 ℃ for 1.5h, reducing pressure to remove low-boiling-point residues, and purifying a crude product through a column to obtain the acylchlorinated 3-benzylmercaptothiocarbonylpropanoic acid.
Wherein the molar ratio of the 3-benzylmercaptothiocarbonylpropanoic acid to the thionyl chloride is 1: 1.2-1.5.
2. Adding 1,3, 5-tris (2-hydroxyethyl) cyanuric acid into a branched flask, adding dichloromethane, heating to 40 ℃, dropwise adding an acid-binding agent and a dichloromethane solution of acyl chloride 3-benzylmercaptothiocarbonylpropanoic acid, reacting for 3 hours at 40 ℃, reducing pressure to remove a solvent after the reaction is finished, and purifying a crude product through a column to obtain the flame-retardant chain transfer agent.
Wherein the molar ratio of the 1,3, 5-tri (2-hydroxyethyl) cyanuric acid to the acyl chloride 3-benzylmercaptothiocarbonylpropanoic acid to the acid-binding agent is 1:1:1 or 1:2:2 or 1:3: 3.
Preferably, the acid binding agent is pyridine, triethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, potassium carbonate, ammonium carbonate, sodium carbonate and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the synthesis process of the chain transfer agent with flame retardance, which is prepared by the invention, is simple to operate, does not generate toxic by-products, and the synthesis raw materials are low in price.
(2) The chain transfer agent with good flame retardance is prepared by the invention.
(3) In addition, the chain transfer agent with good flame retardance prepared by the invention can also be used as a lubricating oil additive, and during the friction process, the chain transfer agent can be decomposed and subjected to chemical reaction on the surface of a friction pair to generate a layer of organic sulfide compact protective film, so that the abrasion and wear of the surface of the steel ball friction pair are effectively reduced, and the anti-wear effect is achieved to a certain extent.
Drawings
FIG. 1 is a graph of the effect of having a mass fraction of a flame retardant chain transfer agent additive on the wear scar diameter.
Detailed Description
Example 1
Adding 3-phenylmethylmercaptothiocarbonylpropanoic acid (5mmol) into a 100mL flask, adding 30mL of dichloromethane, slowly adding thionyl chloride (7.5mmol) dropwise, reacting at 40 deg.C for 1.5h, removing low-boiling residue under reduced pressure, extracting with ethyl acetate/water, washing the combined organic phases with water, brine, and Na2SO4Drying, filtering and concentrating, using 10% EtOAc-n-hexane (v/v) as eluent, purifying by column chromatography to obtain the acylchlorinated 3-benzylmercaptothiocarbonylpropanoic acid in 85.4% yield.
Example 2
Adding 1,3, 5-tris (2-hydroxyethyl) cyanuric acid (5mmol) into a 100mL flask with a branch, adding 20mL dichloromethane, heating to 40 ℃, dropwise adding a dichloromethane solution of pyridine (5mmol) and acylchlorinated 3-benzylmercaptothiocarbonylpropanoic acid (5mmol), reacting at 40 ℃ for 3h, extracting with ethyl acetate/water after the reaction is finished, washing the combined organic phase with water and brine, and washing with Na2SO4Drying, filtration and concentration, 5% EtOAc-n-hexane (v/v) as eluent, column purification gave the chain transfer agent 1a with flame retardant properties in 88.1% yield.1H-NMR (400MHz,CDCl3),(ppm):7.31-7.25(m,5H,Ph),4.82(s,2H,OH),4.60(s,2H, CH2),4.51(t,2H,CH2),3.63(t,4H,CH2),3.45(t,2H,CH2),3.38(t,4H,CH2),3.27(t, 2H,CH2),2.89(t,2H,CH2).13C-NMR(100MHz,CDCl3),(ppm):226.31,171.45, 148.32,136.15,128.78,127.72,127.21,60.10,57.24,47.83,45.22,44.51,35.45, 30.45.
Example 3
Adding 1,3, 5-tris (2-hydroxyethyl) cyanuric acid (5mmol) into a 100mL flask with a branch, adding 20mL dichloromethane, heating to 40 ℃, dropwise adding a dichloromethane solution of pyridine (10mmol) and acylchlorinated 3-benzylmercaptothiocarbonylpropanoic acid (10mmol), reacting at 40 ℃ for 3h, extracting with ethyl acetate/water after the reaction is finished, washing the combined organic phase with water and brine, and washing with Na2SO4Drying, filtration and concentration, 5% EtOAc-n-hexane (v/v) as eluent, column purification, to obtain chain transfer agent 2a with flame retardancy in 82.4% yield.1H-NMR (400MHz,CDCl3),(ppm):7.38-7.26(m,10H,Ph),4.91(s,1H,OH),4.67(s,4H, CH2),4.55(t,4H,CH2),3.75(t,2H,CH2),3.53(t,4H,CH2),3.46(t,2H,CH2),3.32(t, 4H,CH2),2.91(t,4H,CH2).13C-NMR(100MHz,CDCl3),(ppm):227.24,172.14, 149.85,136.96,129.52,128.46,127.87,61.24,57.97,49.20,45.89,44.78,37.20, 32.04.
Example 4
Adding 1,3, 5-tris (2-hydroxyethyl) cyanuric acid (5mmol) into a 100mL flask with a branch, adding 20mL dichloromethane, heating to 40 ℃, dropwise adding a dichloromethane solution of pyridine (15mmol) and acylchlorinated 3-benzylmercaptothiocarbonylpropanoic acid (15mmol), reacting at 40 ℃ for 3h, extracting with ethyl acetate/water after the reaction is finished, washing the combined organic phase with water and brine, and washing with Na 2SO4Drying, filtration and concentration, 2% EtOAc-n-hexane (v/v) as eluent, column purification gave the chain transfer agent 3a with flame retardant properties in 79.3% yield.1H-NMR (400MHz,CDCl3),(ppm):7.40-7.24(m,15H,Ph),4.71(s,6H,CH2),4.67(t,6H, CH2),3.59(t,6H,CH2),3.42(t,6H,CH2),2.99(t,6H,CH2).13C-NMR(100MHz, CDCl3),(ppm):227.55,172.21,149.01,137.01,129.71,128.22,127.71,61.08, 46.30,45.61,36.52,31.41.
Example 5
Dissolving the flame-retardant chain transfer agent 1a (0.1mmol) synthesized in the example 2 and styrene (10mmol) in 30mL dioxane, adding azobisisobutyronitrile (0.01mmol), reacting for 12h under the protection of oil bath nitrogen at 70 ℃, putting into ice water bath to terminate the reaction, precipitating and washing the reaction product with diethyl ether, continuously precipitating and washing for 3 times, freeze-drying the purified product, drying to constant weight at 35 ℃ in vacuum to obtain polystyrene modified by the flame-retardant chain transfer agent, vacuum-drying the polystyrene modified by the flame-retardant chain transfer agent at 80 ℃ for 12h, adding 100 wt% of the polystyrene modified by the flame-retardant chain transfer agent into an open type heat mixer with 235 ℃ temperature, melting and roll-wrapping the polystyrene, mixing for 10min, uniformly taking out sheets, hot-pressing the sheets on a flat plate vulcanizing machine for 10min at 240 ℃, cold-pressing the sheets for 8min at room temperature, taking out the sheets, preparing various standard sample bars on a universal sampling machine, and (4) carrying out flame retardant performance.
Example 6
Dissolving the chain transfer agent 2a (0.1mmol) with flame retardance synthesized in the embodiment 3 and styrene (20mmol) in 30mL dioxane, adding azobisisobutyronitrile (0.01mmol), reacting for 12h under the protection of oil bath nitrogen at 70 ℃, putting the mixture into an ice water bath to terminate the reaction, precipitating and washing the reaction product with diethyl ether, continuously precipitating and washing for 3 times, freeze-drying the purified product, drying the product to constant weight at 35 ℃ in vacuum to obtain polystyrene modified by the flame retardant chain transfer agent, vacuum-drying the polystyrene modified by the flame retardant chain transfer agent at 80 ℃ for 12h, adding 100 wt% of polystyrene modified by the flame retardant chain transfer agent into an open type heat mill with 235 ℃ of double-roll temperature, melting and roll-wrapping the polystyrene, mixing for 10min, uniformly taking out sheets, hot-pressing the sheets on a flat plate vulcanizing machine for 10min at 240 ℃, cold-pressing the sheets for 8min at room temperature, taking out the sheets, preparing various standard sample bars on a universal sampling machine, and (4) carrying out flame retardant performance.
Example 7
Dissolving the flame-retardant chain transfer agent 3a (0.1mmol) synthesized in the example 4 and styrene (30mmol) in 30mL dioxane, adding azobisisobutyronitrile (0.01mmol), reacting for 12h under the protection of oil bath nitrogen at 70 ℃, putting into ice water bath to terminate the reaction, precipitating and washing the reaction product with diethyl ether, continuously precipitating and washing for 3 times, freeze-drying the purified product, drying to constant weight at 35 ℃ in vacuum to obtain polystyrene modified by the flame-retardant chain transfer agent, vacuum-drying the polystyrene modified by the flame-retardant chain transfer agent at 80 ℃ for 12h, adding 100 wt% of polystyrene modified by the flame-retardant chain transfer agent into an open type heat mill with 235 ℃ temperature, melting and roll-wrapping, mixing for 10min, uniformly discharging sheets, hot-pressing for 10min at 240 ℃ on a flat plate vulcanizing machine, cold-pressing for 8min at room temperature, discharging the sheets, preparing various standard sample bars on a universal sampling machine, and (4) carrying out flame retardant performance.
Comparative example 1
Before processing, polystyrene is dried in vacuum at 80 ℃ for 12h, 100 wt% of polystyrene is added on an open type heat mixing machine with the double-roll temperature of 235 ℃, after the polystyrene is melted and coated on a roll, the polystyrene is mixed for 10min and then evenly taken out, hot pressing is carried out on a flat vulcanizing machine at 240 ℃ for 10min, cold pressing is carried out at room temperature for 8min, and the polystyrene is taken out, so that various standard sample strips are prepared on a universal sampling machine for carrying out flame retardant property.
Limiting oxygen index test: the instrument is FTAII (1600) type limit oxygen index instrument of RS company in UK, test standard GB/T2406.2-2009, spline specification 100mm x 6mm x 3mm, and a group of 5-10, before test, the spline is placed in an environment with temperature 23 + -2 deg.C and humidity 50 + -5% and adjusted for more than 88 h.
UL-94 vertical burning test: the instrument is an CZF-5A horizontal vertical combustion tester of Jiangning analytical instruments factory for carrying out UL-94 vertical combustion test, the specification of the sample bar is 125mm multiplied by 13mm multiplied by 3.2mm, and the test standard is UL94ISBN 0-7629 and 0082-2. Before testing, the sample is put in an environment with the temperature of 23 +/-2 ℃ and the humidity of 50 +/-5% and is adjusted for more than 48 h.
The diameter of the abrasion marks: measuring by using a reading microscope (the precision is 0.01 mm); the base oil is 100N mineral oil; the experimental steel ball material is GCr15, and the diameter is 12.7 mm.
The flame retardant property of the polystyrene modified by the flame retardant chain transfer agent is evaluated by the limit oxygen index and the UL-94 vertical burning test, and the result is shown in Table 1.
According to the invention, the anti-wear performance of the flame retardant chain transfer agent as the lubricating oil base oil additive is evaluated by the influence of the mass fraction of the flame retardant chain transfer agent additive on the wear-scar diameter, and the result is shown in figure 1.
Table 1 shows the flame retardant properties of chain transfer agents having flame retardant properties.
| Sample (I) | Example 5 | Example 6 | Example 7 | Comparative example 1 |
| LOI(％) | 33.2 | 31.8 | 30.5 | 22.5 |
| UL-94 | V-0 | V-1 | V-1 | N.R |
As can be seen from Table 1, the chain transfer agent with flame retardance prepared by the invention can effectively improve the flame retardance of polystyrene. As can be seen from the comparison of the data of examples 5-7 and comparative example 1, the LOI of pure PS is only 22.5%, and when polystyrene is modified by a chain transfer agent with flame retardance, the LOI can reach 33.2%, so that the flame retardance of the polystyrene is effectively improved.
As shown in FIG. 1, the variation curve of the wear-resisting spot diameter along with the mass fraction of the additive with the flame-retardant chain transfer agent shows that the wear-resisting property of the base oil can be improved by the additive with the flame-retardant chain transfer agent as the steel ball wear-resisting spot diameter is reduced along with the increase of the mass fraction of the flame-retardant chain transfer agent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (6)
1. A chain transfer agent with flame retardance, which is characterized by having a structural formula shown as a formula (I):
Wherein R is1、R2、R3Are respectively as
Or H.
2. The method for preparing a chain transfer agent having flame retardancy according to claim 1, comprising the steps of:
(1) dissolving 3-benzylmercaptothiocarbonylpropanoic acid in dichloromethane, slowly dropwise adding thionyl chloride, reacting at 40 ℃ for 1.5h, reducing pressure to remove low-boiling-point residues, and purifying a crude product through a column to obtain the acylchlorinated 3-benzylmercaptothiocarbonylpropanoic acid.
(2) Adding 1,3, 5-tris (2-hydroxyethyl) cyanuric acid into a branched flask, adding dichloromethane, heating to 40 ℃, dropwise adding an acid-binding agent and a dichloromethane solution of acyl chloride 3-benzylmercaptothiocarbonylpropanoic acid, reacting for 3 hours at 40 ℃, reducing pressure to remove a solvent after the reaction is finished, and purifying a crude product through a column to obtain the flame-retardant chain transfer agent.
3. The method for preparing a chain transfer agent having flame retardancy as claimed in claim 2, wherein in the step (1), the molar ratio of the 3-benzylmercaptothiocarbonylpropanoic acid to thionyl chloride is 1:1.2 to 1.5.
4. The method for preparing a chain transfer agent with flame retardancy according to claim 2 or 3, wherein in the step (2), the molar ratio of the 1,3, 5-tris (2-hydroxyethyl) cyanuric acid to the acyl chloride 3-benzylmercaptothiocarbonylpropanoic acid and the acid-binding agent is 1:1:1 or 1:2:2 or 1:3: 3.
5. The method of preparing a chain transfer agent having flame retardancy according to claim 4, wherein in the step (2), the acid-binding agent is pyridine, triethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, potassium carbonate, ammonium carbonate, sodium carbonate, or the like.
6. Use of a chain transfer agent with flame retardancy according to claim 1 for the preparation of polyolefin materials.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112831055A (en) * | 2021-01-13 | 2021-05-25 | 邱元栏 | Degradable flame-retardant polystyrene block copolymer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328437A (en) * | 2011-02-15 | 2013-09-25 | 3M创新有限公司 | Addition-fragmentation agents |
| JP2014080481A (en) * | 2012-10-15 | 2014-05-08 | Fujifilm Corp | Sealing agent for semiconductor light-emitting device, sealing agent of semiconductor light-emitting device using the same and semiconductor light-emitting device |
| CN104761670A (en) * | 2015-03-19 | 2015-07-08 | 中科院广州化学有限公司 | Caged silsesquioxane-based star polymer, preparation method and application thereof |
| CN105503755A (en) * | 2016-01-10 | 2016-04-20 | 江苏博砚电子科技有限公司 | Six-membered-carbon-nitrogen-heteroccle-based acrylate resin for colored light resistance and preparing method thereof |
| CN110157041A (en) * | 2019-06-04 | 2019-08-23 | 北京理工大学 | It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application |
| CN110903422A (en) * | 2019-12-09 | 2020-03-24 | 万华化学集团股份有限公司 | Polymerization inhibitor and preparation method and application thereof |
-
2020
- 2020-07-05 CN CN202010637662.5A patent/CN111848529A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328437A (en) * | 2011-02-15 | 2013-09-25 | 3M创新有限公司 | Addition-fragmentation agents |
| JP2014080481A (en) * | 2012-10-15 | 2014-05-08 | Fujifilm Corp | Sealing agent for semiconductor light-emitting device, sealing agent of semiconductor light-emitting device using the same and semiconductor light-emitting device |
| CN104761670A (en) * | 2015-03-19 | 2015-07-08 | 中科院广州化学有限公司 | Caged silsesquioxane-based star polymer, preparation method and application thereof |
| CN105503755A (en) * | 2016-01-10 | 2016-04-20 | 江苏博砚电子科技有限公司 | Six-membered-carbon-nitrogen-heteroccle-based acrylate resin for colored light resistance and preparing method thereof |
| CN110157041A (en) * | 2019-06-04 | 2019-08-23 | 北京理工大学 | It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application |
| CN110903422A (en) * | 2019-12-09 | 2020-03-24 | 万华化学集团股份有限公司 | Polymerization inhibitor and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| AKANE SUZUKI ET AL.: "Synthesis of of Well-Defined Three-Armed Polystyrene Having Thiourethane–Isocyanurate as the Core Structure Derived from Trifunctional Five-Membered Cyclic Dithiocarbonate", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
| SHENGHONG YAO ET AL.: "Synthesis of a Conductive Copolymer and Phase Diagram of Its Suspension with Single-Walled Carbon Nanotubes by Microfluidic Technology", 《MACROMOLECULES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112831055A (en) * | 2021-01-13 | 2021-05-25 | 邱元栏 | Degradable flame-retardant polystyrene block copolymer and preparation method thereof |
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