CN117088746A - Preparation method of parylene series products and parylene series products - Google Patents

Preparation method of parylene series products and parylene series products Download PDF

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CN117088746A
CN117088746A CN202311092823.7A CN202311092823A CN117088746A CN 117088746 A CN117088746 A CN 117088746A CN 202311092823 A CN202311092823 A CN 202311092823A CN 117088746 A CN117088746 A CN 117088746A
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parylene
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ammonium salt
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孟俊秀
袁永坤
夏金成
杨庆锁
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Jining Yake New Material Technology Co ltd
Suzhou Yacoo Science Co ltd
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Jining Yake New Material Technology Co ltd
Suzhou Yacoo Science Co ltd
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    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C07C1/323—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a nitrogen atom
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    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/70—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a condensed ring system consisting of at least two, mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic ring, e.g. cyclophanes
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    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
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    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes

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Abstract

The invention providesA preparation method of a parylene series product comprises the following steps: s1, reacting a compound 1 and a compound 2 with N, N, N ', N' -tetramethyl diaminomethane to obtain a bisquaternary ammonium salt; s2, carrying out elimination reaction on the biquaternary ammonium salt and a catalyst under an alkaline condition to obtain a perrelin series product with a general formula shown in formula I;the structural formulas of the compound 1, the compound 2 and the double quaternary ammonium salt are respectively shown as formulas II, III and IV:

Description

Preparation method of parylene series products and parylene series products
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a preparation method of a parylene series product and the parylene series product.
Background
Parylene is a novel conforma coating material developed and applied in the 70 s of the last century, which is a polymer of para-xylene. The raw materials used for the parylene coating are cyclic paraxylene dimers, and the parylene powder can be divided into parylene N powder, parylene C powder, parylene D powder, parylene F powder, parylene HT powder and the like according to different chemical structures of the cyclic paraxylene dimers.
When the parylene powder is used, firstly, the different series of annular paraxylene dimer powder is placed in an evaporation furnace of coating equipment, solid raw materials are raised to be gaseous under the condition of vacuum 150 ℃, and then the gaseous raw materials are cracked into reactive monomers under the condition of 650-700 ℃ pyrolysis, and the reactive monomers can form linear polymers, namely transparent insulating coatings under the conditions of vacuum and temperature reduction, so that a complete high-quality protective coating is provided for elements, and the damage of acid, salt fog, mold and various corrosive gas parts is resisted. At present, the parylene coating technology is widely applied to the fields of aerospace, new energy automobiles, circuit boards, magnetic materials, sensors, silicone rubber, sealing elements, medical devices, precious cultural relics and the like.
The current chemical synthesis method of the parylene powder series mainly comprises a photolysis desulfurization method, a metal coupling method and a Huffman elimination method. The methods generally have the defects of expensive raw materials, low production efficiency, unfavorable mass production and the like.
MasaakiIwata et al uses a photolysis desulfurization method to desulfurize the cyclic disulfide under the irradiation of a high-pressure mercury lamp to prepare the perrelin N powder derivative, and the laboratory yield can be more than 50%. However, the raw material of the cyclic disulfide is required to be prepared at an ultra-dilute concentration, so that the production efficiency is extremely low, and the cyclic disulfide is not suitable for large-scale production (Bull. Chem. Soc. Jpn.,58, 2502-2514).
The american special coating system company discloses a method for preparing perrelin HT powder using a metal coupling method (WO 1998041490 A1), but generates sevoflurane impurities, which is not easily separated and purified.
In 2018 Shanghai long-noded pit viper Xin new material science and technology Co., ltd, reported a method for preparing perrelin F powder by zinc powder-mediated coupling reaction by taking 2,3,5, 6-tetrafluoro-p-dichlorobenzene as a raw material (CN 109232168A). The method can produce trimer and polymer, and has the advantages of difficult separation and purification and low yield.
When the method for preparing the parylene powder by utilizing the metal coupling is used, intermediate raw materials 2,3,5, 6-tetrafluoro p-dichloro methylbenzene (TFC) and 1, 4-bis (chlorodifluoromethyl) benzene (DCTF) with dibenzyl chloride structures are required to be used, the DCTF and the TFC can be prepared by a plurality of steps of harsh reactions, the production and manufacturing cost is high, and the industrial application of the technology is severely restricted.
The university of hong Kong Hak-FunChow et al discloses a method for preparing perrelin N powder by taking quaternary ammonium salt of p-methyl chlorobenzyl as raw material and carrying out Huffman elimination reaction, and the disadvantage is that the yield is only 10-20%.
In the research and development process of the synthetic process of the parylene powder series, scientists in all countries have found that the traditional quaternary ammonium salt Huffman elimination method is easy to generate the following linear polymerization reaction which is connected end to end and is shown in the specification, the main product becomes a polymer, and finally, the yield of the target product is extremely low, and the cost cannot be effectively controlled.
Therefore, there is a need in industry to develop a method for preparing parylene series products with simple process and low cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the preparation method which has simple process and can efficiently prepare the parylene series products, and the reaction yield is improved.
To achieve the purpose, the invention adopts the following technical scheme:
the first aim of the invention is to provide a preparation method of a parylene series product, which comprises the following steps:
s1, reacting a compound 1 and a compound 2 with N, N, N ', N' -tetramethyl diaminomethane to obtain a bisquaternary ammonium salt;
s2, carrying out elimination reaction on the biquaternary ammonium salt and the catalyst under alkaline conditions to obtain a perrelin series product with a general formula shown in formula I;
the structural formulas of the compound 1, the compound 2 and the double quaternary ammonium salt are respectively shown as formulas II, III and IV:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from the group consisting of hydrogen, halogen, amino, nitro, ester, aldehyde, methoxy, ethoxy, cyano, trifluoromethyl, ethynyl, vinyl, saturated alkyl; x, Y are each independently selected from fluorine, chlorine, bromine and iodine atoms.
Preferably, the saturated alkyl group has not more than 8 carbon atoms and includes at least one of a straight-chain or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The reaction flow of the invention is as follows:
specifically, in step S2, the elimination reaction forms a para-quinone dimethane intermediate of the general formula shown in formula v:
the intermediate state of the para-quinone dimethane is subjected to ring closure reaction to form a parylene series product with a general formula shown in a formula I, wherein m is at least one of 1,2, 3 and 4, and n is at least one of 5,6, 7 and 8.
Specifically, in the step S2, the catalyst is quaternary ammonium salt and/or quaternary phosphonium salt;
preferably, the catalyst comprises at least one of triphenyl methyl phosphonium bromide, tetraphenyl phosphonium bromide, tetrabutyl phosphonium hydroxide, benzyl triphenyl phosphonium chloride, cetyl tributyl phosphonium chloride, cetyl trihexyl phosphonium chloride, allyl triphenyl phosphonium chloride, amyl tributyl phosphonium chloride, benzyl tributyl phosphonium chloride, quaternary phosphonium salts such as propyl triphenyl phosphonium chloride, benzyl tributyl ammonium chloride, tetrabutyl ammonium bromide and tetrabutyl ammonium chloride.
Specifically, in step S1, compound 1 and compound 2 are each independently selected from at least one of the following structural formulas:
specifically, the parylene series products are selected from at least one of the following structural formulas:
specifically, the step S2 is performed under alkaline conditions, and the selected alkali is inorganic alkali;
preferably, the inorganic strong base is selected from NaOH, KOH, liOH, rbOH, csOH, grOH, ca (OH) 2 、Sr(OH) 2 、Ba(OH) 2 And Ra (OH) 2 One of them.
Specifically, in the step S1, the feeding molar ratio of the compound 1 to the compound 2 is 1:1, and the feeding ratio of the compound 1 to the N, N, N ', N' -tetramethyl diamino methane is (0.9-1): 1;
preferably, the temperature of the reaction is 10-50 ℃ and the time is 2-5h.
Specifically, in the step S2, the molar ratio of the total feed of the compound 1 and the compound 2 to the feed of the catalyst is 100 (0.1-1);
preferably, the temperature of the elimination reaction is 90-120 ℃ and the time is 18-30h.
Wherein, preferably, the feed ratio of the compound 1 and the N, N' -tetramethyl diaminomethane may be 0.9:1, 0.91:1, 0.92:1, 0.93:1, 0.94:1, 0.95:1, 0.96:1, 0.97:1, 0.98:1, 0.99:1, 1:1, or the like; more preferably, the temperature of the reaction may be 10 ℃, 15 ℃, 20 ℃,25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or the like, and the time may be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or the like, but not limited to the above-listed values, and other non-listed values within the above-listed value ranges are equally applicable.
Wherein, preferably, in step S2, the molar ratio of the total feed of the compound 1 and the compound 2 to the feed of the catalyst is 100:0.1, 100:0.2, 100:0.3, 100:0.4, 100:0.5, 100:0.6, 100:0.7, 100:0.8, 100:0.9 or 100:1, etc.; more preferably, the temperature of the elimination reaction may be 90 ℃, 95 ℃,100 ℃, 105 ℃,110 ℃, 115 ℃ or 120 ℃, and the time may be 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h, etc., but not limited to the above-listed values, and other non-listed values within the above-listed value range are equally applicable.
Specifically, the step S1 further includes a first solvent, where the first solvent is one selected from dichloromethane, methanol, ethanol, isopropanol, tetrahydrofuran, toluene, 1, 4-dioxane, and N, N-dimethylformamide; the step S2 also comprises a second solvent with a boiling point of more than 85 ℃, wherein the second solvent is at least two selected from dimethylbenzene, dimethyl sulfoxide, toluene, anisole, 1, 4-dioxane, mesitylene and chlorobenzene.
The second object of the present invention is to provide a parylene series product, which is prepared by the preparation method as described above, wherein the parylene series product is at least one selected from the following structural formulas:
compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a perrelin series product and the perrelin series product, which adopts various benzyl halides to react with N, N, N ', N' -tetramethyl diaminomethane to prepare biquaternary ammonium salt with a connecting arm; the biquaternary ammonium salt with the connecting arm eliminates the intramolecular degradation of the reaction in the presence of a catalyst and an alkaline condition, releases N, N, N ', N' -tetramethyl diamino methane and forms a p-quinone dimethane intermediate state at the same time, and because the pi-pi conjugation of two benzene rings of the p-quinone dimethane intermediate state is more prone to face-to-face ring closing reaction, the linear polymerization side reaction of the p-quinone dimethane intermediate state in an end-to-end connection mode can be effectively avoided, the reaction yield is greatly improved, and the p-rayleine N powder, C powder, D powder, F powder, halogen-free C powder and other p-rayleine series products can be efficiently prepared.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a parylene series product (parylene N powder) and the parylene series product, and the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 4- (chloromethyl) -1-methylbenzene (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into dichloromethane (500 ml), stirring at 20 ℃ for reaction for 5 hours, removing a solvent under reduced pressure after the reaction is detected to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-1 (0.45 mol) with the yield of 90%;
s2, an aqueous solution (669 g) containing 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl triphenyl phosphonium chloride (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-1 was added dropwise at 90℃under stirring, and the reaction was carried out for 24 hours at 90℃under an internal temperature. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 750ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 58.3 g of perrelin N powder (0.28 mol) with the yield of 70%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ3.09(s,8H,ArCH 2 ),6.50(s,8H,ArH)。
example 2
The present example provides a method for preparing a parylene series product (parylene N powder) and the parylene series product, which comprises the following steps, which are basically the same as those of example 1, except that in step S1, the benzyl halide selected is 4- (bromomethyl) -1-methylbenzene (1.1 mol), and the bis-quaternary ammonium salt JA-9 (0.46 mol) is obtained, the yield is 92%; in the S2 step, an aqueous solution (500 ml) containing 0.4mol of biquaternary ammonium salt JA-0 was added dropwise at 90℃to finally obtain 56.2 g of perrelin N powder (0.27 mol) in a yield of 68%.
Example 3
The embodiment provides a preparation method of a parylene series product (parylene M powder) and the parylene series product, wherein the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 1- (chloromethyl) -1,3, 4-trimethylbenzene (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into ethanol (500 ml), stirring at 40 ℃ for reaction for 4 hours, removing solvent under reduced pressure after the reaction is detected to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-5 (0.44 mol), and obtaining the yield of 88%;
s2, an aqueous solution (669 g) containing 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl tributyl ammonium chloride (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-5 was added dropwise at 100℃under stirring, and the reaction was carried out at 100℃for 20 hours while keeping the internal temperature at 100 ℃. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 750ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 58.2 g of parylene M powder (0.22 mol) with a yield of 55%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ2.24(s,12H,CH 3 )，2.73(m,4H,CH 2 )，3.16(m,4H,CH 2 )6.40(s,4H,ArH)。
example 4
The embodiment provides a preparation method of a parylene series product (parylene B powder) and the parylene series product, wherein the reaction equation is as follows:
the method comprises the following steps:
s1, adding N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into dichloromethane (300 ml), dropwise adding 100ml of dichloromethane solution containing 0.5mol of 4- (chloromethyl) -1-methylbenzene at 20 ℃, stirring and reacting for 3 hours, dropwise adding 100ml of dichloromethane solution containing 0.5mol of 2-bromo-4- (chloromethyl) -1-methylbenzene, stirring and reacting for 3 hours, removing solvent under reduced pressure to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-7 (0.42 mol), and obtaining the yield of 84%.
S2, adding 51% KOH (6.09 mol) aqueous solution (669 g), toluene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl triphenyl phosphonium chloride (0.004 mol) into the reaction flask; an aqueous solution (500 ml) containing 0.4mol of biquaternary ammonium salt JA-7 was added dropwise under stirring at 100℃for 4 hours, and the reaction was carried out at 100℃for 22 hours while keeping the internal temperature. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 500ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 54.6 g of perrelin B powder (0.19 mol) with a yield of 48%.
Nuclear magnetic characterization data are as follows： 1 HNMR(400MHz,CDCl 3 )：δ2.76-2.88(m,8H),6.93(dd,1H,ArH),7.06-7.11(m,5H,ArH),7.17(d,1H,ArH)。
Example 5
The embodiment provides a preparation method of a parylene series product (parylene C powder) and the parylene series product, wherein the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 3-chloro-4-methyl chlorobenzyl (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into toluene (500 ml), stirring at 50 ℃ for reaction for 4 hours, removing solvent under reduced pressure after detection reaction is finished to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-2 (0.46 mol) with the yield of 93%;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and tetrabutylammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-2 was added dropwise under stirring at 90℃for 4 hours, and the reaction was carried out at 90℃for 24 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 300ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ gave 63.8 g of perrelin C powder (0.23 mol) in 58% yield.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ2.80–2.84(m,2H,CH 2 ),2.95-2.99(m,2H,CH 2 ),3.13–3.20(m,2H,CH 2 )，3.51–3.57(m,2H,CH 2 )，6.31(d,2H,ArH)，6.47(d,2H,ArH)，7.06(dd,2H,ArH)。
example 6
The embodiment provides a preparation method of a parylene series product (parylene F powder) and the parylene series product, wherein the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 1,2,4, 5-tetrafluorobromobenzyl (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into dichloromethane (500 ml), stirring at 20 ℃ for reaction for 5 hours, removing a solvent under reduced pressure after the reaction is detected to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-4 (0.46 mol) with a yield of 92%;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and tetrabutylammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-4 was added dropwise under stirring at 110℃for 4 hours, and the reaction was carried out at 110℃for 18 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 350ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 101.4 g of parylene F powder (0.29 mol) with the yield of 73%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ3.30(s,8H,CH 2 )。
example 7
The embodiment provides a preparation method of a parylene series product (parylene D powder) and the parylene series product, wherein the reaction equation is as follows:
the method comprises the following steps:
s1, sequentially adding 2, 4-dichloro-4-methyl chlorobenzyl (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into toluene (500 ml), stirring at 50 ℃ for reaction for 5 hours, removing a solvent under reduced pressure after the reaction is detected to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-3 (0.45 mol) with the yield of 90%;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl tributyl ammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-3 was added dropwise with stirring at 90℃to react for 24 hours at 90℃after 4 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 300ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 96.9 g of perrelin D powder (0.28 mol) with a yield of 70%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ2.89(m,4H,ArCH 2 ),3.28(m,4H,ArCH 2 ),6.95(s,4H,ArH)。
example 8
The embodiment provides a preparation method of a parylene series product (parylene P-5 powder) and the parylene series product, wherein the reaction equation is as follows:
the method comprises the following steps:
s1, sequentially adding 2, 4-dibromo-4-methyl bromobenzyl (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into dichloromethane (500 ml), stirring at 20 ℃ for reaction for 5 hours, removing a solvent under reduced pressure after the reaction is detected to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-18 (0.47 mol), and obtaining 94% yield;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), toluene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl tributyl ammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-18 was added dropwise under stirring at 90℃for 4 hours, and the reaction was carried out at 90℃for 28 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 300ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 152 g of perrelin P-5 powder (0.29 mol) with a yield of 72.5%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ7.20(s,4H,Ar-H),3.29-3.18(m,4H,CH 2 ),3.04-2.93(m,4H,CH 2 )。
example 9
The embodiment provides a preparation method of a parylene series product (parylene E powder) and the parylene series product, wherein the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 2-ethyl-4-methyl bromobenzyl (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into tetrahydrofuran (500 ml), stirring at 40 ℃ for reaction for 3 hours, removing solvent under reduced pressure after the reaction is detected to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-12 (0.46 mol) with the yield of 92%;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl tributyl ammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-12 was added dropwise with stirring at 90℃for a period of 4 hours, and the reaction was carried out at 90℃for 30 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 300ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 66 g of perrelin E powder (0.25 mol) with the yield of 62.5%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 )：δ6.60-6.56(m,2H,ArH),6.31-6.29(m,2H,ArH),6.14(bs,2H,ArH),3.38-3.30(m,2H,CH 2 ),3.06-2.96(m,4H,CH 2 ),2.83-2.72(m,2H,CH 2 ),2.32-2.22(m,4H,CH 2 -CH 3 ),1.18-1.38(m,6H,CH 3 )。
example 10
The embodiment provides a preparation method of a parylene series product (parylene P-3 powder) and the parylene series product, wherein the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 3-bromo-4-methyl bromobenzyl (1.1 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into dichloromethane (500 ml), stirring at 20 ℃ for reaction for 5 hours, removing solvent under reduced pressure after detection reaction is finished to obtain a solid crude product, pulping methyl tertiary butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-6 (0.45 mol) with the yield of 91%;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and tetrabutylammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-6 was added dropwise under stirring at 90℃for 4 hours, and the reaction was carried out at 90℃for 24 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 300ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ to obtain 102.5 g of perrelin P-3 powder (0.28 mol) with a yield of 70%.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 ):δ＝7.17(d,2H),6.60(d,2H),6.47(dd,2H),3.36–3.25(m,2H),3.11–3.01(m,4H),2.93–2.83(m,2H)。
example 11
The embodiment provides a preparation method of a parylene series product (parylene P-8 powder) and the parylene series product, wherein the reaction equation is as follows:
the method specifically comprises the following steps:
s1, sequentially adding 3-trifluoromethyl-4-methyl bromobenzyl (0.5 mol) and N, N, N ', N' -tetramethyl diaminomethane (0.5 mol) into dichloromethane (500 ml), stirring at 20 ℃ for reaction for 3 hours, dropwise adding 100ml of dichloromethane solution containing 0.5mol of 4- (bromomethyl) -1-methylbenzene, stirring for reaction for 3 hours, ending, removing solvent under reduced pressure after detection reaction is ended to obtain a solid crude product, pulping methyl tert-butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-11 (0.45 mol), and obtaining the yield of 91%;
s2, an aqueous solution (669 g) of 51% KOH (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml) and tetrabutylammonium bromide (0.004 mol) were added to the reaction flask, and an aqueous solution (500 ml) containing 0.4mol of bis-quaternary ammonium salt JA-11 was added dropwise under stirring at 90℃for 4 hours, and the reaction was carried out at 90℃for 24 hours. Standing the reaction solution for layering, taking an upper xylene phase, washing with water, decolorizing with active carbon, distilling and concentrating filtrate to 300ml, and cooling for crystallization to obtain white crystals; vacuum drying at 50 ℃ gave 71.84 g of perrelin P-8 powder (0.26 mol) in 65% yield.
The nuclear magnetic characterization data are as follows: 1 HNMR(400MHz,CDCl 3 ):δ＝2.90–3.30(m,6H,CH 2 ),3.41–3.57(m,2H,CH 2 ),6.36–6.94(m,7H,ArH)。
the applicant states that the present invention describes a method for preparing a parylene series of products according to the present invention by means of the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be carried out in dependence on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. The preparation method of the parylene series products is characterized by comprising the following steps:
s1, reacting a compound 1 and a compound 2 with N, N, N ', N' -tetramethyl diaminomethane to obtain a bisquaternary ammonium salt;
s2, carrying out elimination reaction on the biquaternary ammonium salt and the catalyst under alkaline conditions to obtain a perrelin series product with a general formula shown in formula I;
the structural formulas of the compound 1, the compound 2 and the double quaternary ammonium salt are respectively shown as formulas II, III and IV:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from the group consisting of hydrogen, halogen, amino, nitro, ester, aldehyde, methoxy, ethoxy, cyano, trifluoromethyl, ethynyl, vinyl, saturated alkyl; x, Y are each independently selected from fluorine, chlorine, bromine and iodine atoms.
2. The method of claim 1, wherein in step S2, the elimination reaction is followed by formation of a para-quinone dimethane intermediate of the general formula v:
the intermediate state of the para-quinone dimethane is subjected to ring closure reaction to form a parylene series product with a general formula shown in a formula I, wherein m is at least one of 1,2, 3 and 4, and n is at least one of 5,6, 7 and 8.
3. The preparation method according to claim 1 or 2, wherein in the step S2, the catalyst is a quaternary ammonium salt and/or a quaternary phosphonium salt;
preferably, the catalyst comprises at least one of triphenyl methyl phosphonium bromide, tetraphenyl phosphonium bromide, tetrabutyl phosphonium hydroxide, benzyl triphenyl phosphonium chloride, cetyl tributyl phosphonium chloride, cetyl trihexyl phosphonium chloride, allyl triphenyl phosphonium chloride, amyl tributyl phosphonium chloride, benzyl tributyl phosphonium chloride, quaternary phosphonium salts such as propyl triphenyl phosphonium chloride, benzyl tributyl ammonium chloride, tetrabutyl ammonium bromide and tetrabutyl ammonium chloride.
4. A process according to any one of claims 1 to 3, wherein in step S1, compound 1 and compound 2 are each independently selected from at least one of the following structural formulae:
5. the method according to any one of claims 1 to 4, wherein the parylene series of products is selected from at least one of the following structural formulas:
6. the process according to any one of claims 1 to 5, wherein step S2 is carried out under alkaline conditions, the base selected being an inorganic strong base;
preferably, the inorganic strong base is selected from NaOH, KOH, liOH, rbOH, csOH, grOH, ca (OH) 2 、Sr(OH) 2 、Ba(OH) 2 And Ra (OH) 2 One of them.
7. The process according to any one of claims 1 to 6, wherein in step S1, the molar ratio of the compound 1 to the compound 2 is 1:1, and the feed ratio of the compound 1 to the N, N' -tetramethyldiaminomethane is (0.9-1): 1;
preferably, the temperature of the reaction is 10-50 ℃ and the time is 2-5h.
8. The process according to any one of claims 1 to 7, wherein in step S2, the molar ratio of the total charge of compound 1 and compound 2 to the charge of the catalyst is 100 (0.1 to 1);
preferably, the temperature of the elimination reaction is 90-120 ℃ and the time is 18-30h.
9. The method according to any one of claims 1 to 8, wherein step S1 further comprises a first solvent selected from the group consisting of dichloromethane, methanol, ethanol, isopropanol, tetrahydrofuran, toluene, 1, 4-dioxane, and N, N-dimethylformamide; the step S2 also comprises a second solvent with a boiling point of more than 85 ℃, wherein the second solvent is at least two selected from dimethylbenzene, dimethyl sulfoxide, toluene, anisole, 1, 4-dioxane, mesitylene and chlorobenzene.
10. A parylene series product, characterized in that the parylene series product is prepared by the preparation method according to any one of claims 1-9, wherein the parylene series product is selected from at least one of the following structural formulas:
CN202311092823.7A 2023-08-29 2023-08-29 Preparation method of parylene series products and parylene series products Pending CN117088746A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117776834A (en) * 2023-12-26 2024-03-29 深圳方寸达科技有限公司 Preparation method of parylene material monomer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117776834A (en) * 2023-12-26 2024-03-29 深圳方寸达科技有限公司 Preparation method of parylene material monomer

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