CN114751829A - Polymerizable nonionic surfactant containing adamantane structure and preparation method thereof - Google Patents
Polymerizable nonionic surfactant containing adamantane structure and preparation method thereof Download PDFInfo
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- CN114751829A CN114751829A CN202110036781.XA CN202110036781A CN114751829A CN 114751829 A CN114751829 A CN 114751829A CN 202110036781 A CN202110036781 A CN 202110036781A CN 114751829 A CN114751829 A CN 114751829A
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- nonionic surfactant
- adamantane
- polyethylene glycol
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002736 nonionic surfactant Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 27
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- -1 adamantane acyl chloride Chemical class 0.000 claims abstract description 12
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 3
- MIBQYWIOHFTKHD-UHFFFAOYSA-N adamantane-1-carbonyl chloride Chemical group C1C(C2)CC3CC2CC1(C(=O)Cl)C3 MIBQYWIOHFTKHD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- AOTQGWFNFTVXNQ-UHFFFAOYSA-N 2-(1-adamantyl)acetic acid Chemical compound C1C(C2)CC3CC2CC1(CC(=O)O)C3 AOTQGWFNFTVXNQ-UHFFFAOYSA-N 0.000 claims description 2
- HLQSEJBREPQBRW-UHFFFAOYSA-N 2-(1-adamantyl)acetyl chloride Chemical compound C1C(C2)CC3CC2CC1(CC(=O)Cl)C3 HLQSEJBREPQBRW-UHFFFAOYSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000003814 drug Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- SOWKRIJYYAXRGM-UHFFFAOYSA-N adamantane;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.C1C(C2)CC3CC1CC2C3 SOWKRIJYYAXRGM-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CWNOIUTVJRWADX-UHFFFAOYSA-N 1,3-dimethyladamantane Chemical compound C1C(C2)CC3CC1(C)CC2(C)C3 CWNOIUTVJRWADX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- LYJCLXIGWFHNIF-UHFFFAOYSA-N C1(=C2C(=CC=C1)B2)C2C1CC3CC(CC2C3)C1 Chemical compound C1(=C2C(=CC=C1)B2)C2C1CC3CC(CC2C3)C1 LYJCLXIGWFHNIF-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- CKBZJTAMRPPVSR-UHFFFAOYSA-N adamantane-1-carboxamide Chemical class C1C(C2)CC3CC2CC1(C(=O)N)C3 CKBZJTAMRPPVSR-UHFFFAOYSA-N 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 229940052761 dopaminergic adamantane derivative Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
The invention provides a polymerizable nonionic surfactant containing a adamantane structure and a preparation method thereof. The polymerizable nonionic surfactant is synthesized by carrying out esterification reaction on adamantane acyl chloride and polyethylene glycol acrylate in an organic solvent under the condition that organic base is used as an acid-binding agent; or the compound is obtained by esterification reaction of adamantane carboxylic acid and polyethylene glycol acrylate in an organic solvent by using a catalyst. The end group of the reacted product molecule contains polymerizable double bond structure, which can be used as hydrophobic monomer in polymerization reaction, and the product has surface activity.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a polymerizable nonionic surfactant containing a adamantane structure and a preparation method thereof.
Background
Adamantane is a highly symmetrical and very stable compound, and the special cage-shaped structure of the compound arouses great interest in the chemical boundary and promotes the birth of the chemical structure of the cage-shaped compound. Until the discovery later, the adamantane derivative has antiviral activity and gets more remarkable attention from the pharmaceutical field, and a plurality of documents and patents report the application prospect of the adamantane derivative as a medicament; systematic studies of adamantane around the chemical world have formed an independent discipline: adamantane chemistry. In the usual patents and literature, attention is being given to the use of adamantane in pharmaceuticals and in new materials. CN105829284A discloses a method for synthesizing adamantane carboxamide compounds, which can be applied to the aspects of medicines and cosmetics; CN 108117567 discloses adamantane tetrakis (4-boranophenyl) adamantane, which can be applied as covalent organic framework material with tetrahedral structure; CN106008135 discloses a preparation method of 1, 3-dimethyl adamantane which can be used as an intermediate drug for treating senile dementia. Although there are many kinds of adamantane-based derivatives, most of them are currently limited to drugs and new materials, and more adamantane derivatives are yet to be developed in order to meet the various application requirements. In recent years, researchers have been studying the introduction of adamantane structure-containing substances into polymers to improve the hydrophobic properties of polymers to meet the application requirements under different scenes [ Loebel C, Rodell C B, Chen M H, et al, shear-linking and self-crosslinking hydrogels as injectable therapeutics and for 3D-printing [ J ] Nature Protocols,2017,12(8): 1521-.
As the development of oil and gas fields is carried out, the application of the hydrophobically associating polyacrylamide in the aspects of fracture acidizing, three-time oil extraction and the like is greatly developed, and the key point of producing the hydrophobically associating polyacrylamide is to use a proper hydrophobic monomer. Based on the fact that the prior art does not relate to the synthesis of hydrophobic associative polymers with adamantane structures as hydrophobic monomers, it is necessary to explore the application of adamantane structures in hydrophobic monomers.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to provide a polymerizable nonionic surfactant having a adamantane structure, which is a novel monomer having good water solubility and can be used as a hydrophobic monomer for synthesizing a hydrophobically associating polymer.
Another object of the present invention is to provide a process for producing the above polymerizable nonionic surfactant.
In order to achieve the above object, in one aspect, the present invention provides a polymerizable nonionic surfactant containing a adamantane structure, wherein the polymerizable nonionic surfactant has the following structural formula:
wherein R1 is a methyl group or a hydrogen atom; and R2 is alkyl containing adamantane stereo structure.
According to some embodiments of the invention, R2 is 1-methyladamantyl or 1-ethyladamantyl.
According to some embodiments of the invention, the number n of polyoxyethylene chain repeating units is from 8 to 36, preferably from 8 to 20, more preferably from 8 to 12.
According to some embodiments of the invention, the linkage between the adamantane structure and the polyoxyethylene chain, and between the allyl or methallyl group and the polyoxyethylene chain, are ester groups.
The invention also provides a preparation method of the polymerizable nonionic surfactant containing the adamantane structure, wherein the preparation method is selected from one of the following methods: the method comprises the following steps: using equal molar ratio of acyl chloride containing adamantane structure and polyethylene glycol acrylate or polyethylene glycol methacrylate, and using equal molar amount of organic base to catalyze and carry out esterification reaction in an organic solvent to obtain the polymerizable nonionic surfactant; the second method comprises the following steps: the polymerizable nonionic surfactant is obtained by using carboxylic acid containing a adamantane structure and polyethylene glycol acrylate or polyethylene glycol methacrylate in an equimolar ratio and carrying out esterification reaction in an organic solvent by using an equimolar amount of catalyst.
According to some embodiments of the invention, in method one, the acid chloride containing an adamantane structure is selected from 1-adamantanecarbonyl chloride or 1-adamantaneacetyl chloride.
According to some embodiments of the invention, in the first method, the esterification reaction uses an organic base as an acid-binding agent.
According to some embodiments of the invention, the organic base is selected from one or a combination of two of triethylamine and pyridine.
According to some embodiments of the invention, in method two, the adamantanecarboxylic acid is selected from 1-adamantanecarboxylic acid or 1-adamantanacetic acid.
According to some embodiments of the invention, in method two, the catalyst in the esterification reaction is selected from one or a combination of two or more of thionyl chloride (also known as thionyl chloride), N-dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
According to some embodiments of the present invention, the organic solvent used in method one or method two is selected from one or a combination of two or more of dichloromethane, tetrahydrofuran, dioxane, diethyl ether, acetone, and ethyl acetate.
Further, a typical preferred starting material and reaction conditions are: under the condition of ice-water bath, the esterification reaction is carried out by using equimolar amounts of polyethylene glycol methacrylate and 1-adamantane formyl chloride in dichloromethane and using equimolar amounts of triethylamine as an acid-binding agent. After stirring for 4 hours, filtering out precipitates, washing the filtrate twice with 1% sodium bicarbonate and 1% diluted hydrochloric acid in sequence, separating the liquid, taking the lower layer, and evaporating to dryness to obtain the product of the polyethylene glycol adamantane methyl methacrylate.
In the present invention, the above two different methods are used for synthesizing the same product, but these are two distinct methods due to the difference in the synthesis mechanism. The specific difference is that the method is a solid-liquid reaction, two oxygen atoms in a new ester formation group obtained by esterification reaction of adamantane acyl chloride and polyethylene glycol acrylate are respectively derived from acyl chloride and polyethylene glycol acrylate, wherein the oxygen atom on the new ester formation carbonyl group is derived from acyl chloride. In the second method, carboxylic acid containing an adamantane structure is used for reacting with polyethylene glycol acrylate, and thionyl chloride is used as a catalyst to obtain a product, wherein oxygen atoms in ester groups newly generated in the product are derived from carboxyl groups, and hydrogen atoms and oxygen atoms on hydroxyl groups at the tail ends of the original polyethylene glycol acrylate are removed; two oxygen atoms in an ester group in a product obtained by catalyzing N, N-dicyclohexylcarbodiimide, diisopropylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide are respectively derived from adamantane carboxylic acid and polyethylene glycol acrylate.
The invention has the beneficial effects that:
(1) in the invention, adamantane acyl chloride or adamantane carboxylic acid and polyethylene glycol acrylate or polyethylene glycol methacrylate are subjected to esterification reaction in an organic solvent to obtain the novel water-soluble polymerizable nonionic surfactant containing cage-type adamantane three-dimensional structure hydrophobic units. Due to the large steric hindrance effect of adamantane and its hydrophobicity, a surface active substance can be formed after the connection with a hydrophilic group.
(2) On the other hand, the molecular end group contains a polymerizable double bond structure, and the surfactant can be used as a reaction monomer in polymerization reaction, so that a novel raw material for producing the hydrophobically associating polyacrylamide is provided.
(3) Because the water solubility of the substance is good, the substance is expected to have application prospect in the aspect of producing polymers for oil field fracturing acidification and tertiary oil recovery only by using a simple solution polymerization method.
(4) The application of the adamantane derivative in the field of surfactants is expanded; and further expands the variety and range of the non-ionic polymerizable monomer.
Drawings
FIG. 1 is a graph showing a comparison of the infrared spectra of polyethylene glycol methacrylate 360 and product A1 in example 1 of the present invention;
FIG. 2 is a graph of concentration versus surface tension for product A1 of example 1 of the present invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following describes embodiments of the present invention in further detail. Where not specifically described, according to routine laboratory procedures.
Examples esterification of polyethylene glycol acrylates of different molecular weights with 1-adamantanecarbonyl chloride, or 1-adamantanecarboxylic acid, was carried out using the starting materials available from Shanghai Aladdin Biotech, Inc. or Shanghai Merlin Biotech, Inc.
Example 1
The embodiment provides a preparation method of a polymerizable nonionic surfactant containing a adamantane structure, which specifically comprises the following steps:
under the condition of ice-water bath, 3.6g of polyethylene glycol methacrylate (Mw 360, CAS number: 25736-86-1) and 2g of 1-adamantane formyl chloride are added into 50mL of dichloromethane and evenly stirred, and triethylamine is slowly and dropwise added1.05g of dichloromethane solution, stirring for 4 hours, filtering to remove precipitates, washing for 2 times by using 20mL of 1% sodium bicarbonate solution and 1% hydrochloric acid in sequence, separating liquid, taking the lower layer liquid, and evaporating to dryness to obtain oily liquid, namely the product methacrylate polyethylene glycol 360 adamantane methyl ester, which is named as A1. FIG. 1 is the IR contrast spectrum of the raw material polyethylene glycol methacrylate and the product A1, compared with the raw material, 1728cm in A1-1The peak of ester carbonyl group is obviously increased, which indicates that new ester carbonyl group-CO-is generated, 2846cm-1Is the C-H absorption of a methylene group on the adamantane structure, 1230cm-1The absorption peak is C-O-C between polyoxyethylene ethers, so that the A1 is proved to contain both an adamantane structure and a polyoxyethylene chain structure, and the esterification reaction is proved to be successfully carried out; FIG. 2 is a graph of A1 concentration versus surface tension, and when the A1 concentration reached 0.1g/L, the surface tension dropped to a plateau of about 35mN/m, indicating that the resulting product A1 had surface activity, demonstrating that esterification had occurred and that the resulting product A1 was a surfactant-like material having both hydrophilic and hydrophobic chains, conforming to the expected design structure.
Example 2
The embodiment provides a preparation method of a polymerizable nonionic surfactant containing a adamantane structure, which comprises the following specific steps:
under the condition of ice-water bath, 5g of polyethylene glycol methacrylate (Mw ═ 500) and 2g of 1-adamantane formyl chloride are taken and added into 50mL of dichloromethane, after uniform stirring, dichloromethane solution containing 1.05g of triethylamine is slowly dripped, after stirring for 4h, precipitates are removed by filtration, 20mL of 1% sodium bicarbonate solution and 1% hydrochloric acid are sequentially used for washing for 2 times, then liquid separation is carried out, the lower layer liquid is taken out, and oily liquid is obtained after evaporation to dryness, namely the product of the polyethylene glycol 500 adamantane methyl methacrylate.
Example 3
The embodiment provides a preparation method of a polymerizable nonionic surfactant containing a adamantane structure, which comprises the following specific steps:
adding 3.6g of polyethylene glycol methacrylate (Mw is 360) and 1.8g of 1-adamantanecarboxylic acid into 50mL of tetrahydrofuran, stirring uniformly, slowly dropwise adding a dichloromethane solution containing 1.5g of thionyl chloride, refluxing at 60 ℃ for 4h, evaporating the solvent to dryness, adding ethyl acetate for dissolving, washing with a sodium bicarbonate ice-water mixture for 2 times, separating liquid, taking the upper layer liquid, and evaporating to dryness to obtain an oily liquid, namely the product methacrylate polyethylene glycol 360-adamantane methyl ester.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications or equivalent substitutions made within the spirit and principle of the present invention should be covered by the claims of the present invention.
Claims (10)
1. A polymerizable nonionic surfactant containing a adamantane structure, wherein the polymerizable nonionic surfactant has the following general structural formula:
wherein R is1Is methyl or a hydrogen atom; r2Is alkyl containing adamantane stereo structure.
2. The polymerizable nonionic surfactant according to claim 1, wherein R2Is 1-methyladamantyl or 1-ethyladamantyl.
3. The polymerizable nonionic surfactant according to claim 1 or 2, wherein n is 8 to 36.
4. A method for producing a polymerizable nonionic surfactant containing a adamantane structure according to any one of claims 1 to 3, wherein the production method is one selected from the following methods:
The method comprises the following steps: using equimolar ratio of acyl chloride containing adamantane structure and polyethylene glycol acrylate or polyethylene glycol methacrylate, and using equimolar amount of organic base to catalyze and carry out esterification reaction in an organic solvent to obtain the polymerizable nonionic surfactant;
the second method comprises the following steps: the polymerizable nonionic surfactant is prepared by using carboxylic acid containing a adamantane structure and polyethylene glycol acrylate or polyethylene glycol methacrylate in an equimolar ratio and performing esterification reaction in an organic solvent by using an equimolar amount of catalyst.
5. The process according to claim 4, wherein the acid chloride containing an adamantane structure is selected from 1-adamantanecarbonyl chloride and 1-adamantaneacetyl chloride.
6. The process according to claim 4 or 5, wherein in the first process, an organic base is used as an acid-binding agent in the esterification reaction.
7. The preparation method according to claim 6, wherein the organic base is one or a combination of two selected from triethylamine and pyridine.
8. The process according to claim 4, wherein the adamantanecarboxylic acid is 1-adamantanecarboxylic acid or 1-adamantanacetic acid.
9. The production process according to claim 4 or 8, wherein in the second process, the catalyst in the esterification reaction is one or a combination of two or more selected from the group consisting of thionyl chloride, N-dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
10. The process according to claim 4, wherein the organic solvent used in the first or second process is one or more selected from the group consisting of dichloromethane, tetrahydrofuran, dioxane, diethyl ether, acetone and ethyl acetate.
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