CN114656340B - Aromatized chain transfer reagent and preparation method thereof - Google Patents

Aromatized chain transfer reagent and preparation method thereof Download PDF

Info

Publication number
CN114656340B
CN114656340B CN202210287849.6A CN202210287849A CN114656340B CN 114656340 B CN114656340 B CN 114656340B CN 202210287849 A CN202210287849 A CN 202210287849A CN 114656340 B CN114656340 B CN 114656340B
Authority
CN
China
Prior art keywords
dibenzyl
compound
methylene
dihydroanthracene
bromide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210287849.6A
Other languages
Chinese (zh)
Other versions
CN114656340A (en
Inventor
朱戎
王文楷
于鹏
吴斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peking University
Peking University School of Stomatology
Original Assignee
Peking University
Peking University School of Stomatology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Peking University, Peking University School of Stomatology filed Critical Peking University
Priority to CN202210287849.6A priority Critical patent/CN114656340B/en
Publication of CN114656340A publication Critical patent/CN114656340A/en
Application granted granted Critical
Publication of CN114656340B publication Critical patent/CN114656340B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/62—Photochemical radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • 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
    • C07C1/34—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 reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/573—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with three six-membered rings
    • C07C13/58—Completely or partially hydrogenated anthracenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F222/00—Copolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F222/00—Copolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Biophysics (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides an aromatizing chain transfer reagent and a preparation method thereof, in particular to a 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound with free radical addition fragmentation chain transfer activity and a preparation method thereof; the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound has a stilbene skeleton so as to have quite high free radical addition activity, and a fragmentation way of aromatization provides high fragmentation cracking driving force for the compound; when the compound is added into an inlet cavity resin material, the polymerization shrinkage stress can be obviously reduced under the condition of not obviously changing the mechanical property and the double bond conversion rate.

Description

Aromatized chain transfer reagent and preparation method thereof
Technical Field
The invention belongs to the technical field of free radical addition fragmentation cracking chain transfer reagents, relates to an aromatizing chain transfer reagent and a preparation method thereof, and particularly relates to a 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound and a preparation method thereof.
Background
Resin composites composed of difunctional monomers (e.g., bisGMA, TEGDMA, etc.), photoinitiators and inorganic fillers are important dental restorative materials that cure rapidly by free radical polymerization under photo-initiation to give high strength, clear and natural tooth-colored resins. However, this system rapidly gels at a conversion of about 20%, and the volume shrinkage effect of the subsequent conversion results in a continuous accumulation of shrinkage stresses up to 1MPa inside the resin. This may lead to detachment of the bond, creation of interfacial gaps, and even secondary caries.
By introducing the addition fragmentation chain transfer agent into the polymerization system, the molecular weight can be reduced and averaged in a chain transfer mode, so that the gel point can be delayed, the shrinkage stress can be released, and the problems of the dental restorative material can be relieved.
(a)
Figure BDA0003558988510000011
(b)
Figure BDA0003558988510000012
Typical addition fragmentation chain transfer reagents have a terminal double bond for addition capture of free radicals and a leaving group in the allylic position of the double bond to effect fragmentation, the mechanism of which is shown in figure (a). The introduction of an activating group next to the double bond can increase the chain transfer constant (ratio of chain transfer rate constant to chain growth rate constant) of the reagent, for example, when an ester group is used as the activating group, the chain transfer constant is about 1, which is similar to the addition activity of methacrylate monomers. The leaving ability of the leaving group will then determine the extent to which the rate of polymerization is slowed down after addition of the chain transfer agent.
Some of the currently reported additive cracking Chain Transfer agents have the structural formula shown in FIG. (b), including Allyl sulfide (part HY, et al. Novel depth reduction materials growth low polymerization strain by Addition-Fragmentation Chain Transfer. Dent. Mat. 28, 1113-9), allyl sulfone (Gorsche C, et al. Beta. -Allyl sulfides Addition-Fragmentation Chain Transfer reactions: A. Tool for Addition therapy and Mechanical Properties of molecular networks. Macrostemes 47, 27-7336), alkenyl sulfonates (Gorsche C, et al. Rapid for conversion of molecular networks. Macro. 2014. 7347), alkenyl sulfonates (chemical reagent C, et al. Rapid for conversion of molecular Transfer, PK, as a monomer, growth regulator, PK, 13-2016-14, for growth Chain Transfer, 13-2016, and 14-growth Chain Transfer molecules; wherein, the chain transfer constants of the latter three are close to 1, and the addition amount of the chain transfer constants in the resin compound is about 5-20%; the relatively low chain transfer constant of allyl sulfide, in turn, makes it useful not as an additive but as a novel resin monomer in a particular application.
Therefore, through proper molecular design, it is important to synthesize and characterize a class of free radical addition fragmentation chain transfer agents that have novel structures and have stronger chain transfer activity, but at the same time do not significantly inhibit polymerization.
Disclosure of Invention
Aiming at the defects and defects of the prior art, the invention aims to provide a 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound with free radical addition fragmentation chain transfer activity and a preparation method thereof. The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound has a stilbene skeleton so as to have quite high free radical addition activity, and the aromatization fragmentation path provides high fragmentation cracking driving force for the compound. When the compound is added into an inlet cavity resin material, the polymerization shrinkage stress can be obviously reduced under the condition of not obviously changing the mechanical property and the double bond conversion rate.
The technical scheme adopted by the invention for solving the technical problem is as follows:
9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound, which has the following structural general formula:
Figure BDA0003558988510000031
wherein R is hydrogen, alkoxy or ester group.
In the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound described above, as a preferred embodiment, the R group is located at the ortho, meta, or para position of the benzene ring; preferably, the R group is located in the para position of the phenyl ring.
The ortho, meta or para position of the phenyl ring in the present invention is the position of the R group on the phenyl ring relative to another substituent group; since 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene does not directly correlate with the position on the phenyl ring of the R group during free radical addition fragmentation, 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene with a differently substituted R group has similar effects during free radical addition fragmentation.
In the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound described above, as a preferable embodiment, the alkoxy group is an alkoxy group having 1 to 10 carbon atoms (for example, 2, 3, 5, 7, 9); preferably, the alkoxy group is a methoxy group.
In the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound described above, as a preferred embodiment, the ester group is a saturated monocarboxylic acid ester group; preferably, the ester group is a methyl formate group.
The invention designs, synthesizes and characterizes a 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound with a brand-new structure and high free radical addition fragmentation chain transfer activity, the principle of the chain transfer is shown in the following figure, firstly a polymerization chain end free radical is captured to obtain an intermediate, and then fragmentation cracking is carried out to obtain an anthracene derivative and release a new free radical.
Figure BDA0003558988510000041
The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound has a stilbene skeleton, so that the compound has quite high free radical addition activity; the fragmentation pathway of its aromatization provides it with a higher fragmentation cracking driving force (the leaving of the R1 group allows the formation of a larger aromatic system (anthracene) and thus a higher reaction tendency for the fragmentation process) so that polymerization is not inhibited. Due to its Aromatization fragmentation properties, this class of materials is used as Aromatization Chain Transfer Agent (ACTA).
The invention provides a preparation method of 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound, which comprises the following steps:
step (1): adding acetone and benzyl bromide compounds into a mixture of anthrone, 18-crown-6, potassium iodide and potassium hydroxide, and reacting at a certain temperature for a period of time to obtain an intermediate 10,10-dibenzyl-9-anthrone compound;
step (2): reacting methyl triphenyl phosphonium bromide with n-butyl lithium in tetrahydrofuran at-5 to 5 ℃ (such as-3 ℃, minus 1 ℃,0 ℃,1 ℃ and 3 ℃), adding the intermediate obtained in the step (1) at-5 to 5 ℃ (such as-3 ℃, minus 1 ℃,0 ℃,1 ℃ and 3 ℃), and reacting for 8 to 16 hours (such as 10 hours, 12 hours, 14 hours and 15 hours) at 20 to 30 ℃ (such as 22 ℃, 24 ℃, 25 ℃, 27 ℃ and 29 ℃);
or reacting methyl triphenyl phosphonium bromide with potassium tert-butoxide in tetrahydrofuran at-5 ℃ (such as-3 ℃,1 ℃,0 ℃,1 ℃ and 3 ℃), then adding the intermediate obtained in the step (1) at-25 ℃ to-15 ℃ (such as-22 ℃, 20 ℃, 19 ℃, 18 ℃ and 16 ℃), and continuing to react at the temperature for 8-16 hours (such as 10 hours, 12 hours, 14 hours and 15 hours); the final product 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is obtained.
In the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound, when R is an ester group, an alkaline substance potassium tert-butoxide and a lower reaction temperature are selected in the synthetic method of the target product with the ester group as the target product is unstable under a strong alkali condition; when R is hydrogen or alkoxy, the target product can stably exist under a strong alkali condition, so that the reaction is carried out under the conditions of a basic substance n-butyl lithium and room temperature in the synthesis method of the target product with the R being hydrogen or alkoxy, and the yield is higher than that of the target product with the R being hydrogen or alkoxy when the basic substance potassium tert-butoxide is selected.
In the above preparation method, as a preferred embodiment, in the step (1), the benzyl bromide compound is one of benzyl bromide, alkoxybenzyl bromide and bromomethylbenzoate; preferably, the alkoxybenzyl bromide is p-methoxybenzyl bromide; preferably, the bromomethylbenzoate is methyl p-bromomethylbenzoate.
In the above production method, as a preferred embodiment, in the step (1), the molar ratio of the anthrone to the benzyl bromide compound to the 18-crown-6 to the potassium hydroxide to the potassium iodide is 1: (1.9-2.2): (0.05-0.10): (2-2.5): (0.10-0.20); preferably, the molar ratio of the anthrone to the benzyl bromide compound to the 18-crown-6 to the potassium hydroxide to the potassium iodide is 1:2:0.07:2.1:0.15.
in the above-mentioned production method, as a preferred embodiment, in the step (1), the reaction temperature is 20 to 30 ℃ (e.g., 22 ℃, 24 ℃, 25 ℃, 27 ℃, 29 ℃) and the reaction time is 3 to 12 hours (e.g., 4 hours, 5 hours, 7 hours, 10 hours).
In the above production method, as a preferable embodiment, in the step (2), the molar ratio of the intermediate, methyltriphenylphosphonium bromide and n-butyllithium is 1: (1.2-1.5): (1.2-2.0); preferably, the molar ratio of the intermediate, methyl triphenyl phosphonium bromide and n-butyl lithium is 1:1.4:1.5.
in the invention, if the molar ratio of the intermediate obtained in the step (1) to the methyl triphenyl phosphonium bromide and the n-butyl lithium is lower than 1: (1.2-1.5): (1.2-2.0), namely, the yield is reduced when the using amount of the methyl triphenyl phosphonium bromide and the n-butyl lithium is reduced; if the molar ratio of the intermediate obtained in step (1) to methyltriphenylphosphonium bromide, n-butyllithium is higher than 1: (1.2-1.5): (1.2-2.0), namely, the use amount of the methyl triphenyl phosphonium bromide and the n-butyl lithium is increased, the raw materials are wasted, and the later separation is inconvenient.
In the above production method, as a preferred embodiment, in the step (2), the molar ratio of the intermediate, methyltriphenylphosphonium bromide, potassium tert-butoxide is 1: (1.2-1.5): (1.2-2.0); preferably, the molar ratio of the intermediate, methyl triphenyl phosphonium bromide and potassium tert-butoxide is 1:1.4:1.5.
in the invention, if the molar ratio of the intermediate obtained in the step (1) to the methyl triphenyl phosphonium bromide and the potassium tert-butoxide is lower than 1: (1.2-1.5): (1.2-2.0), namely, the yield is reduced when the using amount of the methyl triphenyl phosphonium bromide and the potassium tert-butoxide is reduced; if the molar ratio of the intermediate obtained in the step (1) to the methyl triphenyl phosphonium bromide and the potassium tert-butoxide is higher than 1: (1.2-1.5): (1.2-2.0), namely, the use amount of the methyl triphenyl phosphonium bromide and the potassium tert-butoxide is increased, the raw materials are wasted, and the separation at the later stage is inconvenient.
In the invention, the reaction end points of the step (1) and the step (2) are determined by monitoring through thin layer chromatography.
The third aspect of the invention provides an application of 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound as a free radical addition fragmentation cracking chain transfer reagent.
In the above application, as a preferred embodiment, the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is used as a free radical addition fragmentation chain transfer agent in a dental restorative material.
The fourth aspect of the invention provides a resin material, which is prepared by carrying out free radical polymerization and curing on raw materials comprising bisphenol A Bis glycidyl methacrylate (Bis-GMA monomer), triethylene glycol dimethacrylate (TEGDMA monomer), camphorquinone, ethyl p-dimethylaminobenzoate and the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound.
In the above resin material, as a preferred embodiment, the mass ratio of the bisphenol a Bis glycidyl methacrylate (Bis-GMA monomer) to the triethylene glycol dimethacrylate (TEGDMA monomer) is 5:5 to 8:2 (for example, 5.5, 6:4, 7:3; preferably, the mass ratio of the bisphenol A diglycidyl dimethacrylate to the triethylene glycol dimethacrylate is 7:3.
In the above resin material, as a preferred embodiment, the mass fraction of camphorquinone is 0.25% to 0.30% (such as 0.26%, 0.27%, 0.28%, 0.29%) and the mass fraction of ethyl p-dimethylaminobenzoate is 1.0% to 1.2% (such as 1.05%, 1.1%, 1.15%, 1.18%) based on the total mass of the glycidyl bisphenol a dimethacrylate and the triethylene glycol dimethacrylate, and the mass fraction of the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is 0.1% to 1.0% (such as 0.2%, 0.4%, 0.6%, 0.8%); preferably, the mass fraction of the camphorquinone is 0.28%, and the mass fraction of the ethyl p-dimethylaminobenzoate is 1.1%.
The dental restorative material can be formed by adding other inorganic fillers on the basis of the resin material provided by the invention, wherein the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound provided by the invention can be used as a free radical addition fragmentation cracking chain transfer reagent to be applied to the dental restorative material.
Compared with the prior art, the invention has the following positive effects:
(1) The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound has a stilbene skeleton, so that the stilbene skeleton has quite high free radical addition activity, and a fragmentation path of aromatization provides high fragmentation cracking driving force for the stilbene skeleton.
(2) The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound provided by the invention is simple in preparation method and mild in preparation conditions.
(3) The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound can be used as a free radical addition fragmentation cracking chain transfer reagent.
(4) When the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is added into an inlet cavity resin material, the polymerization shrinkage stress can be obviously reduced under the condition of not obviously changing the mechanical property and the double bond conversion rate.
Description of the drawings:
FIG. 1 is a result of a polymerization shrinkage stress test of the resin materials in application examples 1 to 15 of the present invention;
FIG. 2 shows the results of a double bond conversion test of the resin materials in application examples 1 to 15 of the present invention;
FIG. 3 is a graph comparing the results of a double bond conversion test of the resin materials in application examples 1 to 5 of the present invention with those in comparative examples 1 to 5;
FIG. 4 is a result of a bending property test of the resin material in application examples 1 to 5 of the present invention;
FIG. 5 shows the results of the bending properties test of the resin materials in practical examples 6 to 10 of the present invention;
FIG. 6 shows the results of the bending property test of the resin materials in practical examples 11 to 15 of the present invention.
Detailed Description
In order to highlight the objects, technical solutions and advantages of the present invention, the present invention is further illustrated by the following examples, which are presented by way of illustration of the present invention and are not intended to limit the present invention. The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The starting materials used in the following examples and comparative examples are commercially available.
Example 1, 9-bis (4-methoxybenzyl) -10-methylene-9,10-dihydroanthracene, prepared as follows:
Figure BDA0003558988510000081
step (1): anthraphenone (12.0 mmol, 2.33g), 18-crown-6 (0.840 mmol, 0.222g), KI (1.80mmol, 0.299g), KOH (25.2mmol, 1.41g) were charged into a 200mL Schlenk bottle, nitrogen was purged three times, 96mL of acetone and p-methoxybenzyl bromide (24.0 mmol,4.82g, 3.45mL) were sequentially added using a syringe, and the reaction was stirred at room temperature (20-25 ℃ C.) for 5 hours.
The system was spin dried, then water and dichloromethane were added to dissolve, the solution was separated and extracted 2 times with dichloromethane, then the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, spin dried, separated using a flash preparative liquid chromatograph, the resulting solution (petroleum ether-ethyl acetate as the eluent selected in the present chromatographic separation method, and thus the solution obtained after separation was a petroleum ether-ethyl acetate solution) was spin dried and dissolved with a minimum amount of acetone, and petroleum ether was added to recrystallize to give 2.26g of white solid product 2a (yield 43%).
Figure BDA0003558988510000082
Step (2): methyltriphenylphosphonium bromide (4.13mmol, 1.47g) was charged into a 100mL Schlenk flask, nitrogen was purged three times, 8.0mL of tetrahydrofuran was added by syringe, cooled in an ice bath, and then n-butyllithium (4.42mmol, 1.8mL of 2.5M in Hexane (n-Hexane)) was added by syringe, and stirred for 30min in an ice bath. Then, a solution of 2a (2.95mmol, 1.28g) in 14mL of tetrahydrofuran was added by syringe while cooling on ice, and the mixture was allowed to stand at room temperature (20-25 ℃ C.) and stirred for 12 hours.
Adding water to quench the reaction, adding dichloromethane to dilute, separating, extracting with dichloromethane for 2 times, washing an organic phase with saturated saline solution, drying with anhydrous sodium sulfate, filtering, spin-drying, separating by using a fast preparative liquid chromatograph to obtain a solution (an eluent selected in the chromatographic separation method is petroleum ether-ethyl acetate, so the solution obtained after separation is a petroleum ether-ethyl acetate solution), dissolving with a minimum amount of acetone after spin-drying, adding petroleum ether to recrystallize to obtain a white solid product 3a with the mass of 0.567g (the yield is 45%);
the characterization data for this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.65(dd,J＝7.4,1.8Hz,2H),7.31(dd,J＝7.5,1.7Hz,2H),7.24–7.15(m,4H),6.50–6.45(m,4H),6.44–6.40(m,4H),5.43(s,2H),3.64(s,6H),3.39(s,4H). 13 C NMR(101MHz,Chloroform-d)δ157.59,140.77,138.98,135.58,131.20,129.34,127.43,126.66,126.36,123.92,112.76,109.28,55.05,47.92,46.60.HRMS calcd for C 31 H 29 O 2 + :433.2163[M+H] + ,found 433.2164。
example 2, 9-dibenzyl-10-methylene-9,10-dihydroanthracene, prepared as follows:
Figure BDA0003558988510000091
step (1): a100 mL Schlenk flask was charged with anthrone (4.18mmol, 0.811g), 18-crown-6 (0.29mmol, 0.077g), KI (0.63mmol, 0.104g), KOH (8.78mmol, 0.492g), purged with nitrogen three times, 33mL of acetone and benzyl bromide (8.36mmol, 1.43g, 0.99mL) were sequentially added via a syringe, and the mixture was stirred at room temperature (20-25 ℃ C.) for 5 hours.
The system was spin dried, then water and dichloromethane were added to dissolve, the solution was separated and extracted 2 times with dichloromethane, then the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, spin dried, separated using a flash preparative liquid chromatograph, the resulting solution (petroleum ether-ethyl acetate as the eluent selected in the present chromatographic separation method, and thus the solution obtained after separation was a petroleum ether-ethyl acetate solution) was spin dried and dissolved with a minimum amount of acetone, and petroleum ether was added to recrystallize to give 0.88g of white solid product 2b (yield 56%).
Figure BDA0003558988510000101
Step (2): methyltriphenylphosphonium bromide (2.10mmol, 0.750g) was added to a 100mL Schlenk bottle, nitrogen was purged three times, 7.0mL of tetrahydrofuran was added by a syringe, cooling was performed in an ice bath, n-butyllithium (2.25mmol, 0.9mL of 2.5M in Hexane) was added by a syringe, and stirring was performed for 30min in an ice bath. Then, a solution of 2b (1.50mmol, 0.561g) in 4.0mL of tetrahydrofuran was added by syringe while cooling on ice, and the mixture was allowed to stand at room temperature (20-25 ℃ C.) and stirred for 12 hours.
Adding water to quench the reaction, adding dichloromethane to dilute, separating, extracting with dichloromethane for 2 times, washing an organic phase with saturated saline solution, drying with anhydrous sodium sulfate, filtering, spin-drying, and separating by using a fast preparative liquid chromatograph to obtain a solution (an eluent selected in the chromatographic separation method is petroleum ether-ethyl acetate, so that the solution obtained after separation is a petroleum ether-ethyl acetate solution), wherein the mass of a white solid product 3b is 0.213g (the yield is 38%);
the characterization data for this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.66(dd,J＝7.6,1.6Hz,2H),7.31(dd,J＝7.7,1.5Hz,2H),7.19(dtd,J＝14.9,7.4,1.6Hz,4H),7.02–6.96(m,2H),6.95–6.89(m,4H),6.58–6.46(m,4H),5.45(s,2H),3.47(s,4H). 13 C NMR(101MHz,Chloroform-d)δ140.81,138.89,137.26,135.53,130.34,127.48,127.35,126.64,126.48,125.65,124.01,109.49,47.70,47.46.HRMS calcd for C 29 H 25 + :373.1951[M+H] + ,found 373.1950。
example 3, 9-bis (4-methoxybenzyl) -10-methylene-9,10-dihydroanthracene, prepared by the method of:
Figure BDA0003558988510000111
step (1): into a 200mL Schlenk flask were charged anthrone (10.0mmol, 1.94g), 18-crown-6 (0.700mmol, 0.185g), KI (1.50mmol, 0.249g), KOH (21.0mmol, 1.18g), and nitrogen was purged three times, and 60mL of acetone and a 20mL of a solution of methyl p-bromomethylbenzoate (20.0mmol, 4.58g) in 20mL of acetone were successively added by a syringe, and the reaction was stirred at room temperature (20-25 ℃ C.) for 5 hours.
Drying the system by spinning, adding water and dichloromethane for dissolving, separating liquid, extracting for 2 times by using dichloromethane, washing an organic phase by using saturated saline solution, drying by using anhydrous sodium sulfate, filtering, spinning, separating by using a fast preparative liquid chromatograph to obtain a solution (an eluant selected in the chromatographic separation method is petroleum ether-ethyl acetate, so that the solution obtained after separation is a petroleum ether-ethyl acetate solution), spinning, dissolving by using a minimum amount of acetone, adding petroleum ether for recrystallization to obtain a white solid product 2c with the mass of 2.01g (the yield is 41%);
the characterization data for this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ8.06(dt,J＝7.9,1.4Hz,2H),8.00(d,J＝8.0Hz,2H),7.82–7.69(m,2H),7.50–7.33(m,6H),6.36(d,J＝8.0Hz,4H),3.80(s,4H),3.76(d,J＝1.1Hz,6H). 13 C NMR(151MHz,Chloroform-d)δ182.29,166.75,144.52,141.24,133.08,132.64,129.45,128.69,128.16,127.68,127.37,127.17,51.86,50.12,48.73.HRMS calcd for C 32 H 27 O 5 + :491.1853[M+H] + ,found 491.1853；
Figure BDA0003558988510000121
step (2): methyltriphenylphosphonium bromide (5.70mmol, 2.04g) was added to a 100mL Schlenk flask, nitrogen was purged three times, 14.0mL of tetrahydrofuran was added via syringe, cooled in an ice bath, and then potassium tert-butoxide (6.1mmol, 6.1mL of 1.0M in THF) was added via syringe, and stirred for 30min in an ice bath. Cooled to-20 ℃ and 2c (4.10 mmol,2.0 g) in 12.0mL of tetrahydrofuran was added via syringe and stirred at-20 ℃ for 12 hours.
Quenching the reaction with water, diluting with dichloromethane, separating, extracting with dichloromethane for 2 times, washing the organic phase with saturated brine, drying with anhydrous sodium sulfate, filtering, spin-drying, separating with fast preparative liquid chromatograph to obtain a white solid product 3c with a mass of 0.200g (yield of 10%);
the characterization data for this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.65–7.60(m,2H),7.61–7.52(m,4H),7.39–7.30(m,2H),7.25–7.17(m,4H),6.58–6.54(m,4H),5.39(s,2H),3.80(s,6H),3.54(s,4H). 13 C NMR(101MHz,Chloroform-d)δ167.14,142.60,140.06,137.81,135.47,130.24,128.65,127.72,127.65,126.88,126.34,124.20,110.06,51.90,47.92,47.79.HRMS calcd for C 33 H 29 O 4 + :489.2061[M+H] + ,found 489.2060。
application examples 1 to 5
Camphorquinone with a mass fraction of 0.28% and ethyl p-dimethylaminobenzoate with a mass fraction of 1.1% were added to the Bis-GMA monomer and TEGDMA monomer in a mass ratio of 7:3, followed by the addition of the final product (3 a) obtained in example 1 with a mass fraction of 0%, 0.1%, 0.2%, 0.5% and 1.0%, respectively, to give the corresponding resin materials, designated ACTA-OMe-0, ACTA-OMe-1, ACTA-OMe-2, ACTA-OMe-3 and ACTA-OMe-4 (the mass fractions are based on the total mass of the Bis-GMA monomer and TEGDMA monomer).
Application examples 6 to 10
Camphorquinone with a mass fraction of 0.28% and ethyl p-dimethylaminobenzoate with a mass fraction of 1.1% were added to the Bis-GMA monomer and TEGDMA monomer in a mass ratio of 7:3, followed by the addition of the final product (3 b) from example 2 with a mass fraction of 0%, 0.1%, 0.2%, 0.5% and 1.0%, respectively, to provide the corresponding resin materials, designated ACTA-H-0, ACTA-H-1, ACTA-H-2, ACTA-H-3, ACTA-H-4 (the mass fractions are based on the total mass of the Bis-GMA monomer and TEGDMA monomer).
Application examples 11 to 15
Adding camphorquinone with the mass fraction of 0.28% and ethyl p-dimethylaminobenzoate with the mass fraction of 1.1% to the Bis-GMA monomer and the TEGDMA monomer with the mass ratio of 7:3, and then adding the final product (3 c) obtained in example 3 with the mass fractions of 0%, 0.1%, 0.2%, 0.5% and 1.0%, respectively, to obtain the corresponding resin material, which is noted ACTA-CO 2 Me-0、ACTA-CO 2 Me-1、ACTA-CO 2 Me-2、ACTA-CO 2 Me-3、ACTA-CO 2 Me-4 (the mass fractions are based on the total mass of Bis-GMA monomer and TEGDMA monomer).
Comparative examples 1 to 5
Adding camphorquinone with the mass fraction of 0.28% and ethyl p-dimethylaminobenzoate with the mass fraction of 1.1% into BisGMA and TEGDMA with the mass ratio of 7:3, and then respectively adding 1,1-stilbene with the mass fractions of 0, 0.1%, 0.2%, 0.5% and 1.0% to obtain corresponding resin materials which are marked as DPE-0, DPE-1, DPE-2, DPE-3 and DPE-4.
And (3) performance testing:
the resin material obtained in the invention is respectively subjected to a polymerization shrinkage stress test, a double bond conversion rate test and a bending property test.
The polymerization shrinkage stress test specifically comprises the following steps: two PMMA columns (diameter 5 mm) are coaxially fixed on a universal tester from top to bottom, and the distance between the two PMMA columns is 0.70mm. To this was added the resin material obtained in each of application examples 1 to 15 (the same mass was added for each of the application examples) and a photocuring lamp (1000 mW/cm) 2 ) The resin material was cured by irradiation for 20 seconds, the stress generated was recorded on a force sensor of a universal tester and then converted into pressure, and the test results are shown in FIG. 1, which shows that the polymerization shrinkage stress of the resin material obtained by adding 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound in examples 1 to 3 of the present invention was significantly reduced.
The double bond conversion test specifically comprises: pressing a KBr sheet in a stainless steel mold to collect a background, coating a layer of the resin material obtained in each application example 1-15 and each comparative example 1-5 on the surface of the KBr sheet, collecting an infrared absorption signal (the absorbance of an absorption peak of 1637 wavenumber of the resin material measured by infrared after each application example and each comparative example is 0.6-0.7, namely the coating is qualified), and using a photocuring lamp (1000 mW/cm) 2 ) The cured material was irradiated for 20 seconds, and the infrared absorption signal was collected again. The double bond conversion rate was obtained by calculating the strong reduction ratio of the peak at 1637 wavenumbers (double bond absorption peak) with reference to the peak at 1608 wavenumbers, and the results of the test of application examples 1 to 15 are shown in FIG. 2, and the results of the double bond conversion rate test of the resin materials of application examples 1 to 5 of the present invention are shown in FIG. 3, which shows that the double bond conversion rate was not greatly affected by the addition of 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound of examples 1 to 3 of the present invention, while the conversion rate was slightly increased by the addition of less 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound, and the double bond conversion rate was greatly decreased by the addition of stilbene.
The bending property test specifically comprises the following steps: the resin materials obtained in each of application examples 1 to 15 (the same mass was added for each set of application examples) were charged into a tetrafluoroethylene mold of 2 mm. Times.2 mm. Times.25 mm and then cured with a photocuring lamp (1000 mW/cm) 2 ) The irradiation is carried out to solidify the resin,the cured sample was then removed from the mold and stored in a dark place at 37 ℃ for 1 day. The test pieces were crushed by a three-point test (the distance between the support points on both sides was 20mm, and the falling speed of the tip was 1 mm/min) to obtain flexural strength and flexural modulus data, and the test results are shown in FIGS. 4 to 6, respectively. The results show that the addition of 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound in inventive examples 1-3 slightly but not significantly reduced the flexural strength and flexural modulus of the resin material.
In conclusion, the chain transfer agent (ACTA) designed and synthesized in the present invention significantly reduces the polymerization shrinkage stress with a low addition amount, while having little effect on the double bond conversion rate and bending properties.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (14)

1. The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is characterized in that the structural general formula of the compound is as follows:
Figure QLYQS_1
wherein R is hydrogen, alkoxy or ester group.
2. The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound of claim 1, wherein the R group is located at the ortho, meta, or para position of the benzene ring;
the alkoxy is an alkoxy group having 1 to 10 carbon atoms.
3. The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound of claim 1, wherein said alkoxy group is a methine group; the ester group is a saturated monocarboxylic ester group.
4. The 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound of claim 3, wherein said ester group is a methyl formate group.
5. A method of preparing 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound of claim 1, comprising:
step (1): adding acetone and benzyl bromide compounds into a mixture of anthrone, 18-crown-6, potassium iodide and potassium hydroxide, and reacting at a certain temperature for a period of time to obtain an intermediate 10,10-dibenzyl-9-anthrone compound;
step (2): reacting methyl triphenyl phosphonium bromide with n-butyl lithium in tetrahydrofuran at the temperature of-5 to 5 ℃, adding the intermediate obtained in the step (1) at the temperature of-5 to 5 ℃, and reacting for 8 to 16 hours at the temperature of 20 to 30 ℃;
or reacting methyl triphenyl phosphonium bromide with potassium tert-butoxide in tetrahydrofuran at-5 ℃, then adding the intermediate obtained in the step (1) at-25 ℃ to-15 ℃, and continuing to react for 8-16 hours at the temperature; the final product 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is obtained.
6. The method according to claim 5, wherein in the step (1), the benzyl bromide compound is one of benzyl bromide, alkoxybenzyl bromide and bromomethylbenzoate.
7. The method according to claim 6, wherein the alkoxybenzyl bromide is p-methoxybenzyl bromide; the bromomethylbenzoate is methyl p-bromomethylbenzoate.
8. The process according to any one of claims 5 to 7, wherein in the step (1), the molar ratio of the anthrone to the benzyl bromide compound to the 18-crown-6 to the potassium hydroxide to the potassium iodide is 1: (1.9-2.2): (0.05-0.10): (2-2.5): (0.10-0.20);
in the step (1), the reaction temperature is 20-30 ℃ and the reaction time is 3-12 hours.
9. The method according to claim 5, wherein in the step (2), the molar ratio of the intermediate, methyl triphenyl phosphonium bromide and n-butyl lithium is 1: (1.2-1.5): (1.2-2.0).
10. The method according to claim 5, wherein in the step (2), the molar ratio of the intermediate, methyl triphenyl phosphonium bromide and potassium tert-butoxide is 1: (1.2-1.5): (1.2-2.0).
11. Use of 9,9-dibenzyl-10-methylene-9,10-dihydroanthracenes as free radical addition fragmentation chain transfer agents as claimed in any of claims 1 to 4.
12. Use according to claim 11, characterized in that the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is used as a free radical addition fragmentation chain transfer agent in dental restorative materials.
13. A resin material obtained by radical polymerization curing of raw materials comprising bisphenol A bis glycidyl methacrylate, triethylene glycol dimethacrylate, camphorquinone, ethyl p-dimethylaminobenzoate, and 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound as set forth in any one of claims 1 to 4.
14. The resin material according to claim 13, wherein the mass ratio of the bisphenol a bis-glycidyl methacrylate to the triethylene glycol dimethacrylate is 5:5 to 8:2;
based on the total mass of the bisphenol A glycidyl dimethacrylate and the triethylene glycol dimethacrylate, the mass fraction of the camphorquinone is 0.25-0.30%, the mass fraction of the ethyl p-dimethylaminobenzoate is 1.0-1.2%, and the mass fraction of the 9,9-dibenzyl-10-methylene-9,10-dihydroanthracene compound is 0.1-1.0%.
CN202210287849.6A 2022-03-22 2022-03-22 Aromatized chain transfer reagent and preparation method thereof Active CN114656340B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210287849.6A CN114656340B (en) 2022-03-22 2022-03-22 Aromatized chain transfer reagent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210287849.6A CN114656340B (en) 2022-03-22 2022-03-22 Aromatized chain transfer reagent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114656340A CN114656340A (en) 2022-06-24
CN114656340B true CN114656340B (en) 2023-03-21

Family

ID=82031203

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210287849.6A Active CN114656340B (en) 2022-03-22 2022-03-22 Aromatized chain transfer reagent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114656340B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103664499B (en) * 2012-09-24 2016-03-02 中国科学院上海有机化学研究所 The synthetic method of tetracene and pentacene compounds
CN112920039A (en) * 2021-02-05 2021-06-08 大连理工大学 Diarylacetylene compound containing methylene quinone, preparation method and application thereof
CN113443970B (en) * 2021-08-03 2023-04-07 新乡医学院 Synthesis method of 4-alkoxy phenol compound
CN114149438A (en) * 2021-12-03 2022-03-08 华东师范大学 Quinoxaline and diazole derivatives based on 9, 10-dimethyl-9, 10-ethylene anthracene and preparation method thereof

Also Published As

Publication number Publication date
CN114656340A (en) 2022-06-24

Similar Documents

Publication Publication Date Title
KR101135771B1 (en) Calixarene compound, process for producing the same, intermediate therefor, and composition thereof
Wissner 2-Heterosubstituted silylated ketone acetals: reagents for the preparation of. alpha.-functionalized methylketones from carboxylic acid chlorides
JP2008502697A (en) Low shrinkage and low stress dental composition
CN114656340B (en) Aromatized chain transfer reagent and preparation method thereof
JP2971650B2 (en) Method for forming high temperature resistant polymer
JPH02159A (en) Aromatic compound
CN113061088A (en) Asymmetric column [5] arene and preparation method and application thereof
Yadav et al. Stereoselective synthesis of 10 (S), 11 (R), 12 (R)-trihydroxyeicosa-5 (Z), 8 (Z), 14 (Z)-trienoic acid from d-mannose
US4555574A (en) Methacrylic ester useful as an optical resolving agent
SE436873B (en) 4,5-UNATATED PROSTANIC ACID DERIVATIVE
JP3058642B2 (en) Cationic polymerizable styryloxy resins, their polymerizable compositions, and methods of curing the resins
Farina et al. Stereochemistry of perhydrotriphenylene—II: Absolute rotation and configuration of optically active anti-trans-anti-trans-anti-trans-perhydrotriphenylene
CN101935395A (en) Poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and preparation method thereof
Ferguson et al. 1, 3-Calix [4] arene crown ether conformers with a 3-thienyl pendant functionality at the Lower Rim
FR2613718A1 (en) MONOFUNCTIONALIZED CYCLIC TETRAMINES, PROCESS FOR THEIR PREPARATION, POLYMERS AND USE THEREOF
JP3968414B2 (en) Monomers for producing poly [3] rotaxane and methods for producing the same.
Satsangi et al. Synthesis of low‐shrinkage polymerizable methacrylate liquid‐crystal monomers
Antonucci et al. Dimethacrylates derived from hydroxybenzoic acids
Klemm et al. New polymers with coronand structure
Prieto et al. Crosslinking of poly (epibromohydrin) containing the aryl prop‐2‐ynyl ether terminated side group
EP0218722B1 (en) Use of polymerizable compositions producing polymers having good thermal properties and applications of the obtained polymers
Sharma et al. An abbreviated synthesis of 7, 12-dimethylbenz [a] anthracene and benzo [c] chrysene metabolites using the Suzuki reaction
JP2620109B2 (en) Polyfunctional phenoxyarene compounds and their preparation
Zhang et al. Preparation of hyperbranched polymer via single electron transfer living radical polymerization
CN116947686A (en) N-aryl-N-alkyl-O-allylhydroxylamine compound and synthesis method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant