CN114656340A - Aromatized chain transfer reagent and preparation method thereof - Google Patents
Aromatized chain transfer reagent and preparation method thereof Download PDFInfo
- Publication number
- CN114656340A CN114656340A CN202210287849.6A CN202210287849A CN114656340A CN 114656340 A CN114656340 A CN 114656340A CN 202210287849 A CN202210287849 A CN 202210287849A CN 114656340 A CN114656340 A CN 114656340A
- Authority
- CN
- China
- Prior art keywords
- compound
- dibenzyl
- methylene
- bromide
- dihydroanthracene
- 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.)
- Granted
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)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (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 path of aromatization provides high 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
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)
(b)
Typical addition fragmentation chain transfer reagents have a terminal double bond for addition trapping 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 methacrylate monomer addition activity. 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 Addition Fragmentation Chain Transfer Reagents have the structural formula shown in FIG. 7, and include Allyl sulfide (partial HY, et al. novel polymerization reaction materials with strain by Addition-Fragmentation Chain Transfer. Dent. Mater; 28:1113-9), Allyl sulfone (Gorsche C, et al. beta. -Allyl sulfides Addition-Fragmentation Chain Transfer Reagents: A. Tool for Addition therapy and Mechanical Properties of copolymers. macromolecules 2014; 47:7327-36), alkenyl sulfonate (G. radial for conversion of strain by Addition-polymerization reaction; 9: modified polymerization reaction, 9-polymerization reaction, 9: modified polymerization reaction, 9-polymerization reaction, and 3. copolymer, 2016. as well as growth molecules of monomer for growth of molecular Chain Transfer reaction, polym Chem 2017; 8: 4339-51); wherein, the chain transfer constants of the last three are close to 1, and the addition amount of the three 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 a fragmentation path of aromatization provides high 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:
a9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound has a structural general formula as follows:
wherein R is hydrogen, alkoxy or ester group.
In the above 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound, as a preferable embodiment, the R group is located at the ortho-position, meta-position 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 the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound is not directly related to the position of the R group on the benzene ring in the free radical addition fragmentation process, the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound with different substituted R groups has similar effects in the free radical addition fragmentation process.
In the above 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound, 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 above 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound, as a preferable 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 cracking chain transfer activity, the chain transfer principle 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.
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).
In a second aspect, the present invention provides a process for the preparation of a 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound, comprising:
step (1): adding acetone and benzyl bromide compound into the 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 ℃ (such as-3 ℃, minus 1 ℃,0 ℃,1 ℃ and 3 ℃), adding the intermediate obtained in the step (1) at-5 ℃ (such as-3 ℃, minus 1 ℃,0 ℃,1 ℃ and 3 ℃), and reacting for 8-16 hours (such as 10 hours, 12 hours, 14 hours and 15 hours) at 20-30 ℃ (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 for 8-16 hours (such as 10 hours, 12 hours, 14 hours and 15 hours) at the temperature; to obtain the final product 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound.
In the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound, when R is an ester group, a target product is unstable under a strong alkali condition, so that a basic substance potassium tert-butoxide and a lower reaction temperature are selected in the synthesis method of the target product with the R being the ester group; 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 to 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 preparation 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 preferred embodiment, in the step (2), the molar ratio of the intermediate, methyltriphenylphosphonium bromide, 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 to 2.0) that a decrease in the amount of methyltriphenylphosphonium bromide or n-butyllithium results in a decrease in the yield; 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), that is, the use of methyltriphenylphosphonium bromide and n-butyllithium increases, which results in waste of raw materials and inconvenience in separation at a later stage.
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), that is, the use of methyl triphenyl phosphonium bromide and potassium tert-butoxide increases, which results in waste of raw materials and inconvenience in separation at a later stage.
In the invention, the reaction end points of the step (1) and the step (2) are determined by monitoring through thin layer chromatography.
In a third aspect, the invention provides the use of a 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound as a free radical addition fragmentation 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.
In a fourth aspect, the present invention provides a resin material, which is obtained by radical polymerization curing of raw materials including bisphenol a Bis glycidyl methacrylate (Bis-GMA monomer), triethylene glycol dimethacrylate (TEGDMA monomer), camphorquinone, ethyl p-dimethylaminobenzoate, and the above 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, 5.5:4.5, 6:4, 7: 3); preferably, the mass ratio of the bisphenol A diglycidyl methacrylate 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% (e.g., 0.26%, 0.27%, 0.28%, 0.29%), the mass fraction of ethyl p-dimethylaminobenzoate is 1.0% to 1.2% (e.g., 1.05%, 1.1%, 1.15%, 1.18%), and the mass fraction of the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound is 0.1% to 1.0% (e.g., 0.2%, 0.4%, 0.6%, 0.8%), in terms of mass percentage, based on the total mass of the glycidyl bis-methacrylate and triethylene glycol dimethacrylate; preferably, the mass fraction of the camphorquinone is 0.28%, and the mass fraction of the ethyl p-dimethylaminobenzoate is 1.1%.
On the basis of the resin material provided by the invention, other inorganic fillers are added to form the dental prosthetic material, 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 prosthetic 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 high free radical addition activity, and the aromatization fragmentation path 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 material 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 materials in application examples 1 to 5 of the present invention;
FIG. 5 is a result of a bending property test of the resin materials in application 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 19, 9-bis (4-methoxybenzyl) -10-methylene-9, 10-dihydroanthracene, prepared as follows:
step (1): in a 200mL Schlenk flask were added anthrone (12.0mmol,2.33g), 18-crown-6 (0.840mmol,0.222g), KI (1.80mmol,0.299g), KOH (25.2mmol,1.41g), nitrogen was purged three times, 96mL of acetone and p-methoxybenzyl bromide (24.0mmol,4.82g,3.45mL) were sequentially added by 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%).
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 via syringe, cooled in an ice bath, and then n-butyllithium (4.42mmol,1.8mL of 2.5M in Hexane (n-Hexane)) was added via 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:1H 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).13C 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 C31H29O2 +:433.2163[M+H]+,found 433.2164。
example 29, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene, prepared by the following method:
step (1): anthracene ketone (4.18mmol,0.811g), 18-crown-6 (0.29mmol,0.077g), KI (0.63mmol,0.104g), KOH (8.78mmol,0.492g) were charged into a 100mL Schlenk flask, nitrogen was purged three times, 33mL of acetone and benzyl bromide (8.36mmol,1.43g,0.99mL) were sequentially added thereto via 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 0.88g of white solid product 2b (yield 56%).
Step (2): methyltriphenylphosphonium bromide (2.10mmol,0.750g) was charged to a 100mL Schlenk flask, nitrogen was purged three times, 7.0mL of tetrahydrofuran was added via syringe, cooled in an ice bath, then n-butyllithium (2.25mmol,0.9mL of 2.5M in Hexane) was added via syringe, and stirred 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 warm to 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:1H 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).13C 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 C29H25 +:373.1951[M+H]+,found 373.1950。
example 39, 9-bis (4-methoxycarbonylbenzyl) -10-methylene-9, 10-dihydroanthracene, prepared by the following method:
step (1): anthracene ketone (10.0mmol,1.94g), 18-crown-6 (0.700mmol,0.185g), KI (1.50mmol,0.249g), KOH (21.0mmol,1.18g) were charged into a 200mL Schlenk bottle, nitrogen gas was purged three times, 60mL of acetone and 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 ℃) 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:1H 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).13C 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 C32H27O5 +:491.1853[M+H]+,found 491.1853；
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 (4.10mmol,2.0g) in 12.0mL tetrahydrofuran was added via syringe and stirred at-20 ℃ for 12 h.
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:1H 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).13C 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 C33H29O4 +:489.2061[M+H]+,found 489.2060。
application 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 a Bis-GMA monomer and a TEGDMA monomer with the mass ratio of 7:3, and then respectively adding the final product (3a) obtained in the example 1 with the mass fractions of 0%, 0.1%, 0.2%, 0.5% and 1.0% to obtain corresponding resin materials which are marked as ACTA-OMe-0, ACTA-OMe-1, ACTA-OMe-2, ACTA-OMe-3 and ACTA-OMe-4 (the mass fractions are all based on the total mass of the Bis-GMA monomer and the TEGDMA monomer).
Application examples 6 to 10
Camphorquinone with the mass fraction of 0.28 percent and ethyl p-dimethylaminobenzoate with the mass fraction of 1.1 percent are added into the Bis-GMA monomer and the TEGDMA monomer with the mass ratio of 7:3, and then the final product (3b) obtained in the example 2 with the mass fractions of 0 percent, 0.1 percent, 0.2 percent, 0.5 percent and 1.0 percent are respectively added to obtain corresponding resin materials which are marked as ACTA-H-0, ACTA-H-1, ACTA-H-2, ACTA-H-3 and ACTA-H-4 (the mass fractions are all based on the total mass of the Bis-GMA monomer and the 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 Bis-GMA monomer and TEGDMA monomer with the mass ratio of 7:3, and then adding the final product (3c) 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 marked as ACTA-CO2Me-0、ACTA-CO2Me-1、ACTA-CO2Me-2、ACTA-CO2Me-3、ACTA-CO2Me-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-diphenylethylene 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 polymerization shrinkage stress test, double bond conversion rate test and bending property test.
The polymerization shrinkage stress test specifically comprises the following steps: two PMMA columns (diameter 5mm) are coaxially fixed on a universal tester up and down, and the distance between the two PMMA columns is 0.70 mm. To this was added the resin material obtained in each of application examples 1 to 15 (the same mass was added for each application example) and a photocuring lamp (1000 mW/cm)2) The resin material obtained by adding the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound of examples 1 to 3 of the present invention was cured by irradiation for 20 seconds, and 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.
The double bond conversion test specifically comprises the following steps: pressing KBr sheet in a stainless steel mold to collect background, coating resin materials obtained in application examples 1-15 and comparative examples 1-5 on the surface of the KBr sheet, and collecting infrared absorption signals (absorption of absorption peak of 1637 wave number measured by infrared after coating of application examples and comparative examples)The light intensity is between 0.6 and 0.7, namely the coating is qualified), and then a light curing lamp (1000 mW/cm) is used2) 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 tests of application examples 1 to 15 are shown in FIG. 2, and the results of the double bond conversion rate tests of the resin materials of application examples 1 to 5 of the present invention are shown in FIG. 3, which indicates that the addition of 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound of examples 1 to 3 of the present invention has little effect on the double bond conversion rate, while the addition of a smaller amount of 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound slightly increases the conversion rate, and the addition of stilbene greatly decreases the double bond conversion rate.
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 a photocuring lamp (1000 mW/cm)2) After curing by irradiation, the cured sample was taken out of the mold and stored in a dark place dried 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 1mm/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 the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound in inventive examples 1-3 resulted in a slight, but not significant, decrease in 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 (10)
1. A9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound is characterized in that the compound has the following structural general formula:
wherein R is hydrogen, alkoxy or ester group.
2. The 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound according to claim 1, wherein 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 alkoxy is an alkoxy group with 1-10 carbon atoms; preferably, the alkoxy group is a methoxy group; preferably, the ester group is a saturated monocarboxylic ester group; preferably, the ester group is a methyl formate group.
3. A method for preparing 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compounds is characterized by comprising the following steps:
step (1): adding acetone and benzyl bromide compound into the 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 ℃, adding the intermediate obtained in the step (1) at-5 ℃, and reacting for 8-16 hours at 20-30 ℃;
or reacting methyl triphenyl phosphonium bromide with potassium tert-butoxide in tetrahydrofuran at-5 ℃, then adding the intermediate obtained in the step (1) at-25-15 ℃, and continuing to react for 8-16 hours at the temperature; to obtain the final product 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound.
4. The method according to claim 3, wherein 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; the bromomethylbenzoate is methyl p-bromomethylbenzoate.
5. The method according to claim 3 or 4, 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);
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;
preferably, in the step (1), the reaction temperature is 20-30 ℃ and the reaction time is 3-12 hours.
6. The production method according to any one of claims 3 to 5, wherein in the step (2), the molar ratio of the intermediate, methyltriphenylphosphonium bromide, 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.
7. the production method according to any one of claims 3 to 5, characterized in that 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.
8. use of a 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound according to claim 1 or 2 as a free radical addition fragmentation chain transfer reagent; preferably, 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.
9. A resin material obtained by curing by radical polymerization raw materials comprising bisphenol A bis (glycidyl methacrylate), triethylene glycol dimethacrylate, camphorquinone, ethyl p-dimethylaminobenzoate, and the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound according to claim 1 or 2.
10. The resin material according to claim 9, wherein the mass ratio of the bisphenol a bis-glycidyl methacrylate to the triethylene glycol dimethacrylate is 5:5 to 8: 2;
preferably, the mass ratio of the bisphenol A bis-glycidyl methacrylate to the triethylene glycol dimethacrylate is 7: 3;
preferably, the mass fraction of the camphorquinone is 0.25 to 0.30%, the mass fraction of the ethyl p-dimethylaminobenzoate is 1.0 to 1.2%, and the mass fraction of the 9, 9-dibenzyl-10-methylene-9, 10-dihydroanthracene compound is 0.1 to 1.0%, based on the total mass of the bisphenol A glycidyl dimethacrylate and the triethylene glycol dimethacrylate in percentage by mass;
preferably, the mass fraction of the camphorquinone is 0.28%, and the mass fraction of the ethyl p-dimethylaminobenzoate is 1.1%.
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 true CN114656340A (en) | 2022-06-24 |
| CN114656340B 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) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664499A (en) * | 2012-09-24 | 2014-03-26 | 中国科学院上海有机化学研究所 | Synthesis 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 |
| CN113443970A (en) * | 2021-08-03 | 2021-09-28 | 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 |
-
2022
- 2022-03-22 CN CN202210287849.6A patent/CN114656340B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664499A (en) * | 2012-09-24 | 2014-03-26 | 中国科学院上海有机化学研究所 | Synthesis 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 |
| CN113443970A (en) * | 2021-08-03 | 2021-09-28 | 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 |
|---|---|
| CN114656340B (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7705189B2 (en) | Calixarene compound, process for producing the same, intermediate therefor, and composition thereof | |
| Stansbury | Cyclopolymerizable monomers for use in dental resin composites | |
| JP2008502697A (en) | Low shrinkage and low stress dental composition | |
| JPS61263947A (en) | (metha)-acrylic acid esters | |
| EP0700981A2 (en) | Photopolymerisable liquid crystals | |
| JP2971650B2 (en) | Method for forming high temperature resistant polymer | |
| CN114656340B (en) | Aromatized chain transfer reagent and preparation method thereof | |
| EP0730569A1 (en) | Novel triphenylene compounds and process for producing discoidally liquid crystalline cross-linked polymers | |
| Lang et al. | An access route to polyferrocenes via modular conjugation | |
| US5844056A (en) | Star polymers having multiple polyisobutylene arms emanating from a calixarene core, initiators therefor, and method for the synthesis thereof | |
| CN113061088A (en) | Asymmetric column [5] arene and preparation method and application thereof | |
| US4356298A (en) | Polyaromatic ether-ketone-sulfones containing 1,3-butadiene units | |
| JP3058642B2 (en) | Cationic polymerizable styryloxy resins, their polymerizable compositions, and methods of curing the resins | |
| Satsangi et al. | Synthesis of low‐shrinkage polymerizable liquid‐crystal monomers | |
| González‐López et al. | Photopolymerizable multifunctional monomers and their evaluation as reactive Bis‐GMA eluents | |
| Satsangi et al. | Synthesis of low‐shrinkage polymerizable methacrylate liquid‐crystal monomers | |
| JP7129729B2 (en) | Photoresponsive polyvinyl ether compound and photoreversible adhesive | |
| KR101222146B1 (en) | Photocontrolled photochromic electroluminescent and electroconducting polymers for photonics | |
| Antonucci et al. | Dimethacrylates derived from hydroxybenzoic acids | |
| Catel et al. | Synthesis and photopolymerization of phosphonic acid monomers for applications in compomer materials | |
| Chen et al. | Poly (methacrylates) bearing dendritic blocks | |
| Pollack et al. | Butatriene-Based Polymer Chemistry. 2. Synthesis and Characterization of Poly [1, 1, 4, 4-Bis (pentamethylene)-1, 2, 3-butatriene], 1 | |
| EP0218722B1 (en) | Use of polymerizable compositions producing polymers having good thermal properties and applications of the obtained polymers | |
| Hrabák et al. | 3‐and 4‐dimethylaminobenzyl acrylate and methacrylate and their polymers | |
| US20210309778A1 (en) | Hydrolysis-tolerant crosslinked polymers from reverse-acrylate multifunctional monomers |
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 |