CN104447635B - A kind of ester compounds of oxetane group-containing and preparation method thereof - Google Patents
A kind of ester compounds of oxetane group-containing and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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Abstract
The present invention discloses a kind of ester compounds of oxetane group-containing, with polyfunctionality, high stability and high-cation reactivity, and it prepares easy, high income.The ester compounds are applied to that during cationically photocurable formulation very excellent light-cured performance can be shown, and hardening time is extremely short, is significantly better than existing similar compound, and product has excellent pliability and hardness.
Description
Technical field
The invention belongs to organic chemistry filed, and in particular to a kind of oxygen heterocycle butane with high-cation reactivity
Ester compounds of group and preparation method thereof.
Background technology
In cationically photocurable formulation, the ester compounds reactivity of existing oxetane group-containing is universal not
Height, even if long-time illumination can not be fully cured.For example, disclosed in Chinese invention patent application CN1743373 4 kinds it is oxygen-containing
The carboxylate of azetidinyl, its suitable for semiconductor subassembly bottom filling, particularly for lead-free solder in electric wire phase
Connect the bonding at place, but they use heat curing techniques, it is necessary to hot setting；Chinese invention patent application
The carboxylate with similar structures is disclosed in CN100569825, can be used as heat cure and photo-curing material.But, above-mentioned text
The monomer for the oxetane group-containing offered can not be all fully cured under photocuring, it is necessary to which the step such as subsequent heat makes formula
It is fully cured, so as to reduce production efficiency, limits the ester type compound of oxetane group-containing in curing field
Using.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of esterification of oxetane group-containing conjunction
Thing, the compound is applied to that during cationically photocurable formulation very excellent light-cured performance can be shown, and hardening time is extremely short,
It is significantly better than existing similar compound.Also, the compound can assign excellent to the polymerizate formed by the compound
Pliability.
The ester compounds containing oxetane groups of the present invention, with structure shown in formula (1)：
Wherein, R1For n valency groups, selected from substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C6-C30Aryl,
Substituted or unsubstituted C2-C30Heteroaryl；R2Represent C1-C30Alkylene ,-the CH in its main chain2- optionally by oxygen atom
Substitution, condition is that two-O- are not joined directly together and connect；R3Represent substituted or unsubstituted C1-C6Alkyl；N=1,2,3 or 4.
Preferably, in ester compounds shown in formula (1), R1Selected from C1-C6Straight or branched n valencys alkyl or
Replace alkyl, C2-C4Straight or branched n valencys alkenyl, C6-C12N valencys aryl or substituted aryl.It is further preferred that R1Choosing
From methyl, ethyl, propyl group, butyl, amyl group, hexyl ,-(CH2)m- (wherein m=2,3,4,5) ,-CH2-CH(CH3)-CH2-、-
CH2-C(OH)-CH2-, vinyl, 1- methyl ethylenes, n valencys phenyl or xenyl or naphthyl.It is further preferable that R1Selected from first
Base, ethyl, propyl group ,-(CH2)m- (wherein m=2,3,4,5) ,-CH2-C(OH)-CH2-, vinyl, 1- methyl ethylenes, 1,4-
Phenylene, 1,3,4- phenenyls, 2,3,5,6- tetravalence phenyl.
Preferably, in ester compounds shown in formula (1), R2Selected from C2-C8Straight or branched alkylidene, its lead
Chain can carry ether.It is further preferred that R2Selected from-(CH2)m- (wherein m=3,4,5) ,-CH2-CH(CH3)-CH2-、-
CH2-CH(CH3)-(CH2)2-、-(CH2-CH(CH3)-O)m-CH2-CH(CH3)-(wherein m=0,1 or 2) or-(CH2-CH2-O
)m-CH2-CH2- (wherein m=0,1,2 or 3).It is further preferable that R2Selected from-(CH2-CH(CH3)-O)m-CH2-CH(CH3)-(its
2) or-(CH middle m=0,1 or2-CH2-O)m-CH2-CH2- (wherein m=0,1,2 or 3).
Preferably, in ester compounds shown in formula (1), R3Selected from C1-C6Straight or branched alkyl.Further
Preferably, R3Selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, isopropyl.
The present invention also aims to provide the preparation method of the above-mentioned ester compounds containing oxetane groups, bag
Include：The alcohol containing oxetane groups as the ester shown in formula (2) and shown in formula (3) react in the presence of a catalyst and
Into
Wherein, R1、R2、R3Definition with n is as described in formula (1), and R ' represents methyl or ethyl.
Exemplarily, in above-mentioned preparation method, the ester shown in formula (2) is selected from following compounds：
Exemplarily, in above-mentioned preparation method, the alcohol containing oxetane groups shown in formula (3) is selected from followingization
Compound：
In the preparation method of the present invention, ester shown in formula (2) with shown in formula (3) containing oxetane groups
The mol ratio of alcohol is 1:1-10, preferably 1:1.2-5.
The catalyst used in preparation method can be：Lithium amide, such as diisopropylamino lithium, hexamethl disilamine base lithium
Deng；Alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide；Alkali carbonate, such as sodium carbonate, potassium carbonate；Alkali metal
Bicarbonate, such as sodium acid carbonate, saleratus；Titanate esters, such as tetraethyl titanate, tetraisopropyl titanate, metatitanic acid orthocarbonate, titanium
Sour four butyl esters etc..The preferred titanate esters of catalyst, titanate compound can be used in mixed way alone or in any combination, more preferably
Tetraisopropyl titanate.The consumption of catalyst is easily determined to those skilled in the art, it is preferable that catalyst amount is
Ester and the 0.1-20% of the quality sum of the alcohol containing oxetane groups shown in formula (3) shown in formula (2), it is more excellent
Select 1-10%.
The reaction of the present invention is carried out in the presence of the solvent or in the presence of non-.Available solvent is not particularly limited,
As long as not influenceing reaction, for example, can be：The nitrile of acetonitrile, propionitrile, benzonitrile etc.；DMF, N, N- bis-
The amide-type of methylacetamide, 1-METHYLPYRROLIDONE etc.；The ethers of tetrahydrofuran, dioxane etc.；Benzene, toluene, two
The aromatic hydrocarbons class of toluene etc..Solvent optimization aromatic hydrocarbon, more preferably toluene, dimethylbenzene.Furthermore,
Above-mentioned solvent can be used in mixed way alone or in any combination.The usage amount of solvent can be according to the homogeneity of reaction system and stirring property
Suitably adjusted, this is easily determined to those skilled in the art.In general, formula (3) institute relative to 1g
The alcohol containing oxetane groups shown, solvent load is 0-100g, preferably 1-20g.
The above-mentioned reaction of the present invention is carried out in the liquid phase, and reaction temperature is 0-200 DEG C, preferably 50-150 DEG C, reaction pressure
Have no particular limits.
By the reaction of the present invention, the ester containing oxetane groups with structure shown in formula (1) can be obtained
Compound.After reaction terminates, separated and refined using conventional methods such as filtering, layering, concentration, distillations.
The present invention also aims to provide the above-mentioned ester compounds containing oxetane groups in cation photocuring
Application in composition.
It is disclosed by the invention that there are the ester compounds containing oxetane groups of structure shown in formula (1) to have many officials
Energy degree, high stability and high-cation reactivity, and it prepares easy, high income.
Embodiment
The present invention will further be illustrated with embodiment below, but the scope of the present invention is not limited to this
A little embodiments.When following " % " is not particularly illustrated, " quality % " is represented.
Prepare embodiment
The ester compounds containing oxetane groups with following structure are prepared respectively：
Wherein, R is selected from having structure：
In embodiment, the raw polyol of correspondence formula (3) is selected from following structure：
Embodiment 1
The synthesis of compound 1
In the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
160g (1.0mol) raw material 1,500g (5.0mol) methyl methacrylate, keeps 110 DEG C of backflows, and regulation reflux ratio is 3:
1, the system moisture for the treatment of is down to below 500ppm, adds catalyst tetraisopropyl titanate 6.6g (account for total amount of feeding 1%), continues back
Stream 3 hours.After reaction terminates, 70 DEG C are cooled to, 25g water is added, 70 DEG C of insulation half an hour, destroys catalyst, filtering, filtrate is dense
Contracting, obtains the 216g colourless liquids (separation yield of the benchmark of raw material 1:95%)
The structure of product Compound 1 by mass spectrum and1H-NMR is confirmed.
MS(m/e)：229(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (3H), 1.25 (2H), 1.93 (3H), 3.65 (2H), 4.32 (2H), 4.65
(4H), 5.58 (2H), 6.15 (2H).
Embodiment 2
The synthesis of compound 2
Into the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
204g (1.0mol) raw material 2, remaining operation reference implementation example 1.It is concentrated to obtain the 261g colourless transparent liquids (benchmark of raw material 2
Separation yield:96%).
Product structure is confirmed through following physics value.
MS(m/e)：273(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (3H), 1.25 (2H), 1.93 (3H), 3.29 (2H), 3.54 (4H), 3.65
(2H), 4.32 (2H), 4.65 (4H), 5.58 (2H), 6.15 (2H).
Embodiment 3
The synthesis of compound 3
Into the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
248g (1.0mol) raw material 3, remaining operation reference implementation example 1.It is concentrated to obtain the 294g colourless transparent liquids (benchmark of raw material 3
Separation yield:93%).
Product structure is confirmed through following physics value.
MS(m/e)：317(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (3H), 1.25 (2H), 1.93 (3H), 3.29 (2H), 3.54 (8H), 3.65
(2H), 4.32 (2H), 4.65 (4H), 5.58 (2H), 6.15 (2H).
Embodiment 4
The synthesis of compound 3
Into the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
292g (1.0mol) raw material 4, remaining operation reference implementation example 1.It is concentrated to obtain the 324g colourless transparent liquids (benchmark of raw material 4
Separation yield:90%).
Product structure is confirmed through following physics value.
MS(m/e)：361(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (3H), 1.25 (2H), 1.93 (3H), 3.29 (2H), 3.54 (12H),
3.65 (2H), 4.32 (2H), 4.65 (4H), 5.58 (2H), 6.15 (2H).
Embodiment 5
The synthesis of compound 5
Into the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
320g (2.0mol) raw material 1,174g (1.0mol) dimethyl adipate, toluene 400mL, keeps 110 DEG C of backflows, adjusts back
Stream is than being 3:1, the system moisture for the treatment of is down to below 500ppm, adds catalyst tetraisopropyl titanate 5g and (accounts for the pact of total amount of feeding
1%), continue to flow back 3 hours.After reaction terminates, 70 DEG C are cooled to, 25g water is added, 70 DEG C of insulation half an hour, destroys catalyst,
Filtering, filtrate concentration, obtains the 404g colourless liquids (separation yield of dimethyl adipate benchmark：94%).
Product structure is confirmed through following physics value.
MS(m/e)：431(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 1.68 (4H), 2.25 (4H), 3.29 (4H), 3.65
(4H), 4.25 (4H), 4.65 (8H).
Embodiment 6
The synthesis of compound 6
Into the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
408g (2.0mol) raw material 2, remaining operation reference implementation example 5.It is concentrated to obtain 477g colourless liquids (dimethyl adipate base
Accurate separation yield：92%).
Product structure is confirmed through following physics value.
MS(m/e)：519(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 1.68 (4H), 2.25 (4H), 3.29 (4H), 3.54
(8H), 3.65 (4H), 4.25 (4H), 4.65 (8H).
Embodiment 7
The synthesis of compound 7
Into the glass flask of the volume 2000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
496g (2.0mol) raw material 3, remaining operation reference implementation example 5.It is concentrated to obtain 576g colourless liquids (dimethyl adipate base
Accurate separation yield；95%).
Product structure is confirmed through following physics value.
MS(m/e)：607(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 1.68 (4H), 2.25 (4H), 3.29 (4H), 3.54
(16H), 3.65 (4H), 4.25 (4H), 4.65 (8H).
Embodiment 8
The synthesis of compound 8
Into the glass flask of the volume 2000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
584g (2.0mol) raw material 4, remaining operation reference implementation example 5.It is concentrated to obtain 660g colourless liquids (dimethyl adipate base
Accurate separation yield：95%).
Product structure is confirmed through following physics value.
MS(m/e)：695(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 1.68 (4H), 2.25 (4H), 3.29 (4H), 3.54
(24H), 3.65 (4H), 4.25 (4H), 4.65 (8H).
Embodiment 9
The synthesis of compound 9
Into the glass flask of the volume 1000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
320g (2.0mol) raw material 1,194g (1.0mol) dimethyl terephthalate (DMT), toluene 400mL, keeps 110 DEG C of backflows, adjusts
It is 3 to save reflux ratio:1, the system moisture for the treatment of is down to below 500ppm, adds catalyst tetraisopropyl titanate 5g and (accounts for total amount of feeding
About 1%), continue to flow back 3 hours.After reaction terminates, 70 DEG C are cooled to, 25g water, 70 DEG C of insulation half an hour, destruction catalysis is added
Agent, filtering, filtrate concentration obtains the 432g colourless liquids (separation yield of dimethyl terephthalate (DMT) benchmark：96%).
Product structure is confirmed through following physics value.
MS(m/e)：451(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 3.29 (4H), 3.83 (4H), 4.42 (4H), 4.65
(8H), 8.08 (4H).
Embodiment 10
The synthesis of compound 10
Into the glass flask of the volume 1000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
408g (2.0mol) raw material 2, remaining operation reference implementation example 9.It is concentrated to obtain 500g colourless liquids (terephthalic acid (TPA) diformazan
The accurate separation yield of ester group：93%).
Product structure is confirmed through following physics value.
MS(m/e)：539(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 3.29 (4H), 3.54 (8H), 3.83 (4H), 4.42
(4H), 4.65 (8H), 8.08 (4H).
Embodiment 11
The synthesis of compound 11
Into the glass flask of the volume 2000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
496g (2.0mol) raw material 3, remaining operation reference implementation example 9 is concentrated to obtain 588g colourless liquids (terephthalic acid (TPA) diformazan
The accurate separation yield of ester group：94%).
Product structure is confirmed through following physics value.
MS(m/e)：627(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 3.29 (4H), 3.54 (16H), 3.83 (4H),
4.42 (4H), 4.65 (8H), 8.08 (4H).
Embodiment 12
The synthesis of compound 12
Into the glass flask of the volume 2000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
496g (2.0mol) raw material 4, remaining operation reference implementation example 9 is concentrated to obtain 588g colourless liquids (terephthalic acid (TPA) diformazan
The accurate separation yield of ester group：94%).
Product structure is confirmed through following physics value.
MS(m/e)：715(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (6H), 1.25 (4H), 3.29 (4H), 3.54 (24H), 3.83 (4H),
4.42 (4H), 4.65 (8H), 8.08 (4H).
Embodiment 13
The synthesis of compound 13
Into the glass flask of the volume 1000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
240g (1.5mol) raw material 1,117g (0.5mol) trimethyl citrate, toluene 400mL, keeps 110 DEG C of backflows, regulation backflow
Than for 3:1, the system moisture for the treatment of is down to below 500ppm, adds catalyst tetraisopropyl titanate 3.5g and (accounts for the pact of total amount of feeding
1%), continue to flow back 3 hours.After reaction terminates, 70 DEG C are cooled to, 25g water is added, 70 DEG C of insulation half an hour, destroys catalyst,
Filtering, filtrate concentration, obtains the 262g colourless liquids (separation yield of trimethyl citrate benchmark：90%).
Product structure is confirmed through following physics value.
MS(m/e)：619(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (9H), 1.25 (6H), 2.0 (1H), 2.75 (4H), 3.29 (6H), 3.65
(6H), 4.25 (6H), 4.65 (12H).
Embodiment 14
The synthesis of compound 14
Into the glass flask of the volume 1000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
306g (1.5mol) raw material 2, remaining operation reference implementation example 13.It is concentrated to obtain 339g colourless liquid (trimethyl citrates
The separation yield of benchmark：95%).
Product structure is confirmed through following physics value.
MS(m/e)：751(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (9H), 1.25 (6H), 2.0 (1H), 2.75 (4H), 3.29 (6H), 3.65
(6H), 4.25 (6H), 3.54 (12H), 4.65 (12H).
Embodiment 15
The synthesis of compound 15
Into the glass flask of the volume 1000ml with agitating device, thermometer, 60cm packed towers and Rectification head, add
372g (1.5mol) raw material 3, remaining operation reference implementation example 13.It is concentrated to obtain 402g colourless liquid (trimethyl citrates
The separation yield of benchmark：95%).
Product structure is confirmed through following physics value.
MS(m/e)：883(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (9H), 1.25 (6H), 2.0 (1H), 2.75 (4H), 3.29 (6H), 3.65
(6H), 4.25 (6H), 3.54 (24H), 4.65 (12H).
Embodiment 16
The synthesis of compound 16
Into the glass flask of the volume 1000mL with agitating device, thermometer, 60cm packed towers and Rectification head, add
438g (1.5mol) raw material 4, remaining operation reference implementation example 13.It is concentrated to obtain 460g colourless liquid (trimethyl citrates
The separation yield of benchmark：94%).
Product structure is confirmed through following physics value.
MS(m/e)：1015(M+1)
1H-NMR(CDCl3, δ (ppm))：0.96 (9H), 1.25 (6H), 2.0 (1H), 2.75 (4H), 3.29 (6H), 3.65
(6H), 4.25 (6H), 3.54 (36H), 4.65 (12H).
Performance characterization
1st, light-cured performance
Cation photocuring composition to be tested is prepared respectively according to the formula in table 1.
The formula of the light-cured performance composition to be measured of table 1
In table 1, compound 17-20,6110, the structural formula of cation light initiator PAG-202 and sensitizer 1331 are such as
Under：
Compound 18 and 20 is that two kinds mentioned in Chinese invention patent application CN1743373 are used for the oxa- ring of heat cure
Butane compound.Compound 17-20 is obtained by ester exchange reaction synthesis.
Using bar spreader, the cation photocuring composition of preparation is coated into the thick films of 25um on slide
(solventless formulation, without drying, can be directly used for solidification), solidifies, the power of LED is in the case where wavelength is 395nm LED
25mw/cm2.Record hardening time and effect.
Test result is as shown in table 1.It can be seen that, closed compared to the existing esterification containing oxetane groups
Thing, the ester compounds curing rate containing oxetane groups disclosed by the invention with structure shown in formula (1) is obvious
Improve, light-cured performance is more excellent.
In order to more fully understand the light-cured performance of ester compounds shown in the formula (1) of the present invention, match somebody with somebody according to shown in table 2
More cation photocuring compositions are made, and its light-cured performance is characterized using same procedure.
Table 2
As a result show, the ester compounds containing oxetane groups shown in formula (1) of the present invention are solid in cationic photopolymerization
Without what big difference in change system, laser curing velocity quickly is respectively provided with.And then, even if such compound is not pure change
Compound does not interfere with the curing rate of formula system yet, and suitable esterification can be selected to close according to the performance requirement of final products
Thing carries out formula adjustment, so as to provide more selectable raw material to cation photocuring system.
2nd, pliability and hardness
Pliability method of testing：Compound composition is coated into the thick films of 25um, solidification with bar spreader on a pet film
After completely, whether doubling PET film, the film of observation solidification has vestige.
The good and bad criterion of pliability：(1) good-without vestige；(2) in-there is vestige, but do not split；(3) it is poor-to split
Open.
Hardness test mode：After cured film is stood into 24 hours in 25 DEG C, the thermostatic chamber of humidity 60%, according to
The pencil hardness of ISK5600-5-4 test surfaces.
Film-forming flexibility and hardness test result are listed in table 3.
Table 3
6110 are added to by the ester compounds containing oxetane groups shown in formula (1) it can be seen from the result of table 3
In can be very good to adjust the pliability of film-forming, and without the hardness of the original film of reduction, improve the performance of original film.
It in summary it can be seen, the ester compounds for the oxetane group-containing that the present invention is provided are applied to cation photocuring
Very excellent light-cured performance can be shown during formula, hardening time is extremely short, be significantly better than existing similar compound, and produce
Thing has excellent pliability and hardness.
Claims (2)
1. the ester compounds containing oxetane groups, with the structure shown in following compound 5 or compound 13：
2. the answering in cation photocuring composition of the ester compounds containing oxetane groups described in claim 1
With.
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| PCT/CN2015/093608 WO2016066146A1 (en) | 2014-10-31 | 2015-11-02 | Ester compound containing oxetane group and preparation method thereof |
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| US11555022B2 (en) | 2016-07-13 | 2023-01-17 | Changzhou Tronly New Electronic Materials Co., Ltd. | Polyfunctional oxetane-based compound and production method thereof |
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| CN104447635B (en) * | 2014-10-31 | 2017-09-15 | 常州强力电子新材料股份有限公司 | A kind of ester compounds of oxetane group-containing and preparation method thereof |
| CN107621752B (en) | 2016-07-13 | 2019-11-12 | 常州强力先端电子材料有限公司 | One specific admixture type photosensitive resin and preparation method thereof |
| CN109305947B (en) * | 2017-07-27 | 2023-01-13 | 常州强力先端电子材料有限公司 | Oxetane monomer compound and preparation method thereof |
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| US11555022B2 (en) | 2016-07-13 | 2023-01-17 | Changzhou Tronly New Electronic Materials Co., Ltd. | Polyfunctional oxetane-based compound and production method thereof |
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