CN104447635A - Ester compound containing oxetane group and preparation method thereof - Google Patents
Ester compound containing oxetane group and preparation method thereof Download PDFInfo
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- CN104447635A CN104447635A CN201410606649.8A CN201410606649A CN104447635A CN 104447635 A CN104447635 A CN 104447635A CN 201410606649 A CN201410606649 A CN 201410606649A CN 104447635 A CN104447635 A CN 104447635A
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- Prior art keywords
- containing oxetane
- oxetane groups
- ester cpds
- general formula
- ester
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- 0 CCC1(CC(C)*CNC)COC1 Chemical compound CCC1(CC(C)*CNC)COC1 0.000 description 3
- MXLQHBLSOUOYIM-UUEFVBAFSA-N CC1(C)C2(C)[C@H]1COC2 Chemical compound CC1(C)C2(C)[C@H]1COC2 MXLQHBLSOUOYIM-UUEFVBAFSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention discloses an ester compound containing oxetane group. The compound has polyfunctionality, high stability and high cationic reaction activity and is simple and convenient to prepare and high in yield. The ester compound which is applied to a cationic photo-curing formula can represent a very excellent photo-curing property and is extremely short in curing time and obviously superior to the existing similar compound, and moreover, the product has excellent flexibility and hardness.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of to there is ester cpds of the oxetane group-containing of high-cation reactive behavior and preparation method thereof.
Background technology
In cationically photocurable formulation, the ester cpds reactive behavior of existing oxetane group-containing is general not high, even if long-time illumination can not be solidified completely.Such as, disclose the carboxylate of 4 kinds of oxygen heterocyclic ring butane group in Chinese invention patent application CN1743373, its bottom be applicable in semiconductor subassembly is filled, and is interconnected the bonding at place especially for lead-free solder at electric wire, but what they adopted is heat curing techniques, needs hot setting; Disclose the carboxylate with similar structures in Chinese invention patent application CN100569825, can be used as thermofixation and photo-curing material.But, the monomer of the oxetane group-containing in above-mentioned document all can not solidify completely under photocuring, need the steps such as subsequent heat that formula is solidified completely, thus reduce production efficiency, limit the application of ester compound at curing field of oxetane group-containing.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of ester cpds of oxetane group-containing, this compound can show very excellent light-cured performance when being applied to cationically photocurable formulation, and set time is extremely short, is significantly better than existing similar compound.Further, this compound can give excellent snappiness to the polymerisate formed by this compound.
Ester cpds containing oxetane groups of the present invention, has structure shown in general formula (1):
Wherein, R
1for n valency group, be selected from substituted or unsubstituted C
1-C
12alkyl, substituted or unsubstituted C
6-C
30aryl, substituted or unsubstituted C
2-C
30heteroaryl; R
2represent C
1-C
30alkylene ,-the CH in its main chain
2-optionally being replaced by Sauerstoffatom, condition is that two-O-are not directly connected; R
3represent substituted or unsubstituted C
1-C
6alkyl; N=1,2,3 or 4.
Preferably, in ester cpds shown in general formula (1), R
1be selected from C
1-C
6the n valency alkyl of straight or branched or substituted alkyl, C
2-C
4n valency thiazolinyl, the C of straight or branched
6-C
12n valency aryl or substituted aryl.Further preferably, R
1be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl ,-(CH
2)
m-(wherein m=2,3,4,5) ,-CH
2-CH (CH
3)-CH
2-,-CH
2-C (OH)-CH
2-, vinyl, 1-methyl ethylene, n valency phenyl or xenyl or naphthyl.More preferably, R
1be selected from methyl, ethyl, propyl group ,-(CH
2)
m-(wherein m=2,3,4,5) ,-CH
2-C (OH)-CH
2-, vinyl, 1-methyl ethylene, Isosorbide-5-Nitrae-phenylene, 1,3,4-phenenyl, 2,3,5,6-tetravalence phenyl.
Preferably, in ester cpds shown in general formula (1), R
2be selected from C
2-C
8straight or branched alkylidene group, its main chain can with ether.Further preferably, R
2be selected from-(CH
2)
m-(wherein m=3,4,5) ,-CH
2-CH (CH
3)-CH
2-,-CH
2-CH (CH
3)-(CH
2)
2-,-(CH
2-CH (CH
3)-O)
m-CH
2-CH (CH
3)-(be m=0 wherein, and 1 or 2) or-(CH
2-CH
2-O)
m-CH
2-CH
2-(wherein m=0,1,2 or 3).More preferably, R
2be selected from-(CH
2-cH (CH
3)-O)
m-CH
2-CH (CH
3)-(be m=0 wherein, and 1 or 2) or-(CH
2-CH
2-O)
m-CH
2-CH
2-(wherein m=0,1,2 or 3).
Preferably, in ester cpds shown in general formula (1), R
3be selected from C
1-C
6straight or branched alkyl.Further preferably, R
3be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl.
The present invention also aims to the preparation method that the above-mentioned ester cpds containing oxetane groups is provided, comprising: reacted in the presence of a catalyst by the alcohol containing oxetane groups shown in the ester shown in general formula (2) and general formula (3) and form
Wherein, R
1, R
2, R
3with the definition of n as described in general formula (1), R ' represents methyl or ethyl.
Exemplarily, in above-mentioned preparation method, the ester shown in general formula (2) is selected from following compounds:
Exemplarily, in above-mentioned preparation method, the alcohol containing oxetane groups shown in general formula (3) is selected from following compounds:
In preparation method of the present invention, the mol ratio of the alcohol containing oxetane groups shown in the ester shown in general formula (2) and general formula (3) is 1:1-10, is preferably 1:1.2-5.
The catalyzer used in preparation method can be: Lithamide, as diisopropylamino lithium, hexamethl disilamine base lithium etc.; Alkali metal hydroxide, as sodium hydroxide, potassium hydroxide etc.; Alkaline carbonate, as sodium carbonate, salt of wormwood etc.; Alkali metal hydrocarbonate, as sodium bicarbonate, saleratus etc.; Titanic acid ester, as tetraethyl titanate, titanium isopropylate, metatitanic acid orthocarbonate, tetrabutyl titanate etc.The preferred titanic acid ester of described catalyzer, titanate compound can be independent or two or more used in combination, more preferably titanium isopropylate.The consumption of catalyzer is easily determined to those skilled in the art, preferably, catalyst levels is the 0.1-20% of the quality sum of the alcohol containing oxetane groups shown in the ester shown in general formula (2) and general formula (3), more preferably 1-10%.
Reaction of the present invention is carried out in the presence of the solvent or under non-existence.Useable solvents is not particularly limited, only otherwise impact react, can be such as: the nitrile of acetonitrile, propionitrile, benzonitrile etc.; The amides of DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone etc.; The ethers of tetrahydrofuran (THF), dioxane etc.; The aromatic hydrocarbons class of benzene,toluene,xylene etc.Solvent optimization aromatic hydrocarbon, more preferably toluene, dimethylbenzene.Moreover above-mentioned solvent can be independent or two or more used in combination.The usage quantity of solvent suitably can regulate according to the homogeneity of reaction system and stirring property, and this easily determines to those skilled in the art.In general, relative to 1g general formula (3) shown in containing the alcohol of oxetane groups, solvent load is 0-100g, preferred 1-20g.
Above-mentioned reaction of the present invention is carried out in the liquid phase, and temperature of reaction is 0-200 DEG C, and preferred 50-150 DEG C, reaction pressure has no particular limits.
By reaction of the present invention, can obtain having the ester cpds containing oxetane groups of structure shown in general formula (1).After reaction terminates, adopt filtrations, layering, concentrate, the ordinary method such as distillation carries out being separated and refining.
The present invention also aims to provide the above-mentioned application of ester cpds in cation photocuring composition containing oxetane groups.
The ester cpds containing oxetane groups with structure shown in general formula (1) disclosed by the invention has polyfunctionality, high stability and high-cation reactive behavior, and its prepare easy, yield is high.
Embodiment
Below further will illustrate the present invention with embodiment, but scope of the present invention is not limited to these embodiments.When following " % " is not particularly illustrated, all represent " quality % ".
preparation embodiment
Preparation has the ester cpds containing oxetane groups of following structure respectively:
Wherein, R is selected from having structure:
In embodiment, the raw polyol of corresponding general formula (3) is selected from following structure:
Embodiment 1
The synthesis of compound 1
In the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the methyl methacrylate of the raw material 1 of 160g (1.0mol), 500g (5.0mol), keep 110 DEG C of backflows, adjustment reflux ratio is 3:1, the system moisture for the treatment of is down to below 500ppm, add catalyzer titanium isopropylate 6.6g (accounting for 1% of total charging capacity), continue backflow 3 hours.After reaction terminates, be cooled to 70 DEG C, add 25g water, 70 DEG C are incubated half an hour, destroy catalyzer, filter, and filtrate concentrates, and obtains the 216g colourless liquid (separation yield of raw material 1 benchmark: 95%)
The structure of product Compound 1 by mass spectrum and
1h-NMR is confirmed.
MS(m/e)：229(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 2 of 204g (1.0mol), all the other operate reference example 1.261g colourless transparent liquid (the separation yield of raw material 2 benchmark: 96%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：273(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 3 of 248g (1.0mol), all the other operate reference example 1.294g colourless transparent liquid (the separation yield of raw material 3 benchmark: 93%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：317(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 4 of 292g (1.0mol), all the other operate reference example 1.324g colourless transparent liquid (the separation yield of raw material 4 benchmark: 90%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：361(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 1 of 320g (2.0mol), the dimethyl adipate of 174g (1.0mol), toluene 400mL, keep 110 DEG C of backflows, adjustment reflux ratio is 3:1, the system moisture for the treatment of is down to below 500ppm, add catalyzer titanium isopropylate 5g (accounting for about 1% of total charging capacity), continue backflow 3 hours.After reaction terminates, be cooled to 70 DEG C, add 25g water, 70 DEG C are incubated half an hour, destroy catalyzer, filter, and filtrate concentrates, and obtains the 404g colourless liquid (separation yield of dimethyl adipate benchmark: 94%).
Product structure is confirmed through following physics value.
MS(m/e)：431(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 2 of 408g (2.0mol), all the other operate reference example 5.477g colourless liquid (the separation yield of dimethyl adipate benchmark: 92%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：519(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 2000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 3 of 496g (2.0mol), all the other operate reference example 5.576g colourless liquid (the separation yield of dimethyl adipate benchmark is obtained through concentrated; 95%).
Product structure is confirmed through following physics value.
MS(m/e)：607(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 2000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 4 of 584g (2.0mol), all the other operate reference example 5.660g colourless liquid (the separation yield of dimethyl adipate benchmark: 95%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：695(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 1 of 320g (2.0mol), the dimethyl terephthalate (DMT) of 194g (1.0mol), toluene 400mL, keep 110 DEG C of backflows, adjustment reflux ratio is 3:1, the system moisture for the treatment of is down to below 500ppm, add catalyzer titanium isopropylate 5g (accounting for about 1% of total charging capacity), continue backflow 3 hours.After reaction terminates, be cooled to 70 DEG C, add 25g water, 70 DEG C are incubated half an hour, destroy catalyzer, filter, and filtrate concentrates, and obtains the 432g colourless liquid (separation yield of dimethyl terephthalate (DMT) benchmark: 96%).
Product structure is confirmed through following physics value.
MS(m/e)：451(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 2 of 408g (2.0mol), all the other operate reference example 9.500g colourless liquid (the separation yield of dimethyl terephthalate (DMT) benchmark: 93%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：539(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 2000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 3 of 496g (2.0mol), all the other operate reference example 9, obtain the 588g colourless liquid (separation yield of dimethyl terephthalate (DMT) benchmark: 94%) through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：627(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 2000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 4 of 496g (2.0mol), all the other operate reference example 9, obtain the 588g colourless liquid (separation yield of dimethyl terephthalate (DMT) benchmark: 94%) through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：715(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 1 of 240g (1.5mol), 117g (0.5mol) trimethyl citrate, toluene 400mL, keep 110 DEG C of backflows, adjustment reflux ratio is 3:1, the system moisture for the treatment of is down to below 500ppm, add catalyzer titanium isopropylate 3.5g (accounting for about 1% of total charging capacity), continue backflow 3 hours.After reaction terminates, be cooled to 70 DEG C, add 25g water, 70 DEG C are incubated half an hour, destroy catalyzer, filter, and filtrate concentrates, and obtains the 262g colourless liquid (separation yield of trimethyl citrate benchmark: 90%).
Product structure is confirmed through following physics value.
MS(m/e)：619(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 2 of 306g (1.5mol), all the other operate reference example 13.339g colourless liquid (the separation yield of trimethyl citrate benchmark: 95%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：751(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000ml with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 3 of 372g (1.5mol), all the other operate reference example 13.402g colourless liquid (the separation yield of trimethyl citrate benchmark: 95%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：883(M+1)
1H-NMR(CDCl
3，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
To in the glass flask of volume 1000mL with whipping appts, thermometer, 60cm packing tower and Rectification head, add the raw material 4 of 438g (1.5mol), all the other operate reference example 13.460g colourless liquid (the separation yield of trimethyl citrate benchmark: 94%) is obtained through concentrated.
Product structure is confirmed through following physics value.
MS(m/e)：1015(M+1)
1H-NMR(CDCl
3，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
1, light-cured performance
Cation photocuring composition to be tested is prepared respectively according to the formula in table 1.
The formula of table 1 light-cured performance composition to be measured
In table 1, compound 17-20,6110, the structural formula of cation light initiator PAG-202 and sensitizing agent 1331 is as follows:
Compound 18 and 20 is the two kinds of oxetane compounds for thermofixation mentioned in Chinese invention patent application CN1743373.Compound 17-20 is all obtained by transesterification reaction synthesis.
Adopt line rod spreader, the cation photocuring composition of preparation is coated on slide glass the thick film of 25um (solventless formulation, without the need to drying, can be directly used in solidification), be solidify under the LED of 395nm at wavelength, the power of LED is 25mw/cm
2.Record set time and effect.
Test result is as shown in table 1.Can see, compared to the existing ester cpds containing oxetane groups, the ester cpds curing speed containing oxetane groups with structure shown in general formula (1) disclosed by the invention significantly improves, and light-cured performance is more excellent.
In order to more fully understand the light-cured performance of ester cpds shown in general formula of the present invention (1), preparing more cation photocuring composition according to table 2 Suo Shi, and adopting same procedure to characterize its light-cured performance.
Table 2
Result shows, the difference that the ester cpds containing oxetane groups shown in general formula of the present invention (1) is large less than what in cation photocuring system, all has very fast laser curing velocity.And then, even if this compounds is not the curing speed that pure compound also can not affect formula system, suitable ester cpds can be selected to carry out formula adjustment according to the performance requriements of the finished product, thus provide more how selectable starting material to cation photocuring system.
2, snappiness and hardness
Snappiness testing method: compound composition line rod spreader is coated into the thick film of 25um on a pet film, after completion of cure, doubling PET film, whether the film observing solidification has vestige.
The judging criterion of snappiness quality: (1) good-without vestige; (2) in-there is vestige, but do not split; (3) poor-split.
Hardness test mode: by cured film 25 DEG C, leave standstill 24 hours in the thermostatic chamber of humidity 60% after, according to the pencil hardness of ISK5600-5-4 test surfaces.
Film-forming flexibility and hardness test result list in table 3.
Table 3
As can be seen from table 3 result, the ester cpds containing oxetane groups shown in general formula (1) joins the snappiness that can well regulate film-forming in 6110, and does not reduce the hardness of original film, improves the performance of original film.
In summary it can be seen, the ester cpds of oxetane group-containing provided by the invention can show very excellent light-cured performance when being applied to cationically photocurable formulation, set time is extremely short, is significantly better than existing similar compound, and product has excellent snappiness and hardness.
Claims (10)
1. the ester cpds containing oxetane groups, has structure shown in general formula (1):
Wherein, R
1for n valency group, be selected from substituted or unsubstituted C
1-C
12alkyl, substituted or unsubstituted C
6-C
30aryl, substituted or unsubstituted C
2-C
30heteroaryl; R
2represent C
1-C
30alkylene ,-the CH in its main chain
2-optionally being replaced by Sauerstoffatom, condition is that two-O-are not directly connected; R
3represent substituted or unsubstituted C
1-C
6alkyl; N=1,2,3 or 4.
2. the ester cpds containing oxetane groups according to claim 1, is characterized in that: R
1be selected from C
1-C
6the n valency alkyl of straight or branched or substituted alkyl, C
2-C
4n valency thiazolinyl, the C of straight or branched
6-C
12n valency aryl or substituted aryl.
3. the ester cpds containing oxetane groups according to claim 1 and 2, is characterized in that: R
1be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl ,-(CH
2)
m-(wherein m=2,3,4,5) ,-CH
2-CH (CH
3)-CH
2-,-CH
2-C (OH)-CH
2-, vinyl, 1-methyl ethylene, n valency phenyl or xenyl or naphthyl.
4. the ester cpds containing oxetane groups according to claim 1, is characterized in that: R
2be selected from C
2-C
8straight or branched alkylidene group, its main chain can with ether.
5. the ester cpds containing oxetane groups according to claim 1 or 4, is characterized in that: R
2be selected from-(CH
2)
m-(wherein m=3,4,5) ,-CH
2-CH (CH
3)-CH
2-,-CH
2-CH (CH
3)-(CH
2)
2-,-(CH
2-CH (CH
3)-O)
m-CH
2-CH (CH
3)-(be m=0 wherein, and 1 or 2) or-(CH
2-CH
2-O)
m-CH
2-CH
2-(wherein m=0,1,2 or 3).
6. the ester cpds containing oxetane groups according to claim 1, is characterized in that: R
3be selected from C
1-C
6straight or branched alkyl.
7. the ester cpds containing oxetane groups according to claim 1 or 6, is characterized in that: R
3be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl.
8. the preparation method of the ester cpds containing oxetane groups according to any one of claim 1-7, comprising: reacted in the presence of a catalyst by the alcohol containing oxetane groups shown in the ester shown in general formula (2) and general formula (3) and form
，
Wherein, R ' represents methyl or ethyl.
9. preparation method according to claim 8, is characterized in that: the mol ratio of the alcohol containing oxetane groups shown in the ester shown in general formula (2) and general formula (3) is 1:1-10, is preferably 1:1.2-5.
10. the application of ester cpds in cation photocuring composition containing oxetane groups according to any one of claim 1-7.
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| CN109305947A (en) * | 2017-07-27 | 2019-02-05 | 常州强力先端电子材料有限公司 | A kind of oxetane monomers compound and preparation method thereof |
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| WO2022063004A1 (en) * | 2020-09-27 | 2022-03-31 | 常州正洁智造科技有限公司 | Cationic curable composition |
| CN114380809A (en) * | 2021-12-30 | 2022-04-22 | 同济大学 | Ionic liquid containing cationic polymerizable group, preparation method and application |
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| WO2022063004A1 (en) * | 2020-09-27 | 2022-03-31 | 常州正洁智造科技有限公司 | Cationic curable composition |
| CN114380809A (en) * | 2021-12-30 | 2022-04-22 | 同济大学 | Ionic liquid containing cationic polymerizable group, preparation method and application |
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| CN115417835A (en) * | 2022-08-11 | 2022-12-02 | 同济大学 | Itaconic acid oxetane derived free radical-cation hybrid monomer and preparation method and application thereof |
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| WO2016066146A1 (en) | 2016-05-06 |
| CN104447635B (en) | 2017-09-15 |
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