CN104910123A - Adamantyl resin monomer mixture and manufacturing method thereof - Google Patents
Adamantyl resin monomer mixture and manufacturing method thereof Download PDFInfo
- Publication number
- CN104910123A CN104910123A CN201510303782.0A CN201510303782A CN104910123A CN 104910123 A CN104910123 A CN 104910123A CN 201510303782 A CN201510303782 A CN 201510303782A CN 104910123 A CN104910123 A CN 104910123A
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- CN
- China
- Prior art keywords
- adamantyl
- resin monomer
- mixture
- parameter
- tannin
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- XGKDWGVPHMUSQQ-UHFFFAOYSA-N CC1C=C(CCC2)CC2C1 Chemical compound CC1C=C(CCC2)CC2C1 XGKDWGVPHMUSQQ-UHFFFAOYSA-N 0.000 description 1
- 0 CCCC(c1c(*)c(C(*)(CC)C(C2=CC3=*=C3C=C2C(C(C)C)=O)=O)cc(C(C(*)C2*(*)*)Oc3c2ccc(OC(C2=CC4=*=C4C=C2C(O)O)=O)c3C(*)(*)C(C)(CC(C2)C3)C4IC23CCC4)c1)OC(c1c(C(C(C)(C)O)O)cccc1)=O Chemical compound CCCC(c1c(*)c(C(*)(CC)C(C2=CC3=*=C3C=C2C(C(C)C)=O)=O)cc(C(C(*)C2*(*)*)Oc3c2ccc(OC(C2=CC4=*=C4C=C2C(O)O)=O)c3C(*)(*)C(C)(CC(C2)C3)C4IC23CCC4)c1)OC(c1c(C(C(C)(C)O)O)cccc1)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
Abstract
The invention provides an adamantyl resin monomer mixture and a manufacturing method thereof. The adamantyl resin monomer contains a tannin framework, an adamantyl group and a phthalic anhydride group, wherein the adamantyl group can enhance the space volume, structural stability and high temperature resistance of the resin monomer; and the tannin framework is a natural high polymer which can enhance the molecular weight of the monomer and can be separated and extracted from natural plant resources, and is beneficial to enhancing the bioactivity of the resin monomer. The adamantyl epoxy resin monomer also has the phthalic anhydride group capable of enhancing the reaction activity of the resin monomer during polymerization reaction, so that the reaction can easily occur.
Description
Technical field
The present invention relates to adamantyl resin monomer.More particularly, the present invention relates to have and manufacture adamantyl resin monomer and manufacture method.
Background technology
Along with dental compound resin performance update and perfect, its intensity, hardness and wear resistance etc. have satisfied the demands, but the long-time existence of research display dental compound resin curing shrinkage internal stress can cause mechanical strength of resin to reduce, microfracture, even Materials Fracture can be caused, therefore develop high reaction activity, low-shrinkage to have the resin monomer of commercial applications significant.
Diamantane is a kind of ring-type tetrahedron hydrocarbon containing 10 carbon atoms and 16 hydrogen atoms, and its basic structure is chair shape hexanaphthene, and it is a kind of high degree of symmetry and highly stable compound.Diamantane has, and (1) is highly stable to light; (2) lubricating capacity is good; (3) extreme oleophylic: (4) basic odorless is sublimate; (5) although should be active in benzene, the features such as its derivative is very easy to be synthesized.Condensation class tannin contains polyphenol hydroxyl and is natural macromolecular material, be present in the positions such as the leaf of plant, fruit, root and bark widely, it is important natural polyphenol class active substance, it is only second to Mierocrystalline cellulose, hemicellulose and xylogen at the content in plant, reserves are very abundant, can well replace polyhydroxy-benzene intermediate.
Adamantyl and natural macromolecular tannin are introduced resin monomer, resin monomer can possess the advantage of tannin and adamantyl, wherein adamantyl can improve the resistance toheat of resin, oxidation-resistance and thermal stability, increase the intensity of polymkeric substance, and tannin molecule is drawn materials extensively, can give resin good biocompatibility.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, described adamantyl resin monomer contains tannin skeleton, adamantyl and phthalic acid anhydride group, diamantane group, can improve the spatial volume of resin monomer, structural stability and resistance to elevated temperatures; Tannin skeleton be natural polymer can not only improve monomer molecular weight and also can from natural plant resource separation and Extraction, be conducive to improving the biological activity of resin monomer.Based on this discovery, complete the present invention.
An object of the present invention is to solve at least the problems referred to above, and the advantage will illustrated at least is below provided.
The adamantyl epoxy monomer that a further object of the invention is to provide also has phthalic acid anhydride group, reactive behavior when can improve resin monomer polyreaction, makes reaction conditions gentle.
In order to realize according to these objects of the present invention and other advantage, provide a kind of mixture of adamantyl resin monomer, described adamantyl resin monomer structural formula is as follows:
[chemical formula 1]
Wherein, R
2represent C
nh
2n+1or C
3h
6o
2, and parameter n is the integer of 1-10; R
3represent C
nh
2n+1, and parameter n is the integer of 1-10; Parameter m is the integer of 1 ~ 30; Parameter a=0 or 1; Parameter b=0 or 1.
Preferably, wherein, the adamantane derivative that described [chemical formula 2] represents is the skeleton of resin monomer, for tannin and halo diamantane react obtained.
[chemical formula 2]
Wherein, R
1represent C
nh
2n+1or OH, and parameter n is the integer of 1-10, parameter m is the integer of 1-30; Parameter a=0 or 1, parameter b=0 or 1.
Preferably, wherein, described tannin is natural macromolecular, and its molecular weight is between 500-10000.
Preferably, wherein, described tannin also comprises and is selected from following any one or more: larch tannin, black wattle plant tannin and heavily fortified point wood tannin.
Object of the present invention also has a kind of manufacture method of mixture of adamantyl resin monomer, and described method comprises:
Step 1: add adamantane derivative and Tetra hydro Phthalic anhydride and derivative thereof in there-necked flask, add stirring solvent and make reactants dissolved, rear basic catalyst, wherein, there is ring-opening reaction in the amount ratio 1: 0.5 ~ 0.8: 0.08 ~ 0.2 of adamantane derivative and Tetra hydro Phthalic anhydride and derivative and basic catalyst at 80-130 DEG C of temperature;
Step 2: add basic catalyst again, the now amount ratio 1: 0.1 ~ 0.4 of adamantane derivative and basic catalyst, temperature of reaction is adjusted to 30-80 DEG C, and ring-closure reaction occurs, and generates adamantyl resin monomer.
Preferably, wherein, step 1 neutral and alkali catalyzer comprises and is selected from following any one or more: potassium hydroxide, lithium hydroxide, hydrated barta, sodium hydroxide.
Preferably, wherein, in step 1, solvent comprises and is selected from following any one or more: ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, benzene and acetone.
Preferably, wherein, in step 1, the amount ratio of adamantane derivative and Tetra hydro Phthalic anhydride and derivative and basic catalyst is preferably 1: 0.6: 0.1.
Preferably, wherein, in step 2, temperature of reaction is preferably 65 DEG C.
Preferably, wherein, the amount ratio 1: 0.25 of adamantane derivative and basic catalyst in step 2.
The present invention at least comprises following beneficial effect: the natural macromolecular tannin of this diamantane epoxy monomer mixture containing polyphenol hydroxyl instead of raw material polyhydroxy-benzene, and molecular weight and the tannin raw material sources that can not only improve monomer are more extensive; Owing to introducing diamantane group in resin monomer, the spatial volume of resin monomer, structural stability and resistance to elevated temperatures can be improved.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other assembly one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
By as follows for the resin monomer A structural formula of preparation:
< example 1>
Step 1: add adamantane derivative 20g and Tetra hydro Phthalic anhydride 12g in there-necked flask, adds acetone solvent stirring and makes reactants dissolved, add basic catalyst potassium hydroxide 2g, at 80 DEG C of temperature, ring-opening reaction occurs;
Step 2: add basic catalyst potassium hydroxide 3g again, temperature of reaction is adjusted to 65 DEG C, and ring-closure reaction occurs, and generate adamantyl resin monomer A, productive rate is 74.1%.
Adamantane derivative structure is as follows
< example 2>
Step 1: add adamantane derivative 20g and Tetra hydro Phthalic anhydride 12g in there-necked flask, adds acetone solvent stirring and makes reactants dissolved, add basic catalyst potassium hydroxide 2g, at 90 DEG C of temperature, ring-opening reaction occurs;
Step 2: add basic catalyst potassium hydroxide 3g again, temperature of reaction is adjusted to 65 DEG C, and ring-closure reaction occurs, and generate adamantyl resin monomer A, productive rate is 83%.
< example 3>
Step 1: add adamantane derivative 20g and Tetra hydro Phthalic anhydride 12g in there-necked flask, adds acetone solvent stirring and makes reactants dissolved, add basic catalyst potassium hydroxide 2g, at 100 DEG C of temperature, ring-opening reaction occurs;
Step 2: add basic catalyst potassium hydroxide 3g again, temperature of reaction is adjusted to 65 DEG C, and ring-closure reaction occurs, and generate adamantyl resin monomer A, productive rate is 87%.
< example 4>
Step 1: add adamantane derivative 20g and Tetra hydro Phthalic anhydride 12g in there-necked flask, adds acetone solvent stirring and makes reactants dissolved, add basic catalyst potassium hydroxide 2g, at 110 DEG C of temperature, ring-opening reaction occurs;
Step 2: add basic catalyst potassium hydroxide 3g again, temperature of reaction is adjusted to 65 DEG C, and ring-closure reaction occurs, and generate adamantyl resin monomer A, productive rate is 90.3%.
< example 5>
Step 1: add adamantane derivative 20g and Tetra hydro Phthalic anhydride 12g in there-necked flask, adds acetone solvent stirring and makes reactants dissolved, add basic catalyst potassium hydroxide 2g, at 120 DEG C of temperature, ring-opening reaction occurs;
Step 2: add basic catalyst potassium hydroxide 3g again, temperature of reaction is adjusted to 65 DEG C, and ring-closure reaction occurs, and generate adamantyl resin monomer A, productive rate is 91.7%.
< example 6>
Step 1: add adamantane derivative 20g and Tetra hydro Phthalic anhydride 12g in there-necked flask, adds acetone solvent stirring and makes reactants dissolved, add basic catalyst potassium hydroxide 2g, at 130 DEG C of temperature, ring-opening reaction occurs;
Step 2: add basic catalyst potassium hydroxide 3g again, temperature of reaction is adjusted to 65 DEG C, and ring-closure reaction occurs, and generate adamantyl resin monomer A, productive rate is 92.3%.
Table 1
Can find out from upper table 1, the impact of test temperature is discussed: along with increase temperature sage lid in example 1-6, the productive rate of resin improves greatly, when temperature reaches 130 DEG C be, productive rate is up to 92.3%, but the productive rate comparatively implementing 5 only exceeds 0.6%, comes relatively from reaction conditions and productive rate, and when temperature is 120 DEG C, the higher and temperature of reaction of productive rate more easily reaches.
The present invention at least comprises following beneficial effect: this adamantyl resin monomer contains tannin skeleton, adamantyl and phthalic acid anhydride group, and diamantane group can improve the spatial volume of resin monomer, structural stability and resistance to elevated temperatures; Tannin skeleton be natural polymer can not only improve monomer molecular weight and also can from natural plant resource separation and Extraction, be conducive to improving the biological activity of resin monomer.Adamantyl epoxy monomer also has phthalic acid anhydride group, can improve reactive behavior when resin monomer can improve polyreaction, make reaction conditions gentle.
Although embodiment of the present invention are open as above, it is not restricted to listed in specification sheets and embodiment utilization.It can be applied to various applicable the field of the invention completely.For those skilled in the art, can easily realize other amendment.Therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (10)
1. a mixture for adamantyl resin monomer, described adamantyl resin monomer structural formula is as follows:
Wherein, R
2represent C
nh
2n+1or C
3h
60
2, and parameter n is the integer of 1-10; R3 represents C
nh
2n+1, and parameter n is the integer of 1-10; Parameter m is the integer of 1 ~ 30; Parameter a=0 or 1; Parameter b=0 or 1.
2. the mixture of adamantyl resin monomer as claimed in claim 1, the adamantane derivative that described [chemical formula 2] represents is the skeleton of resin monomer, for tannin and halo diamantane react obtained.
Wherein, R
1represent C
nh
2n+1or OH, and parameter n is the integer of 1-10, parameter m is the integer of 1-30; Parameter a=0 or 1, parameter b=0 or 1.
3. the mixture of adamantyl resin monomer as claimed in claim 2, wherein said tannin is natural macromolecular, and its molecular weight is between 500-10000.
4. the mixture of as claimed in claim 2 or claim 3 adamantyl resin monomer, wherein said tannin also comprises and is selected from following any one or more: larch tannin, black wattle plant tannin and heavily fortified point wood tannin.
5. a manufacture method for the mixture of adamantyl resin monomer, described method comprises:
Step 1: add adamantane derivative and Tetra hydro Phthalic anhydride and derivative thereof in there-necked flask, add stirring solvent and make reactants dissolved, rear basic catalyst, wherein, there is ring-opening reaction in the amount ratio 1: 0.5 ~ 0.8: 0.08 ~ 0.2 of adamantane derivative and Tetra hydro Phthalic anhydride and derivative and basic catalyst at 80-130 DEG C of temperature;
Step 2: add basic catalyst again, the now amount ratio 1: 0.1 ~ 0.4 of adamantane derivative and basic catalyst, temperature of reaction is adjusted to 30-80 DEG C, and ring-closure reaction occurs, and generates adamantyl resin monomer.
6. the manufacture method of the mixture of adamantyl resin monomer as claimed in claim 5, wherein step 1 neutral and alkali catalyzer comprises and is selected from following any one or more: potassium hydroxide, lithium hydroxide, hydrated barta, sodium hydroxide.
7. the manufacture method of the mixture of adamantyl resin monomer as claimed in claim 5, wherein in step 1, solvent comprises and is selected from following any one or more: ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, benzene and acetone.
8. the manufacture method of the mixture of adamantyl resin monomer as claimed in claim 5, wherein in step 1, the amount ratio of adamantane derivative and Tetra hydro Phthalic anhydride and derivative and basic catalyst is preferably 1: 0.6: 0.1.
9. the manufacture method of the mixture of adamantyl resin monomer as claimed in claim 5, wherein in step 2, temperature of reaction is preferably 65 DEG C.
10. the manufacture method of the mixture of adamantyl resin monomer as claimed in claim 5, the wherein amount ratio 1: 0.25 of adamantane derivative and basic catalyst in step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510303782.0A CN104910123A (en) | 2015-05-30 | 2015-05-30 | Adamantyl resin monomer mixture and manufacturing method thereof |
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|---|---|---|---|
| CN201510303782.0A CN104910123A (en) | 2015-05-30 | 2015-05-30 | Adamantyl resin monomer mixture and manufacturing method thereof |
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|---|---|
| CN104910123A true CN104910123A (en) | 2015-09-16 |
Family
ID=54079621
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|---|---|---|---|
| CN201510303782.0A Pending CN104910123A (en) | 2015-05-30 | 2015-05-30 | Adamantyl resin monomer mixture and manufacturing method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3580964A (en) * | 1967-09-06 | 1971-05-25 | Sun Oil Co | Curable linear polyesters |
| US20070003862A1 (en) * | 2005-06-16 | 2007-01-04 | Fujitsu Limited | Resist composition, method of forming resist pattern, semiconductor device and method of manufacturing thereof |
| CN101253162A (en) * | 2005-09-01 | 2008-08-27 | 出光兴产株式会社 | Adamantane derivative, resin composition containing same, and optical electronic component using same |
| CN101258178A (en) * | 2005-09-05 | 2008-09-03 | 出光兴产株式会社 | Adamantane derivative, epoxy resin, and optical electronic component using resin composition containing same |
| CN101370797A (en) * | 2006-01-27 | 2009-02-18 | 出光兴产株式会社 | Adamantane derivative, resin composition containing the derivative, and optical electronic component and electronic circuit sealing agent using the same |
| CN101747310A (en) * | 2008-12-11 | 2010-06-23 | 住友化学株式会社 | Compound and chemically amplified resist composition containing the same |
| US20110236827A1 (en) * | 2010-03-26 | 2011-09-29 | Sumitomo Chemical Company, Limited | Resin and photoresist composition containing the same |
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-
2015
- 2015-05-30 CN CN201510303782.0A patent/CN104910123A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3580964A (en) * | 1967-09-06 | 1971-05-25 | Sun Oil Co | Curable linear polyesters |
| US20070003862A1 (en) * | 2005-06-16 | 2007-01-04 | Fujitsu Limited | Resist composition, method of forming resist pattern, semiconductor device and method of manufacturing thereof |
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| CN101370797A (en) * | 2006-01-27 | 2009-02-18 | 出光兴产株式会社 | Adamantane derivative, resin composition containing the derivative, and optical electronic component and electronic circuit sealing agent using the same |
| CN101747310A (en) * | 2008-12-11 | 2010-06-23 | 住友化学株式会社 | Compound and chemically amplified resist composition containing the same |
| US20110236827A1 (en) * | 2010-03-26 | 2011-09-29 | Sumitomo Chemical Company, Limited | Resin and photoresist composition containing the same |
| CN102276468A (en) * | 2011-05-04 | 2011-12-14 | 常州大学 | Resin containing adamantanes, preparation method and application of resin |
| CN102311346A (en) * | 2011-06-20 | 2012-01-11 | 常州大学 | Adamantane-containing resin as well as preparation method and application thereof |
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Application publication date: 20150916 |
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