[non-patent literature 1] Zh.Obshch.Khim.1552-1555.49. (1997)
Embodiment
Below, specify embodiment of the present invention.
In addition, in the following description, shown in the general formula (2) in the cage-type silsesquioxane resin, the compound of n=8 is called T8, the compound of n=10 is called T10, the compound of n=12 is called T12, the compound of n=14 is called T14.Cage-type silsesquioxane resin of the present invention is the cage-type silsesquioxane resin shown in the general formula (2) or to contain with it be the resin of principal constituent, can contain the different one-tenth of n number other composition that grades.In addition, when being called " cage-type silsesquioxane resin ", its implication may be interpreted as and comprises oligomer interior.
The structural formula of T8, T10, T12 and T14 is respectively shown in following formula (6), (7), (8) and (9).In addition, in (9), R is meant the organo-functional group that has in (methyl) acryl, glycidyl or the vinyl any one in following formula (6).
[changing 2]
[changing 3]
[changing 4]
[changing 5]
According to the present invention can obtain with among above-mentioned T8, T10, T12 and the T14 any one or the two more than, the mixture that is preferably 3 or 4 is main component, and preferably contains the above silsesquioxane resins of 50wt%.
Especially when organic R of functional group when having the organo-functional group of (methyl) acryl or glycidyl, by T8, T10, and T12 constituted cage-type silsesquioxane resin total, account for more than the overall 50wt%, preferably account for more than the 70wt%.In the case, can set for T8 20 to 40wt%, T10 40 to 50wt% and T12 in 5 to 20wt% scope.
Moreover, when organic functional group belongs to the situation of the functional group with vinyl, by T10, T12, and cage-type silsesquioxane resin that T14 constituted amount to, account for more than the overall 50wt%, preferably account for more than the 70wt%.In the case, can set for T10 10 to 40wt%, T12 20 to 60wt%, and T14 in 5 to 20wt% scope.
Other composition is mainly the compound beyond the different compound except that T8, T10, T12 and T14 of n value, the cage modle etc.
The molecular weight distribution of T8, T10, T12 and T14 (utilizing the gpc measurement method to measure) can be in 1.00 to 1.01 scopes.The molecular weight distribution of cage-type silsesquioxane resin of the present invention (Mw/Mn) below 1.1, is preferably in 1.03 to 1.10 scopes.Molecular weight ranges is that number-average molecular weight is 600 to 2500, in best 1000 to 2000 the scope.
Moreover, if add from the resin that contains above-mentioned T8 to T14, isolating a kind operation among the T8 to T14, also can obtain by wantonly a kind of silsesquioxane resins that is constituted among the T8 to T14 and through isolating wherein a kind silsesquioxane resins.Isolated silsesquioxane resins is also contained in the silsesquioxane resins of the present invention according to this.
In the manufacture method of silsesquioxane of the present invention, at first, in the presence of organic polar solvent and basic catalyst, implement hydrolysis reaction with the silicon compound shown in the general formula (1).In the general formula (1); R is for having the organo-functional group of (methyl) acryl, glycidyl or vinyl; and (methyl) acryl or glycidyl can directly be binding on the Si, preferably add alkyl or other divalent radicals such as alkylene or penylene therebetween.
Best organo-functional group R is shown in general formula (3).In general formula (3), R
1Be H or methyl, m is 1 to 3.If the concrete example of the R that illustration is preferable then can be illustrated as: 3-methacryloxypropyl, methacryloxy methyl, 3-acryloxy propyl group.
In general formula (1), X is water-disintegrable base, can give an example as: alkoxyl group, acetoxyl group etc. are preferably alkoxyl group.Alkoxyl group can give an example as: methoxyl group, oxyethyl group, just with isopropoxy, just, different and the 3rd butoxy etc.Wherein be preferably reactive higher methoxyl group.
In the silicon compound shown in the general formula (1), if the illustration preferred compounds then can be exemplified as: methacryloxy Union carbide A-162, methacryloxy methyltrimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-propylene acyloxy grp propyl trimethoxy silicane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, vinyltrimethoxy silane, vinyltriethoxysilane.Wherein, preferably adopt the 3-methacryloxypropyl trimethoxy silane that can obtain raw material easily.
The basic catalyst that is adopted in the hydrolysis reaction, but illustration is as ammonium hydroxide salt such as alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, cesium hydroxide or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, hydroxide benzyl TMA (TriMethylAmine), hydroxide benzyl three second ammoniums.In these,, preferably adopt tetramethylammonium hydroxide with regard to regard to the higher viewpoint of catalyst activity.Basic catalyst uses with aqueous solution state usually.
In the hydrolysis reaction condition, temperature of reaction is preferably 0 to 60 ℃, is good with 20 to 40 ℃ especially.If temperature of reaction is lower than 0 ℃, speed of response is slack-off, and water-disintegrable base will exist with unreacted state, and its result causes expending the long reaction times; Otherwise, if be higher than 60 ℃,, and carrying out complicated condensation reaction because speed of response is too quick, the result just promotes the polymer of hydrolysate to quantize.In addition, the reaction times was preferably in more than 2 hours.If the reaction times is lower than 2 hours, the reaction that can't fully be hydrolyzed makes water-disintegrable base remaining with unreacted state.
Though hydrolysis reaction must have the existence of water, but it can also can take to add in addition the mode of water by the aqueous solution supply of basic catalyst.The water yield is preferably lower than 1.0 to 1.5 times of theoretical amount at the q.s that is enough to water-disintegrable base is hydrolyzed.In addition, preferably adopt organic solvent during hydrolysis, organic solvent can adopt as alcohols or other polar solvents such as methyl alcohol, ethanol, 2-propyl alcohol.Being preferably that glassware for drinking water is had deliquescent carbon number is 1 to 6 lower alcohols, is good to adopt the 2-propyl alcohol especially.If adopt non-polar solvent, reactive system can't be even, and hydrolysis reaction can't carry out fully, and remaining unreacted alkoxyl group is therefore unsuitable.
Hydrolysis reaction just separates water or aqueous reaction solvent after finishing.The separation of water or aqueous reaction solvent can be adopted means such as reduction vaporization.For moisture, other impurity are removed fully, can adopt and add non-polar solvent dissolving hydrolysate, again this soln using salt solution etc. is cleaned, and then utilized siccative such as anhydrous magnesium sulfate to carry out the method for drying etc.If methods such as non-polar solvent utilization evaporation are carried out isolating words, though recyclable hydrolysate, if can just not need it is separated with non-polar solvent as the non-polar solvent in next reaction.
In hydrolysis reaction of the present invention, will produce the condensation reaction of hydrolyzate with hydrolysis.With the hydrolysate that condensation reaction produced of hydrolyzate, be generally the colorless viscous liquid of number-average molecular weight 500 to 7000.Hydrolysate is for different with reaction conditions, and its number-average molecular weight is at 500 to 3000 resin (or oligomer), the major part of water-disintegrable basic X shown in the general formula (1) (preferably almost whole) is substituted by the OH base, and this OH base most of best more than 95% by condensation.
About the structure of hydrolysate, the silsesquioxane of plural cage modle of planting, ladder type, random is arranged, although adopt the compound of relevant cage modle structure, the ratio of cage modle structure is also less fully, is mainly the incomplete cage modle structure that cage modle is wherein partly opened.So in the present invention, the hydrolysate that will obtain through hydrolysis in the presence of basic catalyst, by heating in organic solvent, make the siloxanes bond produce condensation (claiming " condensation again "), and selectivity is made the silsesquioxane of cage modle structure.
Water or aqueous reaction solution are given after separating, under the existence of non-polar solvent and basic catalyst, carrying out condensation reaction more again.
In the reaction conditions of relevant condensation reaction again, preferably temperature of reaction is good with 110 to 140 ℃ in 100 to 200 ℃ of scopes especially.In addition, low if reaction temperature is spent, can't obtain to carry out enough motivating forces of condensation reaction again, and can't react.Otherwise,,, therefore just need additives such as inhibited reaction temperature or interpolation polymerization retarder because reactive organo-functional group will have the possibility that causes self-polyreaction if temperature of reaction is too high.Reaction times is preferably 2 to 12 hours.The usage quantity of organic solvent only want q.s that solubilized adds hydrolysate just can, the basic catalyst usage quantity is to add in 0.1 to the 10wt% scope of hydrolysate.
Non-polar solvent for only to water not had (or almost not having) deliquescent words just can, be preferably varsol.Relevant varsol is just like lower non-polar solvents of boiling point such as toluene, benzene, dimethylbenzene.Wherein preferably adopt toluene.
Basic catalyst can adopt employed basic catalyst in hydrolysis reaction, can give an example as ammonium hydroxide salt such as alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, cesium hydroxide or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, hydroxide benzyl TMA (TriMethylAmine), hydroxide benzyl three second ammoniums.Be preferably non-polar solvents such as tetra-allkylammoniums is the catalyzer of solubility.
Moreover the hydrolysate that is adopted in the condensation again is though preferably adopt through washing, the material that dewaters and concentrated, even if but implement also can using of washing, dehydration.During this reaction,, still do not need initiatively to add yet, only will from the base catalysis agent solution, the moisture degree of bringing into just can though water can exist.In addition, fully do not carry out under the situation in the hydrolysis of hydrolysate, though remaining water-disintegrable base is being implemented in the hydrolysis, need be at the moisture more than the necessary theoretical amount, reaction usually fully still all will be hydrolyzed.
After the condensation reaction, catalyzer is washed and removed again, obtain silesquioxane mixture through concentrating.
The silsesquioxane resins that is obtained according to the present invention, though different with the state of functional group's kind, reaction conditions, hydrolysate, plant cage-type silsesquioxane but be configured to be divided into plural number shown in the general formula (6) to (9), account for more than the overall 50wt%.The ratio that exists of T8 to T14 can be as above-mentioned.In general formula, when R is the situation of 3-methacryloxypropyl, utilize silane mixture is positioned over below 20 ℃, T8 just can needle crystal separates out and separates.
The invention effect
According to the manufacture method of cage-type silsesquioxane of the present invention, just can make cage-type silsesquioxane with high yield through structure control.The cage-type silsesquioxane that obtains because Siliciumatom all has reactive functional groups, therefore just to (methyl) acrylate, and tool consistency such as Resins, epoxy, can mix arbitrarily, can use raw material widely as the optical polymerism resin combination.In addition,, just can increase the cross-linking density of resin, also can effectively promote thermotolerance, thermostability, resistance, the mechanical property of hardening resin by in the optical polymerism resin combination, adopting cage-type silsesquioxane.
Embodiment
Below, utilize embodiment to be described more specifically the present invention.
Embodiment 1
In the reaction vessel that possesses stirrer, dropping funnel, thermometer, 2-propyl alcohol (IPA) 120ml of the solvent of packing into, with 5% tetramethylammonium hydroxide aqueous solution (the TMAH aqueous solution) 9.4g of basic catalyst.In dropping funnel, pack into IPA 45ml, with 3-methacryloxypropyl trimethoxy silane (MTMS: Dong Leitaokangnike silica gel corporate system, SZ-6300) 38.07g, stirring reaction container on one side then, at room temperature with the IPA solution of MTMS, in 30 minutes, drip on one side.After treating that MTMS drips end, do not stirring 2 hours under the heating state.After stirring 2 hours, solvent is under reduced pressure removed solvent, utilize toluene 250ml to dissolve again.Utilize saturated aqueous common salt to implement washing reaction soln, till becoming neutrality, and then utilize anhydrous magnesium sulfate to dewater.Anhydrous magnesium sulfate is filtered, obtain hydrolysate (silsesquioxane) 25.8g, yield 94% through concentrating.This silsesquioxane is the colorless viscous liquid that dissolves in the various organic solvents.
Measure the GPC of this silsesquioxane, the result as shown in Figure 1.From Fig. 1, the molecular weight distribution of silsesquioxane with have ratio, be to calculate as table 1.The molecular weight distribution of the hydrolysate in this stage (Mw/Mn) is 1.26.
Moreover, carrying out the mass analysis (LC-MS) after high-speed liquid chromatography instrument separates, the result is as shown in Figure 2.T9 (OH), T11 (OH) of the incomplete cage modle structure of opening by the wherein part that observes cage shown in following (10) and (11) among Fig. 2, and the molion that adheres to ammonium ion fully on T8, T10, the T12 of cage modle structure.In the following formula, R is the 3-methacryloxypropyl.
[changing 7]
[changing 8]
Through measure the result of 1H-NMR, observe be derived from methacryloxypropyl than bandwidth signals.In addition, do not observe the signal (3.58ppm) that is derived from methoxyl group.General-C=CH
2With-O-CH
2-the integration ratio compare, the result is 1.999: 2.002.Can confirm not two key initiation reactions thus to methacryloxypropyl.Especially be that silsesquioxane is configured to randomization compound (R type) or ladder type compound (L type) with above-mentioned results verification to spike 1, spike 2 and spike 3.4 of spikes are confirmed as the cage modle construction compound (C type) of cage modle or part unlatching.If the words of calculating from the result of GPC and LC-MS, from GPC calculate compound (C type) be by T8, T10, T12, and incomplete cage modle T9OH, T11OH constituted, and total amount is 24.6%, if cooperate the result of LC-MS, the amount of T8, T10, T12, T9OH, T11OH just calculates as shown in table 1.
Secondly, in possessing the reaction vessel that stirrer, tool smallmouth interface divide water distillation receiver pope (Dean-Stark), cooling tube, pack into the above-mentioned silsesquioxane 20.65g that obtains, toluene 82ml, and 10%TMAH aqueous solution 3.0g, and heating and water heated up in a steamer remove gradually.More be heated to 130 ℃, make toluene under reflux temperature, carry out condensation reaction again.The reaction soln temperature of this moment is 108 ℃.Behind the refluxing toluene again after 2 hours stir, constipation Shu Fanying.Utilize saturated aqueous common salt to implement washing reaction soln, till becoming neutrality, and then utilize anhydrous magnesium sulfate to dewater.Anhydrous magnesium sulfate is filtered, obtain required cage-type silsesquioxane (mixture) 18.77g through concentrating.The cage-type silsesquioxane that is obtained is the colorless viscous liquid that dissolves in the various organic solvents.
Measure the GPC of the reactant after the condensation reaction again, the result as shown in Figure 3.From Fig. 3, be found to Mn2018 (spike 5), Mn1570 (spike 6), Mn1387 (spike 7), reach Mn1192 (spike 8).The molecular weight of each spike, molecular weight distribution, and amount, as shown in table 1.The molecular weight distribution of the reactant after the condensation reaction (Mw/Mn) is 1.04 again.
Moreover, implementing the mass analysis after high-speed liquid chromatography instrument separates, the result is as shown in Figure 4.Confirm T8, T10, T12 molion from Fig. 4 with ammonium ion.
By above result, the silsesquioxane of spike 5 is configured to random or the ladder type compound.Spike 6 can be accredited as T12, and spike 7 can be accredited as T10, and spike 8 can be accredited as T8.
With above-mentioned cage-type silsesquioxane mixture after condensation again, be positioned over below 20 ℃, and separate out needle crystal.Needle crystal is 5.89g after filtering.In addition, needle crystal is implemented gpc measurement, the result only detects spike 8, can confirm that this crystallization is T8.Through measuring the result of 1H-NMR, observe the signal that is derived from methacryloxypropyl, it is the signal of broad before condensation again, is separated into sharp-pointed signal.Deducibility produces the compound (that is the compound of tool cage modle structure) of objectivity excellence thus.In addition, do not observe the signal (3.58ppm) that is derived from methoxyl group.General-C=CH
2With-O-CH
2-the integration ratio compare, the result is 1.999: 1.984.GPC before and after condensation reaction arrangement is as shown in table 1 again.
Table 1
|
Again before the condensation |
Again after the condensation |
Mn (area %) spike (Mw/Mn) type |
4291 (32.7%) 1 (1.07) random ladder types |
2018 (6.3%) 5 (1.00) random ladder types |
Mn (area %) spike (Mw/Mn) type |
2826 (19.6%) 2 (1.00) random ladder types |
1570 (9%) 6 (1.00) (T12) cage modles |
Mn (area %) spike (Mw/Mn) type |
2187 (23.1%) 3 (1.0) random ladder types |
1387 (47.5%) 7 (1.00) (T10) cage modles |
Mn (area %) spike (Mw/Mn) type |
1483 (24.6%) 4 cage modles (containing) not exclusively interior |
1192 (37.2%) 8 (1.00) (T8) cage modles |
By learning in the table 1, before the condensation reaction, the silsesquioxane of spike 1, spike 2 and spike 3 is configured to random or ladder type again, and accounts for overall 75.4%; With respect to this, again after the condensation reaction, these spikes disappear, and the silsesquioxane of spike 6, spike 7 and spike 8 is configured to clear and definite cage modle, and account for overall 93.7%.In other words, demonstrate by implementing condensation reaction again, the silsesquioxane just that tool is random, that ladder type is constructed is converted to the cage modle structure.
Embodiment 2
As embodiment 1, implement the synthetic of silsesquioxane composition with following loadings.With IPA40ml, 5%TMAH aqueous solution 2.2g, and MTMS 8.46g, after dropping, after stirring 2 hours under room temperature when hydrolysis reaction (20 to 25 ℃, will dispel the heat), in reducing pressure, heat up in a steamer except that IPA, utilize toluene 30ml to dissolve again.As the execution condensation reaction again as the embodiment 1, obtain silesquioxane mixture 5.65g, yield 92%.The gpc measurement result of this cage-type silsesquioxane mixture, as shown in Figure 5.Calculate the result of molecular weight Mn, molecular weight distribution mw/mn, type and the amount of each spike from Fig. 5, as shown in table 2.Omit the water-washing step of implementing silsesquioxane composition among the embodiment 2,,, can carry out the synthetic of cage-type silsesquioxane mixture but confirm though the structure ratio of cage modle has minimizing even if do not implement water-washing step.
Embodiment 3
In the reaction vessel that possesses stirrer, dropping funnel, thermometer, the IPA200ml of the solvent of packing into, with the 5%TMAH aqueous solution 15.6g of basic catalyst.In dropping funnel, pack into IPA 30ml, with 3-glycidoxypropyltrime,hoxysilane 60.38g, stirring reaction container on one side then is Yi Bian at room temperature with the IPA solution of 3-glycidoxypropyltrime,hoxysilane, dripped in 60 minutes.After waiting to drip end, do not stirring 6 hours under the heating state.After stirring 6 hours, solvent is under reduced pressure removed IPA, utilize toluene 200ml to dissolve again.
As implementing condensation reaction again as the embodiment 1, obtain silesquioxane mixture.The gpc measurement result of this cage-type silsesquioxane mixture as shown in Figure 6, measures the result of LC-MS, as shown in Figure 7.Calculate the result of molecular weight Mn, molecular weight distribution mw/mn, type and the amount of each spike from Fig. 6 and Fig. 7, as shown in table 2.By above result, spike 9 is compounds of the random or scalariform of silsesquioxane structure with spike 10, and can identify spike 11 and be T12, and spike 12 is T10, and spike 13 is T8.In other words, confirm embodiment 3 and can have cage-type silsesquioxane mixture synthetic that the R of functional group is a glycidyl.
Embodiment 4
In the reaction vessel that possesses stirrer, dropping funnel, thermometer, the IPA120ml of the solvent of packing into, with the 5%TMAH aqueous solution 4.0g of basic catalyst.In dropping funnel, pack into IPA30ml, with vinyltrimethoxy silane 10.2g, stirring reaction container on one side then, on one side under 0 ℃ with the IPA solution of vinyltrimethoxy silane, in 60 minutes, carry out drop.After treating that drop finishes, return back to room temperature gradually, do not stirring 6 hours under the heating state.After stirring 6 hours, solvent is under reduced pressure removed IPA, utilize toluene 200ml to dissolve again.
Secondly, as implementing condensation reaction again as the embodiment 1, obtain silesquioxane mixture.The GPC of this cage-type silsesquioxane mixture and the measuring result of LC-MS are as Fig. 8 and shown in Figure 9.Calculate the result of molecular weight Mn, molecular weight distribution mw/mn, type and the amount of each spike from Fig. 8 and Fig. 9, as shown in table 2.By above result, spike 14,15 and 16 silsesquioxane are configured to the compound of random or scalariform, and can identify spike 17 and be T14, and spike 18 is T12, and spike 19 is T10.In other words, confirm embodiment 4 and can have cage-type silsesquioxane mixture synthetic that the R of functional group is a vinyl.
Comparative example 1
In the reaction vessel that possesses stirrer, dropping funnel, thermometer, the IPA160ml of the solvent of packing into, with 5%TMAH aqueous solution 6.5g.In dropping funnel, pack into IPA 18ml, with MTMS 27.54g, stirring reaction container on one side then is Yi Bian at room temperature with the IPA solution of MTMS, dripped in 30 minutes.After treating that MTMS drips end, under room temperature, stirred 2 hours.Reheat to 95 ℃ after stirring 2 hours.Under the IPA reflux conditions, restir 4 hours.Under reduced pressure heat up in a steamer and desolventize, utilize toluene 377ml to dissolve again.To utilize saturated aqueous common salt to implement washing through toluene dissolved reaction soln, and till becoming neutrality, and then utilize anhydrous magnesium sulfate to dewater.Anhydrous magnesium sulfate is filtered, and spissated reaction soln is washed in saturated aqueous common salt and is neutral, anhydrous magnesium sulfate is dewatered again.Remove filtering anhydrous magnesium sulfate, concentrate and acquisition hydrolysate (silsesquioxane) 19.59g.The silsesquioxane that obtains is the colorless viscous liquid that dissolves in the various organic solvents.
The gpc measurement result of this silsesquioxane, as shown in figure 10.Learn from Figure 10, can't obtain the same waveform as of being watched among the embodiment 1, contain the impurity beyond the cage modle.In other words, the polar solvent that comparative example 1 is presented at as IPA and so on exists down, does not carry out condensation reaction again.In addition, the molecular weight distribution of this silsesquioxane (Mw/Mn) is 1.15.
Comparative example 2
In the reaction vessel that possesses stirrer, dropping funnel, thermometer, the toluene 50ml of the solvent of packing into, with 5%TMAH aqueous solution 3.0g.The solution of packing in dropping funnel and being made of toluene 10ml and MTMS 12.64g, stirring reaction container on one side then is Yi Bian at room temperature with the toluene solution of MTMS, dripped in 10 minutes.After waiting to drip end, under room temperature, stirred 2 hours.Reheat to 135 ℃ after stirring 2 hours.Under refluxing toluene (108 ℃ of solution temperatures) temperature, restir 4 hours.Utilize saturated aqueous common salt to implement washing reaction soln, till becoming neutrality, and then utilize anhydrous magnesium sulfate to dewater.Anhydrous magnesium sulfate is filtered, and spissated reaction soln is washed in saturated aqueous common salt and is neutral, anhydrous magnesium sulfate is dewatered again.Remove the anhydrous magnesium sulfate of filtrations, concentrate and acquisition adds water decomposition resultant 10.78g.The gpc measurement result of the silsesquioxane silicon constituent that is obtained, as shown in figure 11.From Figure 11, observe the MTMS spike of raw material.In other words, comparative example 2 shows that reactive system does not form uniform state, if the toluene of non-polar organic solvent is used for hydrolysis reaction, and the reaction that can't fully be hydrolyzed, quite difficulty is carried out condensation.
Arrangement embodiment 1,2,3 and 4, comparative example 1 and 2 gpc measurement result in the table 2.3-MAP is meant the 3-methacryloxypropyl in the table 2, and 3-GOP means 3-propylene oxide base propyl group.In addition, L refers to ladder type, and R refers to random, and C refers to contain incomplete cage modle.T8 to T14 refers to cage modle.
Table 2
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Embodiment 4 |
Comparative example 1 |
Comparative example 2 |
Functional group |
3-MAP |
3-MAP |
3-GOP |
Vinyl |
3-MAP |
3-MAP |
The hydrolysis reaction solvent is the condensation reaction solvent again |
IPA toluene |
IPA toluene |
IPA toluene |
IPA toluene |
IPA IPA |
Toluene toluene |
Mn; Mn/Mw (area %) |
|
2717;1.01 (3.8%) L.R |
3216;1.02 (9.4%) L.R |
3081;1.04 (12.3%) L.R |
2873 (10.4%) L.R |
2399 (8.5%) |
Mn; Mn/Mw (area %) type |
2018;1.00 (6.3%) L.R |
1994;1.00 (15%) L.R |
2370;1.00 (18.2%) L.R |
2156;1.00 (9.5%) L.R |
2086 (20.6%) L.R |
|
Mn; Mn/Mw (area %) type |
|
|
|
1558;1.00 (18.1%) L.R |
|
|
Mn; Mn/Mw (area %) type |
1570;1.00 (9%) T12 |
1538;1.00 (9.5%) T12 |
1839;1.00 (14.2%) T12 |
977;1.00 (6.9%) T14 |
|
1568 (50.8%) |
Mn; Mn/Mw (area %) type |
1387;1.00 (47.5%) T10 |
1351;1.00 (45.5%) T10 |
1633;1.00 (38.2%) T10 |
795;1.00 (31.5%) T12 |
1341 (69%) C |
|
Mn; Mn/Mw (area %) type |
1192;1.00 (37.2%) T8 |
1159;1.00 (26.2%) T8 |
1396;1.00 (20.0%) T8 |
637;1.00 (21.7%) T10 |
|
|
Mn; Mn/Mw (area %) type |
|
|
|
|
|
547 (40.7%) MTMS |