TW200407358A - Cage-type silsesquioxanes resin cotaining functional group and manufacture method thereof - Google Patents

Abstract

The present invention provides the manufacture method of cage-type silsesquioxanes resin comprising all Si atoms with reactive organic functional groups. Such cage-type silsesquioxanes resin is compatible to (meth)acrylic resin and epoxy resin, and is widely used as the raw material of free radical polymerized resin composition. Under the existence of basic catalyst, silicon compound of formula RSiX3 (wherein, R is the organic functional groups with (meth)acryloyl group, glycidyl group or vinyl group, X is hydrolysis group) proceed the hydrolysis reaction with resulting partial condense, and then under the existence of basic catalyst to re-condense the hydrolytic product to give cage-type silsesquioxanes resin with formula of [RsiO3/2]n (wherein, R is the organic functional group as described above, n is 8, 10, 12 or 14).

Description

200407358 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a cage-type silsesquioxane-based resin and a method for producing the same. Method for producing a cage-type silsesquioxane resin having a reactive functional group composed of a glycidyl group or an organic functional group of an ethylene group [prior art] The general formula [RSl03 / 2] n is half that Siloxane resins can be roughly divided into: cage type, ladder type,! There are three types of polyorganosilsesquioxanes (Polygansil SilSquixane). Among them, the cage-type silsesquioxane resin has a clear molecular structure and a rigid skeleton. In addition, because the molecular structure has been controlled, by using the polymer's buildi ^ block as a basis for the control of molecular structure, if you can perform the activity of structural control, you can expect completely different physical properties. . In other words, even if they are both represented by the general formula [RSi〇3 / 2] n, there may be considerable differences in physical properties depending on the molecular structure of the silsesquioxane resin. The method for synthesizing oxystilbene compounds is known as the method in which phenyltrichlorosilane k is added to water, and then equilibrated with KOH. AAmXhem. Soc, 82, 6194-6 1 9551960) Most methods are represented. In the synthesis method of cage-type silsesquioxane resin, the synthesis method of cage-type silsesquioxane resin with reactive functional group is in Zh. Obshch. Khim · 1 5 52- 1 5 5 5.49 · 1 997 (Non-patent literature!) There are disclosed synthetic methods with vinyl groups. In addition, Japanese Patent Laid-Open Publication No. Hei-2] 964 (Patent Document 1) also discloses a method for producing a silsesquioxane with epoxypropyl group 6 31503] 200407358. However, even with reference to the manufacturing method disclosed in Japanese Patent Laid-Open No. ^ 29640, it is difficult to fully control the molecular weight distribution and structure by implementing a sesquisiloxane resin with (fluorenyl) propenyl: synthesis, As a result, it is not possible to produce a silsesquioxane resin with a clear molecular structure like a cage structure. [Patent Document 1] Japanese Patent Laid-Open Publication [Non-Patent Document 1] Zh. 0bshch. Khim 1552_ 1 555 · 49 Kawasaki [Summary of the Invention] The purpose of silver is to solve the conventional shortcomings, and to provide a molecular weight 2 and a molecule Construct a controlled cage type sesquioxane resin with (meth) acrylic, glycidyl, or ethylene. In addition, a method for producing the above cage type silsesquioxane resin in a yield. In order to solve the above-mentioned problems, the present inventors can solve the problem through in-depth use of special branch materials. In other words, the present invention is a cage-type "two: ... invention. The following general correction) 彳. Method, rs] x3 ⑴ (II: ~ == radical "condensation ... radical, fluorene radical, partial condensation in organic polar solvent and experimental catalyst decomposition reaction, the obtained water content is two = addition: non-polar Solvents and basic catalysis, the product is then obtained according to this manufacturing method 彳 =: two 彳: recondensed. Xioxidation resin, preferably the following 3] 5031 7 200407358 general formula (2) [RSi〇 3/2] n 彳 2) (wherein R is an organic functional group having any of a (fluorenyl) acryl group and a glycidol odor, n is' 8, 10, i or vinyl formula (1 ), R is preferably the following, ten, 3 4 4 4). In addition, take the following general formula (3), [Chemical Formula 1] v j

(3) An integer of (4), where R] is a hydrogen atom or a methyl group, and organic (wherein m is 1 to a functional group. In addition, the hydrolyzed product is in the range of several b to 500 to 7000. : The amount of the knife is best to be a mixture of type and random type sesquioxane oxyfiring. Thousands = material cage type, ladder type half-second oxygen, and from above (;, ...) Choose 3 kinds of u fly (2) No, "is 8," 0,] 2 or more cage-type silsesquioxane production date «is 8,1 〇, 1 2 and〗 4 The total amount of the three-type sesquigenous oxygen sintered dragon with the most scorched property / 0 or more is the total amount of sesquisian gas. In addition, the present invention is a cage-type sesquis oxygen resin with functional groups. S 315031 200407358 In the mixture, the proportion of the dry skirt of the general formula (2), said that the occupation ratio of the semi-siloxane resin is more than 50wt 〇 / 〇 with the right official order * mountain ice ^, there is The cage-type silsesquioxane tree of the moon is said. Among them, the molecular weight distribution (Mw / Mn) of the type of sesquioxane milk resin is preferably in the range of 1.03 to 1.10. [Embodiment] Hereinafter, it will be specifically described. Embodiments of the invention. In the following description, in the cage silsesquioxane resin represented by the general formula ⑺, a compound with η = 8 is referred to as Tδ, a compound with η = ι〇 is referred to as T10, and n The compound of = i2 is called Ding 12 and the compound of ^ 14 is called T 1 4. The cage silsesquioxane resin of the present invention is a cage silsesquioxane resin represented by the general formula (2), or contains The resin containing the main component may contain other components such as a component having a different η number. In addition, when it is referred to as a "plastic-silsesquioxane resin," it can be interpreted to mean oligomers. The structural formulas of 10, T12, and T14 are respectively represented by the following formulas (6), (7), (8), and (9). In addition, in the following formulae (6) to (9), R means having (Fluorenyl) An organic functional group of any of acrylfluorenyl, glycidyl, or vinyl. 315031 200407358 [Chem. 2]

RSi-Ο——SiR 〇 / | / 1 / ο / ο

RSi——〇——SiR I (6)

I RSi-O——SiR 〇 / 〇 / / 〇 1 /

RSi-O——SiR [Chemical 3] v 『oosi rQA'o cj—oc

Rs PSIoIsiR 〇 a, 〇Γ / IRiR είΊο 丨 si, [Chem. 4]

.d, Si-Q

[Chem. 5] 10 3] 5031 200407358

According to the knowledge, according to the present invention, any one of the above T 8, T1 0, T1 2 and T14, or a mixture of two or more, preferably three or four, can be obtained, and the best Contains more than 5 Owt% of sesquiterite oxyfiring resin. Especially when the organic functional group R is an organic functional group having a (fluorenyl) acrylfluorenyl group or a glycidyl group, the total amount of the silsesquioxane resin composed of T8, T10, and T12 accounts for the total 5 Owt% or more, preferably 70wt% or more. In this case, T8 can be set to 20 to 40 wt%, T10 can be set to 40 to 50 wt%, and T12 can be set to a range of 5 to 20 wt%. Furthermore, when the organic functional group is a functional group having a vinyl group, the total amount of cage silsesquioxane resin composed of T10, T12, and T14 accounts for more than 50% by weight, and preferably more than 70% by weight. . In this case, it is possible to set T10 in the range of 10 to 40 wt%, T12 in the range of 20 to 60 wt%, and T14 in the range of 5 to 20 wt%. The other components are mainly compounds other than T8, T10, τΐ2, and T14, and compounds other than cage type, which have different η numbers. The molecular weight distributions of T8, T10, D12, and T14 (measured by Gpc measurement) can range from 1.00 to] .01. The cage-type sesquiside of the present invention 31503] 11 200407358 The molecular weight distribution (Mw / Mn) of the oxane resin is below 1; 1, preferably within the range of 1.03 to 1.10. The molecular weight range coefficient has an average molecular weight in the range of _ to 2500, preferably in the range of 1,000 to 20Ό0. Furthermore, if TS to Ti4 is separated from the resin containing 8 S Tl4 as described above, the operation of type I is also performed, and a silsesquioxane composed of 1 to 8 of butyl 8 to butyl M may also be obtained. Resin and households

:: Xi purchase fat. The silsesquien tree J thus separated is in the silsesquioxane resin of the present invention. In the method for producing sesquioxetane in the present invention, the first compound that does not contain stone is hydrolyzed in an organic polar solvent and test solution. In the general formula ⑴, the ruler is an organic functional beauty with ⑽ = water glyceryl group or vinyl group: "group, or glycidyl group can be directly bonded to (:) acryl group, optional f group, or other The intervention of a divalent group. 1 Take the organic functional group which is the best organic or benzene. R is the general formula R] is Η or methyl, m is not. In the general formula (3), then 玎 such as-, right Examples are not good examples ...-methyl propylene dilute oxypropyl, specific examples, propyl, 3-propenyloxypropyl. Propylene methoxymethyl L Formula (1), X is hydrolyzed Acetyloxy, etc., is preferably oxygen: for example, fired, oxy, or A. From milk, for example: A. isopropyllactyl, n-, iso-, and q-groups, and B are reactive Higher methoxy group. Butyl group, etc. Among them, among the silicon compounds represented by the general formula (1), if it can be, for example, methacryl ethoxy fluorenyl group: terephthalic compound, acetol , Methyl propylene 3] 5〇3] 12 200407358 aryl methyltrimethoxysilane, 3-methyl propyl oxypropyl stone yaki, "kimopropyl propyl triethoxy stone yaki , 3_propyl allyl Cornerstone "End, 3-glycidoxypropyltrimethoxystone: 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilicon :, ethylenetriethoxylate" Finish ... 'It is best to use the 3-, 3-propyl propyl ~ methoxy propyl trimethoxy oxalate that can be easily obtained. The basic catalyst used in the hydrolytic reaction can be exemplified by potassium ammonium oxide, hydrogen Alkali metal hydroxides such as sodium oxide and hydroxide, or ammonium hydroxides such as tetraammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide Among these, from the viewpoint of high activity of the catalyst, tetraammonium hydroxide is preferably used. Basic catalysts are generally used in the form of an aqueous solution. Among hydrolytic reaction conditions, the reaction temperature is preferably 〇 to 60 ° C, especially 20 to 4 (TC is preferred. If the reaction temperature is lower than 0.0, the reaction rate will be slower, and the hydrolyzable group will exist in an unreacted state, which results in a relatively high cost. Long reaction time; conversely, if it is higher than 60, it is because the reaction If the reaction time is too fast, a complicated condensation reaction is performed, and as a result, the molecular weight of the hydrolyzed product is promoted. In addition, the reaction time is preferably more than 2 hours. If the reaction time is less than 2 hours, the hydrodecomposition cannot be performed sufficiently. The reaction causes the hydrolyzable hydrolyzable group to remain in an unreacted state. Although the hydrolyzation reaction requires the presence of water, it can be supplied from an aqueous solution of a test catalyst, or it can be added separately. The amount of water depends on Sufficient amount sufficient for hydrolytic decomposition of hydrolyzable groups, preferably low] 3 15031 200407358 1 0 5 Ί c • · 5 times the theoretical amount. In addition, γ organic solvent is the best when hydrolyzing. Organic solvents can be used. For example: alcohols such as methanol, ethanol, 2 · propanol, or other polar solvents. The carbon number 1 to 6 having solubility in water is preferred, and S-one, '' is particularly preferably propanol. If a non-polar solvent is used: The reaction system will not be homogeneous, and the hydrolytic reaction will not proceed sufficiently, and unreacted alkoxy groups are stored, so it is not suitable. ★ After the reaction of Lihuo knife is completed, water or water-containing reaction solvent is separated. Water or aqueous reaction solvents can be separated by means of evaporation under reduced pressure. In order to fully remove water and other impurities, non-polar solvents can be added to dissolve the hydrolyzed reaction product, and then the solution is washed with brine and other two lines, and then dried with a desiccant such as anhydrous magnesium sulfate. Methods. If the non-polar solvent is separated by evaporation or the like, the hydrolyzed reaction product can be recovered, but if the non-polar solvent can be used as the non-polar solvent in the next reaction, it is not necessary to separate it. In the hydrolytic reaction of the present invention, the hydrolytic decomposition product 'produced by the hydrolytic decomposition reaction " the hydrolytic decomposition reaction " is usually a number average molecular weight of 500 to 7000. Colorless viscous liquid. The hydrolyzed product varies depending on the reaction conditions, and the number average molecular weight of the resin (or agglomerates) ranges from 3 to 3. Most of the force-decomposable group X (preferably almost All) are substituted with OH groups, and most of these OH groups are preferably 95% or more condensed. Regarding the structure of the hydrolyzed product, there are multiple types of cage type, ladder type, and random type of sesquioxane;): End, do the best iq ^ 丨 7 years of dry mouth LU S The ratio of the compound and the complete cage structure is also less. It is mainly the 315031 14 200407358 incomplete cage structure with the cage partially opened. Therefore, in the present invention, the hydrolyzed product obtained through the hydrolytic decomposition is more condensed by heating in an organic solvent in the presence of a test catalyst (called "recondensation") by heating in an organic solvent. "), And selective production of cage-type silsesquioxane. After the water or the aqueous reaction solution is separated, a recondensation reaction is performed in the presence of a non-polar solvent and a basic catalyst. Among the reaction conditions for the related recondensation reaction, the reaction temperature is preferably in the range of 100 to 20 ° C, and more preferably in the range of 110 to 14 t. In addition, if the reaction temperature is too low, it is impossible to obtain a re- Sufficient driving force for the condensation reaction without carrying out the reaction. Conversely, if the reaction temperature is too high, the reactive organic functional group may initiate a self-polymerization reaction, so it is necessary to suppress the reaction / JJZL degree, or add polymerization Additives such as inhibitors. The reaction time should be 2 to 12 hours. The amount of organic solvent used should only be sufficient to dissolve the hydrolytic reaction product. The amount of basic catalyst used is that of the hydrolytic reaction product. 〇 ·; [in the range of j 〇wt〇 / 〇. Oral non-polar, cereals only need to have no (or almost no) solubility in water, it is good to be a hydrocarbon solvent. Related hydrocarbon solvents are as follows · Toluene, benzene, xylene, and other non-polar solvents with low boiling points. Among them, toluene is preferred. I. Biocatalytic catalysts can use basic catalysts used in the hydrolytic reaction. For example, potassium hydroxide, hydrogen Sodium oxide , Alkali metal hydroxides such as cesium hydroxide / do not: or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutyl hydroxide :, benzyltriammonium hydroxide, hydroxide; ammonium hydroxide such as triethylammonium hydroxide The salt is the most soluble catalyst for non-polar solvents such as tetraylammonium. Moreover, the hydrodecomposition product used in the recondensation is preferably 315031] 5 200407358

Washed, dehydrated and concentrated materials can be used, even if they are not washed and dehydrated. In this reaction, although water may be present, it does not need to be actively added, and it is only necessary to bring in the degree of moisture from the alkaline catalyst solution. In addition, when the hydrolytic decomposition of the hydrolyzed product does not advance sufficiently, although the hydrolytic decomposition of the remaining hydrolysable bases requires more than the necessary theoretical amount of water, it is usually sufficient. The hydrolysis reaction is carried out on the ground.

After the reaction, the silsesquioxane mixture was obtained. The sesquiterite oxygen resin obtained according to the present invention ::: depends on the conditions and the state of the hydrolyzed product = it is structured to be W or more that is a plurality of integrals represented by the general formulae (6) to (9) . Τδ to T14 1 ”+ Shi Xi Nian Fei Yuan, Champagne, R is a 3-fluorenyl propylene alkoxy propionate mixture placed at 2 (TC, D ..." Yue handle 'use will be Shi Xifu [Invented by Effect] T T8 can be separated and separated by needle-like crystals. 1q π Long dust is manufactured by semi-silicon cylindrical high-yield through the structure "" method, the dragon-type made by Fu Yigong is half and half tender It is because all the shirt atoms have two: to obtain ^ methyl) acrylic acid, and epoxy resin and other compatible ^ groups, =: can be widely used to make photopolymerizable resin & The photopolymerizable resin M is made of cage-shaped, osmium. The cross-linking density of the resin can also be: milk pudding, sex, heat stability, chemical resistance, mechanical properties, and juice hardening resin 315031 16 200407358 [Examples] The present invention will be described in more detail with reference to the following examples. The actual formula < 歹 1j 1 is placed in a reaction vessel equipped with a stirrer, a drip funnel, and a thermometer; pa) 1 2 0 m 1, with 5% hydroxide

Formazan aqueous solution (aqueous solution of DMAA) 9.4g. A drip funnel was charged with 45 ml of IPA, and 38.07 g of %% propylene propyl oxypropyltrimethoxysilane (MTMS: manufactured by Toray Taconic Silicone Co., Ltd., Sz-6300), and the reaction was then taught In a container, the IPA solution of MTMS was dripped within 30 minutes at room temperature. After the MTMS dripping was completed, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure, and the solution was dissolved in 250 ml of benzene. The reaction solution was washed with saturated β i water and washed with water until it became neutral, and then dehydrated with anhydrous sulfur and beauty. Anhydrous sulfuric acid was filtered and concentrated to obtain 25 8 g of pyrolysis solution (half time; sacrifice), yield 94%. This sesquioxide is a colorless, viscous liquid that can be dissolved in various organic solvents. The GPC of this silsesquioxane was measured, and the results were as good as the first! As shown. From the figure], the molecular weight distribution and the presence ratio of silsesquioxane are calculated as shown in Table]. The molecular weight distribution (Mw / Mn) of the hydrolyzed product at this stage is 1.2 6 〇 ~ N ～ buy weight analysis (L | MS) 'of the group 々 竹 1, and the results are shown in FIG. 2. From the second figure, the following ⑽ and (1 partially incomplete cage structure partially opened t T9 (〇H) 丁] 1 (〇H), and T8, T10, The molecular ion of ammonium ^ 315031 17 200407358 is attached to T12. In the following formula, R is a 3-fluorenylpropenyloxypropyl group. [Chem. 7]

[化 8] I 〇 \ RSi ^ O 'SiRl \ I / | BU 〇 · / ?? RSirRSi- O O \ l RSi-

〇——SiR SiR OH •, 0, I (10)

O

.SiR · 〇- • r -cr (ll) As a result of 1 H-NMR measurement, a broad signal derived from fluorenylpropenyloxypropyl was observed. In addition, no signal derived from fluorenyl group was observed (3.58 p p m). Comparing the integral ratio of -C = C Η 2 and -〇-C Η 2-, the result was 1.999: 2.002. From this, it was confirmed that the reaction was not initiated to the double bond of fluorenylpropenyloxypropyl. In particular, the above results confirmed that the spike 1, spike 2, and spike 3 series silsesquioxane structures are random compounds (R type) or ladder compounds (L type). Spike 4 was identified as a cage-type or partially open cage-type compound (type C). If calculated from the results of GPC and LC-MS, the compound (C type) calculated from GPC is composed of T8, T10, D] 2, and incomplete cage 18 31503] 200407358 type T90H, T110H, and the total amount It is 24 6%. If the results of lc · MS are combined, the amounts of T8, T10, T12, T90H, and T110H are calculated as shown in Table 1. Next, a reaction vessel equipped with a stirrer, a Dean-Stark with a small mouth connection, and a cooling pipe was charged with 20.65 g of the silsesquioxane obtained above, 82 m of toluene, and 100 / 〇TMAH aqueous solution 30g, and gradually heated to distill off the water. The temperature was further increased to 130 r, and toluene was subjected to a recondensation reaction at a reflux temperature. The temperature of the reaction solution at this time was 108 ° C. After the toluene was refluxed for another 2 hours, the reaction was completed. The reaction solution was washed with saturated saline until it became neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain the target cage-type silsesquioxane (mixture HS.Dg.) The obtained Fulong-type silsesquioxane is a colorless viscous liquid that can be dissolved in various organic solvents. ...... Measure the Gpc of the reactants after the recondensation reaction, the results are not shown in Figure 3. From Figure 3, Mn2O18 (spike 5), Mni570 (spike 6 stomach), Mηΐ3δ7 (spike 7) and Mnll92 (spike 8). The molecular position, molecular weight distribution, and presence of each spike are shown in Figure 1. The molecular weight distribution (Mw / Mn) of the reactants after the re-condensation reaction was 1.04. In addition, the mass analysis after high-speed liquid chromatography was performed, and the results are shown in Figure 4. From Figure 4, it was confirmed that the molecular ions of ammonium ions were attached to Ding 8, Ding 10, and τΐ2. As a result, the structure of the sesquisiloxane of the spike 5 was random or the stepped large bowl 6 could be identified as T] 2, and the spike 7 could be silvered as D] 〇5 尖 3] 503] 19 200407358 Peak 8 could be plated It is τ8. The cage-type silsesquioxane mixture after recondensing is placed at 20 C or lower to precipitate needle-like crystals. Needle-like crystals pass through After that, it was 5.89 g. In addition, GPC measurement was performed on the needle-like crystals, and only the peak 8 was detected. It can be confirmed that this crystal is Ding 8. According to the measurement results, it was observed that the The signal is a broad signal before recondensation, and it is separated into a sharp signal. It can be inferred that the compound ❿ (ie, a compound with a cage structure) having excellent objectivity can be inferred. In addition, no osmium-derived oxygen was observed. Base 彳 5 (3'58pPm). Comparing the integral ratio of _C = CH2 and -〇-CH factory, the result is 1.999: 1.984. The GPC finishing before and after the condensation reaction is shown in Table 1. [Table 1 】 Before re-condensation Mn (area%) Spike (Mw / Mn) type 4291 (32.7%) 1 (1.07) random • ladder 2018 (6.3%) 5 (1.00) random • ladder Mn (area ％) Central peak (Mw / Mn) type 2826 (19.6%) 2 (1.00) _ random · ladder type 1 570 (9%) 6 (1.00) (T12) cage Μ η (area%) spike (Mw / Mn) type 2 1 87 (23.1%) 3 (1.0) random · ladder type 1 3 87 (47.5%) 7 (1.00) (T10) cage type M η (area%) spike (Mw / Mn) type 1483 ( 24.6%) 4 Cage type (including incomplete) 1 192 (37.2%) 8 (1.00) (T 8) The cage type is known from Table 1. Before the recondensation reaction, the silsesquioxane structure of the peaks 丨, 2 and 3 was random or ladder-shaped, and accounted for 75.4% of the total; After the condensation reaction, the spikes disappeared. The I-siloxanes of spikes 6, 7, and Da 8 were structured as clear cages, and accounted for 315031 20 200407358 93.7% random, consistent examples, such as consistent examples 1. Scoop the mouth of the sesquisiloxane composition with the following contents | / -this 丄 八 +, 忒 ". Put IPA 40m in 5% TMAH water, six, household 0.

〇. .K, 2.2g of liquid mixture, and MTMS .g 'After instillation, it will be synthesized at room temperature (20 to 25 0 Γ, u ν 为, 为, main C, hydrolytic reaction). 3 Second, proceed After 2 hours of incubation, the PA was poured out in the fort, and then dissolved with 30 ml of solution. The recondensation reaction was performed as in Example 丨, and the post-half 5% oxygen-burned mixture was 5 65 g, and the yield was 92%. The GPC measurement results of this cage-type sesquitarum breast milk compound are shown in Figure 5. From the molecular weights Mn, molecular weight distribution of the different peaks— " Μη, the type, and the results, as shown in Table 2. As shown in Example 2. The step of washing the product with silsesquioxane was omitted in Example 2. Even if the step of washing with water was not performed, although the cage structure ratio was reduced, it was confirmed that cage silsesquioxane can be used. In a reaction vessel equipped with a stirrer, a drip funnel, and a thermometer, 200 ml of IPA / cereal was charged, and 15% of a 5% TMAH aqueous solution with an alkaline catalyst. 30 ml of IPA was charged into a drip funnel, and 60.3 8 g of oxypropoxypropyldimethoxysilane, and while stirring the reaction vessel, At room temperature, the IPA solution of 3-glycidoxypropyltrimethoxysilane was dripped in 60 minutes. After the drip was finished, the mixture was searched without heating for 6 hours. After stirring for 6 hours , IPA was removed from the solvent under reduced pressure, and 200 ml of toluene was used for dissolution. 2] 315031 200407358

A recondensation reaction was performed as in Example 1 to obtain a silsesquioxane mixture. The GPC measurement results of this cage-type silsesquioxane mixture are shown in FIG. 6 and the LC-MS measurement results are shown in FIG. 7. Calculate the molecular weight, molecular weight distribution Mw / Mn,

The results of type and presence are shown in Table 2. From the above results, spike 9 and spike 10 are random or ladder-like compounds of silsesquioxane structure, and it can be seen that spike 11 is D12, spike 12 is T10, and spike 13 is T8. In other words, it was confirmed that Example 3 was capable of synthesizing a cage-type silsesquioxane mixture having a functional group R being a glycidyl group. Example 4 In a reaction vessel equipped with a stirrer, a drip funnel, and a thermometer, 120 ml of IPA, 5% TMAH aqueous solution with an alkaline catalyst, and 30 ml of IpA were added to the drip funnel. Oxygen Shixuan] 0.2g 'Then, while stirring the reaction vessel, the IPA solution of ethylenetrimethoxysilane was dripped within 60 minutes while substituting. After the drip is finished, gradually return to room temperature, and teach it without heating. After mixing for 7 hours with J 7 and dipole, remove the solvent under reduced pressure to remove IpA, and then dissolve it with transcript 2 0 0 m 1 . "People perform the recondensation reaction as in Example 1 to obtain a sesquioxane oxy-fired mixture. This saves! GPC and the measurement results of the dust yak siloxane mixture, as shown in Figure 8 The figure Q is shown in Figure 9 and Figure 9. Figure 8 and Figure 9 calculate the molecular weight M of each peak Θ η knife $ distribution Mw / Mn, shape and existence results, as shown in Table 2 +, No. From the above results, the peaks M, 15 and 16 are sesquioxane structured as helmets, and brothers 4 ladder-like compounds, and can be identified 31503] 22 200407358 Peak 17 is T14, peak 18 is T12 The peak 19 is T10. In other words, it was confirmed that the cage type silsesquioxane mixture having a functional group R is a vinyl group can be synthesized in Example 4. Comparative Example 1 IPA 1 equipped with a stirrer and a drip funnel 60ml and 6.5g of 5% TMAH aqueous solution. Put 18m IPA and 27.54g of MTMS in a dropping funnel, and then stir the reaction vessel, while dropping the IPA solution of MTMS at room temperature, drip in 30 minutes. Wait for MTMS After dripping, stir at room temperature for 2 hours. After stirring for 2 hours, heat to 95 ° C. IpA was refluxed for another 4 hours. The solvent was distilled off under reduced pressure, and then dissolved in toluene at 377mi. The toluene-dissolved reaction solution was washed with saturated brine, until it became neutral again, and then Anhydrous magnesium sulfate is used for dehydration. Filtration of…, dehydrated magnesium is filtered, and the concentrated reaction solution is washed in saturated saline until it is neutral, and then the face is dehydrated; W is dehydrated. Remove the filtered stone Λ acid, β, β, hinder, and get the hydrolyzed product (silsesquik k) 1 9 · 5 9 g. The medium | Department & A colorless pointy liquid in a solvent. The measurement results of GPC of chemical siloxanes are shown in Fig. 10. From the figure of a person driving the word "know", the same as seen in Example 1 cannot be obtained. Waveform, polar dissolving of heterogeneous compounds other than citron type. In other words, Comparative Example 1 is shown as a semi-aerobic burner such as ΪΡΑ; twice, no recondensation reaction is performed. In addition, this time / Knife cloth (Mw / Mn) is 1] 5. 315031 200407358 The reaction vessel of the funnel and the thermometer was charged with 50 ml of solvent and 3.0 g of a 5% TMA aqueous solution. A drip funnel was charged with a solution consisting of 10 ml of toluene and 12.64 g of MTMS, and then the reaction vessel was stirred. At the same time, the toluene solution of MTMS was dripped in 10 minutes at room temperature. After the drip was finished, stirred at room temperature for 2 hours. Stirring: Stir for 2 hours and then heat to 1 35 ° C. Under toluene reflux (solution temperature 108 ° C), it was stirred for another 4 hours. The reaction solution was washed with saturated saline until it became neutral, and then dehydrated with anhydrous sulfuric acid. The anhydrous magnesium sulfate was filtered, and the concentrated reaction solution was washed with water in a saturated sodium chloride solution until neutral, and then the anhydrous magnesium sulfate was dehydrated. The filtered anhydrous magnesium sulfate was removed and concentrated to obtain 10.78 g of a hydrolyzed product. The Gpc measurement results of the obtained silsesquioxane silicon composition are shown in Fig. 11. The sharpness of MTMs of raw materials is observed from the n-th graph. In other words, Comparative Example 2 shows that the reaction system does not form a uniform green sentence. If methylbenzyl, which is a non-polar organic solvent, is used in the hydrolytic reaction, the hydrolytic reaction cannot be sufficiently performed, and it is difficult to shrink. Examples 1, 2, 3, and * are summarized in Table 2;

GPC results of quarters 1 and 2 In Table 2, 3-MAP means 3 · 曱 T-propenyloxypropoxy, and -GOP means 3-glycidylpropyl. In addition, the soil L is known as the ladder type, the R instrument is said ..., the rule is cracked, and C is the incomplete cage type. Ding I 孓 Ding 8 to Ding 14 are cage types. 315031 24 200407358 [Table 2]

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Functional Group Hydrolysis Reaction Solvent Recondensation IPA IPA IPA IPA IPA Toluene Solvent Benzene Benzene Benzene Benzene Benzene IPA Benzene 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 Μη; Mn / Mw (area%) type 1558; 1.00 (18.1%) L · R Μη; Mn / Mw (area%) type 1570; 1.00 (9%) T12 1538; 1.00 (9.5%) Ding 12 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%) T100 1633 ; 1.00 (38.2%) D] 0 795; 1.00 (31.5%) T12 1341 (69%) C Mn; Mn / Mw (area%) type 1192; 1.00 (37.2%) T8 1159; L00 (26.2%) T8 1396 ; 1.00 (20.0%) T8 637; 1.00 (21.7%) T10 Μ η; Mn / Mw (area%) type 547 (40.7%) MTMS

[Schematic description]

Figure 1 shows the GPC of the hydrolyzed product of Example 1 Figure 2 shows the LC-MS of the hydrolyzed product of Example 1 Figure 3 shows the GPC of the recondensation reaction product of Example 1 Figure 4 shows the implementation LC-MS of the recondensation reaction product of Example 1 Figure 5 shows the GPC of the recondensation reaction product of Example 2 25 315031 200407358

Fig. 6 is the GPC of the recondensation reaction product of Example 3 Fig. 7 is the LC-MS of the recondensation reaction product of Example 3 Fig. 8 is the GPC of the recondensation reaction product of Example 4 Fig. 9 LC-MS of the recondensation reaction product of Example 4 FIG. 10 shows the GPC of Comparative Example 1 FIG. 12 shows the GPC of Comparative Example 2

26 315031

Claims (1)

200407358 Scope of patent application: ▲ type silsesquioxane tree general formula (1) U-day clothing method, which is characterized by the following RSiX3 ⑴ (wherein 'R series has (A its p ^ base medium cup) A native hydrazone, glycidyl, or ethylenically functional organic functional group 'X' hydrolyzable group) Shi Xikou, in the presence of organic polar solvents and test catalysts: water: solution: Partial condensation will occur, and the obtained solution will be re-condensed in a non-polar solvent. Re-condensation in the presence of a biochemical agent 2. If the application of the first scope of the patent application * This product is made of Shi Zhilun + Siloxane resin. Among them, the cage type sesquisite resin is based on the following general formula: [RSi〇3 / 2] n (9) (where 'R is , Hundred (methyl violent) C:% fluorenyl, glycidyl, organic functional group of any one of the groups,…% Q is shown by the master Zhu ^ 5] 0,] 2 or 14). 3 · As claimed in the & patent scope! Or 2 of ^ ^ ^,, the production method of Shi Zhelun semi-siloxane resin, wherein the general formula (1) and clothing [化 Π " General formula (3), (4), (5) 3]] 27 200407358 Ri 5〇3 CH2 = CH—— (5) (wherein 'm is an integer from 1 to 3, and R] is a hydrogen atom or a methyl group; all organic functional groups. 4 · A method for producing a cage-type silsesquioxane resin, which is characterized in that the general formula (1) RSiX3 其中 (wherein 'R' has (fluorenyl) acrylfluorenyl, glycidyl, or ethynyl Either the organic functional group, X-based hydrolyzable group) The silicon 6 compound shown in the presence of an organic polar solvent and a basic catalyst undergoes a hydrolytic reaction to cause partial condensation, and obtains a hydrolyzation having a number average molecular weight of 500. The product is then obtained by adding water = decomposing, and then condensing with a non-polar solvent and basic. In the presence of], the cage method is performed according to item 5 of the scope of patent application f 4, wherein the hydrolytic decomposition product is a cage-type: a mixture of birefringent oxygen produced by burning resin and obtained by re-condensation. : And random type of oligomeric resin, which is the following general formula (2) and side-type silsesquioxane 31503] 28 200407358 [Κύ 1 U3 / 2. (Wherein 'R is a (fluorenyl) propenyl) group , Glycidyl, or any of the organic functional groups of vinyl, as shown in n-series 8, i0, i2 < M), and three or more cage-type bifurcated oxygen fired resins are selected from η is MCMUU mixtures thereof, and η is 81 billion Finnish 〇1] 4 from 々 々 not η~ Shu Shu dragon 14 and 112 sesquicarbonate silicon siloxane total set, based 5〇wt% or more of the total siloxane of silicon sesquicarbonate. 6. A fluorene type silsesquioxane resin with a functional group, which is a fluorene type sesquigan grease, and in the mixture, the following formula is not I type sesquigenated oxygen;): End resin In the above, [RSi〇3 / 2] n ⑺ (wherein R is (meth) acryl, (meth) acrylfluorenyl, glycidyl, or vinyl) Dagger tool s, dagger base, 11L series 8, 1052 or M). For example, the fifth scope of the scope of patent application-members of the cage type sesquisilicon firing resin with g 旎 group, where || The average molecular weight distribution (MW / Mn) of upper and lower semi-silica resin is in the range of U3 to L10. 315031 29