CN101260094B - Tri-(oxetane) compounds, preparation method thereof and optical waveguide using the same - Google Patents
Tri-(oxetane) compounds, preparation method thereof and optical waveguide using the same Download PDFInfo
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- CN101260094B CN101260094B CN2007100857344A CN200710085734A CN101260094B CN 101260094 B CN101260094 B CN 101260094B CN 2007100857344 A CN2007100857344 A CN 2007100857344A CN 200710085734 A CN200710085734 A CN 200710085734A CN 101260094 B CN101260094 B CN 101260094B
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Abstract
The invention relates to a tri-(oxetane) compound of the following formula (1): wherein R1 and R3 each represents hydrogen atom or alkyl containing one to six carbon atoms; R2 represents a bivalent fatty chain organic group containing zero to sixteen carbon atoms; and A represents carbon atoms or trivalent organic group obtained from cyclane containing three to twelve carbon atoms. The invention also relates to a preparation method of the compound and optical waveguide comprising the compound.
Description
Technical field
The present invention relates to have three (trimethylene oxide) compounds of the trimethylene oxide ring that can carry out cationoid polymerisation, its preparation method and comprise the optical waveguides of this compound.The Photosetting property resin combination and the hot curing resin composition that comprise three (trimethylene oxide) compounds have water-absorbent, coating planarization (flatness) and the viscosity of excellent thermotolerance, mechanical property, reduction.
Background technology
As carrying out light-initiated cationoid polymerisation or solidified monomer; Oxetane compound causes concern recently; And, the compound method of various oxetane compounds has been proposed along with the exploitation of many simple functions and multi-functional oxetane compound.
As oxetane compound, the oxetane compound by following formula (4) expression is disclosed in patented claim (referring to patent document 1):
R wherein
5Be Wasserstoffatoms, fluorine atom, the alkyl that contains 1-6 carbon atom, the fluoro-alkyl that contains 1-6 carbon atom, allyl group, aryl, furyl, thienyl; R
6For being selected from straight or branched and gathering the multivalence group of (alkylene oxide) group, inferior xylylene, siloxane bond and ester bond; Z is Sauerstoffatom or sulphur atom; With m be 2 to 4 integer).
In addition, the biphenyl derivatives with trimethylene oxide ring by following formula (5) expression has also been proposed:
R wherein
7For Wasserstoffatoms or contain the alkyl of 1-6 carbon atom and by the biphenyl derivatives with trimethylene oxide ring of following formula (6) expression:
R wherein
8To R
11Represent Wasserstoffatoms or methyl separately; And R
12And R
13Represent Wasserstoffatoms separately or contain the alkyl (referring to patent document 2 and 3) of 1-6 carbon atom.
Usually can through use basic metal such as sodium hydroxide and Pottasium Hydroxide as alkali and in the presence of alkali synthetic trimethylene oxide sulphonate and obtain above-claimed cpd with the corresponding divalent phenol compounds of trimethylene oxide sulphonate.In addition, use phase-transfer catalyst such as quaternary ammonium salt as required, the yield when synthesizing this compound to increase.In addition; Oxetane compound had been used material that acts on coating composition and the tackiness agent that is used to increase thermotolerance, increases purposes such as binding property in the past, and had proposed oxetane compound recently as the application (referring to patent document 4 and 5) of optical waveguides formation with material.Optical waveguides is combined in optical waveguide device, optical integrated circuit, the optics running board, and is widely used in optical communication, optical Information Processing and the similarly general optics.
Patent document 1:JP-A-6-16804
Patent document 2:JP-A-11-106380
Patent document 3:JP-A-2001-31665
Patent document 4:JP-A-2000-356720
Patent document 5:JP-A-2003-147045
Summary of the invention
Yet in oxetane compound, biphenyl derivatives is for having low-molecular-weight compound, and has low viscosity, makes it be difficult to for example forming thick film on the base material.In addition, because its difunctionality, biphenyl derivatives undesirably needs the long period to solidify.In addition, the oxetane compound except that biphenyl derivatives has and is difficult to the problem that forms required thick film and be difficult to realize required solidified nature.
When the oxetane compound of this routine is formed when use material as optical waveguides, because being difficult to stably be solidified into, it has identical shaped optical waveguides, there is the waveguide characteristic fluctuation and is difficult to form the problem of thick film with mode easily.
In addition, it is not the problem of quantitatively carrying out that there is the introducing of oxa-cyclobutyl group in the compound method of conventional oxetane compound, causes required oxetane compound yield low.In addition because generated have unreacted hydroxyl compound as by product, need complicated operations to obtain required oxetane compound usually.
Consider that above-mentioned situation accomplished the present invention; The purpose of this invention is to provide novel three (trimethylene oxide) compounds; Said compound can produce the polymkeric substance with excellent thick film formation property, solidified nature, thermotolerance etc.; And the present invention provides the preparation method of this compound and the optical waveguides that comprises this compound is provided.
In other words, the present invention relates to following (1) to (5).
(1) three (trimethylene oxide) compounds shown in the following formula (1):
R wherein
1And R
3Represent Wasserstoffatoms separately or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A representes carbon atom or gets the trivalent organic group of the naphthenic hydrocarbon of a self-contained 3-12 carbon atom.
(2) method of preparation above-mentioned (1) described three (trimethylene oxide) compounds, this method comprises:
Make the phenolic cpd shown in the following formula (2):
R wherein
1Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A represent carbon atom or the trivalent organic group of naphthenic hydrocarbon of a self-contained 3-12 carbon atom,
With the cesium salt reaction, thus the phenates of acquisition caesium; With
Make the phenates and the reaction of the sulphonate shown in the following formula (3) of caesium:
R wherein
3Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom, and X representes methyl, ethyl, phenyl or tolyl.
(3) according to the method for above-mentioned (2), wherein cesium salt is a cesium carbonate.
(4) optical waveguides comprises:
Base material;
Be arranged in the coating on the said base material; With
Have predetermined pattern and be arranged in the core on the said coating, its propagating optical signal,
Constituting one of at least in coating and the core wherein by the resin combination that contains three (trimethylene oxide) compounds shown in the following formula (1):
R wherein
1And R
3Represent Wasserstoffatoms separately or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A representes carbon atom or gets the trivalent organic group of the naphthenic hydrocarbon of a self-contained 3-12 carbon atom.
(5) according to the optical waveguides of (4), wherein in coating and the core one of at least by the resin combination formation that contains three (trimethylene oxide) compounds and the compound that contains epoxy group(ing) or vinyl ether group.
It is excellent and effective oxetane compound of using the polymkeric substance of the material that acts on coating composition, coated material, tackiness agent, lens, optical waveguides etc. that contriver of the present invention seeks aspects such as can being created in thermotolerance, mechanical property, and has carried out extensive studies.After having synthesized all cpds and many experiments that has ad hoc structure separately, they find and might realize above-mentioned purpose through using by novel three (trimethylene oxide) compounds of above-mentioned formula (1) expression, thereby have accomplished the present invention.More specifically, because this novel cpd has three trimethylene oxide rings in a molecule, this novel cpd has quick-setting character, and because its cured product forms highdensity reticulated structure, cured product has excellent thermotolerance etc.In addition; Because novel cpd has and has the different HMW of the low-molecular-weight compound that routinizes separately; Therefore this novel cpd has high viscosity, and it is favourable when being used to form thick film, when forming with material as optical waveguides (coating and core), is favourable particularly; Have identical shaped optical waveguides because might be solidified into stable manner, thus the effect of waveguide characteristic that has realized keeping identical etc.Simultaneously, the inventor is also to having carried out deep research with the compound method of high yield synthesizing new compound.The result; They find and might under predetermined condition, react with high yield synthesizing new compound through the sulphonate that makes 3-alkyl-3-hydroxymethyl trimethylene oxide of being represented by the phenolic cpd and the formula (3) of formula (2) expression, particularly when using cesium salt to synthesize as alkali.
As stated, the present invention relates to novel three (trimethylene oxide) compounds by formula (1) expression.Because this compounds has and the conventional different HMW of low-molecular weight compound, this compounds has high viscosity, makes it form thick film easily.In addition, because this compound has three trimethylene oxide rings in a molecule, so this compound can solidify rapidly through illumination or heating.Therefore; The Photosetting property resin combination and the hot curing resin composition that comprise three (trimethylene oxide) of the present invention compounds have excellent in curing property, thermotolerance, toughness and mechanical property, and have the suction character of reduction, high coating planarization and high viscosity.In addition, can reduce the amount of polymerization starter owing to the hyperergy of this compound, compsn has high transparency and can be used as the material that is used to form coating composition, coated material, tackiness agent, optical lens, optical waveguides etc.
Through under predetermined condition, using cesium salt to make the sulphonate of specific trimethylene oxide and specific phenol reaction, might need not complicated operations with synthetic three (trimethylene oxide) compounds of high yield as alkali.
In addition; When in coating in the optical waveguides and the core one of at least when comprising resin combination by three (trimethylene oxide) compounds of formula (1) expression and constitute, might make optical waveguides stably be solidified into identical shaped and might obtain stable waveguide characteristic etc.
Description of drawings
Fig. 1 is the horizontal cross of an example of expression optical waveguides of the present invention.
Fig. 2 (a) produces the sketch of the step of optical waveguides of the present invention for explanation to 2 (f).
The explanation of reference number and symbol
1: base material
2: coating
3: core
Detailed description of the invention
Embodiment of the present invention are below described.
Three (trimethylene oxide) of the present invention compounds is the compound by following formula (1) expression:
R wherein
1And R
3Represent Wasserstoffatoms separately or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A representes carbon atom or gets the trivalent organic group of the naphthenic hydrocarbon of a self-contained 3-12 carbon atom.Three (trimethylene oxide) of the present invention compounds has the structure that in a molecule, has three trimethylene oxide.In this respect, in formula (1), R
3Respectively do for oneself Wasserstoffatoms or contain alkyl such as methyl, ethyl, propyl group, the butyl of 1-6 carbon atom and preferable methyl or ethyl.
Might be through using by the sulphonate of the 3-alkyl-3-hydroxymethyl trimethylene oxide of the phenolic cpd of following formula (2) expression, following formula (3) expression and alkali as synthetic materials; And make their reactions and preparation by three (trimethylene oxide) compounds of formula (1) expression
R wherein
1Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A representes carbon atom or gets the trivalent organic group of the naphthenic hydrocarbon of a self-contained 3-12 carbon atom;
R wherein
3Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom, and X representes methyl, ethyl, phenyl or tolyl.
Though can use normally used basic metal for example sodium hydroxide and Pottasium Hydroxide as alkali, preferred especially in the present invention cesium salt.Because when using cesium salt, might need not to carry out complex operations with synthetic three (trimethylene oxide) compounds of high yield as alkali.In this case; Said material synthetic is through for example: (i) make the reaction of phenolic cpd and cesium salt; Thereby obtain the phenates of caesium, make the phenates and the reaction of trimethylene oxide sulphonate of caesium then, trimethylene oxide sulphonate and phenolic cpd are reacted in the presence of cesium salt.Preferably, syntheticly carry out according to method (i).Synthesize and in organic solvent (reaction solvent), carry out usually, and after reaction, add entry etc., reaction liquid is separated into water and organic phase, extract required three (trimethylene oxide) compounds from organic phase subsequently to reaction liquid.
The example of cesium salt comprises cesium carbonate, cesium hydroxide, cesium fluoride and cesium formate.This wherein can preferably use cesium carbonate, because it can obtain required three (trimethylene oxide) compounds with high yield.
With respect to 1 moles of phenol hydroxyl of the phenolic cpd of formula (2) expression, the usage quantity of cesium salt can be preferably 0.8 to 2.0 mole, more preferably 1.0 to 1.5 moles.
The phenolic cpd of formula (2) expression can be represented by following formula (2a):
R wherein
1Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom, R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom;
Perhaps can represent by following formula (2b):
R wherein
1Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom, R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom, and Y represent the trivalent organic group of naphthenic hydrocarbon of a self-contained 3-12 carbon atom.
Object lesson by the phenolic cpd of formula (2a) expression includes but not limited to three (4-hydroxy phenyl) methane, 1,1,1-three (4-hydroxy phenyl) ethane, 1; 1,1-three (3-hydroxy phenyl) ethane, 1,2,2-three (4-hydroxy phenyl) propane, 1; 3,3-three (4-hydroxy phenyl) butane, 1,3,3-three (3-hydroxy phenyl) butane, 1; 4,4-three (4-hydroxy phenyl) pentane and 1,4,4-three (3-hydroxy phenyl) pentane.These can use separately or two or more combinations are used.
Object lesson by the phenolic cpd of formula (2b) expression includes but not limited to 1,1,4-three (4-hydroxy phenyl) hexanaphthene, 1,1,4-three (4-hydroxy phenyl) pentamethylene, 1,1,4-three (3-hydroxy phenyl) hexanaphthene and 1,1,4-three (4-hydroxy phenyl) suberane.These can use separately or two or more combinations are used.
The object lesson by the sulphonate of the 3-alkyl-3-methylol trimethylene oxide of formula (3) expression that uses with above-mentioned phenolic cpd comprises methylsulfonic acid-2-(3-oxa-cyclobutyl) propyl ester, phenylbenzimidazole sulfonic acid-2-(3-oxa-cyclobutyl) propyl ester, toluenesulphonic acids-2-(3-oxa-cyclobutyl) propyl ester, methylsulfonic acid-2-(3-oxa-cyclobutyl) butyl ester and toluenesulphonic acids-2-(3-oxa-cyclobutyl) butyl ester.These can use separately or two or more combinations are used.
Might be according to for example at Organic Synthesis, Collective vol.1, the sulphonate of the 3-alkyl-3-hydroxymethyl trimethylene oxide of method synthesis type (3) expression described in the pp.145 (1941), said reference is merged in this paper as a reference.
With respect to 1 moles of phenol hydroxyl of the phenolic cpd of formula (2) expression, the usage quantity of the sulphonate of the 3-alkyl-3-hydroxymethyl trimethylene oxide of formula (3) expression can be preferably 1.5 to 2.0 moles, more preferably 1.0 to 1.5 moles.
Temperature of reaction during preferred preparation three (trimethylene oxide) of the present invention compounds is 0 ℃ to 120 ℃, more preferably 60 ℃ to 100 ℃.In making the situation of phenolic cpd and cesium salt reaction with the phenates that obtains caesium, can preferable reaction temperature be 0 ℃ to 120 ℃, more preferably 40 ℃ to 100 ℃.For the not special restriction of the pressure in the reaction process, it can be normal pressure, pressurization and decompression.For the not special restriction of reaction atmosphere, it can be nitrogen atmosphere or air atmosphere.
When synthetic three (trimethylene oxide) of the present invention compounds, as required, can add basic metal such as sodium and potassium; Alkalimetal hydride such as lithium hydride and sodium hydride; Alkali metal hydroxide such as sodium hydroxide and Pottasium Hydroxide; Alkaline carbonate for example yellow soda ash etc. as synthetic materials.
In addition, as required, can add quaternary ammonium salt 、 quaternary alkylphosphonium salt or the like as the phase-transfer catalyst between water and the organic phase.The example of quaternary ammonium salt includes but not limited to quaternary alkylammonium halides, like Tetrabutyl amonium bromide (TBAB) and tetraethylammonium bromide; With aralkyl trialkyl ammonium halide, like benzyl trimethyl ammonium chloride.For the not special restriction of quaternary alkylphosphonium salt, its example comprises four aryl phosphonium halides, like 4-phenyl phosphonium bromide.
In addition, when preparation three (trimethylene oxide) of the present invention compounds, as stated, use reaction solvent usually.For the not special restriction of reaction solvent, its preferred example comprises aromatic hydrocarbons for example toluene and YLENE; Ethers such as THF and dibutyl ether; With aprotic polar solvent such as N-Methyl pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide and DMAC N,N.These reaction solvents can use separately or two or more combinations are used.
As stated, might be through add entry or ETHYLE ACETATE to reaction liquid; With liquid separation is water and organic phase; Extract organic phase; Collect from above-mentioned materials synthetic three (trimethylene oxide) compounds with the organic phase of extracting with anhydrous magnesium sulfate drying.
Might use the material of three (trimethylene oxide) compounds of acquisition like this as Photosetting property resin and heat-curing resin effectively, said Photosetting property resin and heat-curing resin constitute coating composition, coated material, tackiness agent, lens, optical waveguides etc. separately.
This wherein; For the optical waveguides that comprises base material 1, is arranged in the coating 2 on the base material 1 and has predetermined pattern and be arranged in the core 3 that is used to transmit optical signal on the said coating as shown in Figure 1; When resin combination that use comprises three (trimethylene oxide) compounds be used to form in coating 2 and the core 3 one of at least the time; This compound is for forming the thick film particularly advantageous, because this compound has HMW to obtain high viscosity.In addition, obtain favourable effect, for example be solidified into identical shaped easily and obtain stable waveguide characteristic.In this respect, be necessary that the specific refractory power of regulating coating 2 makes its specific refractory power less than core 3.
Being made up of the resin combination that comprises three (trimethylene oxide) compounds and the compound with epoxy group(ing) or vinyl ether group one of at least in preferred coating 2 and the core 3 is being the excellent in curing material aspect thermotolerance and the wet fastness and improving (exposure) susceptibility of making public because might obtain.As compound, might use any The compounds of this invention that shows with formula (1) expression that those of consistency are arranged with epoxy group(ing).More specifically, the example that has an epoxy compounds of an epoxy group(ing) comprises phenylglycidyl ether and butyl glycidyl base ether; Example with epoxy compounds of two or more epoxy group(ing) comprises dihydroxyphenyl propane diglycidyl ether, two phenoxyethyl alcohol fluorenes diglycidyl ether, trimethylolpropane tris glycidyl ether and bisphenol fluorene four glycidyl group ether; And preferably use 3,4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters, 2, two (the methylol)-1-butanols and 1 of 2-, 2-epoxy-4-(2-oxa-cyclopentyl) conducts such as adducts of hexanaphthene have the compound of alicyclic epoxy base.As compound, might use any The compounds of this invention that shows with formula (1) expression that those of consistency are arranged with vinyl ether group.More specifically, the example that has a compound of a vinyl ether group comprises hydroxyethyl vinyl ether, hydroxybutyl vinyl ether and dodecyl vinyl.As compound, preferably use cyclohexanedimethanol divinyl ether, Tri Ethyleneglycol divinyl ether, phenolic resin type divinyl ether etc. with two or more vinyl ether groups.These compounds can use separately or two or more combinations are used.
Might be through Fig. 2 (a) for example to the step production optical waveguides shown in 2 (f).That is, preparation base material 1 shown in Fig. 2 (a), then as Fig. 2 (b) layout end coating 2a (bottom of coating 2) on the base material that is shown in 1.As Fig. 2 (c) the end coating 2a that is shown in go up to arrange the layer 3 that constitutes by the resin combination that is used to form core 3 '.Shown in Fig. 2 (d), the layer 3 of resin combination ' on arrange and to be used for the photomask 9 that exposure forms predetermined pattern (optical waveguides figure), the layer 3 through photomask 9 usefulness uviolizing resin combinations ' and heat subsequently.Then, shown in Fig. 2 (e), thereby use dissolves and remove the layer 3 of resin combination ' unexposed portion form core 3.Shown in Fig. 2 (f), on core 3, arrange top cladding 2b (top of coating 2) then.Thus, movable required optical waveguides.
Might for example spin coating and coating machine form each layer on base material 1 through ordinary method.Optical waveguides can form film appearance optical waveguides through peeling base material 1 off.Film appearance optical waveguides is excellent aspect flexible.
The optical waveguides that so obtains can be used as linear light waveguide, curved optical waveguides, X-type optical waveguides, Y bifurcated optical waveguides, planar light waveguide, Mach Zender optical waveguides, AWG type optical waveguides, grating, optical waveguide lens etc.Use the example of the optical element of optical waveguides to comprise wave filter, optical switch, optics splitter (optical brancher), optical multiplexer, optical multiplexer/splitter, optical amplifier, waveguide transmodulator, waveguide divider, spectroscope, directional coupler, have the optical transport module that mixes integrated laser diode and photorectifier, or the like.
Embodiment
Through following examples the present invention is described more specifically, but should think that the present invention receives the restriction of these embodiment.
Before embodiment, sulphonate-toluenesulphonic acids-2-(3-oxa-cyclobutyl) butyl ester of the synthetic 3-alkyl-3-hydroxymethyl trimethylene oxide that is described below.
(synthesizing of toluenesulphonic acids-2-(3-oxa-cyclobutyl) butyl ester)
The Tosyl chloride of impouring 190.65g (1.0mol), the Tetrabutyl amonium bromide of 32.24g (0.1mol) and the toluene of 400ml in the three-necked flask of the 2000ml that TM, water cooler, whipping appts and tap funnel are housed, and under agitation in ice bath, be cooled to 5 ℃.After 3-ethyl-hydroxymethyl trimethylene oxide of impouring 116.16g (1.0mmol) in three-necked flask, in 30 minutes, in three-necked flask, drip the 35 weight % sodium hydroxide solutions of 130ml.After dripping, under uniform temp, continue stirring 1 hour, then stirring at room 16 hours.After reaction, the water of impouring 800ml, vigorous stirring subsequently in flask.Mixture is left standstill, will separate organic phase and water.Organic phase is spent the night with anhydrous magnesium sulfate drying with the 400ml water washing then.Then, remove by filter sal epsom, and it is concentrated to filtrate.Separate the crude product so obtain and separate (elute soln: hexane/ethyl acetate), obtain required material, i.e. toluenesulphonic acids-2-of 243.3g (yield 90%) (3-oxa-cyclobutyl) butyl ester with silica gel column chromatography.
In the three-necked flask of the 200ml that TM, cooling tube and whipping appts are housed 1 of impouring 6.13g (20mmol); 1; The N-N-methyl-2-2-pyrrolidone N-of 1-three (4-hydroxy phenyl) ethane and 25ml, and under nitrogen atmosphere, under agitation be heated to 80 ℃, dissolve fully up to material.After dissolving, add the cesium carbonate of 23.46g (72mmol), stirred subsequently 30 minutes.In mixture, add 17.84g (66mmol) synthetic toluenesulphonic acids-2-(3-oxa-cyclobutyl) butyl ester in advance, under nitrogen atmosphere, stirred 20 hours down subsequently at 80 ℃.After reaction,, add 100ml ETHYLE ACETATE and 50ml zero(ppm) water to mixture then with the mixture cool to room temperature.Mixture is left standstill, with water phase separated and organic phase.The organic phase of extraction separation is also used water washing, spends the night with anhydrous magnesium sulfate drying subsequently.Then, remove by filter sal epsom, and distillation obtains reacting coarse product except that desolvating.
Through the crude product that the tlc analysis so obtains, confirm as a spot.In addition, through using ETHYLE ACETATE that the crude product recrystallization is obtained 10.93g (yield: white solid matter 91%).Purity through the liquid chromatographic detection compound is 99% or higher.
From using
1H-NMR with
13The following analytical results that C-NMR (product of JEOLLtd.) obtains confirms that the compound that obtains is 1,1 of following structural formula (7) expression, 1-three { 4-[2-(3-oxa-cyclobutyl)] butoxy phenyl } ethane.
1H-NMR(CDCl
3，400MHZ)：δ(ppm)；0.93(t，J＝7.6Hz，9H，CH
3)，1.87(q，J＝7.6Hz，6H，6H，CH
2)，2.11(s，3H，CH
3)，4.05(s，6H，CH
2)，4.47(d，J＝6.0Hz，6H，CH
2)，4.56(d，J＝5.6Hz，6H，CH
2)，6.83(d，J＝9.2Hz，6H，Ar)，7.01(d，J＝8.8Hz，6H，Ar)
13C-NMR(CDCl
3，400MHZ)：δ(ppm)；8.22，26.70，30.83，43.19，50.66，70.18，78.17，113.70，129.62，142.03，157.05
Structural formula (7)
In the three-necked flask of the 200ml that TM, cooling tube and whipping appts are housed 1 of impouring 6.68g (20mmol); 3; The N-N-methyl-2-2-pyrrolidone N-of 3-three (4-hydroxy phenyl) butane and 25ml, and under nitrogen atmosphere, under agitation be heated to 80 ℃, dissolve fully up to material.After dissolving, add the cesium carbonate of 23.46g (72mmol), stirred subsequently 30 minutes.In mixture, add 17.84g (66mmol) synthetic toluenesulphonic acids-2-(3-oxa-cyclobutyl) butyl ester in advance, under nitrogen atmosphere, stirred 20 hours down subsequently at 80 ℃.After reaction,, in mixture, add 100ml ETHYLE ACETATE and 50ml zero(ppm) water then with the mixture cool to room temperature.Mixture is left standstill, with water phase separated and organic phase.The organic phase of extraction separation is also used water washing, spends the night with anhydrous magnesium sulfate drying subsequently.Then, remove by filter sal epsom, and distillation obtains reacting coarse product except that desolvating.
Through the crude product that the tlc analysis so obtains, confirm as a spot.In addition, (eluting liquid: n-hexane/acetone) the purifying crude product obtains 12.20g (yield: transparent semisolid 97%) through separation and through the silica gel column chromatography separation.Purity through the liquid chromatographic detection compound is 99% or higher.
By use
1H-NMR with
13The following analytical results that C-NMR (product of JEOL Ltd.) obtains confirms that the compound that obtains is by 1,3 of structural formula (8) expression, 3-three (4-(2-(3-oxa-cyclobutyl)) butoxy phenyl) butane.
1H-NMR(DMSO-d
6，400MHz)：δ(ppm)；0.87(t，J＝7.6Hz，3H，CH
3)，0.88(t，J＝7.6Hz，6H，CH
3)，1.62(br，s，3H，CH
3)，1.77(q，J＝7.6Hz，6H，CH
2)，2.66(br，s，4H，CH
2)，4.03(s，2H，CH
2)，4.05(s，4H，CH
2)，4.32(d，J＝6.0Hz，6H，CH
2)，4.41(d，J＝7.6Hz，2H，CH
2)，4.43(d，J＝7.6Hz，4H，CH
2)，6.87(d，J＝8.8Hz，2H，Ar)，6.90(d，J＝8.4Hz，4H，Ar)，7.04(d，J＝8.8Hz，2H，Ar)，7.12(d，J＝8.8Hz，4H，Ar)
13C-NMR(DMSO-d6,100MHz)：δ(ppm)；7.99，26.16，27.34，29.89，42.44，42.46，43.81，44.54，70.00，70.16，76.73，76.77，113.93，114.45，127.89，128.99，134.62，141.61，156.47，156.88
Structural formula (8)
In the three-necked flask of the 200ml that TM, cooling tube and whipping appts are housed 1 of impouring 7.21g (20mmol); 1; The N-N-methyl-2-2-pyrrolidone N-of 4-three (4-hydroxy phenyl) hexanaphthene and 30ml, and under nitrogen atmosphere, under agitation be heated to 80 ℃, dissolve fully up to material.After dissolving, add the cesium carbonate of 23.46g (72mmol), stirred subsequently 30 minutes.In mixture, add 17.84g (66mmol) synthetic toluenesulphonic acids-2-(3-oxa-cyclobutyl) butyl ester in advance, under nitrogen atmosphere, stirred 20 hours down subsequently at 80 ℃.After reaction,, in mixture, add 100ml ETHYLE ACETATE and 50ml zero(ppm) water then with the mixture cool to room temperature.Mixture is left standstill, with water phase separated and organic phase.The organic phase of extraction separation is also used water washing, spends the night with anhydrous magnesium sulfate drying subsequently.Then, remove by filter sal epsom, and distillation obtains reacting coarse product except that desolvating.
Through the crude product that the tlc analysis so obtains, confirm as a spot.In addition, through using ETHYLE ACETATE that the crude product recrystallization is obtained 12.18g (yield: white solid matter 93%).Purity through the liquid chromatographic detection compound is 99% or higher.
By use
1H-NMR with
13The following analytical results that C-NMR (product of JEOL Ltd.) obtains confirms that the compound that so obtains is 1,1 of following structural formula (9) expression, 4-three (4-(2-(3-oxa-cyclobutyl)) butoxy phenyl) hexanaphthene.
1H-NMR(CDCl
3，400MHz)：δ(ppm)；0.90(dt，J＝2.8Hz，J＝7.6Hz，6H，CH
3)，0.95(t，J＝7.6Hz，3H，CH
3)，1.65(br，q，J＝12.0Hz，2H，CH
2)，1.87(m，8H，CH
2)，2.06(br，t，J＝13.6Hz，2H，CH
2)，2.63(br，t，J＝12.0Hz，1H，CH)，2.74(br，d，J＝12.8Hz，2H，CH
2)，4.02(d，J＝3.6Hz，4H，CH
2)，4.08(s，2H，CH
2)，4.45(dd，J＝2.4Hz，J＝6.4Hz，4H，CH
2)，4.48(d，J＝6.0Hz，2H，CH
2)，4.53(d，J＝5.2Hz，2H，CH
2)，4.54(d，J＝5.2Hz，2H，CH
2)，4.59(d，J＝6.0Hz，2H，CH
2)，6.80(d，J＝4.8Hz，2H，Ar)，6.82(d，J＝4.8Hz，2H，Ar)，6.92(d，J＝8.8Hz，2H，Ar)，7.04(d，J＝8.8Hz，2H，Ar)，7.13(d，J＝8.8Hz，2H，Ar)，7.32(d，J＝9.2Hz，2H，Ar)
13C-NMR(CDCl
3，100MHz)：δ(ppm)；8.18，8.25，26.67，26.74，30.78，37.43，43.16，43.19，43.22，43.49，44.53，76.73，77.05，77.36，78.17，78.19，113.97，114.26，114.46，127.13，127.65，128.94，137.65，139.65，144.29，156.67，156.73，157.23
Structural formula (9)
Embodiment 4
Form end coating, core and top cladding through being described below and production optical waveguides (referring to Fig. 1).Then, be described below and carry out the evaluation of optical waveguides.
(formation of end coating)
In pimelinketone dissolving 70 weight parts (below be abbreviated as " part ") in embodiment 2, obtain 1; 3; 3-three (4-(2-(3-oxa-cyclobutyl)) butoxy phenyl) butane, 30 parts be as 3 of alicyclic epoxide compound, 4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters (DaicelChemical Industries; Ltd. product; Celoxide2021P) and 1 part 4, two (two-(beta-hydroxy oxyethyl group) phenyl sulfinyls) the phenyl sulfide-two-hexafluoro antimonate 50%propioncarbide solution of 4-are used to form the polymerisable compound A of coating with preparation.Then, on the surface of glass baseplate (5cm * 5cm * 2mm thickness), through spin application polymerisable compound A, subsequently 100 ℃ of dryings 5 minutes.Use ultraviolet ray with 2 on whole surface, 000mJ/cm
2Radiation quantity irradiation, subsequently 100 ℃ of thermal treatments 30 minutes, to form end coating (referring to Fig. 2 (b)).Using contact-type film thickness survey meter to measure end coating layer ranges in thickness is 30 μ m.This end coating is 1.540 in the specific refractory power of 633nm wavelength.
(formation of core)
Then; In pimelinketone the dissolving 90 parts in embodiment 2, obtain 1; 3; 320) and 1 part 4 (epoxide equivalent:, the 50%propion carbide solution of 4-two [two ((beta-hydroxy oxyethyl group) phenyl sulfinyl] phenyl sulfide-two hexafluoro antimonates is used to form the polymerisable compound B of core with preparation for 3-three (4-(2-(3-oxa-cyclobutyl)) butoxy phenyl) butane, two phenoxyethyl alcohol fluorenes diglycidyl ether of 10 parts.Then, through spin coating polymerisable compound B is coated on (referring to Fig. 2 (c)) on the end coating.With coating 150 ℃ of dryings 20 minutes; On coating, arrange synthetic quartz base chrome mask (photomask) then; Being printed on pitch in the above is the Line of light waveguide figure (referring to Fig. 2 (d)) of 50 μ m, uses ultraviolet ray with 2 through contact exposure method through chrome mask subsequently, 000mJ/cm
2Radiation quantity shine, and 150 ℃ of thermal treatments 30 minutes.Then,, use gamma-butyrolactone solution to develop, heat 30 minutes to form core figure (referring to Fig. 2 (e)) at 150 ℃ subsequently in order to remove not illuminated portion.Using the linear measure microscope to measure the cross-sectional shape of core figure, is the square of 50 μ m width and 50 μ m height.Core is 1.563 in the specific refractory power of 633nm wavelength.
(formation of top cladding)
To be coated on core and the end coating with the identical compsn of polymerisable compound A that preparation is used to form end coating through spin coating.After 100 ℃ of dryings 5 minutes, use ultraviolet ray with 2 on whole surface, 000mJ/cm
2Radiation quantity irradiation, subsequently 150 ℃ of thermal treatments 60 minutes to form top cladding (referring to Fig. 2 (f)).
Thus, having produced the relative refractive index Δ is 1.5% optical waveguides.
(evaluation)
Use cutting unit (Disco Corporation; Model 522) optical waveguides is cut to the length of 10cm, carries out end face processing subsequently.Then, use the cross-sectional shape of linear measure microscopic examination optical waveguides, to confirm that optical waveguides is the multimode lightguide of embedding, end coating layer ranges in thickness is 30 μ m, and core is of a size of 50 μ m * 50 μ m; And the thickness of top cladding is 70 μ m.The laser beam that uses wavelength 850nm is 0.07dB/cm through the loss of light propagation of the optical waveguides that common cutting off (cut-back) method is measured.In addition, can be with the optical waveguides of peeling off from base material as film appearance waveguide.Film appearance waveguide does not have loss to reduce when R is 20mm crooked, and can be that 5mm carries out bending with R, thereby proves that it is good flexible.
Embodiment 5
Form end coating, core and top cladding through being described below and production optical waveguides (referring to Fig. 1).Then, be described below and carry out the evaluation of optical waveguides.
(formation of end coating)
In pimelinketone dissolving 70 weight parts (below be abbreviated as " part ") in embodiment 1, obtain 1; 1; 1-three (4-(2-(3-oxa-cyclobutyl)) butoxy phenyl) ethane, 30 parts as 3 of alicyclic epoxide compound; 4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters (DaicelChemical Industries, the product of Ltd.; Celoxide2021P) and 1 part 4, the 50%propioncarbide solution of two (two (beta-hydroxy oxyethyl group) phenyl sulfinyl) phenyl sulfide-two-hexafluoro antimonates of 4-is used to form the polymerisable compound C of coating with preparation.Then, on the surface of Si base material (5cm * 5cm * 2mm thickness), through spin application polymerisable compound C, subsequently 100 ℃ of dryings 5 minutes.Use ultraviolet ray with 2 on whole surface, 000mJ/cm
2Radiation quantity irradiation, subsequently 100 ℃ of thermal treatments 30 minutes, to form end coating (referring to Fig. 2 (b)).The end coating thickness that uses contact-type film thickness survey meter to measure is 30 μ m.This end coating is 1.547 in the specific refractory power of 633nm wavelength.
(formation of core)
Then; In pimelinketone the dissolving 90 parts in embodiment 1, obtain 1; 1; 320) and 1 part 4 (epoxide equivalent:, the 50%propion carbide solution of 4-two [two ((beta-hydroxy oxyethyl group) phenyl sulfinyl] phenyl sulfide-two hexafluoro antimonates is used to form the polymerisable compound D of core with preparation for 1-three (4-(2-(3-oxa-cyclobutyl)) butoxy phenyl) butane, two phenoxyethyl alcohol fluorenes diglycidyl ether of 10 parts.Then, through spin coating polymerisable compound D is coated on (referring to Fig. 2 (c)) on the end coating.With coating 150 ℃ of dryings 20 minutes; On coating, arrange synthetic quartz base chrome mask (photomask) then; Being printed on pitch above it is the Line of light waveguide figure (referring to Fig. 2 (d)) of 50 μ m, uses ultraviolet ray with 2 through contact exposure method through chrome mask subsequently, 000mJ/cm
2The radiation quantity radiation, and 150 ℃ of thermal treatments 30 minutes.Then,, use gamma-butyrolactone solution to develop, heat 30 minutes to form core figure (referring to Fig. 2 (e)) at 150 ℃ subsequently in order to remove not illuminated portion.Use the linear measure microscope to measure the cross-sectional shape of core figure, be the square of width 50 μ m and width 50 μ m.Core is 1.573 in the specific refractory power of 633nm wavelength.
(formation of top cladding)
To be coated on core and the end coating with the identical compsn of polymerisable compound C that preparation is used to form end coating through spin coating.After 100 ℃ of dryings 5 minutes, use ultraviolet ray with 2 on whole surface, 000mJ/cm
2Radiation quantity irradiation, subsequently 150 ℃ of thermal treatments 60 minutes, to form top cladding (referring to Fig. 2 (f)).Produced the relative refractive index Δ thus and be 1.7% optical waveguides.
(evaluation)
Use cutting unit (Disco Corporation; Model 522) optical waveguides is cut to the length of 10cm, carries out end face processing subsequently.Use the cross-sectional shape of linear measure microscopic examination optical waveguides then, to confirm that optical waveguides is the multimode lightguide of embedding, end coating layer ranges in thickness is 30 μ m, and core is of a size of 50 μ m * 50 μ m; And the thickness of top cladding is 70 μ m.The laser beam that uses wavelength 850nm is 0.07dB/cm through the loss of light propagation of the optical waveguides that common cutback technique is measured.
Three (trimethylene oxide) of the present invention compounds is as the component of Photosetting property resin combination or heat-setting resin combination, and each of two kinds of resin combinations all can be used as the material that is used for coating composition, coated material, tackiness agent, optical lens, optical waveguides etc.The example of optical waveguides comprises linear optical waveguides, curved optical waveguides, X-type optical waveguides, Y bifurcated optical waveguides, planar light waveguide, Mach Zender type optical waveguides, AWG type optical waveguides, grating, optical waveguide lens.Use the example of the optical element of optical waveguides to comprise wave filter, optical switch, optics splitter (optical brancher), optical multiplexer, optical multiplexer/splitter, optical amplifier, waveguide transmodulator, waveguide divider, spectroscope, directional coupler, have and mix the integrated laser diode and the optical transport module of photorectifier.
Though describe the present invention in detail, for a person skilled in the art, obviously can carry out various changes and variation, and not depart from the scope of the present invention with reference to specific embodiments.
The Japanese patent application 2005-262236 that the application submitted to based on September 9th, 2005, its full content is merged in this paper as a reference.
Claims (5)
1. three (trimethylene oxide) compounds shown in the following formula (1):
R wherein
1And R
3Represent Wasserstoffatoms separately or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A representes carbon atom or gets the quadrivalent organic radical group of the naphthenic hydrocarbon of a self-contained 3-12 carbon atom.
2. prepare the method for claim 1 described three (trimethylene oxide) compounds, this method comprises:
Make the phenolic cpd shown in the following formula (2):
R wherein
1Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A represent carbon atom or the quadrivalent organic radical group of naphthenic hydrocarbon of a self-contained 3-12 carbon atom,
With the cesium salt reaction, thus the phenates of acquisition caesium; With
Make the phenates and the reaction of the sulphonate shown in the following formula (3) of caesium:
R wherein
3Expression Wasserstoffatoms or contain the alkyl of 1-6 carbon atom, and X representes methyl, ethyl, phenyl or tolyl.
3. the described method of claim 2, wherein cesium salt is a cesium carbonate.
4. optical waveguides comprises:
Base material;
Be arranged in the coating on the said base material; With
Have predetermined pattern and be arranged in the core on the said coating, its propagating optical signal,
Constituting one of at least in coating and the core wherein by the resin combination that contains three (trimethylene oxide) compounds shown in the following formula (1):
R wherein
1And R
3Represent Wasserstoffatoms separately or contain the alkyl of 1-6 carbon atom; R
2Expression contains the divalent aliphatic chain organic group of 0-16 carbon atom; And A representes carbon atom or gets the quadrivalent organic radical group of the naphthenic hydrocarbon of a self-contained 3-12 carbon atom.
5. the described optical waveguides of claim 4, wherein constituting one of at least in coating and the core by the resin combination that contains three (trimethylene oxide) compounds and the compound that contains epoxy group(ing) or vinyl ether group.
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