CN1508165A - Bisphenol-formaldehyde phenolic resin passive optical waveguide material and use thereof - Google Patents
Bisphenol-formaldehyde phenolic resin passive optical waveguide material and use thereof Download PDFInfo
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- CN1508165A CN1508165A CNA021566380A CN02156638A CN1508165A CN 1508165 A CN1508165 A CN 1508165A CN A021566380 A CNA021566380 A CN A021566380A CN 02156638 A CN02156638 A CN 02156638A CN 1508165 A CN1508165 A CN 1508165A
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Abstract
The present invention belongs to the field of photoelectron optical waveguide material, in particular, it relates to a bisphenol-formolphenolic resin passive optical waveguide material whose optical activity is not dependent on molecular ordered arrangement. Said material can be used for preparing organic thermal optical switch, organic optical interconnection, organic electrooptic modulator or optical waveguide photoelectron waveguide device. Said invention also provides its general formula.
Description
Technical field
The invention belongs to photoelectron optical waveguide material field, specially refer to a kind of optical activity and do not rely on passive optical waveguide material of bis-phenol-formaldehyde phenolic resin that molecular assembly arranges and uses thereof.
Background technology
The organic polymer optical waveguide material has the important use DEVELOPMENT PROSPECT, is one of bright spot of photoelectron material and devices field development, thereby has attracted material and device scientist's extensive concern.The optical application of organic/polymer materials mainly adopts the waveguide form, comprises thin-film waveguide optical fiber.
If the device that need be orientated material molecule in the device preparation is called active part, then the material molecule device that need not to be orientated is called passive device.The polymer materials of passive form has important application in polymeric thermo-optic device, polymer optical fiber and light interconnection and as the aspects such as clad material of polymkeric substance active part.Polymeric thermo-optic switch (PTOS) is based on its specific refractory power and varies with temperature and work.If (TOC) represents with thermo-optical coeffecient, the TOC of Lithium niobium trioxide is 4 * 10
-5The big order of magnitude of TOC ratio lithium niobate of ℃-1 polymkeric substance, and different with Lithium niobium trioxide, and its TOC does not change with wavelength.PTOS has a wide range of applications in the modern optical communication industry, and PTOS research aspect the wavelength-division multiplex about AWG and light has also obtained impressive progress, and PTOS has realized industrialization on Canada and other places.Passive polymer materials also has important application in the light interconnection work of the aspects such as networking of the extensive parallel processing of supercomputer, computer cluster.Also be like this aspect optical communication, laser apparatus, amplifier, electrooptical switching, various assemblies such as modulator and monitor, they are made up of differing materials usually, and size is also inconsistent.It is difficult by electronic interconnection or prism, grating or optical lens these devices effectively being coupled.The expert thinks: the interconnection of polymkeric substance light will become main means in integrated optoelectronic system.
But, hereto, polymeric optical material, particularly the investigation of materials of polymkeric substance passive optical waveguide also seldom, what select for use from the market usually during actual the use is some materials that are used for other purpose, be used for the polyureas alkane material of printed wiring plate coating as those Aktiebolaget Leo (SE) Box 941, S-251 09 Helsingborg, Sweden of frequent use Britain, Britain technical optics company is used for the special tamanori material series of Nolan of tackiness agent etc.People can't require to go to change the performance index of these commodity according to waveguide design.
Summary of the invention
One of purpose of the present invention is requirement and the material characteristics of using according to passive optical waveguide, and selected bis-phenol-formaldehyde phenolic resin is as polymkeric substance passive optical waveguide material.These materials have good stability, high second-order transition temperature, high specific refractory power, and good film forming properties.
Another object of the present invention is that the structure of bis-phenol-formaldehyde phenolic resin is modified, and a kind of modifier of bis-phenol-formaldehyde phenolic resin is provided.
Another object of the present invention provides the purposes of the passive optical waveguide material of a kind of bis-phenol-formaldehyde phenolic resin or its modifier.
Another object of the present invention be to solve bis-phenol-formaldehyde phenolic resin or its modifier the passive optical waveguide application facet the key technical problems such as interlayer refractive index match, thickness adjusting, light, thermostability improvement, synergism low-temperature curing that must solve.
Bis-phenol-formaldehyde phenolic resin of the present invention is formed by bisphenol cpd and formaldehyde condensation polymer, and general formula is:
Wherein, R represents at phenyl ring 3,3 ', 5,5 '-position have 10 carbon atoms following alkyl, alkoxyl group or an ester group substituting group; X represents methylene radical, C, the methylene radical that C-two-three methyl halide bases replace, 1,3 or 1, the phenyl ring that is connected with the phenol ring on the 4-position, 1, hexahydrobenzene that is connected with the phenol ring on the 4-position or sulfuryl etc., C wherein, the halo group in the methylene radical that C-two-three methyl halide bases replace can be fluorine atom, chlorine atom, bromine atoms or iodine atom.
The synthesis preparation method of bis-phenol-formaldehyde phenolic resin is comparative maturity, but reference:
Brydson，J.A.，Plastic?Materials，Newnes-Bufferworths，London，1975，Chap.23；
Schildknecht，C.E.Skeist，Polymerization?Processes，John?Wiley?andSons，New?York，1977，Chap.14.
Bis-phenol-formaldehyde phenolic resin of the present invention is the product of the carbonyl polycondensation of the bisphenol compound that obtains under acid or base catalysis and formaldehyde, the product that particularly various thermosets and novolac resin obtain through further modification.Described modification is etherificate or esterification.In etherification reaction, can use alkyl bromide, chlorallylene, epoxy chloropropane or 2,2 ', 6,6 '-tetramethyl--4 '-hydroxy piperidine etc. reacts with phenolic hydroxyl group; In esterification, can use 3,5-di-t-butyl-4-hydroxy phenylpropionic acid etc. has the material and the phenolic hydroxyl group reaction of antioxidant property.In above-mentioned modified-reaction, the modification degree of phenolic hydroxyl group changes in the 10-100% scope, promptly according to the requirement of thin-film waveguide material, carries out part or all of modification.Therefore, the present invention also comprises the bis-phenol-formaldehyde phenolic resin that obtains by etherificate or esterification process.
In order to reduce solidification value, after in thermoplasticity or heat-reactive phenolic resin molecular structure, connecting photosensitivity groups such as vinylformic acid, methacrylic acid or epoxy group(ing), under auxiliary agent existence conditions such as suitable initiator, can obtain thermochemistry, photochemistry synergism solidified material.Employed sensitizing agent comprises: benzophenone/triethylamine, st-yrax dme, Thiaxanthene, isopropyl thioxanthone, phenyl diazonium hexafluorophosphote, phosphofluoric acid diphenyl iodnium or phosphofluoric acid triphenyl salt etc.Therefore, the present invention also is included in the bis-phenol-formaldehyde phenolic resin that connects photosensitivity groups such as vinylformic acid, methacrylic acid or epoxy group(ing) in thermoplasticity or the heat-reactive phenolic resin molecular structure.
Thermoplasticity of the present invention or thermoset bis-phenol-formaldehyde phenolic resin can further be cured processing, employed solidifying agent for example: Resins, epoxy, isocyanic ester, or with the solidifying agent of thermosetting resin as thermoplastic resin.Solidification value as requested can change between room temperature to 250 ℃.
Under condition more than 160 ℃, bis-phenol-formaldehyde phenolic resin is painted easily.Painted activity and oxidising process with phenolic hydroxyl group is relevant.In the resol molecular structure, key in antioxidant groups by etherificate, esterification; reduce solidification value; particularly by means of introducing photosensitivity groups such as acrylic acid groups, epoxide group; make described resol carry out thermochemistry, photochemistry synergism low-temperature curing; be aided with the atmosphere of inert gases protection in case of necessity, can guarantee that resulting film is colourless substantially.
The synthetic of many resol has been the reaction of comparative maturity, can reference as the synthetic of hot retrospective, heat-reactive phenolic resin:
Brydson，J.A.，Plastic?Materials，Newnes-Bufferworths，London，1975，Chap.23；
Schildknecht，C.E.Skeist，Polyrnerization?Processes，John?Wiley?andSons，New?York，1977，Chap.14.
The esterification of resol and etherification reaction can references:
Dannels，B.F.，et.al.，J.Polym.Sci.，A-1，1968，6，2051；
Knop，A.，et.al.，Chemistry?and?Application?of?Phenolic?Resins，Springer-Verlag，Berlin，Heidelberg，New?York，1979，18，93.
Connecing acrylic acid groups and epoxide group on the resol can reference:
Ind.Vernice?32(11)18-32(1978)
Special public clear 51-28677, special public clear 54-1742.
Optical waveguides is that a kind of light wave that makes is limited in optical medium or device that one dimension or two-dimensional space transmit.Polymer waveguide is made of specific refractory power higher sandwich layer and the lower last under-clad layer of specific refractory power, forms a kind of sandwich structure.Light is always advanced along the high direction of specific refractory power, that is to say, light is limited in propagating in the sandwich layer in waveguide.But the refringence between sandwich layer/covering should be controlled at certain limit, that is to say, the specific refractory power between sandwich layer and the clad material will be mated, and for example, for the thermo-optical switch device, the index contrast Δ n between sandwich layer and covering should be controlled at following scope:
The low-refraction contrast waveguides, Δ n～0.004
The medium refractive index contrast waveguides, Δ n～0.008
High-index contrast waveguides, Δ n～0.011
The waveguide of superelevation index contrast, Δ n～0.015-0.03
Calculate according to Light Wave Guide Theory, the core layer thickness of the monofilm transmission requirement of waveguide, n is inversely proportional to Δ, and Δ n is big, and thickness requirement is little.Like this, though light is bound good, be unfavorable for coupling, and transmission loss reduces with thickness also and increases.
The specific refractory power of phenolic material depend on to a great extent by the synthetic bisphenol cpd.Owing to the difference of connection portion between two phenyl ring, the specific refractory power of these bisphenol cpds has than big difference, is enough to form various sandwich layers and the clad material that refringence meets the waveguide requirement.Be the element of conversion resol, just utilize different bis-phenols, can obtain to have the resin of various specific refractory poweres.Resol is the higher material of a class specific refractory power, and its ranges of indices of refraction changes between 1.47-1.70.Because organic Electro-optical Modulation material film generally all has higher specific refractory power,, select to use resol covering significant with high index in order to make the index contrast between sandwich layer and the covering unlikely too big.
In optical waveguides designs and produces,, and aspect film thickness, strict demand is arranged not only to film refractive index.As described in embodiment example 5, under situation of the present invention, they can be regulated by adding reactive thinner, and obtain desired thickness.
The selected polymkeric substance of optical waveguide material of the present invention meets the conditional request of a series of other strict restrictions.For example, on the one hand, they are to base material such as glass, and silicon chip or metallic coating have good spreadability, on the other hand, after film forming is solidified, add when being coated with the second layer (sandwich layer) with solution morphology, and the solvent of solution can not destroy the bottom that already forms; Already the solidified sandwich layer also is the same, and when adding when being coated with the 3rd layer of top covering, the interface between the 2nd, 3 layer is excellent.
No matter bis-phenol-formaldehyde phenolic resin that the present invention uses is alkaline process or acid system preparation, good solubleness is all arranged in ordinary organic solvents, thereby be coated with fabric film easily.Then, by further heating means, make it to be transformed into insoluble and not molten state.Thereby can guarantee between the film of two kinds of such materials good interface is arranged.And can reach the requirement of device preparation technology, promptly coating for optical waveguides also must satisfy anti-solvent soaking, the requirement that for example anti-acetone and concentrated hydrochloric acid soak.The resol that the present invention uses has high-temperature stability, some resol even ability flame.
Described alkali is aqua ammonia, sodium hydroxide or yellow soda ash etc.
Described acid is oxalic acid, acetic acid or hydrochloric acid etc.
Aspect thermostability, for example make thermo-optical device, the organic passive optical waveguide material of bis-phenol-formaldehyde phenolic resin of the present invention can satisfy 200 ℃ of heatproofs 30 minutes, in 1000 hours requirement of 120 ℃ of heatproofs, and under 90% humidity and the performance that still remained unchanged through 1000 hours under 75 ℃ of temperature.
As mentioned above, can better satisfy passive optical waveguide by the bis-phenol-formaldehyde phenolic resin of indication of the present invention and make required various requirement, be the important organic optoelectronic material of a class, thereby have good application prospects.
The present invention requires and bis-phenol-formaldehyde phenolic resin characteristics according to optical waveguide applications, particularly by esterification, etherificate, introduce anti-oxidant functional group or introduce vinylformic acid, photosensitivity groups such as epoxy, improve material light on the one hand, thermostability, solidify by synergism on the other hand, reduce the material cured temperature, make these materials be more suitable for organic thermo-optical switch, interconnection of organic electrooptic modulator or organic light and the making that comprises the optical waveguide optical electron device of optical fiber, it is good that they have a film forming properties, Heat stability is good, specific refractory power and thickness is characteristics such as adjustable in wide scope.
Embodiment
Embodiment 1:
The preparation of dihydroxyphenyl propane-formaldehyde resin coating
The formalin of 33 grams 40%, the ammoniacal liquor of 32 gram dihydroxyphenyl propanes and 1.8 grams 23% adds in the 250 mL there-necked flasks, mixes, and slowly is warming up to 65 ℃ in 60 minutes, stirring reaction 30 minutes, and then be warming up to 90-95 ℃ slowly, reacted 40-50 minute.Stop to stir, reaction solution is divided into two-layer.Behind the naturally cooling, the supernatant liquid that inclines, water repeatedly wash lower floor's white solid, and dry.Solid after the drying is dissolved in an amount of N,N-DIMETHYLACETAMIDE, films, film was through 50 ℃ of bakings 4 hours, and 100 ℃ were dried by the fire 6 hours, got faint yellow film.
This film has good optical quality, and is insoluble in acetone and DMF, and concentrated hydrochloric acid soaks 15 minutes no changes.This film can be used for passive wave guide the core once layer or the preparation of covering.
Embodiment 2:
Press the faint yellow film of the method acquisition of embodiment 1, as follows in the detecting refractive index data of each important wave band:
| The TE mould | The TM mould | ||||||
| ?830nm | ?1300nm | ?1310nm | ?1550nm | ?830nm | ?1300nm | ?1310nm | ?1550nm |
| ?1.5994 | ?1.5909 | ?1.5864 | ?1.5883 | ?1.5990 | ?1.5905 | ?1.5861 | ?1.5879 |
Double refraction: Δ n=4 * 10-4 (@1300nm); Δ n=4 * 10-4 (@1550nm)
Thermo-optical coeffecient: 1 * 10
-4/ ℃ (@1.5 μ m)
Material has very high specific refractory power, very low double refraction and very high thermo-optical coeffecient.
This material can be used for the making of organic thermo-optical switch or is used for as organic electrooptic modulator clad material.
Embodiment 3:
The preparation and the performance of dihydroxyphenyl propane and bisphenol S resol mixture and epoxy compounds cured product film thereof.
To mix at 1: 1 with weight ratio from two kinds of base catalysis resol that bisphenol S obtains with quadrat method with dihydroxyphenyl propane with embodiment 1, be dissolved in the dimethylacetamide solvent, add the BADGE Resins, epoxy of total resin weight 30% again, film behind the mixing.Through 100 ℃ of bakings 4 hours, 150 ℃ were dried by the fire 6 hours film in nitrogen gas stream, and further crosslinking curing gets colourless substantially or light yellow film.
This film has good optical quality, and is insoluble in acetone and DMF, can soak by anti-concentrated hydrochloric acid.
Specific refractory power is regulated: for example at the 1310nm wavelength, the specific refractory power 1.6182 of the resol that obtains from bisphenol S, the specific refractory power (1.5864) that is higher than the resol that obtains from dihydroxyphenyl propane, thereby the ratio that the specific refractory power of mixture film can be by regulating two kinds of bis-phenol resol or use different solidifying agent Resins, epoxy and a relative broad range change.
Embodiment 4:
Bis-phenol-formaldehyde resin etherification modified
Heat up in a steamer prolong, stir at the bottom of the 50mL garden of magneton and addition funnel in the sesame seed cake 24mL water of packing into, 5.7mL 1-bromopropyl alcohol and 7.4g2,2,6,6-tetramethyl--4-hydroxy piperidine being equipped with back.Mixture heated up in a steamer under the temperature stirring reaction 6 hours returning, and in 1 hour of beginning back to heat up in a steamer, the gradation adding is dissolved in the 2gNaOH in the 7mL water.Tell and discard upper water solution after reaction finishes, unreacted 1-bromopropyl alcohol is removed in decompression, gets the piperidines product of 4-position etherificate, and the latter in the presence of two tetrahydrobenzene carbodiimides (DCC), with linetype bisphenol-formaldehyde phenolic resin reaction, gets the etherificate product again:
Resulting bis-phenol-formaldehyde resin, photo and thermal stability is significantly improved.
Embodiment 5:
The low temperature photocuring of phenolic aldehyde epoxy acrylate
The CN112C60 of Sartomer company novolac epoxy, 3% the st-yrax dme that adds weight resin is done light trigger, place on the clean slide glass, film with sol evenning machine with 2000 rev/mins speed, the gained coating is in distance 250W high voltage mercury lamp 5cm place's illumination after 90 seconds, the coating completely solidified, hardness 6H soaked 15 minutes or soaked 5 minutes with acetone with 37% concentrated hydrochloric acid, and is non-foaming, do not come off, diaphragm quality and color do not change.If spent glycol diacrylate etc. is done thinner letdown resin mixture, thicknesses of layers can be regulated arbitrarily.Very help according to waveguide design controlling diaphragm layer thickness.
Claims (2)
1. a bis-phenol-formaldehyde phenolic resin is formed by bisphenol cpd and formaldehyde condensation polymer, it is characterized in that: this bis-phenol-formaldehyde phenolic resin general formula is:
Wherein, R represents at phenyl ring 3,3 ', 5,5 '-position have 10 carbon atoms following alkyl, alkoxyl group or an ester group substituting group; X represents methylene radical, C, the methylene radical that C-two-three methyl halide bases replace, 1,3 or 1, the phenyl ring that is connected with the phenol ring on the 4-position, 1, hexahydrobenzene that is connected with the phenol ring on the 4-position or sulfuryl, C wherein, the halo group in the methylene radical that C-two-three methyl halide bases replace is fluorine atom, chlorine atom, bromine atoms or iodine atom.
2. the purposes of a bis-phenol-formaldehyde phenolic resin as claimed in claim 1 is characterized in that: described bis-phenol-formaldehyde phenolic resin is used for the material of organic thermo-optical switch, the interconnection of organic light, organic electrooptic modulator or the preparation of optical waveguide optical electronic waveguide device as the passive optical waveguide material.
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| CNA021566380A CN1508165A (en) | 2002-12-17 | 2002-12-17 | Bisphenol-formaldehyde phenolic resin passive optical waveguide material and use thereof |
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| CNA021566380A CN1508165A (en) | 2002-12-17 | 2002-12-17 | Bisphenol-formaldehyde phenolic resin passive optical waveguide material and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304210A (en) * | 2011-06-17 | 2012-01-04 | 北京化工大学常州先进材料研究院 | Bisphenol-S phenolic resin and preparation method thereof |
| CN113929846A (en) * | 2021-10-22 | 2022-01-14 | 西北工业大学 | High-carbon-formation-rate water-soluble phenolic resin and preparation method thereof |
-
2002
- 2002-12-17 CN CNA021566380A patent/CN1508165A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304210A (en) * | 2011-06-17 | 2012-01-04 | 北京化工大学常州先进材料研究院 | Bisphenol-S phenolic resin and preparation method thereof |
| CN113929846A (en) * | 2021-10-22 | 2022-01-14 | 西北工业大学 | High-carbon-formation-rate water-soluble phenolic resin and preparation method thereof |
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