CN1709928A - Aryne resin containing silicone - Google Patents
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- CN1709928A CN1709928A CN 200510027518 CN200510027518A CN1709928A CN 1709928 A CN1709928 A CN 1709928A CN 200510027518 CN200510027518 CN 200510027518 CN 200510027518 A CN200510027518 A CN 200510027518A CN 1709928 A CN1709928 A CN 1709928A
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Abstract
The invention relates to a kind of arylenealkyne resin containing siloxanes. The said resin makes diethynylene benzene (DEB) and silicon alkyl chloride as raw materials, firstly make use of the reaction of magnesium and alkyl bromide to produce Grignard reagent, then react with DEB to produce alkyne Grignard reagent; then react with silicon alkyl chloride, finally hydrolyze and condense in alkaline water liquor, or extend chain with siloxanes chloride, to form a kind of arylenealkyne resin containing siloxanes of new-style structure. The resin designed and synthesized by the invention has good processing property, and can be solidified into crosslinked resin of good thermostability under heat, light or radiative condition. Besides it has good machine capability, electric insulation capability and ceramic performance. So it can be used as the base material of high performance compound material resin, insulation material, the ceramic precursors and so on, and also has wide application prospect in such high technology fields as spaceflight, aviation, navigation and so on.
Description
Technical Field
The invention relates to a thermosetting resin, in particular to a siloxane-containing aryne resin.
Background
The alkyne-containing resin (particularly aromatic alkyne resin) is a heat-resistant resin developed and used in recent years, can be formed without using a solvent in the forming process, does not allow small molecular substances to escape in the curing process, and can be formed at normal pressure or low pressure. The pyrolysis temperature of the cured resin is above 500 ℃, the pyrolysis carbon yield is as high as 80-86%, the weight loss and ablation depth of the carbon fiber reinforced composite material are far lower than those of a phenolic resin/carbon fiber composite material, the linear ablation rate is only 50-60% of that of the conventional phenolic resin composite material, and the cured resin has a compact structure and excellent ablation resistance. However, the rigidity of the cured resin is too high, so that the mechanical properties are not ideal. Therefore, the modification of alkyne-containing resins (particularly aryne resins) becomes a research hotspot.
In the last 80 th century Naval Research laboratory T.M.Keller et al, the study of high temperature resistant unsaturated organosiloxane resins was initiated by introducing an alkyl alkyne-containing polymer- { - ≡ Si-O-Si ≡ type polymer into the main chain thereof2-[-O-Si(Me)2-]n}x[(a)D.Y.Son and T.M.Keller，Macromolecules 1995，28，399；(b)G.Burillo，Polym.Bull.1986，16，257；(c)D.R.Parnell，J.Polym.Sci.Polym.Chem.Ed.1973，11，1107.]And a relative average molecular weight of about 10,000. The polymer can be cured at 289-315 ℃, the cured polymer begins to degrade at 400 ℃ in the air atmosphere, the residual rate at 1000 ℃ is 60%, and the residual rate in the presence of protective atmosphere is 74%. In addition, they have done a lot of related modifications, but the final properties of the materials have not been significantly improved [ (a) l.j.henderson and t.m.keller, Macromolecules 1994, 27, 1660; (b) d.bucca, t.m.keller, j.polym.sci.part a: ym.chem.1999, 37, 4356; (c) d.y.son, t.m.keller, j.polym.sci.parta: ym.chem.1995, 33, 2969; (d) r.a.sundar, t.m.keller, j.polym.sci.part a: ym.chem.1997, 35, 2387; (e) d.bucca, t.m.keller, j.polym.sci.parta: ym.chem.1997, 35, 1033; (f) d.bucca, t.m.keller, ym.prepr.1995, 36, 114.]. MountainThe Dongduo university people try to synthesize phenylethynyl dimethylchlorosilane by a Grignard reagent method, a butyl lithium method and a metal sodium method respectively and then synthesize a compound PhC ≡ C-Si (Me) by a hydrolysis method2-O-Si(Me)2-C≡CPh[Chen Jianhua，Du Zuodong，OrganicChemistry of Silicon，in“Silicon chemistry”，Ed by E.R.Corey，J.Y.Corey and P.P.Gaspar，Halsted Press(John Wiley&Sons)：Oxford，1988，Chapter 10，p105.]And the structure is characterized correspondingly. However, this resin is not suitable for use as a material because the temperature of the curing and crosslinking reaction of the phenylacetylene-terminated resin is high and is not easy to be formed; furthermore, even if the resin is cured and crosslinked at a high temperature, the properties of the resulting material are not good.
Disclosure of Invention
The invention designs and synthesizes the aryne resin containing siloxane based on the molecular structure design. In the resins of the invention, there are arylacetylene groups which can be polymerized by heat, radiation or light to form highly crosslinked polymers; and the existence of the siloxane chain segment endows the polymer with better flexibility and high-temperature ceramic performance. Therefore, the cured and crosslinked polymer has excellent heat resistance and weather resistance, and can generate ceramic reaction at high temperature (800-1800 ℃) to form a silicon-containing ceramic material.
The structure of the aryne resin containing siloxane is shown as the formula (1).
(1) In the formula: r1Is C6H5；R2Is C6H5Or CH3；k＝0～3，n＝0～3。
The method for preparing the siloxane-containing aryne resin comprises the following steps:
1) preparation of bromoethane Grignard reagent and diacetylene benzene Grignard reagent
The synthesis reaction is as follows:
(2)
(3)
(4)
synthesis of bromoethane Grignard reagent:
dripping a tetrahydrofuran solution of bromoethane into a Tetrahydrofuran (THF) suspension containing magnesium powder, wherein the molar ratio of the bromoethane to the magnesium powder is 1.0: 1.0-1.5 (preferably 1.0: 1.1-1.3); controlling the concentration of bromoethane in the solution to be 3-5 mol/L THF, adding a small amount of iodine crystals to initiate a reaction, controlling the reaction to be carried out at 0-30 ℃, heating to 60-66 ℃ after the dropwise addition, and reacting for 2 hours to obtain the bromoethane Grignard reagent [ the compound shown in the formula (2)]. The whole preparation process is carried out under the protection of inert gas (chemically stable gas, such as nitrogen, helium or argon).
Synthesis of diacetylene phenyl grignard reagent:
under the conditions of stirring and ice-bath cooling, the synthesized ethyl bromide Grignard reagent is dropwise added into a tetrahydrofuran solution (with the concentration of 3-5 mol/L THF) of diethynylbenzene (1, 3-diethynylbenzene or a mixture of 1, 3-diethynylbenzene and 1, 4-diethynylbenzene). And after the dripping is finished, reacting for 2 hours at the temperature of 60-66 ℃ to obtain the compound shown in the formula (3) or the formula (4).
Wherein: the molar ratio of the bromoethane to the diacetylene benzene is 1.00-2.50: 1.00 (preferably 1.05-2.00: 1.00), and the whole preparation process is carried out under the protection of inert gas (gas with stable chemical properties, such as nitrogen, helium or argon).
2) Synthesis of siloxane-containing aryne resins
Firstly, reacting a tetrahydrofuran solution of diphenyl dichlorosilane with the diacetylene benzene Grignard reagent [ a compound shown in a formula (3) or/and a formula (4)]prepared in the step 1) at the temperature of 60-66 ℃ for 2 hours to obtain different compounds. Wherein the molar ratio of the diacetylene benzene Grignard reagent to the diphenyl dichlorosilane is 1.00: 1.00-2.50 (preferably 1.00: 1.05-1.60), the concentration of the THF solution of the diphenyl dichlorosilane is controlled to be 3-5 mol/L THF, and the whole reaction process is carried out under the protection of inert gas (gas with stable chemical properties, such as nitrogen, helium or argon). And then hydrolyzing the obtained compound with a sodium hydroxide or potassium hydroxide aqueous solution with the concentration of 0.5-1.25N to obtain a hydrolysate, carrying out condensation reaction on the hydrolysate at 70-80 ℃ for 2-3 hours or reacting the hydrolysate with dimethyldichlorosilane or diphenyldichlorosilane or dichloropolysiloxane in a mixed solvent consisting of tetrahydrofuran and pyridine, wherein the usage amount (mole number) of the hydrolysate is one half of that of the used diphenyldichlorosilane, extracting with toluene after the reaction is finished, washing an organic toluene layer to be neutral by using deionized water, and evaporating to remove the solvent to obtain a target object [ the structure of which is shown in the formula (1)].
The raw materials and reagents used in the above-mentioned production methods are commercially available except for diethynylbenzene. The diacetylene benzene of the invention refers to 1, 3-diacetylene benzene or 1, 4-diacetylene benzene or a mixture thereof, and the preparation method is shown in British patent GB1313524, US 4,997,991 and US 4,120,909.
The aryne resin containing siloxane designed and synthesized by the invention has the following characteristics:
1) the process performance is good, the solvent can be dissolved in a plurality of common solvents, and the application is convenient; the resin is easy to cure, the curing temperature is lower and the heat release is low; 2) the ethynyl can generate curing crosslinking reaction under the action of heat, radiation and even light to form a highly crosslinked polymer, and has excellent heat resistance; 3) no small molecules are released when the resin is cured; 4) the structure and molecular size of the synthesized resin can be controlled by molecular design; 5) the cured resin has good mechanical property and excellent chemical resistance; 6) the curing resin may undergo a ceramization reaction.
In conclusion, the resin can be polymerized by self or copolymerized with other resins to prepare a material with excellent heat resistance, ablation resistance and insulating property, and has wide application prospects in the fields of aviation, aerospace and the like.
Detailed Description
The invention is further illustrated by the following examples, which are intended to provide a better understanding of the contents of the invention. The examples given therefore do not limit the scope of the invention.
Example one
Soaking the magnesium powder for 2-3 min by using 5% dilute hydrochloric acid, and performing suction filtration; then washing for three times by using deionized water, and performing suction filtration; washing with anhydrous ethanol for three times, and vacuum filtering; and finally, washing for three times by using petroleum ether, carrying out suction filtration, and drying to obtain the usable magnesium powder. Vacuumizing a 500ml four-mouth round-bottom flask provided with a constant pressure funnel, a spherical condenser pipe, a vent pipe/thermometer and a stirrer, filling nitrogen, and replacing for three times; under the protection of nitrogen, 3.0g (0.12mol) of magnesium powder and a small amount of iodine crystals are added into a four-neck flask, 30ml of tetrahydrofuran (treated by removing water and oxygen by using sodium metal) is added, and the mixture is stirred uniformly. A mixture of 10.9g (0.10mol) of bromoethane and 30ml of tetrahydrofuran (THF, driedover sodium metal) was added to a constant pressure funnel, dropwise addition of the bromoethane/THF mixture was started, the mixture was stirred rapidly, after the mixed liquid of about 1/5 was continuously added dropwise to the flask, the reaction was exothermic, the remaining mixed liquid was further added dropwise at a rate of about 1/2 drops/sec, and the mixture was cooled with ice water while being added dropwise. The reaction system was seen to change from the original pale brown-yellow to iron-gray and gradually cloudy. And (3) after the dropwise addition, reacting for 2 hours under the heating of an oil bath at the temperature of 60-66 ℃ to obtain the Grignard reagent of the bromoethane.
Adding 30ml of tetrahydrofuran and 0.095mol of 1, 3-diacetylene benzene into a four-neck round-bottom flask provided with a constant-pressure funnel, a spherical condenser pipe, a breather pipe/thermometer and a stirrer, transferring the prepared ethyl bromide Grignard reagent into the constant-pressure funnel under the protection of nitrogen, dropwise adding under the conditions of stirring and cooling in an ice-water bath, and reacting for 2 hours under the heating of an oil bath at 60-66 ℃ after dropwise adding to obtain the diacetylene benzene Grignard reagent.
30ml of tetrahydrofuran and 24.03 g (0.095mol) of diphenyldichlorosilane are added into a 500ml four-neck flask, the diacetylene benzene Grignard reagent prepared above is dripped under the protection of nitrogen, and after dripping is finished, the mixture reacts for 2 hours under the heating of an oil bath at the temperature of 60-66 ℃. After the reaction, a certain amount of 1.25N aqueous potassium hydroxide solution was added dropwise to the flask under cooling in an ice-water bath, and the mixture was subjected to hydrolysis reaction at a temperature of 75 ℃ in an oil bath for 2 hours. Adding toluene 30ml, extracting, separating, washing with deionized water to neutrality, and removing solvent with rotary evaporator to obtain reddish brown liquid resin (with structure shown in formula (5)), yield 55.4%, and viscosity below 400cp at room temperature.
Determination of the infrared spectrum of the resin by coating method: 1085cm-1Shows an Si-O-Si absorption peak at 3291cm-1And 2159cm-1An alkyne triple bond and an alkyne hydrogen absorption peak appear.
Example two
Vacuumizing a 500ml four-mouth round-bottom flask provided with a 100ml constant pressure funnel, a spherical condenser pipe, a vent pipe/thermometer and a stirrer, filling nitrogen, and replacing for three times; under the protection of nitrogen, 3.0g (0.12mol) of the treated magnesium powder (same as in example one) and a small amount of iodine crystals were added to a four-neck flask, and 30ml of tetrahydrofuran (dried over sodium metal) was added and stirred uniformly. A mixture of 0.10mol of bromoethane and 30ml of tetrahydrofuran (THF, which was subjected to a sodium metal dehydration and oxygen removal treatment) was added to a constant pressure funnel, and the bromoethane/THF mixture was added dropwise to the flask, followed by rapid stirring, during which time the reaction system was seen to change from pale brown-yellow to iron-gray and gradually became cloudy. And (3) after the dropwise addition, reacting for 2 hours under the heating of an oil bath at the temperature of 60-66 ℃ to obtain the Grignard reagent of the bromoethane.
30ml of tetrahydrofuran and 0.0713mol of diethynylbenzene (a mixture of 1, 3-diethynylbenzene and 1, 4-diethynylbenzene) are added into a four-neck round-bottom flask provided with a constant-pressure funnel, a spherical condenser tube, a vent tube/thermometer and a stirrer, the prepared bromoethane Grignard reagent is transferred into the constant-pressure funnel under the protection of nitrogen, dropwise addition is carried out under the conditions of stirring and cooling in an ice-water bath, and after the dropwise addition is finished, the reaction is carried out for 2 hours under the heating of an oil bath at 60-66 ℃ to obtain the diethynylbenzene Grignard reagent.
30ml of tetrahydrofuran and 0.095mol of diphenyl dichlorosilane are added into a 500ml four-neck flask, the diacetylene benzene Grignard reagent prepared above is dripped under the protection of nitrogen, and after dripping is finished, the mixture reacts for 2 hours under the heating of an oil bath at 60-66 ℃. After completion of the reaction, a potassium hydroxide aqueous solution having a certain concentration of 1.25N was added dropwise to the flask under cooling in an ice-water bath, and then the mixture was subjected to hydrolysis reaction at an oil bath temperature of 75 ℃ for 2 hours. Adding toluene about 30ml for extraction separation, collecting organic layer, washing with deionized water, washing to neutrality, and removing solvent with rotary evaporator to obtain reddish brown liquid resin (with structure shown in formula (6)) with yield of 73.5%. The relative molecular weight of the resin was 1169 by GPC, and the viscosity at room temperature was 490 cp.
Determination of the infrared spectrum of the resin by coating method: 1085cm-1At Si-O-Si absorption peak of 2159cm-1Is treated as an alkyne absorption peak at 3291cm-1And the peak is shown as an alkyne hydrogen absorption peak.
EXAMPLE III
A500 ml four-neck round-bottom flask provided with a 100ml constant pressure funnel, a spherical condenser tube, a vent pipe/thermometer and a stirrer is vacuumized, filled with nitrogen, dehumidified and deoxygenated, 0.12mol of magnesium powder and a small amount of iodine crystals are added into the four-neck flask under the protection of nitrogen, then 30ml of tetrahydrofuran (dried by metal sodium) is added, and the mixture is stirred uniformly. A mixture of 0.10mol of bromoethane and 30ml of tetrahydrofuran was added dropwise through a constant pressure funnel, and the mixture was cooled in an ice water bath while being added dropwise. In the interim, the reaction system was seen to change from the original pale brown-yellow color to iron gray and gradually became cloudy. And (3) after the dropwise addition, reacting for 2 hours under the heating of an oil bath at the temperature of 60-66 ℃ to obtain the Grignard reagent of the bromoethane.
Adding 30ml of tetrahydrofuran and 0.0633mol of 1, 3-diacetylene benzene into a four-neck round-bottom flask provided with a constant-pressure funnel, a spherical condenser pipe, a breather pipe/thermometer and a stirrer, transferring the prepared ethyl bromide Grignard reagent into the constant-pressure funnel under the protection of nitrogen, dropwise adding the ethyl bromide Grignard reagent into the flask under the cooling of stirring and ice bath, and reacting for 2 hours under the heating of an oil bath at 60-66 ℃ after dropwise adding to obtain the diacetylene benzene Grignard reagent.
30ml of tetrahydrofuran and 0.095mol of diphenyl dichlorosilane are added into a 500ml four-neck flask, the diacetylene benzene Grignard reagent prepared above is dripped under the protection of nitrogen, and after dripping is finished, the mixture reacts for 2 hours under the heating of an oil bath at 60-66 ℃. After completion of the reaction, a certain amount of 1.25N potassium hydroxide aqueous solution was added dropwise to the flask under cooling in an ice bath, and then the reaction was hydrolyzed at 75 ℃ oil bath temperature for 2 hours. Adding toluene to about 30ml, extracting and separating, washing with deionized water to neutrality, and removing solvent with rotary evaporator to obtain reddish brown liquid resin (with structure shown in formula (7)), yield 57.9%, and viscosity of about 500cp at room temperature.
Infrared spectroscopic analysis of the resin measured by coating method: 1082cm-1At an absorption peak of Si-O-Si of 2160cm-1Is treated as an alkyne absorption peak at 3294cm-1And the peak is shown as an alkyne hydrogen absorption peak.
Example four
A500 ml four-neck round-bottom flask provided with a 100ml constant pressure funnel, a spherical condenser tube, a vent pipe/thermometer and a stirrer is vacuumized, then nitrogen is filled for dehumidification and oxygen removal, 0.12mol of magnesium powder and a few iodine crystals are added into the four-neck flask under the protection of nitrogen, then 30ml of tetrahydrofuran (dried by metal sodium) is added, and the mixture is stirred uniformly. A mixture of 0.10mol of bromoethane and 30ml of tetrahydrofuran was added dropwise through a constant pressure funnel, and the mixture was cooled in an ice water bath while being added dropwise. During this period, the reaction system was seen to change from the original pale brown-yellow color to iron-gray color and gradually became cloudy. And (3) after the dropwise addition, reacting for 2 hours under the heating of an oil bath at the temperature of 60-66 ℃ to obtain the Grignard reagent of the bromoethane.
Adding 30ml of tetrahydrofuran and 0.095mol of 1, 3-diacetylene benzene into a four-neck round-bottom flask provided with a constant-pressure funnel, a spherical condenser pipe, a breather pipe/thermometer and a stirrer, transferring the prepared ethyl bromide Grignard reagent into the constant-pressure funnel under the protection of nitrogen, dropwise adding the ethyl bromide Grignard reagent into the flask under the cooling of stirring and ice bath, and reacting for 2 hours under the heating of an oil bath at the temperature of 60-66 ℃ after dropwise adding to obtain the diacetylene benzene Grignard reagent.
30ml of tetrahydrofuran and 0.095mol of diphenyl dichlorosilane are added into a 500ml four-neck flask, the diacetylene benzene Grignard reagent prepared above is dripped under the protection of nitrogen, and after dripping is finished, the mixture reacts for 2 hours under the heating of an oil bath at 60-66 ℃. After the reaction, a certain amount of 0.5N sodium hydroxide aqueous solution was added dropwise to the flask under ice-bath cooling, and after reacting for 2 hours at room temperature, about 30ml of toluene was added for extraction and separation, and the mixture was washed with deionized water, washed to neutrality, and dried. And dissolving and diluting with 20ml of THF, dropwise adding a mixture of 0.048mol of dichlorodimethylsilane (or bis- (dichlorodimethylsiloxy) dimethylsilane) and 20ml of pyridine, reacting at the temperature of 75 ℃ in an oil bath for 3-4 hours, adding water for washing, adding a small amount of 10ml of toluene to extract an organic phase, continuously washing with deionized water to neutrality, drying, and distilling off the solvent to obtain orange viscous liquid resin (the structure of which is shown as the formula (8)), wherein the yield is about 70%.
Determination of the infrared spectrum of the resin by coating method: 2900cm-1Nearby occurrence of-CH3The upper hydrocarbon C-H stretching vibration-absorption peak; at 2158cm-1(iii) a shock absorption peak of alkyne triple bonds present; and is at 1076cm-1The characteristic absorption peak of-Si-O-Si-appears.
EXAMPLE five
The resins obtained in examples 1 to 4 were all miscible in solvents such as acetone, THF, toluene, chloroform, methylene chloride, carbon tetrachloride, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, diethyl ether, toluene and the like, but insoluble in nonpolar solvents such as N-hexane, petroleum ether and the like. The resin can be cured at temperatures above 200 ℃.
Curing the resin obtained in the example 2 in an oven at 130 ℃/1hr +150 ℃/1hr +180 ℃/2.5h +200 ℃/2hr +250 ℃/2hr, and then carrying out post-treatment at 300 ℃/2hr +350 ℃/2hr to obtain a compact hard brown cured product, wherein the thermal stability of the cured resin is excellent, the initial thermal decomposition temperature of the cured resin is over 400 ℃ measured by TGA analysis (10 ℃/min), and the residual rate of the cured resin at 800 ℃ in a nitrogen atmosphere is 81.9%; the residual ratio in air was 29.0%. The temperature of the cured resin is raised to 400 ℃ at the speed of 5-10 ℃/min, then raised to 1300 ℃, and kept for 5-12 hours under the condition of no oxygen or little oxygen, and a white substance is obtained by sintering, namely the cured resin is subjected to ceramic reaction at high temperature.
Therefore, the aryne resin containing siloxane is a novel heat-resistant resin matrix with high potential, has good processing performance, and can be used as a precursor of advanced composite material resin matrix, high-performance insulating material and advanced ceramic material.
Claims (5)
1. A siloxane-containing aryne resin having the structure shown by the formula:
in the formula: r1Is C6H5；R2Is C6H5Or CH3；k＝0～3，n＝0～3。
2. An aryne resin according to claim 1 wherein n-0 and k-0.
3. An aryne resin according to claim 1 wherein n-1 and k-0.
4. An aryne resin according to claim 1 wherein n-0 and k-1.
5. An aryne resin according to claim 1 wherein R is2Is CH3，n＝0，k＝3。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235113B (en) * | 2008-01-04 | 2010-04-14 | 华东理工大学 | Aryne resin containing polysilicone and preparation method thereof |
| CN101139442B (en) * | 2007-08-22 | 2011-12-07 | 华东理工大学 | Organic-inorganic hybrid resin containing sesquialter siloxane and preparation method and use thereof |
| US8217194B2 (en) | 2010-06-11 | 2012-07-10 | The United States Of America As Represented By The Secretary Of The Navy | Polyarylacetylenes containing siloxane, silane, and carborane moieties |
| CN104327111A (en) * | 2014-10-13 | 2015-02-04 | 中国科学院上海有机化学研究所 | Directly-thermocurable organic siloxane, manufacture method and application |
| CN106883415A (en) * | 2017-03-10 | 2017-06-23 | 华东理工大学 | A kind of preparation method of polysiloxane-modified siliceous aryne resin |
| CN110423350A (en) * | 2019-07-11 | 2019-11-08 | 华东理工大学 | A kind of high-fire resistance silicon substrate benzyne resin of low-temperature setting and its preparation method and application |
-
2005
- 2005-07-05 CN CNB2005100275185A patent/CN100497407C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139442B (en) * | 2007-08-22 | 2011-12-07 | 华东理工大学 | Organic-inorganic hybrid resin containing sesquialter siloxane and preparation method and use thereof |
| CN101235113B (en) * | 2008-01-04 | 2010-04-14 | 华东理工大学 | Aryne resin containing polysilicone and preparation method thereof |
| US8217194B2 (en) | 2010-06-11 | 2012-07-10 | The United States Of America As Represented By The Secretary Of The Navy | Polyarylacetylenes containing siloxane, silane, and carborane moieties |
| CN104327111A (en) * | 2014-10-13 | 2015-02-04 | 中国科学院上海有机化学研究所 | Directly-thermocurable organic siloxane, manufacture method and application |
| CN106883415A (en) * | 2017-03-10 | 2017-06-23 | 华东理工大学 | A kind of preparation method of polysiloxane-modified siliceous aryne resin |
| CN110423350A (en) * | 2019-07-11 | 2019-11-08 | 华东理工大学 | A kind of high-fire resistance silicon substrate benzyne resin of low-temperature setting and its preparation method and application |
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|---|---|
| CN100497407C (en) | 2009-06-10 |
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