CN1793150A - Diene silicoxyane linking disbenzocyclobutylene monomer and process for preparing prepolymer - Google Patents
Diene silicoxyane linking disbenzocyclobutylene monomer and process for preparing prepolymer Download PDFInfo
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- CN1793150A CN1793150A CN 200510022478 CN200510022478A CN1793150A CN 1793150 A CN1793150 A CN 1793150A CN 200510022478 CN200510022478 CN 200510022478 CN 200510022478 A CN200510022478 A CN 200510022478A CN 1793150 A CN1793150 A CN 1793150A
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Abstract
The invention discloses a method to make diene siloxane crosslink bibenzo cyclobutene monomer that includes the following steps: whisking alkali and water to dissolve, adding solvent, catalyst, reacting material, reacting for 18-30 hours at 90-150 degree centigrade in nitrogen air, extracting and post processing to gain the monomer. The feature is that it solvent is iron liquid or recycled iron liquid. The invention also discloses the manufacture method for performed polymer. It has no pollution to the environment, low cost, short production cycle, and no influence to yield, lower power consumption.
Description
One, technical field
The invention belongs to the preparing technical field of diene silicoxyane linking disbenzocyclobutylenmonomer monomer and performed polymer, be specifically related in ionic liquid or recovery ionic liquid, prepare a kind of novel method of diene silicoxyane linking disbenzocyclobutylenmonomer monomer and performed polymer.
Two, background technology
In the monomer that contains benzocyclobutene (Benzocyclobutene is called for short BCB) structure, because its specific molecule structure can have linear or cancellated polymkeric substance 200 ℃ of left and right sides open loops formation usually.This base polymer is because of having excellent electric property, low rate of moisture absorption, high planarization, high thermostability and chemical stability, easy even film forming, and excellent properties such as planeness height are used very extensive.As diene radical siloxane bridge-linked double benzocyclobutene (DVS-BCB) resin that wherein has following structure:
This resinoid is formed 200～250 ℃ of thermofixations by monomer, has very high second-order transition temperature (Tg＞350 ℃), it also has very low specific inductivity (2.7/1MHz) in addition, do not produce small-molecule substance after the curing, nonhygroscopic, light transmission good (not absorbing visible light), available light cause advantage such as solidifies, and has been widely used as the organic passivation layer of liquid-crystal display.This organic passivation layer can make and show that image is more clear, and display life prolongs, and the polyimide resin that is better than using always.In addition, this resinoid is in microelectronics industry field also extensive application, mcm (MCM), microelectromechanical-systems (MEMS) have been used it for abroad, fields such as liquid-crystal display encapsulation, macromolecule membrane waveguide, physiologically acceptable medical equipment, minority developed country has used it for fields such as space flight, military affairs.
Though diene radical siloxane bridge-linked double benzocyclobutene (DVS-BCB) resin is widely used, existing lot of documents of performance study that it is relevant and application and patent report, the preparation research report of monomer whose and performed polymer is less.For monomer whose, U.S.Pat.4812588 (1989) and U.S.Pat.5136069 (1992) had once reported its preparation method, but owing to what use in this method is volatile solvent N, the phosphine part that dinethylformamide (DMF) and toxicity are big and expensive, thereby contaminate environment not only, be unfavorable for environmental protection, and also need remove the phosphine part with tertbutanol peroxide or hydrogen peroxide earlier during aftertreatment, the production cost height, the cycle is long.For its performed polymer, US.Pat.5882836 (1999) has reported in the sym-trimethylbenzene solvent, in 140～180 ℃ of methods that prepare the DVS-BCB performed polymer.Solvent used in this method can not reclaim, and polymerization time is long, and power consumption is high, and the molecular weight distribution broad of the performed polymer that obtains.
Three, summary of the invention
One of purpose of the present invention is the deficiency at prior art, and a kind of novel method for preparing diene silicoxyane linking disbenzocyclobutylenmonomer monomer is provided.Two of purpose of the present invention is the deficiencies at prior art, and a kind of novel method for preparing diene radical siloxane bridge-linked double benzocyclobutene prepolymer is provided.
A kind of preparation provided by the invention has the novel method of the diene silicoxyane linking disbenzocyclobutylenmonomer monomer of following array structure,
The preparation technology of this method adds alkali and water stirring and dissolving earlier in reaction vessel, add solvent, catalyst acetic acid palladium, reaction raw materials 1 subsequently successively, 1 '-divinyl tetramethyl-silica alkane and 4-bromobenzene and cyclobutene, mix and under nitrogen atmosphere in 90～150 ℃ the reaction 18～30 hours; With the reaction solution petroleum ether extraction, merge organic phase, the organic phase anhydrous Na then
2SO
4Drying, filtered through silica gel, sherwood oil drip washing, the leacheate concentrating under reduced pressure is as for promptly getting the product monomer, wherein reaction raw materials 1, the mole proportioning of 1 '-divinyl tetramethyl-silica alkane and 4-bromobenzene and cyclobutene is 1: 2, the consumption of alkali is 4-bromobenzene and cyclobutene mole number 1～4 times, catalyst consumption is 0.5～5 ‰ of 4-bromobenzene and a cyclobutene mole number, the consumption of water is 0.5-8 a times of solvent quality, it is characterized in that institute's solubilizing agent is ionic liquid or reclaims ionic liquid, its consumption is reaction raw materials 4-bromobenzene and cyclobutene quality 0.5～10 times, preferred 1.5～4 times.
Wherein added recovery ionic liquid can be to use repeatedly and reclaims 1～10 time ionic liquid.
Added ionic liquid or recovery ionic liquid are any in the following structure:
N=2 in the structural formula, 4,6,8,12,16, and C
nH
2n+1Be straight-chain paraffin.Preferred 1-ethylpyridine hexafluorophosphate, 1-butyl-2 wherein, 3-methylimidazole hexafluorophosphate or 1-dodecyl-2, any in the 3-methylimidazole hexafluorophosphate.
Added alkali can be mineral alkali or organic bases, and mineral alkali is KOAc, NaHCO
3, NaOAc, Na
2CO
3, K
2CO
3, among KOH, the NaOH any; Organic bases is Me
3N, Et
3N, CH
3NHC
2H
5, (C
2H
5)
2BuN, Py,
iPr
3N, Bu
3N,
iBu
3Among the N any.The most handy distilled water of added water.
A kind of preparation provided by the invention has the novel method of the diene radical siloxane bridge-linked double benzocyclobutene prepolymer of following array structure, this method is earlier will be by mass percentage, its content is 5～40% diene silicoxyane linking disbenzocyclobutylenmonomer monomer and solvent, under nitrogen atmosphere in 160 ℃～190 ℃ reactions, then reaction solution is poured in the precipitation agent and precipitated, centrifugation, vacuum-drying promptly gets white performed polymer, it is characterized in that solvent for use is ionic liquid or reclaims ionic liquid, the reaction times is 8～20 hours.
Wherein used recovery ionic liquid can be to use repeatedly and reclaims 1～10 time ionic liquid.
Used ionic liquid or recovery ionic liquid are any in the following structure:
N=2 in the structural formula, 4,6,8,12,16, and C
nH
2n+1Be straight-chain paraffin.Preferred 1-hexadecyl-2 wherein, any in 3-methylimidazole bromine salt or 1-dodecyl-3-Methylimidazole hexafluorophosphate.
The recovery of the ionic liquid of using in the aforesaid method is if the negatively charged ion of ionic liquid is PF
6 -, can wash recovery; If negatively charged ion is Br
-, then by pressure reducing and steaming water, add the methyl alcohol filtered and recycled.These all are known technologies.
In addition, what deserves to be explained is that reaction raw materials 4-bromobenzene that the present invention is used and cyclobutene are according to document Tetrahedron, the method synthetic described in 21,245 (1965).Ionic liquid is according to P.Wasserscheid andT.welton " Ionic Liquid in Synthesis " P7～19 2002 Wiley-VcH Verlag GmbH﹠amp; Method described in the Co.KGaA is synthetic.
Compared with the prior art the present invention has the following advantages:
1, since the present invention in preparation during diene silicoxyane linking disbenzocyclobutylenmonomer monomer, adopted good stability, nonvolatile ionic liquid substitutes the volatile solvent N that prior art is used, the phosphine part that dinethylformamide (DMF) and toxicity are big and expensive, thereby it is free from environmental pollution, help environmental protection, and the operation that has also needed elder generation to remove the phosphine part when having saved aftertreatment with tertbutanol peroxide or hydrogen peroxide, can reduce production costs, shorten the production cycle, also needn't worry the residual negative impact that final material property is produced of phosphine simultaneously.
2, since the present invention in preparation during diene silicoxyane linking disbenzocyclobutylenmonomer monomer, adopted good stability, nonvolatile ionic liquid is used as solvent, ionic liquid and product can reclaim by simple separation after reaction finished in addition, and ionic liquid can recycle repeatedly, thereby can further reduce cost.
3, prepare diene silicoxyane linking disbenzocyclobutylenmonomer monomer with method provided by the invention, can obtain 60%～85% productive rate, reclaim 1～10 time ionic liquid repeatedly, also influence its productive rate hardly even if use.
4, since the present invention in preparation during diene radical siloxane bridge-linked double benzocyclobutene prepolymer, adopted good stability, nonvolatile ionic liquid substitutes the sym-trimethylbenzene solvent that prior art is used, thereby solvent can reclaim by simple separation with product on the one hand, recycle repeatedly, reduce cost, also shortened polymerization time on the other hand greatly, reduced energy consumption.
5, since the present invention in preparation during diene radical siloxane bridge-linked double benzocyclobutene prepolymer, adopted good stability, nonvolatile ionic liquid substitutes the sym-trimethylbenzene solvent that prior art is used, thereby not only can obtain 60～80% productive rate, but also can obtain the narrower performed polymer of molecular weight distribution.
Four, embodiment
Below by embodiment the present invention is specifically described; it is worthy of note that following examples only are used for that the invention will be further described; can not be interpreted as it is limiting the scope of the invention; the professional and technical personnel in this field to some nonessential improvement and adjustment that the present invention makes, must belong to protection scope of the present invention according to the content of the invention described above.
Adopted following code name among the embodiment, hereby explanation.
[C
2Py] PF
61-ethylpyridine hexafluorophosphate.
[C
8C
1Im] PF
61-octyl group-3-Methylimidazole hexafluorophosphate.
[C
4C
1C
1Im] PF
61-butyl-2,3-methylimidazole hexafluorophosphate.
[C
4C
1Im] PF
61-butyl-3-Methylimidazole hexafluorophosphate.
[C
4Py] Br 1-butyl-pyridinium bromine salt.
[C
4C
1C
1Im] Br 1-butyl-2,3-methylimidazole bromine salt.
[C
16C
1Im] PF
61-hexadecyl-3-Methylimidazole hexafluorophosphate.
[C
16C
1C
1Im] Br 1-hexadecyl-2,3-methylimidazole bromine salt.
[C
12C
1Im] PF
61-dodecyl-3-Methylimidazole hexafluorophosphate.
[C
2Py] Br 1-ethylpyridine bromine salt.
[C
12Py] PF
61-dodecyl pyridine hexafluorophosphate
DVS 1,1 '-divinyl tetramethyl-silica alkane.4-BrBCB 4-bromobenzene and cyclobutene.
The DVSBCB diene silicoxyane linking disbenzocyclobutylenmonomer monomer.
Following examples 1～11 are the embodiment of preparation diene silicoxyane linking disbenzocyclobutylenmonomer monomer; Embodiment 12～21 is the embodiment of preparation diene radical siloxane bridge-linked double benzocyclobutene prepolymer.
Embodiment 1
In the 50ml two neck bottles that magnetic stir bar is housed, add 32mmol NaOAc 2.624g, distilled water 5.8ml stirring and dissolving earlier, add [C subsequently successively
2Py] PF
62.9g, Pd (OAc)
24mg, 8mmol DVS 1.488g, 16mmol4-BrBCB 2.912g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 22 hours in 90 ℃; With reaction solution with petroleum ether extraction (3 * 20ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 2.5g, productive rate 80%.
1HNMR(400MHz，CDCl
3)，6.89～7.25(br，6H)，6.31～6.37(d，4H)，3.16(s，8H)，0.23(s，12H)。The ionic liquid washing and drying gets white solid [C
2Py] PF
62.8g.
Embodiment 2
In the 50ml two neck bottles that magnetic stir bar is housed, add 32mmol NaOAc 2.624g, distilled water 5.8ml stirring and dissolving earlier, add successively subsequently and reclaim the 4th time [C
2Py] PF
62.9g, Pd (OAc)
24mg, 8mmol DVS1.488g, 16mmol 4-BrBCB 2.912g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 22 hours in 90 ℃; With reaction solution with petroleum ether extraction (3 * 20ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 2.47g, productive rate 79%.The ionic liquid washing and drying gets white solid [C
2Py] PF
62.78g.
Embodiment 3
In the 50ml two neck bottles that magnetic stir bar is housed, add 32mmol NaOAc 2.624g, distilled water 5.8ml stirring and dissolving earlier, add successively subsequently and reclaim the tenth time [C
2Py] PF
62.9g, Pd (OAc)
24mg, 8mmol DVS1.488g, 16mmol 4-BrBCB 2.912g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 22 hours in 90 ℃; With reaction solution with petroleum ether extraction (3 * 20ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 2.55g, productive rate 81.7%.The ionic liquid washing and drying gets white solid [C
2Py] PF
62.8g.
Embodiment 4
In the 100ml two neck bottles that magnetic stir bar is housed, add 128mmol Et earlier
3N 12.928g, distilled water 5.8ml add [C subsequently successively
8C
1Im] PF
611.648g, Pd (OAc)
228.7mg, 16mmol DVS 2.976g, 32mmol 4-BrBCB 5.824g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 95 ℃ of reactions 28 hours; With reaction solution with petroleum ether extraction (3 * 40ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 3.12g, productive rate 50%.Ionic liquid gets light yellow liquid [C through washing and drying
8C
1Im] PF
611g.
Embodiment 5
In the 250mL two neck bottles that magnetic stir bar is housed, add 72mmol KOAc7.056g, distilled water 52.4ml stirring and dissolving earlier, add [C subsequently successively
4C
1C
1Im] PF
617.472g, Pd (OAc)
210.8mg, 12mmolDVS 2.232g, 24mmol 4-BrBCB 4.368g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 100 ℃ of reactions 24 hours; With reaction solution with petroleum ether extraction (3 * 30ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 4.0g, productive rate 85.5%.Ionic liquid gets light yellow solid [C through washing and drying
4C
1C
1Im] PF
617.3g.
Embodiment 6
In the 250ml two neck bottles that magnetic stir bar is housed, add 72mmol KOAc7.056g, distilled water 52.4ml stirring and dissolving earlier, add successively subsequently and reclaim the 5th time [C
4C
1C
1Im] PF
617.472g, Pd (OAc)
210.8mg, 12mmol DVS 2.232g, 24mmol 4-BrBCB 4.368g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 100 ℃ of reactions 24 hours; With reaction solution with petroleum ether extraction (3 * 30ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 3.9g, productive rate 83.3%.Ionic liquid gets light yellow solid [C through washing and drying
4C
1C
1Im] PF
617.0g.
Embodiment 7
In the 250ml two neck bottles that magnetic stir bar is housed, add 72mmol KOAc7.056g, distilled water 52.4ml stirring and dissolving earlier, add successively subsequently and reclaim the tenth time [C
4C
1C
1Im] PF
617.472g, Pd (OAc)
210.8mg, 12mmol DVS 2.232g, 24mmol 4-BrBCB 4.368g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 100 ℃ of reactions 24 hours; With reaction solution with petroleum ether extraction (3 * 30ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 3.8g, productive rate 81.2%.Ionic liquid gets light yellow solid [C through washing and drying
4C
1C
1Im] PF
617.1g.
Embodiment 8
In the 500ml two neck bottles that magnetic stir bar is housed, add 28.8mmol Na earlier
2CO
33.053g, distilled water 262ml stirring and dissolving, add [C subsequently successively
4C
1Im] PF
652.42g, Pd (OAc)
232.0mg, 14.4mmol DVS2.678g, 28.8mmol 4-BrBCB 5.242g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 100 ℃ of reactions 30 hours; With reaction solution with petroleum ether extraction (3 * 30ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 3.03g, productive rate 54.0%.Ionic liquid gets light yellow liquid [C through washing and drying
4C
1Im] PF
652.2g.
Embodiment 9
In the 250ml two neck bottles that magnetic stir bar is housed, add 76.8mmol KOAc 7.526g, distilled water 112ml stirring and dissolving earlier, add [C subsequently successively
4Py] Br 27.95g, Pd (OAc)
217.0mg, 9.6mmol DVS1.786g, 19.2mmol 4-BrBCB 3.494g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 150 ℃ of reactions 18 hours; With reaction solution with petroleum ether extraction (3 * 30ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 2.77g, productive rate 74.0%.Ionic liquid is evaporated to dried, and methanol wash is filtered, and concentrate drying gets white solid [C
4Py] Br 27.9g.
Embodiment 10
In the 50ml two neck bottles that magnetic stir bar is housed, add 120mmol Py 9.48g, distilled water 4.4ml earlier, add [C subsequently successively
4C
1C
1Im] Br 4.368g, Pd (OAc)
25.4mg, 24mmol DVS 4.464g, 48mmol4-BrBCB 8.736g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 120 ℃ of reactions 25 hours; With reaction solution with petroleum ether extraction (3 * 60ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 6.3g, productive rate 67.0%.Ionic liquid is evaporated to dried, and methanol wash is filtered, and concentrate drying gets light yellow solid [C
4C
1C
1Im] Br 4.34g.
Embodiment 11
In the 150ml two neck bottles that magnetic stir bar is housed, add 60mmol K earlier
2CO
38.28g, distilled water 87.2ml stirring and dissolving, add [C subsequently successively
16C
1Im] PF
610.9g, Pd (OAc)
226.9mg, 20mmol DVS 3.72g, 40mmol 4-BrBCB 7.28g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere in 140 ℃ of reactions 20 hours; With reaction solution with petroleum ether extraction (3 * 50ml), merge organic phase, anhydrous Na
2SO
4Drying, the organic phase filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to dried, gets colourless or light yellow oily liquid 4.68g, productive rate 60.0%.Ionic liquid washing after drying gets white solid [C
16C
1Im] PF
610.5g.
Embodiment 12
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 5g earlier, ionic liquid [C
4C
1Im] PF
695g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 8 hours in 190 ℃; Reaction solution poured in the 500ml methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 3g, productive rate 60%.GPC records Mw=2.0 * 10
4, Mn=2.3 * 10
3, molecular weight distribution is 8.6.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim pale yellow liquid 93g.
Embodiment 13
In the 100ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, ionic liquid [C
16C
1C
1Im] Br 30g,, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 20 hours in 160 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 15.6g, productive rate 78%.GPC records Mw=12.9 * 10
4, Mn=3.3 * 10
4, molecular weight distribution is 3.9.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 29.5g.
Embodiment 14
In the 100ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, reclaim the 5th time ionic liquid [C
16C
1C
1Im] Br 30g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 20 hours in 160 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 15.0g, productive rate 75%.GPC records Mw=12.0 * 10
4, Mn=3.0 * 10
4, molecular weight distribution is 4.0.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 29.7g.
Embodiment 15
In the 100ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, reclaim the tenth time ionic liquid [C
16C
1C
1Im] Br 30g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 20 hours in 160 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 15.2g, productive rate 76%.GPC records Mw=13.0 * 10
4, Mn=3.2 * 10
4, molecular weight distribution is 4.0.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 29.5g.
Embodiment 16
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, ionic liquid [C
12C
1Im] PF
680g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 18 hours in 180 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 16.0g, productive rate 80%.GPC records Mw=13.5 * 10
4, Mn=3.3 * 10
4, molecular weight distribution is 4.1.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 78g.
Embodiment 17
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, reclaim four times ionic liquid [C
12C
1Im] PF
680g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 18 hours in 180 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 15.5g, productive rate 77.5%.GPC records Mw=13.0 * 10
4, Mn=2.9 * 10
4, molecular weight distribution is 4.5.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 78g.
Embodiment 18
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, reclaim eight times ionic liquid [C
12C
1Im] PF
680g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 18 hours in 180 ℃; Reaction solution poured in the 3L propyl carbinol precipitate, centrifugation, vacuum-drying obtain white performed polymer 15.0g, productive rate 75.0%.GPC records Mw=11.0 * 10
4, Mn=2.0 * 10
4, molecular weight distribution is 5.5.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 77g.
Embodiment 19
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 20g earlier, ionic liquid [C
2Py] Br47g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 12 hours in 170 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 13.2g, productive rate 66.0%.GPC records Mw=5.0 * 10
4, Mn=6.4 * 10
3, molecular weight distribution is 7.8.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 78g.
Embodiment 20
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 15g earlier, ionic liquid [C
12Py] PF
685g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 18 hours in 165 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 10.5g, productive rate 70%.GPC records Mw=1.0 * 10
4, Mn=2.4 * 10
3, molecular weight distribution is 4.16.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim white solid 84.5g.
Embodiment 21
In the 150ml two neck bottles that magnetic stir bar is housed, add monomer DVSBCB 25g earlier, ionic liquid [C
4C
1C
1Im] Br 75g, the air in the logical then nitrogen venting reaction flask, and under nitrogen atmosphere, reacted 16 hours in 170 ℃; Reaction solution poured in the 3L methyl alcohol precipitate, centrifugation, vacuum-drying obtain white performed polymer 17g, productive rate 68%.GPC records Mw=2.0 * 10
4, Mn=2.4 * 10
3, molecular weight distribution is 8.3.Ionic liquid is through concentrating under reduced pressure, vacuum-drying reclaim light yellow solid 74g.
Claims (10)
1, a kind of preparation method with diene silicoxyane linking disbenzocyclobutylenmonomer monomer of following array structure,
The preparation technology of this method adds alkali and water stirring and dissolving earlier in reaction vessel, add solvent, catalyst acetic acid palladium, reaction raw materials 1 subsequently successively, 1 '-divinyl tetramethyl-silica alkane and 4-bromobenzene and cyclobutene, mix and under nitrogen atmosphere in 90～150 ℃ the reaction 18～30 hours; With the reaction solution petroleum ether extraction, merge organic phase, the organic phase anhydrous Na then
2SO
4Drying, filtered through silica gel, sherwood oil drip washing, leacheate is evaporated to do and promptly gets the product monomer, wherein reaction raw materials 1, the mole proportioning of 1 '-divinyl tetramethyl-silica alkane and 4-bromobenzene and cyclobutene is 1: 2, the consumption of alkali is 4-bromobenzene and cyclobutene mole number 1～4 times, catalyst consumption is 0.5～5 ‰ of 4-bromobenzene and a cyclobutene mole number, the consumption of water is 0.5-8 a times of solvent quality, it is characterized in that institute's solubilizing agent is ionic liquid or reclaims ionic liquid, its consumption is reaction raw materials 4-bromobenzene and cyclobutene quality 0.5～10 times.
2, the preparation method of diene silicoxyane linking disbenzocyclobutylenmonomer monomer according to claim 1, it is characterized in that the amount that adds ionic liquid or reclaim ionic liquid be reaction raw materials 4-bromobenzene and cyclobutene quality 1.5～4 times.
3, the preparation method of diene silicoxyane linking disbenzocyclobutylenmonomer monomer according to claim 1 and 2 is characterized in that added recovery ionic liquid reclaims 1～10 time ionic liquid for using repeatedly.
4, the preparation method of diene silicoxyane linking disbenzocyclobutylenmonomer monomer according to claim 1 and 2, it is characterized in that to add ionic liquid or reclaim ionic liquid be in the following structure any:
N=2 in the structural formula, 4,6,8,12,16, and C
nH
2n+1Be straight-chain paraffin.
5, the preparation method of diene silicoxyane linking disbenzocyclobutylenmonomer monomer according to claim 1 and 2, it is characterized in that institute adds ionic liquid or reclaims ionic liquid is 1-ethylpyridine hexafluorophosphate, 1-butyl-2,3-methylimidazole hexafluorophosphate or 1-dodecyl-2, any in the 3-methylimidazole hexafluorophosphate.
6, the preparation method of diene silicoxyane linking disbenzocyclobutylenmonomer monomer according to claim 3, it is characterized in that institute adds ionic liquid or reclaims ionic liquid is 1-ethylpyridine hexafluorophosphate, 1-butyl-2,3-methylimidazole hexafluorophosphate or 1-dodecyl-2, any in the 3-methylimidazole hexafluorophosphate.
7, a kind of preparation method of diene radical siloxane bridge-linked double benzocyclobutene prepolymer, this method is earlier will be by mass percentage, its content is 5～40% diene silicoxyane linking disbenzocyclobutylenmonomer monomer and solvent, under nitrogen atmosphere in 160 ℃～190 ℃ reactions, then reaction solution is poured in the precipitation agent and precipitated, centrifugation, vacuum-drying promptly get white performed polymer, it is characterized in that solvent for use is ionic liquid or reclaims ionic liquid, the reaction times is 8～20 hours.
8, the preparation method of diene radical siloxane bridge-linked double benzocyclobutene prepolymer according to claim 7 is characterized in that used recovery ionic liquid reclaims 1～10 time ionic liquid for using repeatedly.
9,, it is characterized in that used ionic liquid or recovery ionic liquid are any in the following structure according to the preparation method of claim 7 or 8 described diene radical siloxane bridge-linked double benzocyclobutene prepolymers:
N=2 in the structural formula, 4,6,8,12,16, and C
nH
2n+1Be straight-chain paraffin.
10, according to the preparation method of claim 7 or 8 described diene radical siloxane bridge-linked double benzocyclobutene prepolymers, it is characterized in that institute adds ionic liquid or reclaims ionic liquid is 1-hexadecyl-2, any in 3-methylimidazole bromine salt or 1-dodecyl-3-Methylimidazole hexafluorophosphate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831053A (en) * | 2010-04-26 | 2010-09-15 | 浙江顺虎德邦涂料有限公司 | Aqueous ultraviolet cured epoxy acrylic resin and preparation method thereof |
| CN101918461B (en) * | 2007-11-08 | 2015-09-16 | 泽西生物医学创新有限责任公司 | For cross-linked polyolefin and the manufacture method thereof of biomedical applications |
| CN105778096A (en) * | 2014-12-19 | 2016-07-20 | 中国科学院上海有机化学研究所 | Manufacturing method and application of benzocyclobutenyl containing silicon resin |
| CN107298764A (en) * | 2017-06-15 | 2017-10-27 | 西南科技大学 | A kind of poly- silacyclobutane type photosensitive siloxane resin and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185391A (en) * | 1991-11-27 | 1993-02-09 | The Dow Chemical Company | Oxidation inhibited arylcyclobutene polymers |
| US5854302A (en) * | 1993-04-29 | 1998-12-29 | The Dow Chemical Company | Partially polymerized divinylsiloxane linked bisbenzocyclobutene resins and methods for making said resins |
-
2005
- 2005-12-30 CN CNB2005100224785A patent/CN100374448C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918461B (en) * | 2007-11-08 | 2015-09-16 | 泽西生物医学创新有限责任公司 | For cross-linked polyolefin and the manufacture method thereof of biomedical applications |
| CN101831053A (en) * | 2010-04-26 | 2010-09-15 | 浙江顺虎德邦涂料有限公司 | Aqueous ultraviolet cured epoxy acrylic resin and preparation method thereof |
| CN105778096A (en) * | 2014-12-19 | 2016-07-20 | 中国科学院上海有机化学研究所 | Manufacturing method and application of benzocyclobutenyl containing silicon resin |
| CN105778096B (en) * | 2014-12-19 | 2019-03-15 | 中国科学院上海有机化学研究所 | The manufacturing method and application of the silicone resin of alkenyl containing benzocyclobutane |
| CN107298764A (en) * | 2017-06-15 | 2017-10-27 | 西南科技大学 | A kind of poly- silacyclobutane type photosensitive siloxane resin and preparation method thereof |
| CN107298764B (en) * | 2017-06-15 | 2020-02-07 | 西南科技大学 | Polysilacyclobutane type siloxane photosensitive resin and preparation method thereof |
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