CN101215472B - Fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof - Google Patents
Fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN101215472B CN101215472B CN2008100326405A CN200810032640A CN101215472B CN 101215472 B CN101215472 B CN 101215472B CN 2008100326405 A CN2008100326405 A CN 2008100326405A CN 200810032640 A CN200810032640 A CN 200810032640A CN 101215472 B CN101215472 B CN 101215472B
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- liquid crystal
- aromatic ring
- crystal polymer
- fluorine
- ring liquid
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 13
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 13
- 239000011737 fluorine Substances 0.000 title claims abstract description 13
- 125000001072 heteroaryl group Chemical group 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 229960001755 resorcinol Drugs 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229920006253 high performance fiber Polymers 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 3
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 abstract 1
- RDWSUXHSRWDTJL-UHFFFAOYSA-N FC(CC(F)(F)F)(F)F.C1(=CC=CC=C1)C(=O)O Chemical compound FC(CC(F)(F)F)(F)F.C1(=CC=CC=C1)C(=O)O RDWSUXHSRWDTJL-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000002657 fibrous material Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229920002577 polybenzoxazole Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a hetero-aromatic ring liquid crystal polymer which contains fluorine and a process for preparation. The process for preparation comprises following steps: firstly, enabling 4,6-diaminoresorcinol hydrochlorate and terephthalic acid to generate copolymerization reaction with (phenylformic acid) hexafluoropropane in polyphosphoric acids, secondly then, reacting for 3-6 hoursunder 130-150 DEG C, then, reacting for 10-14 hours under 170-175 DEG C, lastly, reacting for 16-24 hours under 185-200 DEG C, and then colleting the hetero-aromatic ring liquid crystal polymer whichcontains the fluorine from reaction products. The hetero-aromatic ring liquid crystal polymer which contains fluorine of the invention has good dielectric property and heat-proof property and providesa new material for preparing advanced electronic encapsulating materials, the polymer which is obtained from the invention can prepare high-performance fiber materials or membrane materials through passing through a screw extruder and adopting a method of moistening spinning dryly and can be used in the industry of the advanced electronic encapsulating materials. The molecular structure is displayed by the figure.
Description
Technical field
The present invention relates to hetero-aromatic ring liquid crystal polymer of fluorine and preparation method thereof.
Background technology
Along with the fast development of microelectronics industry, the polymer materials that base plate for packaging is used is also had higher requirement: high heat-resistant stability energy; High glass-transition temperature; High mechanics mechanical property; High electric insulation; Low-hygroscopicity; Low-k and dielectric loss; Low impurity content or the like.For this reason, the synthetic novel polymer material that satisfies above-mentioned requirements is imperative.For traditional electronic package material, the thermotolerance that himself possesses, mechanical property have begun to satisfy the requirements at the higher level that the development of electronic package material material is proposed.
As the high-performance polymer-pbo fiber of the important scientific payoffs of United States Air Force testing laboratory, spin the earliest by Japan the nineties in last century it has been carried out suitability for industrialized production, its commodity are called " Zylon ".The tensile strength of Zylon is 5.8GPa, and tensile modulus is 300GPa, is respectively the twice of PPTA fiber.In addition, Zylon also has excellent thermostability (heat decomposition temperature is up to 650 ℃) and flame retardant resistance (LOI=68).Therefore, Zylon has important use to be worth in fields such as aerospace, military project national defence, communications and transportation, sports equipment, building, high temperature protections, the irreplaceable effect of other material is arranged.
But PBO is difficult to dissolving in common organic solvent, be difficult to machine-shaping.Therefore, need carry out modification to the processing characteristics of PBO.At present, people have carried out fruitful work at aspects such as the dissolving that improves polymkeric substance, fusions.Mainly be included in the flexible group of introducing, fluoro-containing group, big side group etc. in the polymer molecular chain at the solvability aspect.Reduce the molecular chain rigidity, reduce between molecular chain reactive force and suitably reduce molecular weight etc. mainly comprising aspect the meltbility.
Summary of the invention
The purpose of this invention is to provide a kind of fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof,, satisfy the needs of the parties concerned to overcome the defective that prior art exists.
Fluorine-containing hetero-aromatic ring liquid crystal polymer of the present invention has following molecular structure:
Wherein: m=0.9～3.1, n=58～92, number-average molecular weight is 15000～22000.
The preparation method of polymkeric substance of the present invention comprises the steps:
(1) with 4, the 6-diamino resorcin hydrochlorate (is called for short DAR, down together), terephthalic acid (is called for short TPA, in inert atmosphere, (be called for short BIS-B-AF down together) with two (phenylformic acid) HFC-236fa, (be called for short PPA at polyphosphoric acid down together), carry out copolyreaction down together), temperature of reaction is 50～100 ℃, and the reaction times is 25～35 hours;
(2) under 130 ℃～150 ℃, reacted 3-6 hour then, reacted 10～14 hours down at 170-175 ℃ again, reacted 16～24 hours down at 185 ℃～200 ℃ at last, then the fluorine-containing hetero-aromatic ring liquid crystal polymer of collection from reaction product.
In polyreaction, the mol ratio of each component is:
DAR∶(TPA+BIS-B-AF)＝1∶1
TPA∶BIS-B-AF＝0.95～0.99∶0.01～0.05。
Fluorine-containing hetero-aromatic ring liquid crystal polymer of the present invention, have good dielectric properties and resistance toheat, for the preparation of advanced electronic package material provides a kind of new material, the polymers soln that the present invention obtains can be through screw extrusion press, adopt the method for dry-jet wet-spinning to prepare high-performance fiber or mould material, can be used for advanced electronic package material industry.
Embodiment
Embodiment 1
Be equipped with powerful whipping appts, N
2Import and export, capacity is in the 1L reactor, at first feeds high-purity N
2Air is fallen in displacement, at N
2Protection adds 40g 4 down successively, 6-diamino resorcin hydrochlorate (DAR), 30.8620g terephthalic acid (TPA), two (phenylformic acid) HFC-236fa (BIS-B-AF) of 0.7366g, 169.1275g polyphosphoric acid (P
2O
5Concentration is 80wt%) and 115.1605g P
2O
5, 0.2g SnCl
2, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 2 hours, material is further dissolved.
Temperature of reaction kettle is risen to 100 ℃ of reactions 24 hours, be muted color, represent that promptly system removes HCl fully until detecting at gas evolution mouth place with the pH test paper.
Be warming up to 130 ℃ of reactions 3 hours, 150 ℃ were reacted 5 hours, were warming up to 175 ℃ of reactions 10 hours again, 185 ℃ of reactions 24 hours, finished polyreaction at last.
The limiting viscosity of polymerisate [η]=18.0dL/g, number-average molecular weight are 22000, m=0.93 wherein, n=92.
FTIR analytical results: (KBr pressed disc method, cm
-1): 3095,3064,2928,2858,2710,2635,2321,1723,1680,1622,1578,1557,1494,1411,1363,1330,1306,1272,1209,1175,1137,1114,1055,1011,926,913,867,850,822,751,701,629,501,420.
Ultimate analysis:
Each constituent content theoretical value is: C:71.57%, H:2.56%, N:11.85%;
Experimental value is C:70.15%, H:2.67%, N:11.40%.
The specific inductivity (adopting wideband dielectric impedance spectrometer to measure) that adopts the polymkeric substance of this method preparation is that 1.1～2.1 (sweep rate is 10
7～10
-2Hz), heat decomposition temperature is 665.9 ℃ in air.
Embodiment 2
Be equipped with powerful whipping appts, N
2Import and export, capacity is in the 1L reactor, at first feeds high-purity N
2Air is fallen in displacement, at N
2Protection adds 40g 4 down successively, 6-diamino resorcin hydrochlorate (DAR), 30.2385g terephthalic acid (TPA), two (phenylformic acid) HFC-236fa (BIS-B-AF) of 2.2099g, 174.4787g polyphosphoric acid (P
2O
5Concentration is 80wt%) and 114.6056g P
2O
5, 0.2g SnCl
2, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 2 hours, material is further dissolved.Temperature of reaction kettle is risen to 100 ℃ of reactions 24 hours, be muted color, represent that promptly system removes HCl fully until detecting at gas evolution mouth place with the pH test paper.Be warming up to 130 ℃ of reactions 3 hours, 150 ℃ were reacted 5 hours, were warming up to 175 ℃ of reactions 10 hours again, 185 ℃ of reactions 24 hours, finished polyreaction at last.
The limiting viscosity of polymerisate [η]=14.1dL/g, number-average molecular weight are 19120, m=2.38 wherein, n=77.
FTIR analytical results (KBr pressed disc method, cm
-1): 3095,3067,2922,2852,2711,2632,2320,1723,1680,1621,1577,1557,1494,1410,0363,1331,1306,1272,1208,1174,1139,1114,1055,1010,926,913,867,851,820,751,704,629,500,421.Results of elemental analyses: each constituent content theoretical value is: C:71.12%, H:2.54%, N:11.63%; Experimental value is C:70.85%, H:2.76%, N:11.21%.
The specific inductivity that adopts the polymkeric substance of this method preparation is that 1.1～1.6 (sweep rate is 107～10
-2Hz), heat decomposition temperature is 656.5 ℃ in air.
Embodiment 3
Be equipped with powerful whipping appts, N
2Import and export, capacity is in the 1L reactor, at first feeds high-purity N
2Air is fallen in displacement, at N
2Protection adds 50g 4 down successively, 6-diamino resorcin hydrochlorate (DAR), 37.7981g terephthalic acid (TPA), two (phenylformic acid) HFC-236fa (BIS-B-AF) of 4.6040g, 322.4451g polyphosphoric acid (P
2O
5Concentration is 80wt%) and 169.3437g P
2O
5, 0.25g SnCl
2, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 3 hours, material is further dissolved.Temperature of reaction kettle is risen to 100 ℃ of reactions 30 hours, be muted color, represent that promptly system removes HCl fully until detecting at gas evolution mouth place with the pH test paper.Be warming up to 130 ℃ of reactions 1.5 hours, 150 ℃ were reacted 3 hours, were warming up to 175 ℃ of reactions 12 hours again, 185 ℃ of reactions 22 hours, finished polyreaction at last.
The limiting viscosity of polymerisate [η]=9.87dL/g, number-average molecular weight are 15000, m=3.05 wherein, n=58.
FTIR analytical results (KBr pressed disc method, cm
-1): 3094,3067,3037,2920,2851,2715,2637,2289,1932,1864,1617,1576,1555,1495,1412,1364,1328,1306,1273,1207,1174,1142,1114,1052,1011,925,848,819,752,701,512,500,420.
Ultimate analysis:
Each constituent content theoretical value is: C:70.69%, H:2.53%, N:11.41%;
Experimental value is C:70.05%, H:2.61%, N:11.56%.
The specific inductivity that adopts the polymkeric substance of this method preparation is that 1.0～1.4 (sweep rate is 107～10
-2Hz), heat decomposition temperature is 645.0 ℃ in air.
Claims (4)
1. fluorine-containing hetero-aromatic ring liquid crystal polymer is characterized in that, this polymkeric substance has following molecular structure:
Wherein: m=0.9～3.1, n=58～92, number-average molecular weight is 15000～22000.
2. the preparation method of fluorine-containing hetero-aromatic ring liquid crystal polymer according to claim 1 is characterized in that, comprises the steps:
(1) with 4,6-diamino resorcin hydrochlorate, terephthalic acid carry out copolyreaction with two (phenylformic acid) HFC-236fa in polyphosphoric acid in inert atmosphere;
(2) under 130 ℃～150 ℃, reacted 3-6 hour then, reacted 10～14 hours down at 170-175 ℃ again, reacted 16～24 hours down at 185 ℃～200 ℃ at last, then the fluorine-containing hetero-aromatic ring liquid crystal polymer of collection from reaction product.
3. method according to claim 2 is characterized in that, the temperature of reaction of step (1) is 50～100 ℃, and the reaction times is 25～35 hours.
4. according to claim 2 or 3 described methods, it is characterized in that in polyreaction, the mol ratio of each component is:
DAR∶(TPA+BIS-B-AF)＝1∶1
TPA∶BIS-B-AF＝0.95～0.99∶0.01～0.05；
DAR is 4, and the abbreviation of 6-diamino resorcin hydrochlorate, TPA are the abbreviation of terephthalic acid, and BIS-B-AF is the abbreviation of two (phenylformic acid) HFC-236fa.
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|---|---|---|---|
| CN2008100326405A CN101215472B (en) | 2008-01-15 | 2008-01-15 | Fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof |
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|---|---|---|---|
| CN2008100326405A CN101215472B (en) | 2008-01-15 | 2008-01-15 | Fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101215472A CN101215472A (en) | 2008-07-09 |
| CN101215472B true CN101215472B (en) | 2010-06-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254710A (en) * | 1998-09-29 | 2000-05-31 | 住友电木株式会社 | Polybenzoxazole resin and precursor thereof |
| CN1450050A (en) * | 2003-05-06 | 2003-10-22 | 华东理工大学 | Process for preparing 4,6-diamino resorcinol hydrochloride |
| CN1463379A (en) * | 2001-05-31 | 2003-12-24 | 内莫普蒂公司 | Polyimides for anchoring liquid crystals, display devices including same and method for prepn. of said devices |
-
2008
- 2008-01-15 CN CN2008100326405A patent/CN101215472B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254710A (en) * | 1998-09-29 | 2000-05-31 | 住友电木株式会社 | Polybenzoxazole resin and precursor thereof |
| CN1463379A (en) * | 2001-05-31 | 2003-12-24 | 内莫普蒂公司 | Polyimides for anchoring liquid crystals, display devices including same and method for prepn. of said devices |
| CN1450050A (en) * | 2003-05-06 | 2003-10-22 | 华东理工大学 | Process for preparing 4,6-diamino resorcinol hydrochloride |
Non-Patent Citations (4)
| Title |
|---|
| 江建明等.高相对分子质量PBO的聚合及其高性能纤维的成型.材料研究学报20 4.2006,20(4),435-439. |
| 江建明等.高相对分子质量PBO的聚合及其高性能纤维的成型.材料研究学报20 4.2006,20(4),435-439. * |
| 金俊弘等.聚苯撑苯并二 唑(PBO)的合成.东华大学学报(自然科学版)28 6.2002,28(6),122-125. |
| 金俊弘等.聚苯撑苯并二 唑(PBO)的合成.东华大学学报(自然科学版)28 6.2002,28(6),122-125. * |
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