KR100907750B1 - Synthesis of hybrid poly(phenylenemethylene) having functionalized silsesquioxanes - Google Patents
Synthesis of hybrid poly(phenylenemethylene) having functionalized silsesquioxanes Download PDFInfo
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- -1 poly(phenylenemethylene) Polymers 0.000 title claims description 9
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- FCMZRNUHEXJWGB-UHFFFAOYSA-N trichloro(cyclopentyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCC1 FCMZRNUHEXJWGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- VWVZFHRDLPHBEG-UHFFFAOYSA-N 1-(chloromethyl)-4-methylsulfanylbenzene Chemical group CSC1=CC=C(CCl)C=C1 VWVZFHRDLPHBEG-UHFFFAOYSA-N 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000077 silane Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000006467 substitution reaction Methods 0.000 claims 2
- 239000003929 acidic solution Substances 0.000 claims 1
- 239000012798 spherical particle Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- ZFBNNSOJNZBLLS-UHFFFAOYSA-N 2,6-Dimethoxy-4-methylphenol Chemical compound COC1=CC(C)=CC(OC)=C1O ZFBNNSOJNZBLLS-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- QSZCGGBDNYTQHH-UHFFFAOYSA-N 2,3-dimethoxyphenol Chemical compound COC1=CC=CC(O)=C1OC QSZCGGBDNYTQHH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BUTFCJGGGQXOQB-UHFFFAOYSA-N [4-(chloromethyl)phenyl]silane Chemical compound [SiH3]C1=CC=C(CCl)C=C1 BUTFCJGGGQXOQB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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Abstract
Description
본 발명은 기능성 실세스퀴옥산을 가지는 새로운 혼성 폴리(페닐렌메틸렌)(poly(phenylenemethylene), PPM) 및 이의 제조방법에 관한 것이다. The present invention relates to a novel hybrid poly (phenylenemethylene) having a functional silsesquioxane (poly (phenylenemethylene), PPM) and a preparation method thereof.
보다 상세하게는, 본 발명은 하기 화학식 1의 기능성 다면체 올리고머 실세스퀴옥산(polyhedral oligomeric silsesquioxanes; POSS) 을 가지는 혼성 폴리(페닐렌메틸렌)에 관한 것이다. More specifically, the present invention relates to a hybrid poly (phenylene methylene) having a functional polyhedral oligomeric silsesquioxanes (POSS) of formula (1).
[화학식 1][Formula 1]
이 때, 상기 n은 6 이상이다. At this time, n is 6 or more.
본 발명에 따른 POSS-PPM은 POSS-DMP(dimethoxyphenol)와 파라포름알데하이드(paraformaldehyde)를 반응시켜 합성한다. POSS-PPM according to the present invention is synthesized by reacting POSS-DMP (dimethoxyphenol) and paraformaldehyde (paraformaldehyde).
PPM-POSS는 사슬간 응집의 정도가 줄어들어 약 100nm 지름의 구형 입자가 균질하게 분포된 구조를 가지며, POSS 단위체를 가지지 못한 PPM-Benzyl에 비하여 열안정성이 현저히 높다. PPM-POSS has a structure in which spherical particles of about 100 nm diameter are homogeneously distributed due to a decrease in the degree of aggregation between chains, and thermal stability is significantly higher than that of PPM-Benzyl having no POSS monomer.
근래에 다면체 올리고머 실세스퀴옥산(polyhedral oligomeric silsesquioxanes; POSS)을 포함하는 유기-무기 혼성 나노복합재료에 대한 관심이 증대되었는데, 이는 상기 POSS를 사용하여 물리적 및 기계적 성질이 예상치 못할 정도로 개선되었기 때문이다(Lichtenhan, J. D. and Otonari, Y. A., Carr, M. J. Macromolecules 1995, 28, 8435; Feher, F. J. et al., Chem Commun 1997, 1185).In recent years, interest in organic-inorganic hybrid nanocomposites including polyhedral oligomeric silsesquioxanes (POSS) has increased because of the unexpectedly improved physical and mechanical properties using the POSS. (Lichtenhan, JD and Otonari, YA, Carr, MJ Macromolecules 1995, 28, 8435; Feher, FJ et al ., Chem Commun 1997, 1185).
POSS 분자는 (RSiO1 .5)8의 일반식을 가지는 옥타머(octamer)이며, 0.3-0.4 nm의 나노스케일 크기를 가진 경직 입방 실리카 코어와 다중 반응성 기능성 기로 구성된다(Zang, C. et al., J Am Chem Soc 1998, 120, 8380). 이러한 POSS 분자는 공중합 또는 블랜딩을 통하여 용이하게 acrylic(Kim, K. M.; Chujo, Y., J Polym Sci Part A Polym Chem 2001, 39, 4035), styryls(Haddad, T. S.; Lichtenhan, J. D., Macromolecules 1996, 29, 7302) 및 epoxides(Laine, R. M.; Choi, J.; Lee, I., Adv Mater 2001, 13, 800)와 같은 폴리머에 삽입되고, 이 때 POSS에 결합된 다양한 치환체가 가용성을 향상시키기 때문에 합성 과정에서 변형이 거의 혹은 전혀 필요하지 않다. POSS를 포함하는 공중합체 혹은 블랜드는 POSS moieties를 가지지 못하는 경우에 비하여 산소 투과성이 증가되고, 열가소성 혹은 경화성(curable)이며, 산화 저항성을 가지고, 높은 열전달 특성을 가진다. POSS molecules (RSiO 1 .5) and octahydro Murray (octamer) having the general formula 8, is configured as rigid cubic silica core and a multi-reactive functionality with a nano-scale size of 0.3-0.4 nm (Zang, C. et al ., J Am Chem Soc 1998, 120, 8380). Such POSS molecules are easily acrylic (Kim, KM; Chujo, Y., J Polym Sci Part A Polym Chem 2001, 39, 4035), styryls (Haddad, TS; Lichtenhan, JD, Macromolecules 1996, 29) through copolymerization or blending. , 7302) and epoxides (Laine, RM; Choi, J .; Lee, I., Adv Mater 2001, 13, 800), where various substituents bound to POSS enhance the solubility Little or no modification is needed in the process. Copolymers or blends containing POSS have increased oxygen permeability, are thermoplastic or curable, have oxidation resistance, and have high heat transfer properties as compared to POSS moieties.
무기 전구체로 POSS를 이용한 다양한 유기-무기 혼성 나노복합재료가 알려진 바 있다. 그러한 예로는 hybrid micelles(Kim, K. M.; Keum, D. K.; Chujo, Y., Macromolecules 2003, 36, 867), hybrid gels(Kim, K. M.; Chujo, Y., J Mater Chem 2003, 13, 1384), hybrid liquid crystalline polymers(Kim, K. M.; Chujo, Y., J Polym Sci Part A Polym Chem 2001, 39, 4035), hydrophobic CaCO3 composite particles(Keum, D. K.et al., J Mater Chem 2002, 12, 2449) 그리고 분자 수준에 서 결합된 등질 투과 폴리머 혼성 물질(homogeneously transparent polymer hybrid materials)( Kim, K. M.; Chujo, Y., J Polym Sci Part A Polym Chem 2003, 41, 1306; Kim, K. M.; Adachi, K.; Chujo, Y., Polymer 2002, 43, 1171) 등이 있다. Various organic-inorganic hybrid nanocomposites using POSS as inorganic precursors have been known. Examples include hybrid micelles (Kim, KM; Keum, DK; Chujo, Y., Macromolecules 2003, 36, 867), hybrid gels (Kim, KM; Chujo, Y., J Mater Chem 2003, 13, 1384), hybrid Liquid crystalline polymers (Kim, KM; Chujo, Y., J Polym Sci Part A Polym Chem 2001, 39, 4035), hydrophobic CaCO 3 composite particles (Keum, DK et al., J Mater Chem 2002, 12, 2449) and molecules Homogeneously transparent polymer hybrid materials (Kim, KM; Chujo, Y., J Polym Sci Part A Polym Chem 2003, 41, 1306; Kim, KM; Adachi, K .; Chujo , Y., Polymer 2002, 43, 1171).
페놀 수지는 그의 우수한 박피성, 구조적 통합성, 열 안정성 및 용매 저항성 때문에 광범위하게 사용되는 열경화성 수지의 하나이다(Choi, M. H.; Chung, I. J., J Appl Polym Sci 2004, 90, 2316; Kim, Y. J.; Uyama, H.; Kobayashi, S., Polym J 2004, 36, 992). 그러나, 새로운 기능성 페놀계 폴리머는 방향족 폴리머의 합성 분야에 비하여 상대적으로 연구가 미흡한 상태로 남아있다. Phenolic resins are one of the most widely used thermosetting resins because of their excellent peelability, structural integrity, thermal stability and solvent resistance (Choi, MH; Chung, IJ, J Appl Polym Sci 2004, 90, 2316; Kim, YJ; Uyama , H .; Kobayashi, S., Polym J 2004, 36, 992). However, new functional phenolic polymers remain relatively poorly studied compared to the field of synthesis of aromatic polymers.
풍부한 전자를 가진 다양한 방향족 화합물에 버금가도록 페놀 포름알데하이드 수지(phenol formaldehyde resin, novolac)의 화학 분야를 확대시키고, PPM 골격(backbone)에 기초한 새로운 기능성 물질을 만들어 내는 것이 중요하다.It is important to expand the chemistry of phenol formaldehyde resins (novolac) and to create new functional materials based on the PPM backbone to match the various aromatic compounds with rich electrons.
그러나, 현재까지의 지식으로는 PPM 폴리머로 무기 그룹(inorganic group)인 POSS가 도입되는 것은 설명된 바 없다. However, to date, no introduction of the inorganic group POSS into the PPM polymer has been described.
본 발명은 물리적 및 기계적 특성이 우수한 새로운 페놀계 폴리머를 제공하는 것을 그 목적으로 한다. It is an object of the present invention to provide a new phenolic polymer having excellent physical and mechanical properties.
본 발명은 하기 화학식 1의 기능성 다면체 올리고머 실세스퀴옥산(POSS) 을 가지는 혼성 폴리(페닐렌메틸렌)을 제공한다. The present invention provides a hybrid poly (phenylene methylene) having a functional polyhedral oligomeric silsesquioxane (POSS) of the general formula (1).
[화학식 1][Formula 1]
이 때, 상기 n은 6 이상이다. At this time, n is 6 or more.
또한, 본 발명은 POSS-DMP(dimethoxyphenol)와 파라포름알데하이드(paraformaldehyde)를 산성 조건 하에서 반응시켜 POSS-PPM을 합성하는 POSS-PPM의 제조 방법을 제공한다. 이 때 상기 POSS-DMP는 클로로벤질클로로펜틸- POSS(POSS-Cl)과 DMP를 반응시켜 수득한 것이다. In addition, the present invention provides a method for producing POSS-PPM for synthesizing POSS-PPM by reacting POSS-DMP (dimethoxyphenol) and paraformaldehyde (paraformaldehyde) under acidic conditions. At this time, the POSS-DMP is obtained by reacting chlorobenzylchloropentyl-POSS (POSS-Cl) with DMP.
본 발명을 상세히 설명한다. The present invention will be described in detail.
본 발명은 기능성 다면체 올리고머 실세스퀴옥산(POSS) 을 가지는 혼성 폴리(페닐렌메틸렌)(PPM)을 제공한다. The present invention provides a hybrid poly (phenylene methylene) (PPM) having a functional polyhedral oligomeric silsesquioxane (POSS).
우선, 사이클로펜틸트리클로로실란(cyclopentyltrichlorosilane)의 가수분해 응축반응으로 불완전하게 응축된 트리실라놀(incompletely condensed trisilanol, (c-C5H9)7Si7O9(OH)3; POSS-OH)을 합성한다. First, incompletely condensed trisilanol (cC 5 H 9 ) 7 Si 7 O 9 (OH) 3 ; POSS-OH) was synthesized by hydrolysis condensation of cyclopentyltrichlorosilane. do.
그 후 루 등의 방법(Leu, C. M et al., Macromolecules 2003, 36, 9122; Chou, C. H. et al., Macromolecules 2005, 38, 9117)에 따라서 커플링 시약인 트리클로로[(4-클로로메틸)페닐]실란 {trichloro[(4-(chloromethyl)phenyl)silane}과 불완전하게 응축된 트리실라놀(POSS-OH)의 corner-capping reaction으로 클로로벤질클로로펜틸-POSS(POSS-Cl)를 합성한다. Then Lu et al. (Leu, C. M et al., Macromolecules 2003, 36, 9122; Chou, CH et al ., incompletely condensed trisilanol with trichloro [(4-chloromethyl) phenyl] silane {trichloro [(4- (chloromethyl) phenyl) silane} according to Macromolecules 2005, 38, 9117). Chlorobenzylchloropentyl-POSS (POSS-Cl) is synthesized by corner-capping reaction of POSS-OH.
상기 방법으로 수득한 POSS-Cl을 DMP와 염기촉매 하에서 치환반응으로 하기 화학식 2의 POSS-DMP를 합성한다. POSS-Cl obtained by the above method is synthesized by substituting DMP under a base catalyst to POSS-DMP of Chemical Formula 2 below.
[화학식 2][Formula 2]
상기 화학식 2의 POSS-DMP를 산성 조건하에서 파라포름알데하이드와 반응시키면 본 발명에 따른 PPM-POSS를 얻는다. 이 때 산성 조건을 맞추기 위하여 아세트산이나 술폰산을 사용하는 것이 바람직하다. When the POSS-DMP of Chemical Formula 2 is reacted with paraformaldehyde under acidic conditions, PPM-POSS according to the present invention is obtained. At this time, in order to meet acidic conditions, it is preferable to use acetic acid or sulfonic acid.
또한 POSS units 이 열 특성에 미치는 영향을 조사하고 혼성 PPM-POSS의 분자 구조를 연구하기 위하여 PPM-Benzyl을 제조하였다. POSS 및 benzyl groups 을 포함하는 PPM(PPM-POSS 및 PPM-Benzyl)의 합성은 도 7a 및 도 7b 에 나타내었다. In addition, PPM-Benzyl was prepared to investigate the effect of POSS units on thermal properties and to study the molecular structure of hybrid PPM-POSS. Synthesis of PPM (PPM-POSS and PPM-Benzyl) including POSS and benzyl groups is shown in FIGS. 7A and 7B.
상기 과정으로 제조한 PPM-POSS의 분자량(Mn = 5700, Mw = 10,300, Mw/Mn = 1.80) 은 예상보다 작았고, 이는 중합 과정 동안 벌키 POSS units에 의하여 발생한 입체 장애(steric hindrance)에 귀착될 수 있다. The molecular weight (M n = 5700, M w = 10,300, M w / M n = 1.80) of PPM-POSS prepared by the above process was smaller than expected, which caused steric hindrance caused by bulky POSS units during the polymerization process. May result in
본 발명에서 수득한 PPM-POSS는 측쇄에 POSS units를 가지는 새로운 혼성 PPM이다. 즉, 측쇄-테더(tethered) POSS units을 포함하는 이러한 혼성 PPM형태는 주쇄인 선형 강축(rigid-rod) PPM과 주쇄에 결합된 무기 부분인 POSS 분지(branches)로 구성된다. PPM-POSS obtained in the present invention is a new hybrid PPM with POSS units in the side chain. In other words, this hybrid PPM form, which includes tethered POSS units, is an inorganic part that is bound to the main chain, linear-rod PPM, and backbone. It consists of POSS branches.
POSS units를 포함하는 PPM은 경직, 입방 실리카 코어를 가진 POSS units 때문에 POSS units를 가지지 않는 PPM-Benzyl에 비하여 높은 열 안정성을 가지고, 유리 전이 온도가 없다. PPMs containing POSS units have higher thermal stability and no glass transition temperature than PPM-Benzyl, which does not have POSS units because of POSS units with rigid, cubic silica cores.
또한, PPM-POSS 는 벌키 POSS 그룹 사이의 분자간 반발력 때문에 사슬간 응집의 정도가 줄어들어 약 100nm 지름의 구형 입자가 균질하게 분포된 구조를 가지며, 반면에 벤질 그룹을 가진 PPM-Benzyl은 PPM-Benzyl의 페닐기 사이에서 일어나는 방향족 (π-π) 상호작용 때문에 1-5 ㎛ 크기를 가지는 비균질한 거대 중합체 입자 분포를 보인다. In addition, PPM-POSS has a structure in which spherical particles of about 100 nm diameter are homogeneously distributed due to the intermolecular repulsion between bulky POSS groups, whereas PPM-Benzyl having benzyl group has Due to the aromatic (π-π) interactions occurring between the phenyl groups, they exhibit a heterogeneous macromolecular particle distribution with a size of 1-5 μm.
본 발명은 기능성 다면체 올리고머 실세스퀴옥산(POSS)을 가지는 새로운 혼성 PPM을 제공한다. 본 발명에 따른 PPM-POSS는 구형 입자가 균질하게 분포된 구조를 가지며 열 안정성이 우수한 특징을 갖는다. The present invention provides new hybrid PPMs with functional polyhedral oligomeric silsesquioxanes (POSS). PPM-POSS according to the present invention has a structure in which spherical particles are homogeneously distributed and has excellent thermal stability.
또한 본 발명에 따라 물리적 및 기계적 특성이 우수한 새로운 무기-유기 나 노 복합재료인 PPM-POSS 를 간단하게 합성할 수 있다. In addition, according to the present invention, it is possible to simply synthesize PPM-POSS, a new inorganic-organic nanocomposite having excellent physical and mechanical properties.
이하, 본 발명을 실시예에 의하여 상세히 설명한다. 그러나 본 발명의 범위가 하기 실시예에 의하여 한정되지 않는다는 것은 자명하다. Hereinafter, the present invention will be described in detail by way of examples. However, it is obvious that the scope of the present invention is not limited by the following examples.
<< 실시예Example 1> 1> ChlorobenzylcyclopentylChlorobenzylcyclopentyl -- POSSPOSS ( ( POSSPOSS -- ClCl )의 합성) Synthesis
수성 아세톤으로 환류하여 사이클로펜틸트리클로로실란 (Cyclopentyltrichlorosilane, Aldrich)의 가수분해 응축반응으로 불완전하게 응축된 트리실라놀(POSS-OH)을 수득하였다. Reflux with aqueous acetone yielded incompletely condensed trisilanol (POSS-OH) by hydrolysis condensation of cyclopentyltrichlorosilane (Aldrich).
POSS-Cl은 루 등의 방법(Leu, C. M et al., Macromolecules 2003, 36, 9122; Chou, C. H. et al., Macromolecules 2005, 38, 9117)에 따라서 커플링 시약인 트리클로로[(4-클로로메틸)페닐]실란 {trichloro[(4-(chloromethyl)phenyl)silane, Lancaster}과 불완전하게 응축된 트리실라놀의 corner-capping reaction으로 제조하였다. POSS-Cl is a trichloro [(4) coupling reagent according to Lu et al. (Leu, C. M et al., Macromolecules 2003, 36, 9122; Chou, CH et al., Macromolecules 2005, 38, 9117). Trichloro [(4- (chloromethyl) phenyl) silane, Lancaster} and incompletely condensed trisilanol were prepared by the corner-capping reaction.
<< 실시예Example 2> 2> POSSPOSS -- DMP 의Of DMP 합성 synthesis
0.16 g, 0.97 mmol의 4-메틸-2, 6-디메톡시페놀(4-methyl-2,6-dimethoxyphenol, Aldrich) 과 0.13 g, 0.97 mmol의 탄산 칼륨(potassium carbonate) 을 10 ml 의 DMF에 섞고, 반응 혼합물을 1시간 동안 질소 대기 하에 60 ℃로 가열하였다. 0.16 g, 0.97 mmol of 4-methyl-2,6-dimethoxyphenol (Aldrich) and 0.13 g, 0.97 mmol of potassium carbonate are mixed in 10 ml of DMF. The reaction mixture was heated to 60 ° C. under nitrogen atmosphere for 1 hour.
그 후 실시예 1에서 수득한 POSS-Cl 1.00 g, 0.97 mmol과 0.16 g, 0.97 mmol의 요오드화 칼륨(potassium iodide)을 10.0 ml 의 dry Tetrahydrofuran (THF)에 용해시키고, 30분 동안 dropwise로 상기 반응 혼합물에 첨가하였다. Thereafter, 1.00 g of POSS-Cl obtained in Example 1, 0.97 mmol and 0.16 g, 0.97 mmol of potassium iodide were dissolved in 10.0 ml of dry Tetrahydrofuran (THF), and the reaction mixture was dropwise for 30 minutes. Was added.
상기 혼합물을 24시간 동안 환류시키면서 실온으로 냉각시키고, 증류수로 증류한 다음 클로로포름으로 추출하였다. The mixture was cooled to room temperature at reflux for 24 hours, distilled with distilled water and then extracted with chloroform.
추출된 유기층을 증류수로 세척하고 진공상태에서 농축하여 밝은 노란색의 고형 POSS-DMP를 수득하였다(0.50 g, 44%).The extracted organic layer was washed with distilled water and concentrated in vacuo to give a light yellow solid POSS-DMP (0.50 g, 44%).
1H NMR (CDCl3, δ): δ7.7 (d, 2H), 7.4 (d, 2H), 6.4 (s, 2H), 5.0 (s, 2H), 3.8 (s, 6H), 2.3 (s, 3H), 1.4-1.9 (m, 56H), 1.0 (m, 7H). 1 H NMR (CDCl 3 , δ): δ7.7 (d, 2H), 7.4 (d, 2H), 6.4 (s, 2H), 5.0 (s, 2H), 3.8 (s, 6H), 2.3 (s , 3H), 1.4-1.9 (m, 56H), 1.0 (m, 7H).
<< 실시예Example 3> 3> BenzylBenzyl -- DMPDMP 의 제조Manufacture
4-메틸-2, 6-디메톡시페놀 (2.00 g, 0.01 mol) 과 탄산 칼륨 (1.62 g, 0.01 mol)을 아세톤(15 ml)에 섞고, 벤질 브롬화물(benzyl bromide, Aldrich) (1.00 g, 0.01 mol)을 천천히 첨가하였다. 4-methyl-2, 6-dimethoxyphenol (2.00 g, 0.01 mol) and potassium carbonate (1.62 g, 0.01 mol) are mixed with acetone (15 ml) and benzyl bromide (Aldrich) (1.00 g, 0.01 mol) was added slowly.
상기 혼합물을 24시간 동안 환류시키면서 실온으로 냉각시키고, 증류수로 증류한 다음 클로로포름으로 추출하였다. The mixture was cooled to room temperature at reflux for 24 hours, distilled with distilled water and then extracted with chloroform.
추출된 유기층을 증류수로 세척하고 진공상태에서 농축하였다.The extracted organic layer was washed with distilled water and concentrated in vacuo.
수득된 산물은 flash column chromatography(hexane/ethyl acetate 10:90)로 정제하여 흰색 분말을 얻었다(1.23 g, 47%).The obtained product was purified by flash column chromatography (hexane / ethyl acetate 10:90) to obtain a white powder (1.23 g, 47%).
1H NMR (CDCl3, δ): δ7.5 (d, 2H), 7.3-7.2 (m, 3H), 6.4 (s, 2H), 5.0 (s, 2H), 3.8 (s, 6H), 2.3 (s, 3H). 1 H NMR (CDCl 3 , δ): δ 7.5 (d, 2H), 7.3-7.2 (m, 3H), 6.4 (s, 2H), 5.0 (s, 2H), 3.8 (s, 6H), 2.3 (s, 3 H).
<< 실시예Example 4> 4> PPMPPM -- POSSPOSS 및 And PPMPPM -- BenzylBenzyl 의 제조Manufacture
실시예 2에서 수득한 POSS-DMP (0.50 g, 0.43 mmol)와 파라포름알데하이드(paraformaldehyde, Aldrich) (0.38 g, 0.01 mol) 를 아세트산(acetic acid) (15 ml)에 섞고, 술폰산(sulfuric acid) (3 ml) 를 5 ℃에서 dropwise로 첨가하였다. POSS-DMP (0.50 g, 0.43 mmol) and paraformaldehyde (Aldrich) (0.38 g, 0.01 mol) obtained in Example 2 were mixed with acetic acid (15 ml), and sulfonic acid. (3 ml) was added dropwise at 5 ° C.
수득한 혼합물을 10분 동안 실온에서 저었고, 이 후 혼합물을 메탄올 (150 ml)에 부어서 흰색 침전물을 얻었다. The resulting mixture was stirred for 10 minutes at room temperature, after which the mixture was poured into methanol (150 ml) to give a white precipitate.
흰색 침전물을 여과하여 수집하고, 진공 하에서 건조시켰다(0.33 g, 66%). The white precipitate was collected by filtration and dried under vacuum (0.33 g, 66%).
Mn = 5700, Mw = 10,300, Mw/Mn = 1.80, polystyrene standard; eluent, CHCl3. M n = 5700, M w = 10,300, M w / M n = 1.80, polystyrene standard; eluent, CHCl 3 .
1H NMR (CDCl3, δ): δ7.7-7.4 (m, 4H), 5.0 (m, 2H), 3.5-4.1 (m, 8H), 2.2 (m, 3H), 1.4-1.9 (m, 56H), 1.0 (m, 7H). 1 H NMR (CDCl 3 , δ): δ 7.7-7.4 (m, 4H), 5.0 (m, 2H), 3.5-4.1 (m, 8H), 2.2 (m, 3H), 1.4-1.9 (m, 56H), 1.0 (m, 7H).
PPM-Benzyl은 PPM-POSS 와 동일한 과정으로 실시예 3에서 수득한 Benzyl-DMP로부터 제조하였다(0.42 g, 35%).PPM-Benzyl was prepared from Benzyl-DMP obtained in Example 3 in the same manner as PPM-POSS (0.42 g, 35%).
1H NMR (CDCl3, δ): δ7.3-6.9 (m, 5H), 5.0 (m, 2H), 3.5-4.1 (m, 8H), 2.3 (m, 3H). 1 H NMR (CDCl 3 , δ): δ 7.3-6.9 (m, 5H), 5.0 (m, 2H), 3.5-4.1 (m, 8H), 2.3 (m, 3H).
<< 실시예Example 5> 5> 1One H H NMRNMR
1H NMR 스펙트럼은 Bruker AVANCE400 400 MHz FT-NMR spectrometer 를 이용하여 얻었고, 그 결과를 도 1a 내지 도 1d에 나타내었다. 1 H NMR spectra were obtained using a
POSS-Cl 스펙트럼에서, POSS-OH의 OH 피크(6.1 ppm)가 완전히 사라졌고, POSS-Cl의 형성을 입증하는 7.7, 7.4 및 4.6 ppm 에서의 세 개의 피크는 benzylchloride moieties 의 protons으로부터 나온 것이다 (도 1a 및 도 1b참조). In the POSS-Cl spectrum, the OH peak (6.1 ppm) of POSS-OH disappeared completely, and three peaks at 7.7, 7.4 and 4.6 ppm demonstrating the formation of POSS-Cl are from the protons of benzylchloride moieties (FIG. 1A). And FIG. 1B).
POSS-DMP 스펙트럼에서, POSS-Cl의 CH2 피크는 5.0 ppm 아래쪽으로 이동하였고, 4-methyl-2,6-dimethoxyphenol units 로부터 기인한 2.3, 3.8 및 6.4 ppm 의 세 개의 피크가 나타났다(도 1c 참조). In the POSS-DMP spectrum, the CH 2 peak of POSS-Cl shifted below 5.0 ppm, with three peaks of 2.3, 3.8 and 6.4 ppm resulting from 4-methyl-2,6-dimethoxyphenol units (see FIG. 1C). ).
PPM-POSS 스펙트럼에서, POSS-DMP의 6.4 ppm 피크는 사라졌고, 반면 PPM-POSS 의 backbone에 결합된 메틸렌 그룹의 broad peaks 가 3.5 - 4.1 ppm에서 나타 났다(도 1d 참조). In the PPM-POSS spectrum, the 6.4 ppm peak of POSS-DMP disappeared, while broad peaks of methylene groups bound to the backbone of PPM-POSS were seen at 3.5-4.1 ppm (see FIG. 1D).
<< 실시예Example 6> 6> FTFT -- IRIR
Fourier transform infrared (FT-IR) 스펙트럼은 Bio-Rad FTS-6000 infrared spectrometer에서 기록하였다. Fourier transform infrared (FT-IR) spectra were recorded on a Bio-Rad FTS-6000 infrared spectrometer.
그 결과, 도 2는 FT-IR 스펙트럼으로 (a)가 PPM-Benzyl이고 (b)는 PPM-POSS이다. As a result, FIG. 2 shows FT-IR spectra in which (a) is PPM-Benzyl and (b) is PPM-POSS.
PPM-POSS 의 스펙트럼인 (b)에는 POSS moieties (Si-O-Si)와 PPM-POSS에서 이중결합의 특징적 피크가 각각 약 1100 및 1630 cm-1에서 나타났다. In (b), the spectrum of PPM-POSS, characteristic peaks of double bonds in POSS moieties (Si-O-Si) and PPM-POSS were found at about 1100 and 1630 cm −1 , respectively.
PPM-Benzyl의 스펙트럼인 (a)의 경우, POSS units가 존재한다는 것을 확인해 주는 POSS units 에서 기인한 broad Si-O-Si band 가 나타나지 않았다. In the case of the PPM-Benzyl spectrum (a), there was no broad Si-O-Si band attributable to the POSS units confirming the existence of POSS units.
<< 실시예Example 7> 7> ScanningScanning ElectronElectron MicroscopyMicroscopy
도 3은 scanning electron microscopy (SEM) (JEOL JSM-6700/LV)으로 얻은 PPM-Benzyl 및 PPM-POSS의 형태를 나타낸 사진이다. Figure 3 is a photograph showing the form of PPM-Benzyl and PPM-POSS obtained by scanning electron microscopy (SEM) (JEOL JSM-6700 / LV).
PPM-Benzyl의 경우 1-5 ㎛ size를 가진 비균질 PPM-Benzyl 나노복합재료가 서로 연결되어 있다(도 3a 참조). In the case of PPM-Benzyl, heterogeneous PPM-Benzyl nanocomposites having a size of 1-5 μm are connected to each other (see FIG. 3A).
PPM-POSS의 경우, 약 100 nm size를 가진 균질한 나노복합재료가 잘 형성되었다(도3b 참조). In the case of PPM-POSS, homogeneous nanocomposites with a size of about 100 nm were well formed (see FIG. 3b).
이러한 현상은 PPM-POSS에서 벌키 POSS 그룹 사이의 분자간 반발력 때문에 거대 응집체가 나타나지 않았다는 결과이다. This phenomenon is the result of the large aggregates did not appear in PPM-POSS due to the intermolecular repulsion between the bulky POSS groups.
반면, 벌키 POSS moieties가 없는 PPM-Benzyl은 PPM-POSS 보다 비균질한 거대 입자를 보이는데, 이는 PPM-Benzyl에서 phenyl segments 간의 방향족 (π-π) 상호작용에 의한 응집때문이다. On the other hand, PPM-Benzyl without bulky POSS moieties shows a larger heterogeneous particle than PPM-POSS due to the aggregation by aromatic (π-π) interactions between phenyl segments in PPM-Benzyl.
<< 실시예Example 8> 8> EnergyEnergy DispersiveDispersive SpectrumSpectrum
PPM-POSS에 POSS units가 존재하고 또한 균질하게 분산되어 있다는 것을 확인하기 위하여 energy dispersive spectrum (EDS, JEOL JSM-6700/LV) 를 분석하였다 The energy dispersive spectrum (EDS, JEOL JSM-6700 / LV) was analyzed to confirm that the POSS units are present and homogeneously dispersed in the PPM-POSS.
그 결과, 도 4a에 PPM-Benzyl의 EDS 를 나타내고 도 4b에 PPM-POSS의 EDS 를 표시하였다. PPM-POSS의 EDS 에 Si 원소의 피크가 나타난 것은 PPM-POSS 가 무기 다기능성 POSS pendant units와 혼성화되어 있다는 것을 나타낸다. As a result, EDS of PPM-Benzyl is shown in FIG. 4A and EDS of PPM-POSS is shown in FIG. 4B. The peak of Si element in the EDS of PPM-POSS indicates that PPM-POSS is hybridized with inorganic multifunctional POSS pendant units.
<< 실시예Example 9> 9> DifferentialDifferential scanningscanning calorimetrycalorimetry thermogramsthermograms
PPM-Benzyl 및 PPM-POSS의 DSC thermograms을 DSC2010(TA Instruments, Inc)을 이용하여 질소 하에서 heating rate of 10 ℃min- 1 의 조건으로 측정하였다. A PPM-Benzyl DSC thermograms and the PPM-POSS under nitrogen using a DSC2010 (TA Instruments, Inc) heating rate of 10 ℃ min - was measured under the condition of Fig.
그 결과를 도 5에 나타내었고, (a)는 PPM-Benzyl 이고 (b)는 PPM-POSS 이다. The results are shown in Figure 5, (a) is PPM-Benzyl and (b) is PPM-POSS.
PPM-Benzyl은 100 ℃ 에서 유리 전이 온도(glass transition temperature, Tg)를 보이지만, PPM-POSS는 Tg를 보이지 않는다. 이러한 결과는 벌키 POSS moieties가 PPM-POSS의 응집을 감소시킬 뿐 아니라 중합체 주쇄의 운동성을 저하시킨다는 것을 지지한다. PPM-Benzyl shows glass transition temperature (T g ) at 100 ° C., but PPM-POSS does not show T g . These results support that bulky POSS moieties not only reduce the aggregation of PPM-POSS but also reduce the mobility of the polymer backbone.
또한, DSC data 로부터 POSS units 가 어떠한 응집없이 PPM chains에 균질하게 분산되어 있다는 것을 확인하였다. In addition, the DSC data confirmed that the POSS units were homogeneously dispersed in the PPM chains without any aggregation.
<< 실시예Example 10> 10> TGATGA thermogramsthermograms
중합체의 열 행동 특성을 분석하기 위하여 thermogravimetric analysis (TGA) (TGA S-1000, Scinco)를 질소 대기하에서 측정하였다. Thermogravimetric analysis (TGA) (TGA S-1000, Scinco) was measured under nitrogen atmosphere to characterize the thermal behavior of the polymer.
그 결과를 도 6에 도시하였으며 (a)는 4-methyl-2,6-dimethoxyphenol이고, (b)는 PPM-Benzyl이며 (c)는 PPM-POSS이다. The results are shown in Figure 6 (a) is 4-methyl-2,6-dimethoxyphenol, (b) is PPM-Benzyl and (c) is PPM-POSS.
PPM-Benzyl의 열 안정성에 비하여 PPM-POSS의 열 안정성이 크게 증가된 것을 확인하였다. 특히, PPM-POSS 는 높은 온도에서 우수한 열 안정성을 나타내었다. 이러한 결과는 siliceous bulky POSS segments가 PPM-POSS 의 열 안정성을 현저하게 증가시켰음을 의미한다. It was confirmed that the thermal stability of PPM-POSS was significantly increased compared to that of PPM-Benzyl. In particular, PPM-POSS showed good thermal stability at high temperatures. These results indicate that siliceous bulky POSS segments significantly increased the thermal stability of PPM-POSS.
도 1a는 POSS-OH의 1H NMR 스펙트럼이고, 1A is a 1 H NMR spectrum of POSS-OH,
도 1 b는 POSS-Cl 의 1H NMR 스펙트럼이며, 1 b is a 1 H NMR spectrum of POSS-Cl,
도 1c는 POSS-DMP 의 1H NMR 스펙트럼이고, 1C is a 1 H NMR spectrum of POSS-DMP,
도 1d는 PPM-POSS의 1H NMR 스펙트럼이다. 1D is the 1 H NMR spectrum of PPM-POSS.
도 2는 FTIR 스펙트럼으로 (a)가 PPM-Benzyl이고 (b)는 PPM-POSS이다. Figure 2 is the FTIR spectrum (a) is PPM-Benzyl and (b) is PPM-POSS.
도 3a는 PPM-Benzyl의 SEM 사진이고, 3A is an SEM photograph of PPM-Benzyl,
도 3b는 PPM-POSS의 SEM 사진이다. 3b is an SEM photograph of PPM-POSS.
도 4a는 PPM-Benzyl의 EDS 사진이고, Figure 4a is an EDS picture of PPM-Benzyl,
도 4b는 PPM-POSS의 EDS 사진이다. 4B is an EDS picture of PPM-POSS.
도 5는 DSC thermograms 으로 (a)는 PPM-Benzyl 이고 (b)는 PPM-POSS 이다. Figure 5 is DSC thermograms (a) is PPM-Benzyl and (b) is PPM-POSS.
도 6은 TGA thermograms으로 (a)는 4-methyl-2,6-dimethoxyphenol이고, (b)는 PPM-Benzyl이며, (c)는 PPM-POSS이다. Figure 6 is TGA thermograms (a) is 4-methyl-2,6-dimethoxyphenol, (b) is PPM-Benzyl, (c) is PPM-POSS.
도 7a는 PPM-POSS의 합성 모식도이고, 7A is a schematic diagram illustrating the synthesis of PPM-POSS.
도 7b는 PPM-Benzyl의 합성 모식도이다.7B is a synthetic schematic diagram of PPM-Benzyl.
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| Advanced Functional Materials 2003, 13, No.1, 25-29 |
| Macromolecules Vol.36, No.24, 2003, 9122-9127 |
| Macromolecules Vol.38, No.22, 2005, 9117-9123 |
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