TWI651327B - 三嗪系前驅物、製備三嗪系前驅物的方法及三嗪系前驅物的應用 - Google Patents
三嗪系前驅物、製備三嗪系前驅物的方法及三嗪系前驅物的應用 Download PDFInfo
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- TWI651327B TWI651327B TW106127601A TW106127601A TWI651327B TW I651327 B TWI651327 B TW I651327B TW 106127601 A TW106127601 A TW 106127601A TW 106127601 A TW106127601 A TW 106127601A TW I651327 B TWI651327 B TW I651327B
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- Prior art keywords
- triazine
- precursor
- formula
- chloro
- amino
- Prior art date
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002243 precursor Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 36
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- 239000002904 solvent Substances 0.000 claims description 16
- 230000000269 nucleophilic effect Effects 0.000 claims description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 11
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical group C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 claims description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- 231100000475 skin irritation Toxicity 0.000 description 3
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- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- KCZIUKYAJJEIQG-UHFFFAOYSA-N 1,3,5-triazin-2-amine Chemical compound NC1=NC=NC=N1 KCZIUKYAJJEIQG-UHFFFAOYSA-N 0.000 description 2
- HPJKLCJJNFVOEM-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrochloride Chemical compound Cl.NC1=NC(N)=NC(N)=N1 HPJKLCJJNFVOEM-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
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- GSHZTSQQBHBEET-UHFFFAOYSA-N 2-chloro-4,6-dioctoxy-1,3,5-triazine Chemical compound CCCCCCCCOC1=NC(Cl)=NC(OCCCCCCCC)=N1 GSHZTSQQBHBEET-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 239000013553 cell monolayer Substances 0.000 description 1
- 238000003570 cell viability assay Methods 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WOOWBQQQJXZGIE-UHFFFAOYSA-N n-ethyl-n-propan-2-ylpropan-2-amine Chemical compound CCN(C(C)C)C(C)C.CCN(C(C)C)C(C)C WOOWBQQQJXZGIE-UHFFFAOYSA-N 0.000 description 1
- HYBAGXGIPGXQAN-UHFFFAOYSA-N n-hexyl-1,3,5-triazin-2-amine Chemical compound CCCCCCNC1=NC=NC=N1 HYBAGXGIPGXQAN-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical group CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- 238000011587 new zealand white rabbit Methods 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000005188 oxoalkyl group Chemical group 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
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- 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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
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- C07—ORGANIC CHEMISTRY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N5/00—Radiation therapy
- A61N5/06—Radiation therapy using light
- A61N5/0613—Apparatus adapted for a specific treatment
- A61N5/0625—Warming the body, e.g. hyperthermia treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
-
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
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- C07D251/70—Other substituted melamines
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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- A61N5/00—Radiation therapy
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- A61N2005/0659—Radiation therapy using light characterised by the wavelength of light used infrared
- A61N2005/066—Radiation therapy using light characterised by the wavelength of light used infrared far infrared
Abstract
一種三嗪系前驅物,由式(I)所示:
式(I) X及Y各自選自於-NR
1R
2、-OR
3或-SR
4;R
1選自於氫、未經取代的C
1至C
22的直鏈烷基,或未經取代的C
1至C
22的支鏈烷基;R
2、R
3及R
4各自選自於未經取代的C
1至C
22的直鏈烷基、未經取代的C
1至C
22的支鏈烷基;且Z表示-NH-R
5-Si(OR
6)
3,R
5表示C
2至C
4的伸烷基,且每一個R
6各自表示C
1至C
2的烷基。
Description
本發明是有關於一種三嗪系前驅物、製備三嗪系前驅物的方法及三嗪系前驅物的應用,特別是指一種含有矽氧烷基團的三嗪系前驅物、一種製備該三嗪系前驅物的方法,及一種該三嗪系前驅物的應用。
中國大陸專利公開第104349848號揭示一種表面處理劑,且該表面處理劑包含式(1)所示的三嗪基矽氧烷化合物及式(2)所示的三嗪基矽氧烷化合物。
式(1)
式(2)
雖該表面處理劑具有較佳的密著性且因可應用至許多且不同的材料的表面上而具有多樣性。然而,當該表面處理劑用來與四乙氧基矽烷反應而形成二氧化矽粒子時,由於該表面處理劑含有式(2)所示的三嗪基矽氧烷化合物,使得所獲得的二氧化矽粒子的粒徑分布廣而不集中,甚至可能存在有呈
結構的串聯狀型態的二氧化矽材與網狀型態的二氧化矽材,使得應用至一些產品(例如化妝品或醫療用品等)中時不利於分散在該等產品中。在該串聯狀型態的二氧化矽材中,該X為由該四乙氧基矽烷所形成的二氧化矽,而Y為由式(2)所示的三嗪基矽氧烷化合物所形成並透過B及C與X連接。
Adv. Mater. 2012, 24, 2409–2412揭示一種用於使織物的表面具有疏水性的表面處理劑,包含聚二甲基矽氧烷(polydimethylsiloxane,簡稱PDMS)、具有氟烷基矽烷基團[(fluorinated alkyl)silanyl group]的二氧化矽奈米粒子,及(氟烷基)矽烷(fluorinated alkyl silane)。該具有氟烷基矽烷基團的二氧化矽奈米粒子是由四乙氧基矽烷(tetraethylorthosilicate)與氟烷基矽烷在鹼性條件下進行共水解(co-hydrolysis)及共縮聚合(co-condensation)反應所形成。該氟烷基矽烷為CF
3-(CF
2)
5-(CH
2)
2-Si(OC
2H
5)
3。然而,該氟烷基矽烷易產生自聚現象,而存在有儲存安定性不佳的問題,且使得該具有氟烷基矽烷基團的二氧化矽奈米粒子的產率不佳。再者,由於該具有氟烷基矽烷基團的二氧化矽奈米粒子含有氟,對人體具有傷害性,而不利於應用至醫療用品、化妝品或保養品中。
因此,本發明之第一目的,即在提供一種具有儲存安定性的三嗪系前驅物。
於是,本發明三嗪系前驅物,由式(I)所示:
式(I) X及Y各自選自於-NR
1R
2、-OR
3或-SR
4; R
1選自於氫、未經取代的C
1至C
22的直鏈烷基,或未經取代的C
1至C
22的支鏈烷基; R
2、R
3及R
4各自選自於未經取代的C
1至C
22的直鏈烷基,或未經取代的C
1至C
22的支鏈烷基;且 Z表示-NH-R
5-Si(OR
6)
3,R
5表示C
2至C
4的伸烷基,且每一個R
6各自表示C
1至C
2的烷基。
本發明之第二目的,即在提供一種製備上述三嗪系前驅物的方法。
本發明製備上述三嗪系前驅物的方法,包含以下步驟:步驟(a),使2,4,6-三氯-1,3,5-三嗪與一個表示為H-X的第一親核化合物在一個第一溶劑的存在下且在一個第一溫度範圍為0℃至25℃下進行一個第一置換反應,形成一個式(i)所示的第一中間物,
式(i);步驟(b),使該式(i)所示的第一中間物與一個表示為H-Y的第二親核化合物在一個第二溶劑的存在下且在一個第二溫度範圍為15℃至40℃下進行一個第二置換反應,形成一個式(ii)所示的第二中間物,
式(ii);步驟(c),使該式(ii)所示的第二中間物與一個表示為H-Z的第三親核化合物在一個第三溶劑的存在下且在一個第三溫度範圍為35℃至75℃下進行一個第三置換反應,形成該三嗪系前驅物。
本發明之第三目的,即在提供一種製備二氧化矽微米複合粒子的方法。
本發明製備二氧化矽微米複合粒子的方法,包含:使上述的三嗪系前驅物與四烷基矽酸酯進行水解及縮聚合反應。
本發明之第四目的,即在提供一種具有放射紅外線、對細胞無毒害且對皮膚無刺激的效果的二氧化矽微米複合粒子。
本發明二氧化矽微米複合粒子,係由上述製備二氧化矽微米複合粒子的方法所形成。
本發明之功效在於:透過
的設計,使得該三嗪系前驅物不易產生自聚現象,而具有安定性,且透過使用三嗪系前驅物,使得該二氧化矽微米複合粒子具有對細胞無毒害且對皮膚無刺激的效果。
以下將就本發明內容進行詳細說明。
<三嗪系前驅物>
在本發明三嗪系前驅物中,透過
產生的立體障礙的設計,增加該三嗪系前驅物中Z的穩定性,而使該三嗪系前驅物不易產生自聚現象,因而具有安定性,且透過R
1、R
2、R
3及R
4的設計,使得該三嗪系前驅物用來成為二氧化矽微米複合粒子中的一部分時,可使得該二氧化矽微米複合粒子不具有細胞毒性及皮膚刺激性。
為使該三嗪系前驅物更不易自聚而具有更佳的儲存安定性,較佳地,R
1選自於氫、未經取代的C
2至C
16的直鏈烷基,或未經取代的C
2至C
16的支鏈烷基;R
2、R
3及R
4各自選自於未經取代的C
2至C
16的直鏈烷基,或未經取代的C
2至C
16的支鏈烷基。
<製備三嗪系前驅物的方法>
該第一親核化合物選自於HNR
1R
2、HOR
3,或HSR
4,其中,R
1選自於氫、未經取代的C
1至C
22的直鏈烷基,或未經取代的C
1至C
22的支鏈烷基;R
2、R
3及R
4各自選自於未經取代的C
1至C
22的直鏈烷基,或未經取代的C
1至C
22的支鏈烷基。
該第一溶劑可單獨一種使用或混合多種使用,且該第一溶劑例如但不限於己烷(n-hexane)、環己烷(cyclohexane)、二氯甲烷(dichloromethane)、1,2-二氯乙烷(1,2-dichloroethane)、氯仿(chloroform)、丙酮(acetone)、乙酸乙酯(ethyl acetate)、四氫呋喃(tetrahydrofuran)、乙醚 (ether)、甲醇(methanol)、乙醇(ethanol),或異丙醇(isopropanol)等。
在該第一置換反應中,是在第一鹼性試劑的存在下進行。該第一鹼性試劑可單獨一種使用或混合多種使用,且該第一鹼性試劑例如但不限於氫化鈉(sodium hydride)、碳酸氫鈉(sodium bicarbonate)、碳酸鈉(sodium carbonate)、氫氧化鈉(sodium hydroxide)、碳酸鉀(potassium carbonate)、氫氧化鉀(potassium hydroxide)、三乙基胺(triethylamine)、吡啶(pyridine)、N,N-二異丙基乙基胺(N,N-diisopropylethylamine)、4-二甲胺基吡啶(4-dimethylaminopyridine)、3-甲基吡啶(3-picoline),或2,4,6-三甲基吡啶(2,4,6-collidine)等。
該第二親核化合物與該第一親核化合物可為相同或不同。該第二溶劑與該第一溶劑可為相同或不同。在該第二置換反應中,是在第二鹼性試劑的存在下進行。該第二鹼性試劑與該第一鹼性試劑可為相同或不同。
該第三親核化合物選自於H
2N-R
5-Si(OR
6)
3,其中,R
5表示C
2至C
4的伸烷基,且每一個R
6各自表示C
1至C
2的烷基。該第三溶劑與該第一溶劑可為相同或不同。在該第三置換反應,是在第三鹼性試劑的存在下進行。該第三鹼性試劑與該第一鹼性試劑可為相同或不同。
<製備二氧化矽微米複合粒子的方法及二氧化矽微米複合粒子>
該四烷基矽酸酯例如但不限於四乙氧基矽烷。該水解及縮聚合反應的操作溫度範圍為25℃至60℃。該水解及縮聚合反應的操作時間範圍為24小時至72小時。在該水解及縮聚合反應的過程中,該四烷基矽酸酯會形成二氧化矽物質,而該三嗪前驅物中的-Si(OR
6)
3會轉變成-Si(O
-)
3,並透過-Si(O
-)
3而鍵結至該二氧化矽物質上,使得該二氧化矽微米複合粒子具有複數個表示為
的基團。再者,由於該三嗪系前驅物不易產生自聚現象,使得所獲得的二氧化矽微米複合粒子的粒徑均一、粒徑分布集中,且純度高。
由於該二氧化矽微米複合粒子具有放射紅外線功能,特別是遠紅外線,而可應用於醫療用品、保健用品或生活用品中。該醫療用品例如但不限於醫療級照射燈。該保健用品例如但不限於護膝用具或熱敷墊等。該生活用品例如但不限於化妝品或織物等。
本發明將就以下實施例來作進一步說明,但應瞭解的是,該實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。
實施例1 (C
8H
17O)((C
8H
17)
2N)-Tz-Si(OEt)
3
步驟a:將容置有30mL的乾燥二氯甲烷的100mL的單口反應瓶置於0°C的冰水浴中。將1.84克(10mmol)的三聚氰氯加入至該反應瓶中,並使該三聚氰氯溶解。然後,將2.41克(10 mmol)的二辛胺緩慢滴入該反應瓶中。待反應10分鐘後,緩慢加入1.01克(10 mmol)的三乙基胺。待反應20分鐘後,使用30mL的0.5M的氫氧化鈉水溶液進行兩次萃取處理,收集有機層。將50 mL的清水加入有機層中進行萃取處理,再次收集有機層。接著,將無水硫酸鎂加入有機層中除水,然後過濾,可得一濾液。使用減壓濃縮機將該濾液中的二氯甲烷移除,得到3.69克(9.5 mmol)的2,4-二氯-6-二辛基胺基-1,3,5-三嗪。
步驟b:將含有20mL乾燥二氯甲烷及3.88克(10 mmol)2,4-二氯-6-二辛基胺基-1,3,5-三嗪的50mL的單口反應瓶置於0°C的冰水浴中。將0.4克(10mmol)的60%氫化鈉與1.3克(10mmol)的1-辛醇混合並反應2分鐘,形成一混合溶液,接著將該混合溶液緩慢加入至該反應瓶中,反應10分鐘後,移置室溫環境下反應12小時。接著,加入30mL的0.5M氫氧化鈉水溶液進行兩次萃取處理,收集有機層。將50 mL的清水加入有機層中進行萃取處理,再次收集有機層。然後,將無水硫酸鎂加入有機層中除水過濾,可得一濾液。使用減壓濃縮機將該濾液中的二氯甲烷移除,得到4.54克(9.4mmol)的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪。
步驟c:將4.83克(10mmol)的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪溶於50ml的四氫呋喃中,加入2.44克(11mmol)的3-(三乙氧基矽烷基)丙基胺及2.6克(20mmol)的N,N-二異丙基乙基胺。將溫度升至65℃進行48小時的反應。然後,使用減壓濃縮機將四氫呋喃移除。加入30mL的二氯甲烷及30mL的0.5M 氫氧化鈉水溶液進行兩次萃取處理,並收集有機層。接著,將50mL的清水加入有機層中進行萃取處理,再次收集有機層。將無水硫酸鎂加入有機層中進行除水及過濾,可得一濾液。使用減壓濃縮機將該濾液中的二氯甲烷移除,可得一濃縮物。將該濃縮物利用矽膠管柱(管徑為2.6cm且長度為15cm)進行純化處理,且該純化處理是利用己烷與四氫呋喃作為沖提液,而該己烷與該四氫呋喃的體積比為5:1。得到4.48克(6.7mmol)的2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪,且總產率為59.8%。
該2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.64 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.86 (t, J = 6.3 Hz, 9H, 3×CH
3), 1.20 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.26 (s, broad, 30H, 15×CH
2), 1.55 (s, broad, 4H, 2×CH
2-CN), 1.60~1.78 (m, 4H, CH
2-CSi+CH
2-CO), 3.33~3.51 (m, 6H, 3×CH
2-N), 3.80 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.21 (s, broad, 2H, CH
2-O), 5.05 (t, J = 5.7 Hz, 1H, N-H)。MS: m/z 668.51 (M+H)
+。化學結構為
。
實施例2 (C
2H
5O)((C
8H
17)
2N)-Tz-Si(OEt)
3
該實施例2與該實施例1不同處在於:將實施例1的步驟b中的1-辛醇置換成乙醇,而於步驟b完成後形成化合物為2-氯-4-二辛基胺基-6-乙基氧基-1,3,5-三嗪。且將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-二辛基胺基-6-乙基氧基-1,3,5-三嗪,而於步驟c完成後形成化合物為2-二辛基胺基-4-乙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例2的總產率為47.0%。
該2-二辛基胺基-4-乙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3,δ(ppm): 0.62 (t, J = 8.1 Hz, 2H, CH
2-Si), 0.86 (t, J = 6.3 Hz, 6H, 2×CH
3), 1.20 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.27(s, broad, 23H, 10×CH
2+CH
3), 1.55 (s, broad, 4H, 2×CH
2-CN), 1.60~1.78 (m, 2H, CH
2-CSi), 3.33~3.51 (m, 6H, 3×CH
2-N), 3.80 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.25 (s, broad, 2H, CH
2-O), 5.05 (t, J = 5.7 Hz, 1H, N-H)。MS: m/z 584.79(M+H)
+。化學結構為
。
實施例3 ((CH
3)
2CHO)((C
6H
13)
2N)-Tz-Si(OEt)
3
該實施例3與該實施例1不同處在於:將實施例1的步驟a中的二辛胺置換成二己胺,而於步驟a完成後形成化合物為2,4-二氯-6-二己基胺基-1,3,5-三嗪。將實施例1的步驟b中的1-辛醇置換成異丙醇,而於步驟b完成後形成化合物為2-氯-4-二己基胺基-6-異丙基氧基-1,3,5-三嗪。且將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-二己基胺基-6-異丙基氧基-1,3,5-三嗪,而於步驟c完成後形成化合物為2-二己基胺基-4-異丙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例3的總產率為38.3%。
該2-二己基胺基-4-異丙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.65 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.88 (t, J = 6.0 Hz, 6H, 2×CH
3), 1.21 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.31 (s, broad, 18H, 9×CH
2), 1.56 (s, broad, 4H, 2×CH
2-CN), 1.60~1.75 (m, 2H, CH
2-CSi), 3.33~3.51 (m, 6H, 3×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 5.19 (s, broad, 1H, CH-O), 5.01 (t, J = 4.5 Hz, 1H, N-H)。MS: m/z 542.83 (M+H)
+。化學結構為
。
實施例4 (C
2H
5O)((2-(C
2H
5)(C
6H
12))
2N)-Tz-Si(OEt)
3
該實施例4與該實施例1不同處在於:將實施例1的步驟a中的二辛胺置換成二(2-乙基己基)胺,而於步驟a完成後形成化合物為2,4-二氯-6-二(2-乙基己基)胺基-1,3,5-三嗪。將實施例1步驟b中的1-辛醇置換成乙醇,而於步驟b完成後形成化合物為2-氯-4-二(2-乙基己基)胺基-6-乙基氧基-1,3,5-三嗪。且將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-二(2-乙基己基)胺基-6-乙基氧基-1,3,5-三嗪,而於步驟c完成後形成化合物為2-二(2-乙基己基)胺基-4-乙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例4的總產率為41.0%。
該2-二(2-乙基己基)胺基-4-乙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.66 (t, J = 8.1 Hz, 2H, CH
2-Si), 0.86 (t, J = 6.9 Hz, 12H, 4×CH
3), 1.22 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.26 (s, broad, 16H, 8×CH
2), 1.34 (t, J = 7.5 Hz, 3H, 1×CH
3), 1.64~1.80 (m, 4H, CH
2-CSi+2×CH), 3.37~3.44 (m, 6H, 3×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.31 (t, J = 6.6 Hz, 2H, CH
2-O), 4.95 (s, broad, 1H, H-N)。MS: m/z 584.92 (M+H)
+。化學結構為
。
實施例5 (C
8H
17NH)((C
8H
17)
2N)-Tz-Si(OEt)
3
該實施例5與該實施例1不同處在於:將實施例1的步驟b中的1-辛醇置換成1-辛胺,而於步驟b完成後形成化合物為2-氯-4-辛基胺基-6-二辛基胺基-1,3,5-三嗪。將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-辛基胺基-6-二辛基胺基-1,3,5-三嗪,於步驟c完成後形成化合物為2-辛基胺基-4-二辛基胺基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例5的總產率為49.3%。
該2-辛基胺基-4-二辛基胺基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.68 (t, J = 8.7 Hz, 2H, CH
2-Si), 0.88 (t, J = 6.3 Hz, 9H, 3×CH
3), 1.21 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.26 (s, broad, 30H, 15×CH
2), 1.51~1.80 (m, 8H, CH
2-CSi+3×CH
2-CN), 3.33~3.51 (m, 8H, 4×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 5.01 (s, broad, 1H, H-N), 5.35 (t, J = 4.8 Hz, 1H, H-N)。MS:m/z 667.35 (M+H)
+。化學結構為
實施例6 (C
8H
17S)((C
8H
17)
2N)-Tz-Si(OEt)
3
該實施例6與該實施例1不同處在於:將實施例1步驟b中的1-辛醇置換成1-辛硫醇,而於步驟b完成後形成化合物為2-氯-4-二辛基胺基-6-辛基硫基-1,3,5-三嗪。將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-二辛基胺基-6-辛基硫基-1,3,5-三嗪,於步驟c完成後形成化合物為2-二辛基胺基-4-辛基硫基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例6的總產率為53.3%。
該2-二辛基胺基-4-辛基硫基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.65 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.88 (t, J = 6.3 Hz, 9H, 3×CH
3), 1.22 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.27 (s, broad, 30H, 15×CH
2), 1.42 (s, broad, 4H, 2×CH
2-CN), 1.60~1.78 (m, 4H, CH
2-CSi+CH
2-CO), 3.01(t, J = 7.2 Hz, 2H, CH
2-S), 3.36~3.51 (m, 6H, 3×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 5.01 (t, J = 5.7 Hz, 1H, H-N)。MS:m/z 683.78 (M)
+。化學結構為
。
實施例7 (C
8H
17S)(C
8H
17NH)-Tz-Si(OEt)
3
該實施例7與該實施例1不同處在於:將實施例1步驟a中的二辛胺置換成1-辛胺,而於步驟a完成後形成化合物為2,4-二氯-6-辛基胺基-1,3,5-三嗪。將實施例1步驟b中的1-辛醇置換成1-辛硫醇,而於步驟b完成後形成化合物為2-氯-4-辛基胺基-6-辛基硫基-1,3,5-三嗪。將步驟c中2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-辛基胺基-6-辛基硫基-1,3,5-三嗪,於步驟c完成後形成化合物為2-辛基胺基-4-辛基硫基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例7的總產率為43.1%。
該2-辛基胺基-4-辛基硫基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.66 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.88 (t, J = 6.3 Hz, 6H, 2×CH
3), 1.23 (t, J = 7.2 Hz, 9H, 3×CH
3-COSi), 1.26 (s, broad, 20H, 10×CH
2), 1.48~1.78 (m, 6H, CH
2-CSi+CH
2-CN+CH
2-CS), 3.03(t, J = 7.2 Hz, 2H, CH
2-S), 3.34~3.51 (m, 4H, 2×CH
2-N), 3.82 (q, J = 6.6 Hz, 6H, 3×CH
2-OSi), 5.03 (s, broad, 1H, H-N), 5.35 (t, J = 5.1, 1H, H-N)。MS:m/z 571.83 (M)
+。化學結構為
。
實施例8 (C
8H
17O)(C
8H
17NH)-Tz-Si(OEt)
3
該實施例8與該實施例1不同處在於:將實施例1的步驟a中的二辛胺置換成1-辛胺,而於步驟a完成後形成化合物為2,4-二氯-6-辛基胺基-1,3,5-三嗪。將步驟b中的2,4-二氯-6-二辛基胺基-1,3,5-三嗪置換成2,4-二氯-6-辛基胺基-1,3,5-三嗪,於步驟b完成後形成2-氯-4-辛基胺基-6-辛基氧基-1,3,5-三嗪。將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-辛基胺基-6-辛基氧基-1,3,5-三嗪,而於步驟c完成後形成2-辛基胺基-4-辛基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例8的總產率為35.2%。
該2-辛基胺基-4-辛基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm):0.69 (t, J = 7.2 Hz, 2H, CH
2-Si), 0.88 (t, J = 6.6 Hz, 6H, 2×CH
3), 1.22 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.26 (s, broad, 20H, 10×CH
2), 1.49~1.8. (m, 6H, CH
2-CSi+2×CH
2-CO), 3.22~3.51 (m, 4H, 2×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.16~4.39 (m, 2H, CH
2-O), 5.01 (s, broad, 1H, H-N), 5.35 (t, J = 5.1, 1H, H-N)。MS:m/z 556.54 (M+H)
+。化學結構為
。
實施例9 (C
16H
33O)((C
4H
9)
2N)-Tz-Si(OEt)
3
該實施例9與該實施例1不同處在於:將實施例1步驟a中的二辛胺置換成二丁胺,而於步驟a完成後形成化合物為2,4-二氯-6-二丁基胺基-1,3,5-三嗪。將實施例1步驟b中的1-辛醇置換成1-十六醇,而於步驟b完成後形成化合物為2-氯-4-二丁基胺基-6-十六基氧基-1,3,5-三嗪。將步驟c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置換成2-氯-4-二丁基胺基-6-十六基氧基-1,3,5-三嗪,於步驟c完成後形成化合物為2-二丁基胺基-4-十六基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪。該實施例9的總產率為38.3%。
該2-二丁基胺基-4-十六基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.64 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.88 (t, J = 6.9 Hz, 9H, 3×CH
3), 1.22 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.31 (s, broad, 30H, 15×CH
2), 1.51~1.73 (m, 8H, 2×CH
2-CN)+CH
2-CSi+CH
2-CO), 3.33~3.58 (m, 6H, 3×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.21 (s, broad, 2H, CH
2-O), 5.7 (t, J = 5.1 Hz, 1H, H-N)。MS:m/z 568.71 (M+H)
+。化學結構為
。
實施例10 Bis-((C
4H
9)
2N)-Tz-Si(OEt)
3
步驟a:將容置有50mL的乾燥二氯甲烷的100mL的單口反應瓶置於0°C的冰水浴中。將1.84克(10mmol)三聚氰氯加入至該反應瓶中,並使該三聚氰氯溶解。然後,將2.81克(22mmol)的二丁胺緩慢滴入該反應瓶中。待反應20分鐘後,緩慢加入2.53克(25mmol)的三乙基胺,並持續反應20分鐘。
步驟b:然後,移置室溫環境(約 27度)下再反應12小時。接著,使用60mL的0.5M的氫氧化鈉水溶液進行兩次萃取處理,收集有機層。將50mL的清水加入有機層中進行萃取處理,再次收集有機層。接著,將無水硫酸鎂加入有機層中進行除水及過濾,可得一濾液。使用減壓濃縮機將該濾液中的二氯甲烷移除,得到3.37克(9.2mmol)的2-氯-4,6-雙(二丁基胺基)-1,3,5-三嗪。
步驟c:將3.67克(10mmol)的2-氯-4,6-雙(二丁基胺基)-1,3,5-三嗪溶於50ml四氫呋喃中,接著,加入2.44克(11mmol)的3-(三乙氧基矽烷基)丙基胺及2.6克(20mmol)的N,N-二異丙基乙基胺。將溫度升至50℃進行24小時的反應。然後,使用減壓濃縮機將四氫呋喃移除。加入30mL的二氯甲烷並使用30mL的0.5M氫氧化鈉水溶液進行兩次的萃取處理,並收集有機層。接著,將50mL的清水加入有機層中進行萃取處理,再次收集有機層。然後,將無水硫酸鎂加入有機層中進行除水及過濾,可得一濾液。使用減壓濃縮機將該濾液中的二氯甲烷移除,可得一濃縮物。將該濃縮物利用矽膠管柱(管徑為2.6cm且長度為15cm)進行純化處理,且該純化處理是利用己烷與四氫呋喃作為沖提液,而該己烷與該四氫呋喃的體積比為5:1,得到1.99克(3.6 mmol)的2,4-雙(二丁基胺基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪,且總產率為33.1%。
該2,4-雙(二丁基胺基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.67 (t, J = 6.3 Hz, 2H, CH
2-Si), 0.92 (t, J = 7.2 Hz, 12H, 4×CH
3), 1.21 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.30 (q, J = 7.5 Hz, 8H, 4×CH
2-CN), 1.60~1.71 (m, 10H, CH
2-CSi+4×CH
2-CN), 3.30 (q, J = 6.6 Hz, 2H, CH
2-N), 3.43 (t, J = 7.8 Hz, 8H, 4×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.73 (t, J = 6.0 Hz, 1H, H-N)。MS: m/z 555.79 (M+H)
+。化學結構為
。
實施例11 Bis-(C
8H
17S)-Tz-Si(OEt)
3
該實施例11與該實施例10不同處在於:將實施例10的步驟a中的二丁胺置換成1-辛硫醇、三乙基胺換成N,N-二異丙基乙基胺,且於步驟b完成後形成化合物為2-氯-4,6-二(辛基硫基)-1,3,5-三嗪。將步驟b中的2-氯-4,6-雙(二丁基胺基)-1,3,5-三嗪置換成2-氯-4,6-二(辛基硫基)-1,3,5-三嗪,而於步驟c完成後形成化合物為2,4-二(辛基硫基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪,該實施例11的總產率為58.3%。
該2,4-二(辛基硫基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm): 0.65 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.87 (t, J = 7.2 Hz, 6H, 2×CH
3), 1.22 (t, J = 7.2 Hz, 9H, 3×CH
3-COSi), 1.271 (s, broad, 16H, 8×CH
2), 1.34~1.49 (m, 4H, 2×CH
2), 1.67~1.79 (m, 6H, CH
2-CSi+2×CH
2-CS), 3.05 (t, J = 6.6 Hz, 4H, 2×CH
2-S), 3.41 (q, J = 6.3 Hz, 2H, CH
2-N), 3.82 (q, J = 6.6 Hz, 6H, 3×CH
2-OSi), 5.46 (s, broad, 1H, H-N)。MS: m/z 589.90 (M+H)
+。化學結構為
。
實施例12 Bis-(C
8H
17O)-Tz-Si(OEt)
3
該實施例12與該實施例10不同處在於:將實施例10步驟a中的二丁胺置換成1-辛醇、三乙基胺換成氫化鈉,且於步驟b完成後形成化合物為2-氯-4,6-二(辛基氧基)-1,3,5-三嗪。將步驟c中的2-氯-4,6-雙(二丁基胺基)-1,3,5-三嗪置換成2-氯-4,6-二(辛基氧基)-1,3,5-三嗪,於步驟c完成後形成2,4-二(辛基氧基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪,該實施例12的總產率為68.4%。
該2,4-二(辛基氧基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3, 298K),δ(ppm): 0.66 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.88 (t, J = 8.4 Hz, 6H, 2×CH
3), 1.23 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.28 (s, broad, 16H, 8×CH
2), 1.34~1.49 (m, 4H, 2×CH
2), 1.67~1.79 (m, 6H, CH
2-CSi+2×CH
2-CO), 3.44 (q, J = 6.3 Hz, 2H, CH
2-N), 3.82 (q, J = 6.6 Hz, 6H, 3×CH
2-OSi), 4.3(t, J =8.1 Hz, 4H, 2×CH
2-O), 5.42 (t, J = 5.1, 1H, H-N)。MS: m/z 557.83 (M+H)
+。化學結構為
。
實施例13 Bis-(C
8H
17NH)-Tz-Si(OEt)
3
該實施例13與該實施例10不同處在於:將實施例10步驟a中的二丁胺置換成1-辛胺,而於步驟a完成後形成化合物為2-氯-4,6-二(辛基胺基)-1,3,5-三嗪化合物。將步驟b中的2-氯-4,6-雙(二丁基胺基)-1,3,5-三嗪置換成2-氯-4,6-二(辛基胺基)-1,3,5-三嗪,於步驟b完成後形成化合物為2,4-二(辛基胺基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪,該實施例13的總產率為52.3%。
該2,4-二(辛基胺基)-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪的光譜分析:
1H NMR (300 MHz, CDCl
3),δ(ppm):0.66 (t, J = 8.4 Hz, 2H, CH
2-Si), 0.87 (t, J = 6.3 Hz, 6H, 2×CH
3), 1.21 (t, J = 6.9 Hz, 9H, 3×CH
3-COSi), 1.28 (s, broad, 20H, 10×CH
2), 1.41~1.79 (m, 6H, CH
2-CSi+2×CH
2-CN), 3.32 (s, broad, 6H, 3×CH
2-N), 3.81 (q, J = 6.9 Hz, 6H, 3×CH
2-OSi), 4.84 (s, broad, 3H, 3×H-N)。MS:m/z 555.44 (M+H)
+。化學結構為
。
應用例1
將6.68克(10mmol)的實施例1的2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪、20.8克(100mmol)的四乙氧基矽烷及30mL的乙醇均勻攪拌3分鐘,然後,緩慢加入22mL的35%的氨水水溶液,並反應24小時。待反應24小時後,進行過濾處理,獲得一濾餅,接著,以熱水清洗該濾餅兩次並進行乾燥處理,得到6.5克的包含複數個二氧化矽微米複合粒子的產物,且產率為58.6%。
應用例2
該應用例2與該應用例1不同處在於:將2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪置換成實施例2的2-二辛基胺基-4-乙基氧基-6-(3-三乙氧基矽烷基丙基)胺基-1,3,5-三嗪,而形成6.3克的包含複數個二氧化矽微米複合粒子的產物,且產率為57.4%。
比較應用例1
將20.8克(100mmol)的四乙氧基矽烷及30mL的乙醇均勻攪拌3分鐘,然後,緩慢加入22mL的35%的氨水水溶液,並反應24小時。待反應後,進行過濾處理,獲得一濾餅,接著,以熱水清洗該濾餅兩次並進行乾燥處理,得到5.1克的包含複數個二氧化矽粒子的產物,且產率為85%。
評價項目
粒徑(單位:μm)量測:將應用例1的產物、應用例2的產物及比較應用例1的產物分散於乙醇中,並使用粒徑及界面電位分析儀(particle size and zeta potential analyzer;廠牌:Otsuka Electronics;型號:NanoPlus)進行量測。
遠紅外線放射率(單位:%):將應用例1的產物、應用例2的產物及比較應用例1的產物製備成長約13mm、寬約13mm且厚度小於2mm的片狀檢測樣品。使用傅里葉變換紅外光光譜儀(廠牌:Bruker Optics;型號:VERTEX 70)對該等檢測樣品進行量測。該量測條件:量測溫度為40℃;環境溫度為25±3℃且相對濕度為60±10%;量測波長範圍4μm至14μm。
皮膚刺激性測試:依據ASTM F719-81及ISO 10993-10的規範。先剃除紐西蘭白兔背部毛髮,並檢查背部皮表是否完整,若背部皮表有刮痕或皮膚病,則不予使用。為方便描述測試過程,以應用例1的產物進行說明,而應用例2的產物及比較應用例1的產物亦依照該方式進行測試。將2克的應用例1的產物與10毫升的生理食鹽水(normal saline)混合,形成一個濃度為0.2克/mL的檢測樣品。將兩片紗布分別浸入0.5mL的檢測樣品與作為對照組的0.5mL的生理食鹽水中72小時,形成兩片浸濕的紗布。接著,將該等浸濕的紗布間隔設置並覆蓋在已剔除毛髮的背部皮表上,然後以透氣繃帶固定。4 小時後,移除該等浸濕的紗布,接著,於1、24、48 及 72 小時後,觀察並紀錄測背部皮表是否存在有紅斑或水腫等的現象。
細胞毒性測試A:利用瓊脂擴散試驗法(Agar Diffusion Test)進行細胞毒性測試(Cytotoxicity test)。將小鼠纖維母細胞(L929, mouse fibroblast cells, CCRC 60091 NCTN Clone 929, of strain L)植入6井培養盤(6-well plate)的各井中,並分別在各井中加入含有10%的血清及1%的抗生素之最低必需培養基(minimum essential medium,簡稱MEM)培養,待細胞長至八分滿(sub-confluent cell monolayer),再加入2mL的1.5%的瓊脂(Agar)。待瓊脂凝固後,再將一檢測樣品置於其中一個井中,而剩餘的井不放置該檢測樣品並作為對照組。接著,放置於37℃且含有5%的二氧化碳的培養箱中培養24小時,以中性紅(Neutral Red)染色並計數活細胞的數目。該檢測樣品共進行3次測試,定性的結果依據 ISO10993-5 及 ASTM F895-11。評估三重複中個別的等級重複的等級平均後,即為定性評分。測試結果R.I. >1/1即樣品具細胞毒性。依據細胞死亡比例與細胞變形比例獲得反應指數(Response Index,簡稱RI),且RI值愈低,表示細胞毒性愈低。為清楚描述該檢測樣品的配置過程,以應用例1的產物進行說明,而應用例2的產物及比較應用例1的產物亦依照該方式進行配置。將0.2克的應用例1的產物與含有10%的血清及1%的抗生素之最低必需培養基混合,形成濃度為0.2g/mL的檢測樣品。在測試應用例1時的對照組的反應指數為0/0。在測試應用例2時的對照組的反應指數為0/0。在測試比較應用例1時的對照組的反應指數為5/5。
細胞毒性測試B:利用MTT分析法進行細胞毒性測試(Cytotoxicity test)。將小鼠纖維母細胞(L929, mouse fibroblast cells, CCRC 60091 NCTN Clone 929, of strain L)植入96井培養盤(96-well plate)的各井中,並分別在各井中加入含有10%的血清及1%的抗生素之最低必需培養基培養。待細胞長滿(sub-confluent monolayer),則將0.1mL的檢測樣品加入96井培養盤的部分井中,而剩餘的井不放置檢測樣品並作為對照組。接著,放置於37℃且含有5%的二氧化碳的培養箱中培養24小時,再以MTT法進行細胞存活率(Cell Viability)分析。該檢測樣品共進行3次測試,並取其平均值。為清楚描述檢測樣品的配置過程,以應用例1的產物進行說明,而應用例2的產物及比較應用例1的產物亦依照該方式進行配置。將0.2克的應用例1的產物與含有10%的血清及1%的抗生素之最低必需培養基混合,形成濃度為0.2g/mL的檢測樣品。在測試應用例1時的對照組的細胞存活率為73.3±5.7%。在測試應用例2時的對照組的細胞存活率為102.9±6.8%。在測試比較應用例1時的對照組的細胞存活率為35.4±4.9%。
表1
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 二氧化矽微米複合粒子 </td><td> 應用例 </td><td> 比較應用例 </td></tr><tr><td> 1 </td><td> 2 </td><td> 1 </td></tr><tr><td> 反應物 </td><td> 實施例1 </td><td> 實施例2 </td><td> -- </td></tr><tr><td> Si(OC<sub>2</sub>H<sub>5</sub>)<sub>4</sub></td></tr><tr><td> 粒徑 (μm) </td><td> 145.4~280.9 </td><td> 2.1~51.4 </td><td> 24.6~45.4 </td></tr><tr><td> 遠紅外線放射率(%) </td><td> 0.88 </td><td> 0.87 </td><td> 0.82 </td></tr><tr><td> 皮膚刺激性測試 </td><td> 無紅斑 </td><td> 無紅斑 </td><td> 無測試 </td></tr><tr><td> 無水腫 </td><td> 無水腫 </td><td> 無測試 </td></tr><tr><td> 細胞毒性測試A </td><td> 無 </td><td> 無 </td><td> 有 </td></tr><tr><td> RI為0/0 </td><td> RI為0/0 </td><td> RI為5/5 </td></tr><tr><td> 細胞毒性測試B </td><td> 無 </td><td> 無 </td><td> 有 </td></tr><tr><td> 細胞存活率為 73.3±5.7 </td><td> 細胞存活率為102.9±6.8% </td><td> 細胞存活率為35.4±4.9% </td></tr></TBODY></TABLE>
惟以上所述者,僅為本發明之實施例而已,當不能以此限定本發明實施之範圍,凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。
Claims (6)
- 一種三嗪系前驅物,由式(I)所示: 式(I) X及Y各自選自於-NR 1R 2、-OR 3或-SR 4; R 1選自於氫、未經取代的C 1至C 22的直鏈烷基,或未經取代的C 1至C 22的支鏈烷基; R 2、R 3及R 4各自選自於未經取代的C 1至C 22的直鏈烷基,或未經取代的C 1至C 22的支鏈烷基;且 Z表示-NH-R 5-Si(OR 6) 3,R 5表示C 2至C 4的伸烷基,且每一個R 6各自表示C 1至C 2的烷基。
- 一種製備請求項1所述的三嗪系前驅物的方法,包含以下步驟: 步驟(a),使2,4,6-三氯-1,3,5-三嗪與一個表示為H-X的第一親核化合物在一個第一溶劑的存在下且在一個第一溫度範圍為0℃至25℃下進行一個第一置換反應,形成一個式(i)所示的第一中間物, 式(i); 步驟(b) 使該第一中間物與一個表示為H-Y的第二親核化合物在一個第二溶劑的存在下且在一個第二溫度範圍為15℃至40℃下進行一個第二置換反應,形成一個式(ii)所示的第二中間物, 式(ii); 步驟(c) 使該第二中間物與一個表示為H-Z的第三親核化合物在一個第三溶劑的存在下且在一個第三溫度範圍為35℃至75℃下進行一個第三置換反應,形成該三嗪系前驅物。
- 如請求項2所述的製備請求項1所述的三嗪系前驅物的方法,其中,在該步驟(b)中,該第一親核化合物與該第二親核化合物為相同,且該第一溶劑與第二溶劑為相同。
- 一種製備二氧化矽微米複合粒子的方法,包含:使請求項1所述的三嗪系前驅物與四烷基矽酸酯進行水解及縮聚合反應。
- 如請求項4所述的製備二氧化矽微米複合粒子的方法,其中,該四烷基矽酸酯是四乙氧基矽烷。
- 一種二氧化矽微米複合粒子,係由請求項4所述的製備二氧化矽微米複合粒子的方法所形成。
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TW106127601A TWI651327B (zh) | 2017-08-15 | 2017-08-15 | 三嗪系前驅物、製備三嗪系前驅物的方法及三嗪系前驅物的應用 |
US15/977,391 US20190055270A1 (en) | 2017-08-15 | 2018-05-11 | Process for Preparing a Triazine-Based Precursor, the Precursor Prepared Thereby, a Method for Producing a Micro-Particulate Complex Using the Precursor, and the Micro-Particulate Complex Produced Thereby |
CN201810914631.2A CN109400543B (zh) | 2017-08-15 | 2018-08-13 | 三嗪系前驱物、制备三嗪系前驱物的方法及三嗪系前驱物的应用 |
US16/988,775 US11299504B2 (en) | 2017-08-15 | 2020-08-10 | Process for preparing a triazine-based precursor, the precursor prepared thereby, a method for producing a micro-particulate complex using the precursor, and the micro-particulate complex produced thereby |
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