JPH0439327A - Azidized polyether having terminal azide group - Google Patents
Azidized polyether having terminal azide groupInfo
- Publication number
- JPH0439327A JPH0439327A JP14527790A JP14527790A JPH0439327A JP H0439327 A JPH0439327 A JP H0439327A JP 14527790 A JP14527790 A JP 14527790A JP 14527790 A JP14527790 A JP 14527790A JP H0439327 A JPH0439327 A JP H0439327A
- Authority
- JP
- Japan
- Prior art keywords
- azide
- polyether
- formula
- terminated
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 36
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 3
- 150000001540 azides Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004014 plasticizer Substances 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000004449 solid propellant Substances 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- -1 oxybutylene group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野）
本発明は分子末端にアジド基を有するアジ化ポリエーテ
ルに関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an azide polyether having an azide group at the end of the molecule.
このアジ化ポリエーテルは、高エネルギー可塑剤として
、例えば固体推進薬用の可塑剤として有用なものである
。The azide polyethers are useful as high energy plasticizers, such as solid propellant plasticizers.
〈従来の技術〉
アジ化ポリマーとしては、ポリエピクロルヒドリンをア
ジ化ナトリウムと反応させた次式１〜６の水酸基含有化
合物残基を示し、ａ、ｂ及びＣは平均付加モル数を示し
、ａ＝Ｏ〜１０、ｂ＝１〜３０及びＣ＝Ｏ〜１０の整数
であり、且つａ＋ｂ＋ｃは５０以下の整数である。ｍは
１〜６の整数である。）で表わされるアジド末端アジ化
ポリエーテル。<Prior Art> The azide polymer is a hydroxyl group-containing compound residue of the following formulas 1 to 6 obtained by reacting polyepichlorohydrin with sodium azide, where a, b and C represent the average number of moles added, and a= O~10, b=1~30, and C=O~10, and a+b+c is an integer of 50 or less. m is an integer from 1 to 6. ) azide-terminated azide polyether.
で表わされるものが知られている（米国特許第４２６８
４５０号明細書）。(U.S. Pat. No. 4,268)
450 Specification).
又、高エネルギー可塑剤として、硝酸ポリエピクロルヒ
ドリンから得られた次式
で表わされるアジド末端アジ化ポリマーも知られている
（特開昭６３−３０９５１４号公報）。Furthermore, an azide-terminated azide polymer obtained from polyepichlorohydrin nitrate and represented by the following formula is also known as a high-energy plasticizer (Japanese Patent Application Laid-open No. 309514/1983).
〈発明が解決しようとする課題〉
前記従来のアジ化ポリマーを、例えば固体推進薬用の可
塑剤として用いた場合、可塑剤としての効果及び燃焼エ
ネルギーの面で未だ十分ではなく、更に改良されたもの
が望まれていた。<Problems to be Solved by the Invention> When the conventional azide polymers are used as plasticizers for solid propellants, for example, they are still insufficient in terms of effectiveness as a plasticizer and combustion energy. was desired.
そこで、本発明者らは、一連のアジ化ポリマーについて
長期にわたり研究した結果、特定の新規化合物であるア
ジド末端アジ化ポリエーテルが前記の問題を解決できる
との知見を得て本発明を完成した。As a result of long-term research on a series of azide polymers, the present inventors completed the present invention based on the knowledge that a specific new compound, azide-terminated azide polyether, can solve the above problems. .
〈課題を解決するための手段〉
本発明は一般式
１〜６の水酸基含有化合物残基を示し、ａ、ｂ及びＣは
平均付加モル数を示し、ａ；０〜１０、ｂ＝ｉ〜３０及
びｃ＝０〜１ｏの整数であり、且つａ＋ｂ＋ｃは５０以
下の整数である。ｍは１〜６の整数である。）で表わさ
れるアジド末端アジ化ポリエーテルに関するものである
。<Means for Solving the Problems> The present invention represents hydroxyl group-containing compound residues of general formulas 1 to 6, where a, b and C represent the average number of added moles, a; 0 to 10, b = i to 30. and c=an integer of 0 to 1o, and a+b+c is an integer of 50 or less. m is an integer from 1 to 6. ) This relates to an azide-terminated azide polyether represented by:
本発明の前記一般式（Ｉ）で表わされるアジ化ポリエー
テル中のＡで示される炭素数２〜４のオキシアルキレン
基としては、オキシエチレン基、オキシプロピレン基、
オキシブチレン基、オキシテトラメチレン基などがある
。又同式中Ｍで示される炭素数１〜６の水酸基含有化合
物残基としては、メタノール、エタノール、プロパツー
ル、インプロパツール、ブタノール、ペンタノール、ヘ
キサノール等のｍ個脂肪族アルコール、エチレングリコ
ール、プロピレングリコール、テトラメチレングリコー
ル、ヘキサメチレングリコール、グリセリン、ジグリセ
リン、ポリグリセリン、トリメチロールエタン、トリメ
チロールプロパン、ペンタエリスリトール、ソルビトー
ル、ソルバイト、ジペンタエリスリトール等の二価以上
の脂肪族アルコール残基がある。The oxyalkylene group having 2 to 4 carbon atoms represented by A in the azide polyether represented by the general formula (I) of the present invention includes an oxyethylene group, an oxypropylene group,
Examples include oxybutylene group and oxytetramethylene group. In the same formula, the residue of a hydroxyl group-containing compound having 1 to 6 carbon atoms is represented by m aliphatic alcohols such as methanol, ethanol, propatool, impropatol, butanol, pentanol, hexanol, ethylene glycol, Contains dihydric or higher aliphatic alcohol residues such as propylene glycol, tetramethylene glycol, hexamethylene glycol, glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbite, dipentaerythritol, etc. .
本発明の前記一般式（Ｉ）で表わされるアジ化ポリエー
テル中の平均付加モル数であるａ及びｂが１０を越える
と、環状化合物等の副産物が生成したり、結晶性が発現
したりするため可塑剤として好ましくなく、又すが３０
を越えたり、ａ＋ｂ十ｃが５０を越えたものは粘度が大
であるため可塑剤としては好ましくな（、又すが１未満
では高エネルギーという目的を外れるので好ましくな（
、更にｍが６を越えると粘度が上昇して可塑剤として好
ましくない。If the average number of added moles a and b in the azide polyether represented by the general formula (I) of the present invention exceeds 10, by-products such as cyclic compounds may be produced or crystallinity may develop. Therefore, it is not preferable as a plasticizer, and it is
If the value exceeds 1 or a + b + c exceeds 50, it has a high viscosity, so it is not preferred as a plasticizer (However, if it is less than 1, it misses the purpose of high energy, so it is not preferred).
Furthermore, if m exceeds 6, the viscosity will increase, making it undesirable as a plasticizer.
本発明のアジ化ポリエーテルは、ハロゲン末端ハロゲン
化ポリエーテルを有機溶媒の存在下でアジ化ナトリウム
と反応させることにより得られる。The azide polyether of the present invention is obtained by reacting a halogen-terminated halogenated polyether with sodium azide in the presence of an organic solvent.
前記製造に用いられる有機溶媒としては、例えばＮ、Ｎ
−ジメチルホルムアミド、ジメチルスルホキシド、ヘキ
サメチルリン酸トリアミド、トルエン等である。又アジ
化ナトリウムの添加量は、ハロゲン末端ハロゲン化ポリ
エーテルの塩素量に対し、通常１〜３倍量用いる。又有
機溶媒の量は、目的のアジ化ポリマーの種類によって適
宜増減することができる。又反応温度は、通常６０〜８
０℃程度であり、反応時間は２５〜７２時間程度である
。Examples of the organic solvent used in the production include N, N
-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, toluene, etc. The amount of sodium azide added is usually 1 to 3 times the amount of chlorine in the halogen-terminated halogenated polyether. Further, the amount of the organic solvent can be appropriately increased or decreased depending on the type of the target azide polymer. In addition, the reaction temperature is usually 60 to 8
The temperature is about 0°C, and the reaction time is about 25 to 72 hours.
前記ハロゲン末端ハロゲン化ポリエーテルは、アルキレ
ンオキシド、エビハロヒドリン及び３゜３′ ビスクロ
ルメチルオキセタンより誘導されるポリエーテルの分子
末端をハロゲン原子で胃換して得られるものである。The halogen-terminated halogenated polyether is obtained by gastrically replacing the molecular terminal of a polyether derived from alkylene oxide, ebihalohydrin and 3°3' bischloromethyloxetane with a halogen atom.
場合には、その各構成単位の結合様式は、ランダムでも
ブロックでも、ランダム−ブロック型でもよい。In some cases, the bonding manner of each of its constituent units may be random, block, or random-block type.
本発明のアジド末端アジ化ポリエーテルは、赤外線吸収
スペクトルにより、塩素原子の消失とアジド基の検出に
より、又元素分析により構造式が確認される。The structural formula of the azide-terminated azide polyether of the present invention is confirmed by infrared absorption spectroscopy, by the disappearance of chlorine atoms and detection of azide groups, and by elemental analysis.
〈発明の効果〉
本発明のアジド末端アジ化ポリエーテルは新規化合物で
あり、固体推進薬用の可塑剤として優れた性質を持って
いる。<Effects of the Invention> The azide-terminated azide polyether of the present invention is a new compound and has excellent properties as a plasticizer for solid propellants.
〈製造例・実施例〉 本発明を製造例、実施例により具体的に説明する。<Manufacturing example/Example> The present invention will be specifically explained with reference to production examples and examples.
（ハロゲン化ポリエーテルの製造例）
製造例 １
撹拌器、温度計、冷加温装置及び圧入管を取付けた３℃
反応容器にメタノール３２ｇ（１モル）と三フッ化ホウ
素のエーテル錯塩２．Ｏｇ及び反応溶媒としてトルエン
１６０ｇを３０℃ニ保持シ窒素雰囲気下でエピクロルヒ
ドリン７５９ｇ（８，２モル）の圧入を開始し、３０〜
４０℃、０．５〜５ 、０ ｋｇ／ｃｍ”の加圧下で６
時間を要し添加した。更に同温度で熟成後反応を完結し
た０次いで未反応のエピクロルヒドリンを減圧下で除去
した。更に１０％炭酸ナトリウム水溶液で触媒である三
フフ化ホウ素のエーテル錯塩を中和した。(Manufacturing example of halogenated polyether) Manufacturing example 1 3℃ with stirrer, thermometer, cooling/heating device and press-in tube installed
32 g (1 mole) of methanol and an ether complex salt of boron trifluoride were placed in a reaction vessel.2. Og and 160 g of toluene as a reaction solvent were held at 30°C. Pressure injection of 759 g (8.2 mol) of epichlorohydrin was started under a nitrogen atmosphere.
6 at 40°C under pressure of 0.5~5,0 kg/cm''
It took time to add it. After further aging at the same temperature, the reaction was completed and unreacted epichlorohydrin was removed under reduced pressure. Further, the ether complex salt of boron trifluoride, which was a catalyst, was neutralized with a 10% aqueous sodium carbonate solution.
その後８０〜１００℃に加温し減圧下に水を除去し、濾
過後無色透明液体のヒドロキシハロゲン化ポリエーテル
を７７２ｇ得た。このヒドロキシハロゲン化ポリエーテ
ル１モルを撹拌器、窒素ガス吹込み管、温度計、冷却管
及び滴下口を取付けた５ρ４０フラスコに入れ、更に触
゛媒であるトリエチルアミン１１２ｇ （１，２モル）
及びクロロホルム１５００ｇを入れ、５０℃に保持した
。次ぎに１時間以内にハロゲン化試薬である塩化チオニ
ル２３８ｇ （２モル）を加え窒素雰囲気下で、撹拌し
ながら５０℃で滴下した。更に５時間リフラックスし反
応を完結させた。次ぎに副生じたトリエチルアンモニウ
ムクロライドを除去するため５０℃の温水を１２加え、
１時間静置後有機層と水層に分離し水層を除去した。そ
の後希アルカリ水で同様の条件で４回繰返し水洗を行な
い有機層を得た。この有機層を減圧下でクロロホルムを
留去し褐色透明液体を得た。この液体の赤外吸収スペク
トルや元素分析等による同定結果から表１の製造例１に
示すハロゲン化ポリエーテルであることが確認された。Thereafter, the mixture was heated to 80 to 100°C, water was removed under reduced pressure, and after filtration, 772 g of hydroxyhalogenated polyether as a colorless transparent liquid was obtained. One mole of this hydroxyhalogenated polyether was placed in a 5μ40 flask equipped with a stirrer, nitrogen gas blowing tube, thermometer, condenser tube, and dropping port, and 112 g (1.2 moles) of triethylamine as a catalyst was added.
and 1500 g of chloroform were added and maintained at 50°C. Next, within 1 hour, 238 g (2 mol) of thionyl chloride, which is a halogenating reagent, was added dropwise at 50° C. under a nitrogen atmosphere with stirring. Reflux was further performed for 5 hours to complete the reaction. Next, 50°C warm water was added for 12 hours to remove triethylammonium chloride produced as a by-product.
After standing for 1 hour, the mixture was separated into an organic layer and an aqueous layer, and the aqueous layer was removed. Thereafter, water washing was repeated four times under the same conditions with dilute alkaline water to obtain an organic layer. Chloroform was distilled off from this organic layer under reduced pressure to obtain a brown transparent liquid. Identification results from infrared absorption spectra and elemental analysis of this liquid confirmed that it was the halogenated polyether shown in Production Example 1 in Table 1.
即ち元素分析では塩素４０．０％（理論値４０．４％）
であり、第２図に示す赤外吸収スペクトルでは３５００
ｃ＋ａ−’には水酸基は検出されず、水酸基価は１．５
（反応率９７，９％）、動粘度は１４０ｃｓｔ （４０
℃）であった。In other words, elemental analysis shows 40.0% chlorine (theoretical value 40.4%)
In the infrared absorption spectrum shown in Figure 2, it is 3500
No hydroxyl group was detected in c+a-', and the hydroxyl value was 1.5.
(reaction rate 97.9%), kinematic viscosity was 140 cst (40
℃).
表１に得られたハロゲン化ポリエーテル、そのＣβ％、
動粘度及び製造条件を示す。The halogenated polyethers obtained in Table 1, their Cβ%,
Kinematic viscosity and manufacturing conditions are shown.
製造例２
製造例１と同じ反応容器にメタノール６４ｇ（２モル）
と四塩化錫５．０ｇ及び反応溶媒としてトルエン２００
ｇを加えた。この溶液を４０℃に保持し窒素雰囲気下で
プロピレンオキサイド：エピクロルヒドリン＝１：２（
モル比）の比率に混合したもの４８６ｇを圧入開始し、
４０〜５０℃、０．５〜５．０ｋｇ／ｃｍ”の加圧下で
３時間要し添加した。次ぎにエピクロルヒドリン９３４
ｇを６時間要し付加反応を行ない、更に同温度で熟成し
反応を完結させた０次いで未反応のモノマーを減圧下で
除去した。更に１０％炭酸ナトリウム水溶液で触媒であ
る四塩化錫を中和した。その後８０〜１００℃に加温、
減圧下に水を除去後濾過精製し無色透明液体のランダム
−ブロック型ヒドロキシハロゲン化ポリエーテルを＋４
５０ｇ得た。このヒドロキシハロゲン化ポリエーテルを
用い、トリエチルアミン１．２モルを１．５モルに変え
、塩化チオニル２．０モルを２．５モルに変え、反応時
間５時間を７時間に変えた以外は製造例１に準じた方法
で反応を行なった。Production Example 2 64 g (2 moles) of methanol was placed in the same reaction vessel as Production Example 1.
and 5.0 g of tin tetrachloride and 200 g of toluene as a reaction solvent.
g was added. This solution was kept at 40°C and propylene oxide:epichlorohydrin=1:2 (
Start press-fitting 486g of the mixture in the ratio of molar ratio),
The addition took 3 hours at 40-50°C and a pressure of 0.5-5.0 kg/cm. Next, epichlorohydrin 934 was added.
The addition reaction was carried out for 6 hours, and the reaction was completed by further aging at the same temperature.Then, unreacted monomers were removed under reduced pressure. Furthermore, the catalyst, tin tetrachloride, was neutralized with a 10% aqueous sodium carbonate solution. Then heated to 80-100℃,
After removing water under reduced pressure, filtering and purifying the colorless transparent liquid random block type hydroxyhalogenated polyether +4
I got 50g. Production example except that this hydroxyhalogenated polyether was used, 1.2 mol of triethylamine was changed to 1.5 mol, 2.0 mol of thionyl chloride was changed to 2.5 mol, and the reaction time was changed from 5 hours to 7 hours. The reaction was carried out in the same manner as in 1.
得られた液体について、製造例１と同じ方法で同定した
結果、表１の製造例２に示すハロゲン化ポリエーテルで
あることが確認された。The obtained liquid was identified by the same method as in Production Example 1, and it was confirmed that it was the halogenated polyether shown in Production Example 2 in Table 1.
製造例３〜１３
製造例１に準じた方法で各々のヒドロキシハロゲン化ポ
リエーテルを製造し、次いで表１及び２に示す条件で、
各々のハロゲン化ポリエーテルを製造した。各々のハロ
ゲン化ポリエーテルについて製造例１と同じ方法でその
構造式を確認し、表１に示した。Production Examples 3 to 13 Each hydroxyhalogenated polyether was produced in a manner similar to Production Example 1, and then under the conditions shown in Tables 1 and 2,
Each halogenated polyether was produced. The structural formulas of each halogenated polyether were confirmed in the same manner as in Production Example 1, and are shown in Table 1.
本発明のアジド末端アジ化ポリエーテルの製造実施例
１
撹拌器、窒素ガス吹込み管、温度計、冷却管を取付けた
１℃四四ツフラスコ製造例１で製造したハロゲン化ポリ
エーテルＬｏｇ （０，０１２モル）をＮ、Ｎ−ジメチ
ルホルムアミド３７ｍβに溶解したものを入れ、次いで
アジ化ナトリウム１５ｇ （０，２３モル）を添加し、
６０℃で２５時間反応させた。反応後、反応液を室温ま
で冷却し、塩化メチレンを５０ｍρ加え、次いで水洗を
８回行なった。水洗した溶液を硫酸ナトリウムで乾燥後
、シリカゲルのカラムを通過させた。Production example of azide-terminated azide polyether of the present invention
1 1°C 44 flask equipped with a stirrer, nitrogen gas blowing tube, thermometer, and cooling tube Dissolve the halogenated polyether Log (0,012 mol) produced in Production Example 1 in 37 mβ of N,N-dimethylformamide. and then add 15 g (0.23 mol) of sodium azide.
The reaction was carried out at 60°C for 25 hours. After the reaction, the reaction solution was cooled to room temperature, 50 mρ of methylene chloride was added, and then washed with water 8 times. The water-washed solution was dried with sodium sulfate and then passed through a silica gel column.
分離した溶液を濃縮してアジド末端アジ化ポリエーテル
９．２ｇを得た。この溶液の赤外吸収スペクトルを第１
図に示す。又元素分析結果はＮ２４４．１％（理論値４
４．５％）従ってｃｐからＮへの転化率は９９．０％で
ある。又水酸基値は１、 ５ （ＫＯＨｍｇ／ｇ） 、
赤外吸収スペクトルテハ２１００ｃｍ−’のアジド基が
検出され７５０ｃｍ−’のＣＩ２基が消失しており、こ
のアジド末端アジ化ポリエーテルは表３に示す構造式を
持つことが確認された。表２に製造条件を、表３に得ら
れたアジド末端アジ化ポリエーテルの構造式、特性を示
す。The separated solution was concentrated to obtain 9.2 g of azide-terminated azide polyether. The infrared absorption spectrum of this solution is
As shown in the figure. In addition, the elemental analysis result was N244.1% (theoretical value 4
4.5%) Therefore, the conversion rate from cp to N is 99.0%. Also, the hydroxyl group value is 1.5 (KOHmg/g),
The azide group at 2100 cm-' in the infrared absorption spectrum was detected, and the CI2 group at 750 cm-' disappeared, and it was confirmed that this azide-terminated azide polyether had the structural formula shown in Table 3. Table 2 shows the manufacturing conditions, and Table 3 shows the structural formula and properties of the azide-terminated azide polyether obtained.
実施例２〜１３
実施例１に準じて、表２に示す条件で各々のアジド末端
アジ化ポリエーテルを製造した。各々のアジド末端アジ
化ポリエーテルについて実施例１と同様な方法で同定し
、結果を表３に示した。Examples 2 to 13 According to Example 1, each azide-terminated azide polyether was produced under the conditions shown in Table 2. Each azide-terminated azide polyether was identified in the same manner as in Example 1, and the results are shown in Table 3.
又各々のアジド末端アジ化ポリエーテルの構造式が表３
に示すものであることを確認した。The structural formulas of each azide-terminated azide polyether are shown in Table 3.
It was confirmed that the
第１図は本発明の実施例１で得られたアジド末端アジ化
ポリエーテルの赤外吸収スペクトル図であり、第２図は
製造例１で製造されたハロゲン化ポリエーテルの赤外線
吸収スペクトル図である。Figure 1 is an infrared absorption spectrum diagram of the azide-terminated azide polyether obtained in Example 1 of the present invention, and Figure 2 is an infrared absorption spectrum diagram of the halogenated polyether produced in Production Example 1. be.
Claims (1)
−ＣＨ＿２ＣＨ＿２Ｎ＿３、▲数式、化学式、表等があ
ります▼、−（ＣＨ＿２）＿４Ｎ＿３、▲数式、化学式
、表等があります▼または▲数式、化学式、表等があり
ます▼；Ｍは炭素数 １〜６の水酸基含有化合物残基を示し、ａ、ｂ及びｃは
平均付加モル数を示し、ａ＝０〜１０、ｂ＝１〜３０及
びｃ＝０〜１０の整数であり、且つａ＋ｂ＋ｃは５０以
下の整数である。ｍは１〜６の整数である。）で表わさ
れるアジド末端アジ化ポリエーテル。[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, A is an oxyalkylene group having 2 to 4 carbon atoms; Y is -CH_2CH_2N_3, ▲ Numerical formula, chemical formula, table, etc. Yes ▼, -(CH_2)_4N_3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; M indicates the residue of a compound containing a hydroxyl group with 1 to 6 carbon atoms, a, b and c indicates the average number of moles added, a = 0 to 10, b = 1 to 30, and c = an integer of 0 to 10, and a + b + c is an integer of 50 or less. m is an integer of 1 to 6. ) is an azide-terminated azide polyether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14527790A JPH0439327A (en) | 1990-06-05 | 1990-06-05 | Azidized polyether having terminal azide group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14527790A JPH0439327A (en) | 1990-06-05 | 1990-06-05 | Azidized polyether having terminal azide group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0439327A true JPH0439327A (en) | 1992-02-10 |
Family
ID=15381417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14527790A Pending JPH0439327A (en) | 1990-06-05 | 1990-06-05 | Azidized polyether having terminal azide group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0439327A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014208828A (en) * | 2003-10-09 | 2014-11-06 | アンブレツクス・インコーポレイテツド | Azide- or acetylene-terminated water-soluble polymer |
-
1990
- 1990-06-05 JP JP14527790A patent/JPH0439327A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014208828A (en) * | 2003-10-09 | 2014-11-06 | アンブレツクス・インコーポレイテツド | Azide- or acetylene-terminated water-soluble polymer |
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