JPS63270738A - Polyamine/polysiloxane block copolymer - Google Patents
Polyamine/polysiloxane block copolymerInfo
- Publication number
- JPS63270738A JPS63270738A JP10694487A JP10694487A JPS63270738A JP S63270738 A JPS63270738 A JP S63270738A JP 10694487 A JP10694487 A JP 10694487A JP 10694487 A JP10694487 A JP 10694487A JP S63270738 A JPS63270738 A JP S63270738A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyamine
- block copolymer
- polysiloxane
- formula
- 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.)
- Granted
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 60
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 38
- 229920000768 polyamine Polymers 0.000 title claims abstract description 28
- -1 polysiloxane Polymers 0.000 claims abstract description 61
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- BBFCEQFUUOTJPD-UHFFFAOYSA-N 1-tert-butylaziridine Chemical compound CC(C)(C)N1CC1 BBFCEQFUUOTJPD-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 150000003459 sulfonic acid esters Chemical group 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 2
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFLJKKQTWDAGQO-UHFFFAOYSA-N 1-(2,2-dimethylpropyl)aziridine Chemical compound CC(C)(C)CN1CC1 LFLJKKQTWDAGQO-UHFFFAOYSA-N 0.000 description 1
- MMMPMWQSPXSMAH-UHFFFAOYSA-N 1-propan-2-ylaziridine Chemical compound CC(C)N1CC1 MMMPMWQSPXSMAH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101150030723 RIR2 gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JWAJUTZQGZBKFS-UHFFFAOYSA-N n,n-diethylprop-2-en-1-amine Chemical compound CCN(CC)CC=C JWAJUTZQGZBKFS-UHFFFAOYSA-N 0.000 description 1
- XWAKKPDDQPWGAQ-UHFFFAOYSA-N n,n-dimethylbut-1-en-1-amine Chemical compound CCC=CN(C)C XWAKKPDDQPWGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920000765 poly(2-oxazolines) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明はポリアミン−ポリシロキサンブロック共重合体
に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to polyamine-polysiloxane block copolymers.
ポリジオルガノシロキサンと極性をもつ各種の直鎖状有
機ポリマーとのブロック共重合体ないしグラフト共重合
体はよく知られている。たとえばポリオキシアルキレン
とのブロックないしグラフト共重合体は界面活性剤や整
泡剤として用いられ、またポリウレタンとのブロック共
重合体には生体適合体があると言われている。Block copolymers or graft copolymers of polydiorganosiloxane and various polar linear organic polymers are well known. For example, block or graft copolymers with polyoxyalkylene are used as surfactants and foam stabilizers, and block copolymers with polyurethane are said to be biocompatible.
しかし、ポリアミンとのブロック共重合体は知られてい
ない。とくに、シロキサン鎮および/またはポリアミン
鎖の鎖長のそろった上記共重合体は知られていない。However, block copolymers with polyamines are not known. In particular, the above-mentioned copolymers in which the chain lengths of siloxane chains and/or polyamine chains are uniform are not known.
なお、ヒドロキシ基含有ポリシロキサン−ポリオキシア
ルキレンブロック共重合体とポリアミンを有機ポリイソ
シアネートと反応させてブロック共重合体を得る方法が
開示されている(特開昭52−57295号公報)が、
これはポリシロキサン含有ポリウレタン弾性体を目的と
したもので、ポリシロキサンとポリアミンとの間にポリ
オキシアルキレン鎮とウレタン結合が存在し、本発明の
ブロック共重合体とは、分子構造、目的、性状の異なる
ものである。Incidentally, a method for obtaining a block copolymer by reacting a hydroxy group-containing polysiloxane-polyoxyalkylene block copolymer and a polyamine with an organic polyisocyanate has been disclosed (Japanese Patent Application Laid-Open No. 57295/1989).
This is intended for a polyurethane elastomer containing polysiloxane, and there are polyoxyalkylene and urethane bonds between polysiloxane and polyamine, and the block copolymer of the present invention has a molecular structure, purpose, and properties. are different.
本発明者らは先に、ポリシロキサン−ポリオキサゾリン
ブロック共重合体を合成した(風聞、手順、今井;高分
子学会予稿集、第35巻第336ページ(1986)
)。このブロック共重合体は、本発明のポリアミン−ポ
リシロキサンブロック共重合体のような生理活性を示さ
ないし、水で乳化することができない。また、本発明の
ブロック共重合体のようにポリアミン鎖の長さをそろえ
る方法を見出すに至らなかった。The present inventors previously synthesized a polysiloxane-polyoxazoline block copolymer (hearsay, procedure, Imai; Proceedings of the Society of Polymer Science, Vol. 35, p. 336 (1986)
). This block copolymer does not exhibit physiological activity like the polyamine-polysiloxane block copolymer of the present invention and cannot be emulsified with water. Furthermore, no method has been found to make the lengths of polyamine chains uniform as in the block copolymer of the present invention.
本発明の目的は、新規なポリアミン−ポリシロキサンブ
ロック共重合体を提供することにある。とくに本発明に
よって、ポリシロキサン鎖および/またはポリアミン鎖
の長さのそろった上記共重合体を提供することができる
。An object of the present invention is to provide a novel polyamine-polysiloxane block copolymer. In particular, the present invention can provide the above copolymer in which the lengths of polysiloxane chains and/or polyamine chains are uniform.
すなわち本発明は、一般式
(式中、R1はアルキル基、フェニル基、またはアルケ
ニル基を示し、R2は互いに同一または相異なるアルキ
ル基を示し、R3は炭素数3以上のアルキル基を示し、
R4はアルキル基を示し R5は互いに同一または相異
なるアルキル基を示し、nは平均5〜1,000 、r
nは平均5〜1,000 、pは3〜10の数を示す。That is, the present invention relates to the general formula (wherein R1 represents an alkyl group, phenyl group, or alkenyl group, R2 represents an alkyl group that is the same or different from each other, and R3 represents an alkyl group having 3 or more carbon atoms,
R4 represents an alkyl group, R5 represents an alkyl group that is the same or different from each other, n is 5 to 1,000 on average, r
n represents a number from 5 to 1,000 on average, and p represents a number from 3 to 10.
)
または一般式
(式中、R’、 R”、 R3,n、 m、 pは前
述のとおり、Aは連鎖停止基を示す。)
で表されるポリアミン−ポリシロキサンブロック共重合
体に関する。) or the general formula (wherein R', R'', R3, n, m, p are as described above, and A represents a chain-terminating group).
本発明において R1はアルキル基、フェニル基、また
はアルケニル基である。アルキル基としてはメチル基、
エチル基、プロピル基、ブチル基、ペンチル基、ヘキシ
ル基、オクチル基、デシル基、ドデシル基など、またア
ルケニル基としてはビニル基、アリル基などが例示され
る。In the present invention, R1 is an alkyl group, a phenyl group, or an alkenyl group. As an alkyl group, a methyl group,
Examples of the alkenyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and a vinyl group and an allyl group.
この中で、耐熱性の点からはメチル基又はフェニル基が
好ましいが、シロキサン鎮の長さのそろった共重合体を
得る場合はR1はR’Liに由来するので、その取り扱
いの容易なことから、ブチル基が好ましい。Among these, methyl group or phenyl group is preferable from the viewpoint of heat resistance, but when obtaining a copolymer with uniform length of siloxane group, R1 is derived from R'Li, so it is easy to handle. Therefore, a butyl group is preferred.
R2は互いに同一または相異なるアルキル基であり、メ
チル基、エチル基、プロピル基、ブチル基、ペンチル基
、ヘキシル基、オクチル基、デシル基、ドデシル基など
が例示されるが、取り扱い及び原料人手の容易なことと
、耐熱性、撥水性、柔軟性など、ポリシロキサンの性質
を最も良く発揮することから、メチル基が好ましい。R2 is an alkyl group that is the same or different from each other, and examples thereof include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, and dodecyl group. A methyl group is preferred because it is easy to use and best exhibits the properties of polysiloxane, such as heat resistance, water repellency, and flexibility.
nは平均5〜1,000 、好ましくは20〜200の
整数である。nが平均5未満のものは合成しにくく、n
が平均1.000を越えると粘度が上がりすぎて取り扱
いが困難なばかりか、制御よく合成することが困難にな
る。n is an integer of 5 to 1,000 on average, preferably 20 to 200. Those with n less than 5 on average are difficult to synthesize;
When the average value exceeds 1.000, the viscosity increases so much that not only is it difficult to handle, but also difficult to synthesize in a well-controlled manner.
pは3〜10の整数である。pが1のものはヒドロシリ
ル化反応では合成できないし、pが2の場合は加水分解
反応に対する抵抗が少ない。p is an integer from 3 to 10. A compound with p of 1 cannot be synthesized by a hydrosilylation reaction, and a compound with p of 2 has little resistance to the hydrolysis reaction.
またpが10を越えると、系の見掛は粘度が上昇し、ま
た耐熱性が低下する。この中で合成の容易なことから、
pが3であることが好ましい。When p exceeds 10, the apparent viscosity of the system increases and the heat resistance decreases. Among these, because it is easy to synthesize,
Preferably, p is 3.
R3は炭素数3以上のアルキル基であり、プロピル基、
ブチル基、ペンチル基、ヘキシル基、オクチル基、デシ
ル基、ドデシル基などが例示されるが、ポリアミン鎖部
分の分子量が大きく、かつ鎖長のそろったブロック共重
合体を得るには、イソプロピル基、tert−ブチル基
、ネオペンチル基のような分岐状のものがよく、その中
で、取扱いおよび原料入手の容易なことから、tert
−ブチル基がさらに好ましい。メチル基またはエチル基
では、ポリアミン鎖を所望の長さに伸ばすことができな
い。R3 is an alkyl group having 3 or more carbon atoms, a propyl group,
Examples include butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc., but in order to obtain a block copolymer with a large molecular weight and uniform chain length in the polyamine chain portion, isopropyl group, Branched ones such as tert-butyl group and neopentyl group are preferred, and among them, tert
-butyl group is more preferred. Methyl or ethyl groups cannot extend the polyamine chain to the desired length.
R4はアルキル基であり、メチル基、エチル基、プロピ
ル基などが例示される。R4 is an alkyl group, and examples thereof include a methyl group, an ethyl group, and a propyl group.
R5は互いに同一または相異なるアルキル基であり、メ
チル基、エチル基、プロピル基、ブチル基などが例示さ
れるが、反応性の大きいことから、メチル基が好ましい
。R5 is an alkyl group that is the same or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a methyl group is preferred because of its high reactivity.
mは平均5〜1,000 、好ましくは20〜200の
整数である。mが平均5未満のものはブロック共重合体
の特徴を十分に発揮しない。またmが平均1.000を
越えると粘度が上がりすぎて取り扱いが困難なばかりか
、制御よく合成することが困難になる。m is an integer of 5 to 1,000 on average, preferably 20 to 200. If m is less than 5 on average, the characteristics of a block copolymer will not be fully exhibited. Moreover, when m exceeds 1.000 on average, the viscosity increases so much that it is not only difficult to handle, but also difficult to synthesize in a well-controlled manner.
Aは連鎖停止反応によって共重合体中に導入された基、
またはそれより後処理中に生じた基であり、反応条件や
反応終了後の洗浄の仕方によって異なるが、環状ポリア
ミン基、水酸基、メトキシ基、ニドキシ基などが例示さ
れる。A is a group introduced into the copolymer by a chain termination reaction,
Alternatively, it is a group generated during post-treatment, and examples thereof include a cyclic polyamine group, a hydroxyl group, a methoxy group, a nidoxy group, etc., depending on the reaction conditions and the method of washing after the reaction is completed.
式(I)で示されるブロック共重合体は、たとえば次の
ようにして得ることができる。すなわち、一般式
(式中、R1,R2,R8,nおよびpは前述のとおり
)
で表される末端アミン型ポリシロキサンと、一般式
(式中、R3,R4およびmは前述のとおり)で表され
るポリアミンと反応させて得ることができる。The block copolymer represented by formula (I) can be obtained, for example, as follows. That is, a terminal amine type polysiloxane represented by the general formula (wherein R1, R2, R8, n and p are as described above) and a terminal amine type polysiloxane represented by the general formula (wherein R3, R4 and m are as described above). It can be obtained by reacting with the represented polyamine.
末端アミン型ポリシロキサン(I)は、次のようにして
合成することができる。すなわち、一般式(R2□5i
n)s (ただし、R2は前述のとおり)で表されるヘ
キサオルガノトリシロキサンをテトラヒドロフラン中で
一般式R’Li (ただし R1は前述のとおり)で示
されるオルガノリチウム化合物の存在下に重合し、つい
で一般式R2□H3iC1(ただし、R2は前述のとあ
り)で表されるジオルガノクロロシランと脱塩反応させ
て、一般式R’ (R’2SIO)−R’2SIH(た
だし、R’、 R’及びnは前述のとおり)で示される
片末端ヒドロシリル結合含有ポリシロキサンを得る(風
聞、平塚、今井;第35回高分子討論会予稿集、第35
巻第1684ページ(1986))。これに、白金系触
媒の存在下にジメチルアリル・アミン、ジエチルアリル
アミン、ジイソプロピルアリルアミン、ジメチルブテニ
ルアミンのようなジアルキルアルケニルアミンをヒドロ
シリル化反応させることによって、末端アミン型ポリシ
ロキサン(I[I)を得ることができる。The terminal amine type polysiloxane (I) can be synthesized as follows. That is, the general formula (R2□5i
n) Polymerizing hexaorganotrisiloxane represented by s (where R2 is as described above) in tetrahydrofuran in the presence of an organolithium compound represented by the general formula R'Li (wherein R1 is as described above), Then, a desalting reaction is performed with a diorganochlorosilane represented by the general formula R2□H3iC1 (wherein R2 is as described above) to form the general formula R'(R'2SIO)-R'2SIH (wherein R', R ' and n are as described above) to obtain a polysiloxane containing a hydrosilyl bond at one end (Fubon, Hiratsuka, Imai; Proceedings of the 35th Polymer Symposium, No. 35
Volume No. 1684 (1986)). This is subjected to a hydrosilylation reaction with a dialkylalkenylamine such as dimethylallylamine, diethylallylamine, diisopropylarylamine, or dimethylbutenylamine in the presence of a platinum-based catalyst to form a terminal amine type polysiloxane (I[I). Obtainable.
この場合、第1段階の反応で、重量平均分子量の数平均
分子量に対する比(分散度)が1.0〜1.2、条件に
より1.1以下の、シロキサン鎖長のそろったポリシロ
キサンが得られるので、末端アミン型ポリシロキサン(
III)も、同様にシロキサン鎖長のそろったものを得
ることができる。In this case, the first stage reaction yields a polysiloxane with uniform siloxane chain lengths, with a ratio of weight average molecular weight to number average molecular weight (dispersity) of 1.0 to 1.2, depending on the conditions, 1.1 or less. terminal amine type polysiloxane (
In III), it is also possible to obtain products with uniform siloxane chain lengths.
また、このような末端アミン型ポリシロキサン(III
) は、例えばRIR2□5iC1と[R22SiO
〕。In addition, such terminal amine type polysiloxane (III
) is, for example, RIR2□5iC1 and [R22SiO
].
(ただし、R’、 R2は前述のとおり、qは3または
4の整数を示す)の間のテロメリゼーション゛ また
は開環平衡化反応によってR’ [R22SiO]、R
2,5iC1(ただし、R1,R2及びnは前述のとお
り)を得、この末端の塩素原子をLIAI84などで水
素化したのち、同様にジアルキルアルケニルアミンと反
応させて得ることもできる。ただし、この方法ではシロ
キサン鎮の長さをそろえることはできない。(However, as mentioned above, R' and R2 are telomerization or ring-opening equilibration reaction during which q is an integer of 3 or 4).
It can also be obtained by obtaining 2,5iC1 (wherein R1, R2 and n are as described above), hydrogenating the terminal chlorine atom with LIAI84 or the like, and then reacting it with a dialkylalkenylamine in the same manner. However, with this method, it is not possible to make the lengths of the siloxane blocks the same.
ポリアミン(EV)は、たとえばヘキサメチルホスホト
リアミドとテトラヒドロフランの混合溶媒中で、トリフ
ルオロメタンスルホン酸メチルのようなトリフルオロメ
タンスルホン酸アルキルを反応開始剤として、N−アル
キルアジリジンを開環重合することによって溶液状で得
ることができる。この方法によれば、得られるポリアミ
ン (TV)は分散度が1.0〜1.2、条件により1
.1以下の、アミン鎖長のそろったポリアミンが得られ
る。N−アルキルアジリジンとしては、N−イソプロピ
ルアジリジン、N−tert−ブチルアジリジン、N−
ネオペンチルアジリジンのような分岐状アルキル基をも
つものが収率よく高重合体を与える。Polyamine (EV) can be produced by ring-opening polymerization of N-alkylaziridine in a mixed solvent of hexamethylphosphotriamide and tetrahydrofuran using an alkyl trifluoromethanesulfonate such as methyl trifluoromethanesulfonate as a reaction initiator. It can be obtained in solution form. According to this method, the polyamine (TV) obtained has a dispersity of 1.0 to 1.2, depending on the conditions, 1.
.. Polyamines with uniform amine chain lengths of 1 or less can be obtained. Examples of N-alkylaziridine include N-isopropylaziridine, N-tert-butylaziridine, N-
Products with branched alkyl groups, such as neopentylaziridine, give high polymers in good yields.
末端アミン型ポリシロキサン(I[)とポリアミン(I
V)の反応は、たとえば(III)をヘキサメチルホス
ホトリアミドのような非プロトン極性溶媒とテトラヒド
ロフランの混合溶媒に溶解した溶液に(IV)のテトラ
ヒドロフラン溶液を加えて、常温で進行、させることが
できる。また、末端アミン型ポリシロキサン(III)
を均一に溶解して、反応を円滑に進行させるために、テ
トラヒドロフランなどの有機溶媒を共存させてもよい。Terminal amine type polysiloxane (I[) and polyamine (I
The reaction V) can be carried out at room temperature by adding a tetrahydrofuran solution of (IV) to a solution of (III) dissolved in a mixed solvent of tetrahydrofuran and an aprotic polar solvent such as hexamethylphosphotriamide. can. In addition, terminal amine type polysiloxane (III)
An organic solvent such as tetrahydrofuran may also be present in order to uniformly dissolve and allow the reaction to proceed smoothly.
式(II)で示されるブロック共重合体は、たとえば次
のよう゛にして得ることができる。すなわち、一般式
(式中、R’、 R”、 nおよびpは前述のとおり
、R8は1価の炭化水素基を示す。)
で表される末端スルホン酸エステル型ポリシロキサンに
より、一般式
(式中、R3は前述のとおり)で示されるN−アルキル
アジリジンを、テトラヒドロフランおよび非プロトン極
性溶媒の存在下に開通重合して得ることができる。The block copolymer represented by formula (II) can be obtained, for example, as follows. That is, by using the terminal sulfonic acid ester type polysiloxane represented by the general formula (wherein R', R'', n and p are as described above, and R8 represents a monovalent hydrocarbon group), the general formula ( An N-alkylaziridine represented by the formula (wherein R3 is as described above) can be obtained by open polymerization in the presence of tetrahydrofuran and an aprotic polar solvent.
式(V)にふいて、R6としてはメチル基、エチル基、
フェニル基、p−)’Jル基などが例示されるが、反応
性の大きいことから、p−)!Jル基が好ましい。In formula (V), R6 is a methyl group, an ethyl group,
Examples include phenyl group and p-)'J group, but due to their high reactivity, p-)! A J group is preferred.
末端スルホン酸エステル型ポリシロキサン(V)は、(
I[I)の中間原料である片末端ヒドロシリル結合含有
ポリシロキサンに、白金系触媒の存在下にアリルアコー
ル、3−ブテニルアルコールのようなアルケニルアルコ
ールをヒドロシリル化させたのち、一般式R’SO□C
1(ただし、R6は前述のとおり〉で示されるクロロス
ルフリル化合物を反応させて得ることができる。The terminal sulfonic acid ester type polysiloxane (V) is (
After hydrosilylating polysiloxane containing a hydrosilyl bond at one end, which is an intermediate raw material for I[I], with an alkenyl alcohol such as allyl alcohol or 3-butenyl alcohol in the presence of a platinum catalyst, the general formula R'SO is obtained. □C
It can be obtained by reacting a chlorosulfuryl compound represented by 1 (where R6 is as described above).
この場合も(III)と同様に、用いる片末端ヒドロシ
リル結合含有ポリシロキサンの製法によっては、シロキ
サン鎖長のそろったものを得ることができる。In this case, as in (III), depending on the method for producing the polysiloxane containing a hydrosilyl bond at one terminal end, it is possible to obtain a polysiloxane having a uniform chain length.
末端スルホン酸エステル型ポリシロキサン(V)によっ
てN−アルキルアジリジン(VI)を開環重合して本発
明の共重合体を得る反応は、たとえば上記のポリシロキ
サン(V)をヘキサメチルホスホトリアミドのような非
プロトン極性溶媒またはそれに必要に応じてテトラヒド
ロフランのような上記ポリシロキサン(V)の良溶媒を
加えた混合溶媒に溶解し、これにN−アルキルアジリジ
ン(■)を加えて80〜120℃の温度で進めることが
できる。この場合も、N−アルキルアジリジンとしては
、前述のような分岐状アルキル基をもつものが、高重合
体を得る点で好ましい。反応終了後、得られた混合物か
ら溶媒および未反応物を除去し、共重合体を炭化水素系
溶媒のような溶媒に溶解して、凍結乾燥によって精製し
た共重合体(I[)が得られる。The reaction of ring-opening polymerizing N-alkylaziridine (VI) with terminal sulfonic acid ester type polysiloxane (V) to obtain the copolymer of the present invention can be carried out, for example, by converting the above-mentioned polysiloxane (V) into hexamethylphosphotriamide. The above polysiloxane (V) is dissolved in an aprotic polar solvent such as or a mixed solvent containing a good solvent such as tetrahydrofuran if necessary, and N-alkylaziridine (■) is added thereto and heated at 80 to 120°C. The process can be carried out at a temperature of In this case, the N-alkyl aziridine is preferably one having a branched alkyl group as described above in terms of obtaining a high polymer. After the reaction is completed, the solvent and unreacted materials are removed from the resulting mixture, the copolymer is dissolved in a solvent such as a hydrocarbon solvent, and the purified copolymer (I[) is obtained by freeze-drying. .
この開環重合の際に、連鎖停止反応によってAが形成さ
れる。Aの内容は本発明にとって本質的ではない。たと
えば成長するポリアミン鎮がピペラジン環のようなポリ
アミン環を形成して停止する場合がある。また、系中に
存在する水や後処理に使用する水、アルコールなどによ
って、水酸基またはメトキシ基、エトキシ基、イソプロ
ポキシ基のようなアルコキシ基を形成することがある。During this ring-opening polymerization, A is formed by a chain termination reaction. The content of A is not essential to the invention. For example, a growing polyamine chain may terminate by forming a polyamine ring such as a piperazine ring. Furthermore, depending on the water present in the system or the water or alcohol used in post-treatment, a hydroxyl group or an alkoxy group such as a methoxy group, an ethoxy group, or an isopropoxy group may be formed.
本発明のポリアミン−ポリシロキサンブロック共重合体
は、その合成法によって(I)または(n)の構造式で
表すことができ、いずれもポリシロキサン鎖とポリアミ
ン鎖をポリメチレン結合を介して結合させたもので、本
質的には同様のものである。ただし、式(I)で表され
るものは、ポリアミン鎖部分の分散度が1.0〜1.2
という鎖長のそろったものを得ることができる。また、
いずれの構造式で表されるものも、片末端ヒドロシリル
基含有ポリシロキサンの製法によっては、シロキサン鎖
部分の分散度が1.0〜1.2という鎖長のそろったも
のを得ることができる。The polyamine-polysiloxane block copolymer of the present invention can be represented by the structural formula (I) or (n) depending on the synthesis method, and both have a polysiloxane chain and a polyamine chain bonded via a polymethylene bond. They are essentially the same thing. However, in the case of formula (I), the degree of dispersion of the polyamine chain portion is 1.0 to 1.2.
It is possible to obtain products with the same chain length. Also,
Regardless of the structural formula, it is possible to obtain a polysiloxane having a uniform chain length with a degree of dispersion of 1.0 to 1.2 in the siloxane chain portion, depending on the method of manufacturing the polysiloxane containing a hydrosilyl group at one end.
本発明によって提供されるジブロック型ポリアミン−ポ
リシロキサンブロック共重合体は、水で容易に乳化でき
、化学的に安定で、生理活性を有し、マイナス電荷をも
つ物質との相互作用、金属に対する配位性、および特異
な配向性をもつ表面形成能がある。とくにブロック共重
合体の一方または相方のセグメントの鎖長をそろえたも
のは、種々の興味ある性質を示す。たとえば、このこと
によって相分離構造を制御することができる。ポリアミ
ン鎖の鎖長をそろえると生体の蛋白質への応答性を制御
できるし、ポリシロキサン鎖の鎖長をそろえると、表面
張力や水との接触角など、共重合体の表面性質を制御で
きる。また、両セグメントの鎖長をそろえたものは界面
活性剤としての特性の安定したものが得られる。The diblock type polyamine-polysiloxane block copolymer provided by the present invention can be easily emulsified with water, is chemically stable, has physiological activity, and is resistant to interactions with negatively charged substances and metals. It has coordinating properties and the ability to form surfaces with unique orientation. In particular, block copolymers in which one or the other segment have the same chain length exhibit various interesting properties. For example, this allows the phase separation structure to be controlled. By matching the chain lengths of polyamine chains, it is possible to control the responsiveness of living organisms to proteins, and by matching the chain lengths of polysiloxane chains, it is possible to control the surface properties of copolymers, such as surface tension and contact angle with water. Furthermore, when the chain lengths of both segments are made the same, a surfactant with stable properties can be obtained.
したがって、本発明のポリアミン−ポリシロキサンブロ
ック共重合体は、界面活性剤、防菌・防カビ剤、防汚塗
料の成分、染色性向上剤、繊維処理剤として有用である
。Therefore, the polyamine-polysiloxane block copolymer of the present invention is useful as a surfactant, an antibacterial/antifungal agent, a component of an antifouling paint, a dyeability improver, and a fiber treatment agent.
以下、本発明を合成例、実施例および比較例によって説
明する。これらの例において、部は重量部を表す。The present invention will be explained below using synthesis examples, examples, and comparative examples. In these examples, parts represent parts by weight.
合成例1〜3
ヘキサメチルシクロトリシロキサンをテトラヒドロフラ
ン中でブチルリチウムにより重合させ、更にジメチルク
ロロシランと反応させて得た、シロキサン鎖の数平均重
合度が30で、重量平均分子量と数平均分子量の比が1
.08の、片末端ヒドロシリル基、他の末端がブチル基
で閉塞されたポリジメチルシロキサン25.1部を反応
容器に仕込み、容器内を窒素で置換したのち、38.6
部のジメチルアリルアミンを加え、さらに0.34部の
5%の白金を含むカーボン担持白金を加えて均一に撹拌
しつつ、温度を90℃に保ってヒドロシリル化反応を行
った。反応を8時間続け、’ H−NMRを測定した結
果、5i−H結合は完全に消滅し、反応が完全に進行し
たことを確認した。Synthesis Examples 1 to 3 Hexamethylcyclotrisiloxane was polymerized with butyllithium in tetrahydrofuran and further reacted with dimethylchlorosilane, and the number average degree of polymerization of the siloxane chain was 30, and the ratio of weight average molecular weight to number average molecular weight. is 1
.. 25.1 parts of polydimethylsiloxane of No. 08 in which one end was blocked with a hydrosilyl group and the other end was blocked with a butyl group was charged into a reaction vessel, and after purging the inside of the vessel with nitrogen, 38.6
0.34 parts of carbon-supported platinum containing 5% platinum were added, and the hydrosilylation reaction was carried out while stirring uniformly and maintaining the temperature at 90°C. The reaction was continued for 8 hours, and as a result of measuring 'H-NMR, it was confirmed that the 5i-H bond completely disappeared, and the reaction proceeded completely.
生成物を水で洗浄して過剰のジメチルアリルアミンを除
き、常法により脱水、濾過を行って、末端にジメチルア
ペノ基をもつポリシロキサンS−1を得た。The product was washed with water to remove excess dimethylallylamine, followed by dehydration and filtration in a conventional manner to obtain polysiloxane S-1 having dimethylapeno groups at the ends.
同様にして、シロキサン鎮の数平均重合度が50および
100の、同様に鎖長のそろった片末端ヒドロシリル結
合含有ポリシロキサンから、同様の配合比と反応条件に
よって、末端にジメチルアミノ基をもつポリシロキサン
S−2およびS−3を得た。原料シロキサンの数平均重
合度と分散度、ならびにS−1〜S−3の重量平均およ
び数平均分子量を第1表に示す。またS−2の’ H−
NMRのチャートを第1図に示す。Similarly, from polysiloxanes containing a hydrosilyl bond at one end and having a number average degree of polymerization of 50 and 100 and having the same chain length, polysiloxanes having a dimethylamino group at the end were prepared using the same compounding ratio and reaction conditions. Siloxanes S-2 and S-3 were obtained. Table 1 shows the number average degree of polymerization and dispersion of the raw material siloxane, as well as the weight average and number average molecular weight of S-1 to S-3. Also, S-2' H-
An NMR chart is shown in FIG.
第1表
合成例4〜6
合成例1〜3で用いたのと同様の3種類のヒドロシリル
基含有ポリシロキサンそれぞれ20.0部を69.4部
のトルエンに溶解し、窒素気流中において、0.34部
の5%の白金を含むカーボン担持白金および25.2部
のアリルアルコールを加え、撹拌しつつ第2表に示す条
件でヒドロシリル化反応を行った。ついで、メンブレン
フィルターを用いてカーボン担持白金を濾別し、トルエ
ンと未反応アリルアルコールを減圧蒸留によって除いた
のち、メタノールで数回洗浄を行って、ベンゼン中より
凍結乾燥して、ヒドロキシプロピル基含有ポリシロキサ
ンを得た。Table 1 Synthesis Examples 4 to 6 20.0 parts of each of the three types of hydrosilyl group-containing polysiloxanes used in Synthesis Examples 1 to 3 were dissolved in 69.4 parts of toluene, and in a nitrogen stream, .34 parts of carbon-supported platinum containing 5% platinum and 25.2 parts of allyl alcohol were added, and a hydrosilylation reaction was carried out under the conditions shown in Table 2 while stirring. Next, carbon-supported platinum was filtered out using a membrane filter, toluene and unreacted allyl alcohol were removed by vacuum distillation, and then washed several times with methanol and freeze-dried in benzene to obtain a hydroxypropyl group-containing product. A polysiloxane was obtained.
このヒドロキシプロピル基含有ポリシロキサン10.0
部を第2表に示す量の塩化メチレンに溶解し、第2表に
示す量の塩化トシノペトリエチルアミン、4−ジメチル
アミノピリジンを加えて、20℃で22時間撹拌して反
応を行った。反応生成物を39.5部のn−ヘキサンで
抽出し、メタノール中で繰返し沈澱させて精製し、ベン
ゼン中より凍結乾燥して、トシル基含有ポリシロキサン
T−1〜T−3を得た。This hydroxypropyl group-containing polysiloxane 10.0
Tosinopetriethylamine chloride and 4-dimethylaminopyridine were added in the amounts shown in Table 2, and the mixture was stirred at 20° C. for 22 hours to carry out a reaction. The reaction product was extracted with 39.5 parts of n-hexane, purified by repeated precipitation in methanol, and freeze-dried in benzene to obtain tosyl group-containing polysiloxanes T-1 to T-3.
原料シロキサンの数平均重合度および分散度、ヒドロシ
リル化反応の条件、ヒドロキシプロピル基含有ポリシロ
キサンの収率、トシル基含有ポリシロキサンの収率、な
らびにその重量平均および数平均分子量を第2表に示す
。またT−2の’ H−NMRのチャートを第2図に示
す。Table 2 shows the number average degree of polymerization and dispersion of the raw material siloxane, the conditions for the hydrosilylation reaction, the yield of hydroxypropyl group-containing polysiloxane, the yield of tosyl group-containing polysiloxane, and the weight average and number average molecular weight thereof. . Further, the 'H-NMR chart of T-2 is shown in FIG.
第2表
実施例1〜4
N−tert−ブチルアジリジンをヘキサメチルホスホ
トリアミドとテトラヒドロフランの混合溶媒に溶解し、
これにトリフルオロメタンスルホン酸メチルを加えて、
撹拌しつつ15℃で20分間、開通重合を行った。それ
ぞれの仕込量は第3表に示すとおりである。得られた反
応溶液から一部を抜き出して、生成したポリアミンの重
量平均および数平均分子量を求めたところ、第3表のよ
うに、分散度はいずれも1.1以下であった。Table 2 Examples 1 to 4 Dissolving N-tert-butylaziridine in a mixed solvent of hexamethylphosphotriamide and tetrahydrofuran,
Add methyl trifluoromethanesulfonate to this,
Open polymerization was carried out at 15° C. for 20 minutes while stirring. The amount of each preparation is shown in Table 3. When a portion was extracted from the obtained reaction solution and the weight average and number average molecular weights of the produced polyamine were determined, as shown in Table 3, the degree of dispersion was 1.1 or less in all cases.
得られた反応溶液中に、合成例1〜3で得られたジメチ
ルアミノ基含有ポリシロキサンS−1〜S−3のテトラ
ヒドロフラン溶液を加えた。添加量は第3表のとおりで
ある。この混合物を30℃で2時間撹拌してカップリン
グ反応を行った。Tetrahydrofuran solutions of dimethylamino group-containing polysiloxanes S-1 to S-3 obtained in Synthesis Examples 1 to 3 were added to the obtained reaction solution. The amounts added are shown in Table 3. This mixture was stirred at 30° C. for 2 hours to perform a coupling reaction.
反応生成物をメタノールに注いで単離し、さらにイソプ
ロパツールで繰返し洗浄したのち、ベンゼンに溶解して
凍結乾燥を行い、ポリアミン−ポリシロキサンブロック
共重合体を得た。収量、重量平均および数平均分子量、
NMRより積分比として求めた共重合体中のポリアミン
セグメントの割合を第3表に示す。The reaction product was isolated by pouring it into methanol, washed repeatedly with isopropanol, dissolved in benzene, and freeze-dried to obtain a polyamine-polysiloxane block copolymer. Yield, weight average and number average molecular weight,
Table 3 shows the proportion of polyamine segments in the copolymer determined as an integral ratio from NMR.
また、実施例4で得られたブロック共重合体の’ H−
NMRおよびIRのチャートをそれぞれ第3図および第
4図に、その帰属を第5表に示す。In addition, ' H- of the block copolymer obtained in Example 4
NMR and IR charts are shown in FIGS. 3 and 4, respectively, and their attributions are shown in Table 5.
実施例5〜7
合成例4〜6で得られたトシル基含有ポリシロキサンT
−1−T−3を反応容器に仕込み、脱気、チッ素置換し
たのち、ヘキサメチルホスホトリアミドをテトラヒドロ
フランを加え、さらにN−tert−ブチルアジリジン
を添加して撹拌しつつ加熱して、トシル基含有ポリシロ
キサンを開始剤とするtert−ブチルアジリジンの開
環重合を行った。それぞれの仕込量および反応条件は第
4表に示すとおりである。Examples 5-7 Tosyl group-containing polysiloxane T obtained in Synthesis Examples 4-6
-1-T-3 was charged into a reaction vessel, degassed and nitrogen-substituted, then hexamethylphosphotriamide was added with tetrahydrofuran, and further N-tert-butylaziridine was added and heated with stirring. Ring-opening polymerization of tert-butylaziridine was carried out using a group-containing polysiloxane as an initiator. The amounts charged and reaction conditions for each are shown in Table 4.
反応終了後、未反応のN−tert−ブチルアジリジン
、ヘキサメチルホスホトリアミドおよびテトラヒドロフ
ランを減圧蒸留によって留去し、エタノールと水の1=
1混合液を加えてポリマーを析出させた。さらにエタノ
ールと水の1:1混合液で洗浄を繰り返して、副生じた
環状ポリアミンオリゴマーを除去した。ついで、ベンゼ
ンを加えて凍結乾燥することにより、精製したポリアミ
ン−ポリシロキサンブロック共重合体を得た。After completion of the reaction, unreacted N-tert-butylaziridine, hexamethylphosphotriamide, and tetrahydrofuran were distilled off under reduced pressure, and 1=1 of ethanol and water was distilled off.
1 mixture was added to precipitate the polymer. Furthermore, washing was repeated with a 1:1 mixture of ethanol and water to remove by-product cyclic polyamine oligomers. Then, a purified polyamine-polysiloxane block copolymer was obtained by adding benzene and freeze-drying.
得られたブロック共重合体は無色の粘性固体であり、ヘ
キサン、ベンゼン、テトラヒドロフラン、クロロホルム
、四塩化炭素に可溶で、アセトン、メタノール、ジメチ
ルスルホキシド、水に不溶であった。また、このブロッ
ク共重合体は希塩酸中で乳化作用を示した。The obtained block copolymer was a colorless viscous solid, soluble in hexane, benzene, tetrahydrofuran, chloroform, and carbon tetrachloride, and insoluble in acetone, methanol, dimethyl sulfoxide, and water. Moreover, this block copolymer showed emulsifying effect in dilute hydrochloric acid.
ブロック共重合体の収量、平均分子量、共重合体中のポ
リアミンセグメントの割合、tert−ブチルアジリジ
ンの反応率、および開始剤の効率を第4表に示す。実施
例7で得られたブロック共重合体の’ H−NMRおよ
びIRのチャートはそれぞれ第3図および第4図と同じ
特性吸収を示した。The yield of the block copolymer, the average molecular weight, the proportion of polyamine segments in the copolymer, the reaction rate of tert-butylaziridine, and the efficiency of the initiator are shown in Table 4. The 'H-NMR and IR charts of the block copolymer obtained in Example 7 showed the same characteristic absorption as in FIGS. 3 and 4, respectively.
第5表
比較例1
ヘキサメチルホスホトリアミドを用いず、テトラヒドロ
フランの代りに700部の塩化メチレンを溶媒として用
い、反応条件を0℃、48時間とした以外は実施例5と
同様の実験を行ったところ、反応は全く行われず、目的
のポリアミン−ポリシロキサン共重合体は得られなかっ
た。Table 5 Comparative Example 1 The same experiment as Example 5 was carried out except that hexamethylphosphotriamide was not used, 700 parts of methylene chloride was used as a solvent instead of tetrahydrofuran, and the reaction conditions were 0°C for 48 hours. However, no reaction occurred at all, and the desired polyamine-polysiloxane copolymer could not be obtained.
比較例2
ヘキサメチルホスホトリアミドを用いず、テトラヒドロ
フランの量を466部とし、反応条件を60℃、26時
間とした以外は実施例7と同様の実験を行ったところ、
反応は全く行われず、目的のポリアミン−ポリシロキサ
ン共重合体は得られなかった。Comparative Example 2 An experiment similar to Example 7 was conducted, except that hexamethylphosphotriamide was not used, the amount of tetrahydrofuran was 466 parts, and the reaction conditions were 60 ° C. for 26 hours.
No reaction took place and the desired polyamine-polysiloxane copolymer was not obtained.
第1図は合成例2で得られたジメチルアミノ基含有ポリ
シロキサンの’ H−NMRのチャート、第2図は合成
例5で得られたトシル基含有ポリシロキサンの’ H−
NMRのチャート、第3図および第4図は実施例4で得
られたポリアミン−ポリシロキサンブロック共重合体の
’ H−NMRおよびIRチャートを示す。Figure 1 is the 'H-NMR chart of the dimethylamino group-containing polysiloxane obtained in Synthesis Example 2, and Figure 2 is the 'H-NMR chart of the tosyl group-containing polysiloxane obtained in Synthesis Example 5.
NMR charts, FIGS. 3 and 4 show 'H-NMR and IR charts of the polyamine-polysiloxane block copolymer obtained in Example 4.
Claims (1)
ケニル基を示し、R^2は互いに同一または相異なるア
ルキル基を示し、R^3は炭素数3以上のアルキル基を
示し、R^4はアルキル基を示し、R^5は互いに同一
または相異なるアルキル基を示し、nは平均5〜1,0
00、mは平均5〜1,000、pは3〜10の数を示
す。)または一般式 ▲数式、化学式、表等があります▼・・・(II) (式中、R^1、R^2、R^3、n、m、pは前述の
とおり、Aは連鎖停止基を示す。) で表されるポリアミン−ポリシロキサンブロック共重合
体。 2、R^1がブチル基である特許請求の範囲第1項記載
のポリアミン−ポリシロキサンブロック共重合体。 3、R^2がメチル基である特許請求の範囲第1項記載
のポリアミン−ポリシロキサンブロック共重合体。 4、シロキサン鎖部分の重量平均分子量の数平均分子量
に対する比が1.0〜1.2である特許請求の範囲第1
項記載のポリアミン−ポリシロキサンブロック共重合体
。 5、pが3である特許請求の範囲第1項記載のポリアミ
ン−ポリシロキサンブロック共重合体。 6、R^3がtert−ブチル基である特許請求の範囲
第1項記載のポリアミン−ポリシロキサンブロック共重
合体。 7、一般式( I )で表される共重合体において、アミ
ン鎖部分の重量平均分子量の数平均分子量に対する比が
1.0〜1.2である特許請求の範囲第1項記載のポリ
アミン−ポリシロキサンブロック共重合体。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R^1 represents an alkyl group, phenyl group, or alkenyl group, and R^2 is Represents an alkyl group that is the same or different from each other, R^3 represents an alkyl group having 3 or more carbon atoms, R^4 represents an alkyl group, R^5 represents an alkyl group that is the same or different from each other, and n is the average 5-1,0
00, m indicates an average of 5 to 1,000, and p indicates a number of 3 to 10. ) or general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) (In the formula, R^1, R^2, R^3, n, m, p are as mentioned above, A is chain termination A polyamine-polysiloxane block copolymer represented by: 2. The polyamine-polysiloxane block copolymer according to claim 1, wherein R^1 is a butyl group. 3. The polyamine-polysiloxane block copolymer according to claim 1, wherein R^2 is a methyl group. 4. Claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight of the siloxane chain portion is 1.0 to 1.2.
The polyamine-polysiloxane block copolymer described in 1. 5. The polyamine-polysiloxane block copolymer according to claim 1, wherein p is 3. 6. The polyamine-polysiloxane block copolymer according to claim 1, wherein R^3 is a tert-butyl group. 7. The polyamine according to claim 1, wherein in the copolymer represented by general formula (I), the ratio of the weight average molecular weight of the amine chain portion to the number average molecular weight is 1.0 to 1.2. Polysiloxane block copolymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10694487A JPH0826158B2 (en) | 1987-04-30 | 1987-04-30 | Polyamine-polysiloxane block copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10694487A JPH0826158B2 (en) | 1987-04-30 | 1987-04-30 | Polyamine-polysiloxane block copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63270738A true JPS63270738A (en) | 1988-11-08 |
JPH0826158B2 JPH0826158B2 (en) | 1996-03-13 |
Family
ID=14446486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10694487A Expired - Lifetime JPH0826158B2 (en) | 1987-04-30 | 1987-04-30 | Polyamine-polysiloxane block copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0826158B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5928566A (en) * | 1995-11-29 | 1999-07-27 | International Business Machines Corporation | Plasticized, antiplasticized and crystalline conducting polymers |
US5932143A (en) * | 1995-11-29 | 1999-08-03 | International Business Machines Corporation | Polycrystalline conducting polymers and precursors thereof having adjustable morphology and physical properties |
WO2006121937A1 (en) | 2005-05-09 | 2006-11-16 | Ndsu Research Foundation | Anti-fouling materials containing polyamine cross-linked polysiloxanes |
JPWO2022059492A1 (en) * | 2020-09-15 | 2022-03-24 |
-
1987
- 1987-04-30 JP JP10694487A patent/JPH0826158B2/en not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5928566A (en) * | 1995-11-29 | 1999-07-27 | International Business Machines Corporation | Plasticized, antiplasticized and crystalline conducting polymers |
US5932143A (en) * | 1995-11-29 | 1999-08-03 | International Business Machines Corporation | Polycrystalline conducting polymers and precursors thereof having adjustable morphology and physical properties |
US6616863B1 (en) | 1995-11-29 | 2003-09-09 | International Business Machines Corporation | Plasticized, antiplasticized and crystalline conducting polymers and precursors thereof |
WO2006121937A1 (en) | 2005-05-09 | 2006-11-16 | Ndsu Research Foundation | Anti-fouling materials containing polyamine cross-linked polysiloxanes |
EP1879972A1 (en) * | 2005-05-09 | 2008-01-23 | NDSU Research Foundation | Anti-fouling materials containing polyamine cross-linked polysiloxanes |
EP1879972A4 (en) * | 2005-05-09 | 2008-10-15 | Ndsu Res Foundation | Anti-fouling materials containing polyamine cross-linked polysiloxanes |
JP2008543602A (en) * | 2005-05-09 | 2008-12-04 | エヌディーエスユー リサーチ ファウンデーション | Antifouling substance containing polyamine-crosslinked polysiloxane |
JPWO2022059492A1 (en) * | 2020-09-15 | 2022-03-24 | ||
WO2022059492A1 (en) * | 2020-09-15 | 2022-03-24 | Dic株式会社 | Silicone chain-containing polymer and coating composition containing said polymer |
Also Published As
Publication number | Publication date |
---|---|
JPH0826158B2 (en) | 1996-03-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
YíIgör et al. | Segmented organosiloxane copolymers. 1. Synthesis of siloxane—urea copolymers | |
EP1799729B1 (en) | Functional siloxanes and their vinyl co-polymers | |
US20040254325A1 (en) | Organopolysiloxane/polyurea/polyurethane block copolymers | |
US20040024098A1 (en) | Nonionic telechelic polymers incorporating polyhedral oligosilsesquioxane (POSS) and uses thereof | |
KR100517068B1 (en) | New block copolymers and preparation thereof | |
JP2000186150A (en) | Organosilicon compound, its production and its use | |
JP2538308B2 (en) | Organosiloxane | |
US6492480B1 (en) | Method of polymerizing a silalkylenesiloxane | |
EP1757631B1 (en) | Amphiphilic triblock copolymers comprising poly(2-vinyl pyridine) block and poly(alkyl isocyanate) block, and the preparation method thereof | |
WO2004011525A1 (en) | Nonionic telechelic polymers incorporating polyhedral oligosilsesquioxane (poss) and uses thereof | |
JPS63270738A (en) | Polyamine/polysiloxane block copolymer | |
US6800713B2 (en) | Methods for making silicone-organic copolymers | |
EP0666279B1 (en) | Strain-crystallizing poly(methyl(3,3,3-trifluoropropyl)-siloxane) elastomers and methods for making | |
EP0666280B1 (en) | Stereoregular poly(methyl(3,3,3-trifluoropropyl)-siloxane) polymers and methods for making | |
JPH0370737A (en) | Organopolysiloxane and its preparation | |
JP3724782B2 (en) | Method for producing branched organopolysiloxane | |
JPH0369932B2 (en) | ||
JP2624036B2 (en) | Siloxane compound and method for producing the same | |
JPH107799A (en) | Production of polyorganosiloxane by interfacial polymerization | |
US20040171783A1 (en) | Methods for making silicone-organic copolymers | |
JPH0643494B2 (en) | Process for producing linear thermotropic copolymer composed of aromatic azomethine type mesogenic unit and polysiloxane spacer | |
JPH0774255B2 (en) | Silicone modified PVC | |
US5183874A (en) | Polyorganosiloxane-polyamide block copolymers | |
JP2538309B2 (en) | Method for producing polysiloxane | |
JP3000089B2 (en) | Polydiorganosiloxane-polyether block copolymer and method for producing the same |