JPH04359018A - Production of silane-crosslinkable alkylene oxide polymer - Google Patents
Production of silane-crosslinkable alkylene oxide polymerInfo
- Publication number
- JPH04359018A JPH04359018A JP16007791A JP16007791A JPH04359018A JP H04359018 A JPH04359018 A JP H04359018A JP 16007791 A JP16007791 A JP 16007791A JP 16007791 A JP16007791 A JP 16007791A JP H04359018 A JPH04359018 A JP H04359018A
- Authority
- JP
- Japan
- Prior art keywords
- alkylene oxide
- group
- oxide polymer
- ester bond
- silane
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 125000003277 amino group Chemical group 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- -1 silane compound Chemical class 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003566 sealing material Substances 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- MACVNMKPAKPZQG-UHFFFAOYSA-N dioctyltin(2+);methanolate Chemical compound CCCCCCCC[Sn](OC)(OC)CCCCCCCC MACVNMKPAKPZQG-UHFFFAOYSA-N 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004492 methyl ester group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は新規なシラン架橋性アル
キレンオキシド重合体の製造方法に関するものである。
本発明により得られたアルキレンオキシド重合体は、建
築用シール材、コーティング材、電気、電子部品のシー
ル材、ポッティング材、繊維の表面処理剤などの基材と
して有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel silane crosslinkable alkylene oxide polymer. The alkylene oxide polymer obtained by the present invention is useful as a base material for architectural sealing materials, coating materials, sealing materials for electrical and electronic parts, potting materials, surface treatment agents for fibers, and the like.
【０００２】0002
【従来の技術】従来、シラン架橋性アルキレンオキシド
重合体の製造方法として、アルキレンオキシド重合体の
水酸基を一度アリルエーテル基に変換し、ヒドロアルコ
キシシランを付加させて得る方法（特開昭５０−１５６
５９９号公報参照）、アルキレンオキシド重合体末端の
水酸基をイソシアネートシランと反応させる方法（特開
昭５７−１６４１２３号公報参照）などが提案されてい
る。[Prior Art] Conventionally, as a method for producing a silane-crosslinkable alkylene oxide polymer, the hydroxyl group of the alkylene oxide polymer is first converted into an allyl ether group, and then a hydroalkoxysilane is added thereto (Japanese Patent Laid-Open No. 50-156
599) and a method of reacting the terminal hydroxyl group of an alkylene oxide polymer with isocyanate silane (see JP-A-57-164123).
【０００３】しかしながら、前者の方法は反応が２段階
であり、その際アリルエーテル基のイソプロペニルオキ
シ基への副次的な転位により、ヒドロシリル化過程の反
応率が最終的に９０％程度までしか達成されない等の問
題がある。後者の方法では重合体中にウレタン結合が存
在するためウレタン架橋型と基本的には変わりなく、純
粋なシラン架橋型ではない。However, in the former method, the reaction is carried out in two steps, and due to the secondary rearrangement of the allyl ether group to the isopropenyloxy group, the reaction rate of the hydrosilylation process ultimately reaches only about 90%. There are problems such as not being achieved. In the latter method, since urethane bonds are present in the polymer, it is basically the same as the urethane crosslinked type, and is not a pure silane crosslinked type.
【０００４】0004
【発明が解決しようとする課題】上述のような状況から
、本発明は、シラン架橋性アルキレンオキシド重合体を
容易に収率よく製造する方法を新規に提供しようとして
なされたものである。SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention was made in an attempt to provide a new method for easily producing a silane crosslinkable alkylene oxide polymer with good yield.
【０００５】[0005]
【課題を解決するための手段】本発明は、前記の課題を
解決した新規なシラン架橋性アルキレンオキシド重合体
の製造方法に関するものであり、この発明は、分子鎖末
端にエステル結合を有するアルキレンオキシド重合体の
エステル結合部位と、一般式[Means for Solving the Problems] The present invention relates to a method for producing a novel silane crosslinkable alkylene oxide polymer that solves the above-mentioned problems. Ester bonding site of polymer and general formula
【０００６】[0006]
【化２】[Chemical 2]
【０００７】（式中、Ｒ１ は２価の有機基、Ｒ２、Ｒ
３ は同一または異種の１価の有機基、ａは０または１
）で示されるシラン化合物のアミノ基とを反応させるこ
とを特徴とする、シラン架橋性アルキレンオキシド重合
体の製造方法、を要旨とするものである。(In the formula, R1 is a divalent organic group, R2, R
3 is the same or different monovalent organic group, a is 0 or 1
The gist of the present invention is a method for producing a silane crosslinkable alkylene oxide polymer, which is characterized by reacting the amino group of a silane compound represented by the following formula.
【０００８】以下に本発明について詳しく説明する。本
発明では、原料の分子鎖末端にエステル結合を有するア
ルキレンオキシド重合体として、他方の原料であるシラ
ン化合物のアミノ基との反応を阻害しないものであれば
いずれも用いることができる。The present invention will be explained in detail below. In the present invention, any alkylene oxide polymer having an ester bond at the end of the molecular chain of the raw material can be used as long as it does not inhibit the reaction with the amino group of the other raw material, the silane compound.
【０００９】この重合体の末端を構成するエステル結合
構造の具体例としては、
−ＯＣ３Ｈ６ＣＯＯＣＨ３、 −ＯＣＨ２ＣＨ（ＣＨ３
）ＣＨ２ＣＯＯＣＨ３、 −ＯＣＨ２ＣＯＯＣＨ３、
−ＯＣ３Ｈ６ＣＯＯＣ２Ｈ５、−ＯＣＨ２ＣＨ（ＣＨ３
）ＣＨ２ＣＯＯＣ２Ｈ５、 −ＯＣＨ２ＣＯＯＣ２Ｈ５
などが例示されるが、エステル結合構造は１種類のみで
なく、２種類以上のエステル結合構造が混合していても
よい。Specific examples of ester bond structures constituting the terminals of this polymer include -OC3H6COOCH3, -OCH2CH(CH3
)CH2COOCH3, -OCH2COOCH3,
-OC3H6COOC2H5, -OCH2CH(CH3
)CH2COOC2H5, -OCH2COOC2H5
For example, the number of ester bond structures is not limited to one type, and two or more types of ester bond structures may be mixed.
【００１０】主鎖を構成するアルキレンオキシ単位の具
体例としては、−ＣＨ２ＣＨ２Ｏ−、−ＣＨ２ＣＨ（Ｃ
Ｈ３）Ｏ−、 −ＣＨ２ＣＨ（ＣＨ２ＣＨ３）Ｏ−、
−ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ−などが挙げられるが、
この単位は１種類のみでなく２種類以上の単位が混合さ
れていてもよい。特に−ＣＨ２ＣＨ（ＣＨ３）Ｏ− 単
位が好ましいものである。Specific examples of alkyleneoxy units constituting the main chain include -CH2CH2O-, -CH2CH(C
H3)O-, -CH2CH(CH2CH3)O-,
Examples include -CH2CH2CH2CH2O-,
This unit may be a mixture of not only one type but two or more types. In particular, -CH2CH(CH3)O- units are preferred.
【００１１】また、これらのアルキレンオキシ重合体の
基本単位に対し、前述したシラン化合物のアミノ基との
反応を阻害する構造を持たない他の原子団からなる構造
単位が３モル％以下含まれていてもよい。具体的には、
−Ｃ３Ｈ６Ｓｉ（ＣＨ３）２Ｃ３Ｈ６−、 −Ｃ３Ｈ６
Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２Ｃ３Ｈ６−、 −
ＣＨ２Ｓｉ（ＣＨ３）２ＣＨ２−、−ＣＨ２Ｓｉ（ＣＨ
３）２ＯＳｉ（ＣＨ３）２ＣＨ２−、 −Ｃ３Ｈ６Ｓｉ
（ＣＨ３）２Ｏ［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３
）２Ｃ３Ｈ６−、などの構造単位が例示される。[0011] Furthermore, the basic unit of these alkyleneoxy polymers contains 3 mol% or less of a structural unit consisting of another atomic group that does not have a structure that inhibits the reaction with the amino group of the silane compound mentioned above. You can. in particular,
-C3H6Si(CH3)2C3H6-, -C3H6
Si(CH3)2OSi(CH3)2C3H6-, -
CH2Si(CH3)2CH2-, -CH2Si(CH
3) 2OSi(CH3)2CH2-, -C3H6Si
(CH3)2O[Si(CH3)2O]nSi(CH3
)2C3H6-, and other structural units are exemplified.
【００１２】アルキレンオキシド重合体の分子鎖形態は
、直鎖状、分岐状、環状あるいはこれらの構造の組合せ
でもよい。また、この重合体の分子量については特に制
限はないが、入手の容易さを考慮すると分子量が２，０
００から１２，０００のものが好ましい。The molecular chain form of the alkylene oxide polymer may be linear, branched, cyclic, or a combination of these structures. There is no particular restriction on the molecular weight of this polymer, but considering its ease of availability, the molecular weight is 2.0.
00 to 12,000 is preferred.
【００１３】次に、本発明で用いるアミノ基含有アルコ
キシシラン化合物は、一般式Next, the amino group-containing alkoxysilane compound used in the present invention has the general formula
【００１４】[0014]
【化３】[C3]
【００１５】（式中、Ｒ１ は２価の有機基、Ｒ２、Ｒ
３ は同一または異種の１価の有機基、ａは０または１
）で示されるもので、このＲ１ の２価有機基としては
、メチレン基、エチレン基、プロピレン基、メチルエチ
レン基、テトラメチレン基、ヘキサメチレン基等のアル
キレン基、フェニレン基、トリレン基等のアリーレン基
、あるいは−Ｃ２Ｈ４−ＮＨ−Ｃ２Ｈ４−、−Ｃ２Ｈ４
−ＮＨ−Ｃ３Ｈ６−等のイミノ基含有アルキレン基など
が挙げられ、また、Ｒ２、Ｒ３ の１価有機基としては
、メチル基、エチル基、プロピル基、ブチル基等のアル
キル基、ビニル基、アリル基等のアルケニル基、フェニ
ル基、トリル基等のアリール基、シクロヘキシル基等の
シクロアルキル基、ベンジル基、フェニルエチル基等の
アラルキル基、あるいはこれらの基の水素原子の一部ま
たは全部がハロゲン原子、アルコキシ基等で置換された
クロロメチル基、３，３，３−トリフルオロプロピル基
、メトキシエチル基、エトキシエチル基などの、炭素数
１〜１０、好ましくは炭素数１〜６の非置換または置換
の１価炭化水素基が挙げられるが、Ｒ２ としてはアル
キル基、アルケニル基、アリール基、Ｒ３ としてはア
ルキル基、アルコキシ置換アルキル基が好適に使用され
る。(In the formula, R1 is a divalent organic group, R2, R
3 is the same or different monovalent organic group, a is 0 or 1
), and the divalent organic group of R1 includes alkylene groups such as methylene group, ethylene group, propylene group, methylethylene group, tetramethylene group, and hexamethylene group, and arylene groups such as phenylene group and tolylene group. group, or -C2H4-NH-C2H4-, -C2H4
Examples include imino group-containing alkylene groups such as -NH-C3H6-, and monovalent organic groups for R2 and R3 include alkyl groups such as methyl, ethyl, propyl, and butyl groups, vinyl groups, and allyl groups. Alkenyl groups such as phenyl groups, aryl groups such as tolyl groups, cycloalkyl groups such as cyclohexyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, or some or all of the hydrogen atoms of these groups are halogen atoms. unsubstituted or unsubstituted or Substituted monovalent hydrocarbon groups are mentioned, and R2 is preferably an alkyl group, alkenyl group, or aryl group, and R3 is an alkyl group or an alkoxy-substituted alkyl group.
【００１６】上記一般式で示されるシラン化合物として
は、具体的には、
Ｈ２Ｎ−Ｃ３Ｈ６−Ｓｉ（ＯＣＨ３）３、 Ｈ２Ｎ−Ｃ
３Ｈ６−Ｓｉ（ＯＣ２Ｈ５）３、 Ｈ２Ｎ−Ｃ３Ｈ６−
Ｓｉ（ＣＨ３）（ＯＣＨ３）２、Ｈ２Ｎ−Ｃ３Ｈ６−Ｓ
ｉ（ＣＨ３）（ＯＣ２Ｈ５）２、 Ｈ２Ｎ−Ｃ３Ｈ６−
Ｓｉ（Ｃ６Ｈ５）（ＯＣＨ３）２、Ｈ２Ｎ−Ｃ３Ｈ６−
Ｓｉ（Ｃ６Ｈ５）（ＯＣ２Ｈ５）２、 Ｈ２Ｎ−Ｃ３Ｈ
６−Ｓｉ（ＣＨ＝ＣＨ２）（ＯＣＨ３）２、Ｈ２Ｎ−Ｃ
３Ｈ６−Ｓｉ（ＣＨ＝ＣＨ２）（ＯＣ２Ｈ５）２、 Ｈ
２Ｎ−Ｃ２Ｈ４−ＮＨ−Ｃ３Ｈ６−Ｓｉ（ＯＣＨ３）３
、Ｈ２Ｎ−Ｃ２Ｈ４−ＮＨ−Ｃ３Ｈ６−Ｓｉ（ＯＣ２Ｈ
５）３、 Ｈ２Ｎ−Ｃ２Ｈ４−ＮＨ−Ｃ３Ｈ６−Ｓｉ（
ＣＨ３）（ＯＣＨ３）２、Ｈ２Ｎ−Ｃ２Ｈ４−ＮＨ−Ｃ
３Ｈ６−Ｓｉ（ＣＨ３）（ＯＣ２Ｈ５）２、 Ｈ２Ｎ−
Ｃ２Ｈ４−ＮＨ−Ｃ３Ｈ６−Ｓｉ（Ｃ６Ｈ５）（ＯＣＨ
３）２、Ｈ２Ｎ−Ｃ２Ｈ４−ＮＨ−Ｃ３Ｈ６−Ｓｉ（Ｃ
６Ｈ５）（ＯＣ２Ｈ５）２、 Ｈ２Ｎ−Ｃ２Ｈ４−ＮＨ
−Ｃ３Ｈ６−Ｓｉ（ＣＨ＝ＣＨ２）（ＯＣＨ３）２、Ｈ
２Ｎ−Ｃ２Ｈ４−ＮＨ−Ｃ３Ｈ６−Ｓｉ（ＣＨ＝ＣＨ２
）（ＯＣ２Ｈ５）２、などが例示される。[0016] Specific examples of the silane compound represented by the above general formula include H2N-C3H6-Si(OCH3)3, H2N-C
3H6-Si(OC2H5)3, H2N-C3H6-
Si(CH3)(OCH3)2, H2N-C3H6-S
i(CH3)(OC2H5)2, H2N-C3H6-
Si(C6H5)(OCH3)2, H2N-C3H6-
Si(C6H5)(OC2H5)2, H2N-C3H
6-Si(CH=CH2)(OCH3)2, H2N-C
3H6-Si(CH=CH2)(OC2H5)2, H
2N-C2H4-NH-C3H6-Si(OCH3)3
, H2N-C2H4-NH-C3H6-Si(OC2H
5) 3, H2N-C2H4-NH-C3H6-Si(
CH3)(OCH3)2, H2N-C2H4-NH-C
3H6-Si(CH3)(OC2H5)2, H2N-
C2H4-NH-C3H6-Si(C6H5)(OCH
3) 2, H2N-C2H4-NH-C3H6-Si(C
6H5)(OC2H5)2, H2N-C2H4-NH
-C3H6-Si(CH=CH2)(OCH3)2,H
2N-C2H4-NH-C3H6-Si(CH=CH2
)(OC2H5)2, etc. are exemplified.
【００１７】これらのシラン化合物のアミノ基と、先に
示した、分子鎖末端にエステル結合を有するアルキレン
オキシド重合体のエステル結合部位とを反応させるには
、エステル結合部位に対し１〜１０倍モルのアミノ基を
有するアルコキシシラン化合物を反応させればよい。
この反応における両者の組合せは、エステル結合および
アルコキシ基の加水分解により生成するアルコールが同
一であるものが特に好ましい。この場合、０℃から３０
０℃の温度範囲で、無溶剤もしくはトルエン、キシレン
などの溶剤の存在下で反応を行えばよい。特に好ましい
反応温度範囲は１００℃から１５０℃である。また、反
応の進行を円滑にするため、窒素などの不活性気体を流
し、生成するアルコールを系外に取り除くことが望まし
い。In order to react the amino group of these silane compounds with the ester bond site of the alkylene oxide polymer having an ester bond at the end of the molecular chain, a molar amount of 1 to 10 times the ester bond site is required. What is necessary is just to react the alkoxysilane compound which has an amino group of. It is particularly preferred that the combination of the two in this reaction is one in which the ester bond and the alcohol produced by hydrolysis of the alkoxy group are the same. In this case, from 0℃ to 30℃
The reaction may be carried out in the temperature range of 0° C. without a solvent or in the presence of a solvent such as toluene or xylene. A particularly preferred reaction temperature range is 100°C to 150°C. Furthermore, in order to facilitate the progress of the reaction, it is desirable to flow an inert gas such as nitrogen to remove the generated alcohol from the system.
【００１８】[0018]
【実施例】次に、本発明の実施例を挙げる。
実施例１
加熱真空乾燥により脱水した、分子量３，１００の分子
鎖末端が−ＯＣＨ２ＣＯＯＣＨ３で示される構造で封鎖
されたポリプロピレングリコール１００ｇに、１５ｇの
γ−アミノプロピルトリメトキシシランを添加し、窒素
気流下１５０℃で４時間反応させた。反応終了後、反応
溶液中の揮発分を加熱減圧下に取り除くことにより、生
成物を透明感のある粘ちょうな液体として１１３ｇ（９
９％）回収した。[Examples] Next, examples of the present invention will be given. Example 1 15 g of γ-aminopropyltrimethoxysilane was added to 100 g of polypropylene glycol with a molecular weight of 3,100, which had been dehydrated by heating and vacuum drying and whose molecular chain terminals were capped with a structure represented by -OCH2COOCH3, and the mixture was dried under a nitrogen stream. The reaction was carried out at 150°C for 4 hours. After the reaction is complete, the volatile matter in the reaction solution is removed under heating and reduced pressure, yielding 113 g (9 ml) of the product as a transparent and viscous liquid.
9%) recovered.
【００１９】得られた生成物の分子量は３，５００であ
った。また、核磁気共鳴スペクトル分析、赤外吸収スペ
クトル分析及びアルカリ分解法によるＳｉ−ＯＣＨ３
基量測定分析により、γ−アミノプロピルトリメトキシ
シランのアミノ基とポリプロピレングリコールの末端メ
チルエステル基が脱メタノール反応により化学量論的に
アミド結合を形成していることを確認した。また、生成
物１００重量部に対し、ジオクチルスズジメトキサイド
１重量部を添加した組成物からはゴム弾性を示す硬化物
が得られた。The molecular weight of the product obtained was 3,500. In addition, Si-OCH3 by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and alkaline decomposition method
By base weight measurement analysis, it was confirmed that the amino group of γ-aminopropyltrimethoxysilane and the terminal methyl ester group of polypropylene glycol stoichiometrically formed an amide bond through a demethanol reaction. Furthermore, a cured product exhibiting rubber elasticity was obtained from a composition in which 1 part by weight of dioctyltin dimethoxide was added to 100 parts by weight of the product.
【００２０】実施例２
加熱真空乾燥により脱水した、分子量１１，０００の分
子鎖末端が
−ＯＣＨ２ＣＯＯＣＨ３ で示される構造で封鎖されか
つ主鎖中に−Ｃ３Ｈ６Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３
）２Ｃ３Ｈ６− で示される構造単位を３個含有するポ
リプロピレングリコール１００ｇに、１０ｇのγ−アミ
ノプロピルトリメトキシシランを添加し、窒素気流下１
５０℃で４時間反応させた。反応終了後、反応溶液中の
揮発分を加熱減圧下に取り除くことにより、生成物を透
明感のある粘ちょうな液体として１０７ｇ（９８％）回
収した。Example 2 A polymer with a molecular weight of 11,000 was dehydrated by heating and vacuum drying, and the terminal end of the molecular chain was blocked with a structure represented by -OCH2COOCH3, and -C3H6Si(CH3)2OSi(CH3
) 2C3H6- 10g of γ-aminopropyltrimethoxysilane was added to 100g of polypropylene glycol containing three structural units represented by
The reaction was carried out at 50°C for 4 hours. After the reaction was completed, the volatile matter in the reaction solution was removed under reduced pressure under heating to recover 107 g (98%) of the product as a transparent viscous liquid.
【００２１】得られた生成物の分子量は１２，０００で
あった。また、核磁気共鳴スペクトル分析、赤外吸収ス
ペクトル分析及びアルカリ分解法によるＳｉ−ＯＣＨ３
基量測定分析により、γ−アミノプロピルトリメトキ
シシランのアミノ基とポリプロピレングリコールの末端
メチルエステル基が脱メタノール反応により化学量論的
にアミド結合を形成していることを確認した。また、生
成物１００重量部に対し、ジオクチルスズジメトキサイ
ド１重量部を添加した組成物からはゴム弾性を示す硬化
物が得られた。The molecular weight of the product obtained was 12,000. In addition, Si-OCH3 by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and alkaline decomposition method
By base weight measurement analysis, it was confirmed that the amino group of γ-aminopropyltrimethoxysilane and the terminal methyl ester group of polypropylene glycol stoichiometrically formed an amide bond through a demethanol reaction. Furthermore, a cured product exhibiting rubber elasticity was obtained from a composition in which 1 part by weight of dioctyltin dimethoxide was added to 100 parts by weight of the product.
【００２２】実施例３
加熱真空乾燥により脱水した、分子量１１，０００の分
子鎖末端が
−ＯＣＨ２ＣＯＯＣ２Ｈ５で示される構造で封鎖されか
つ主鎖中に−Ｃ３Ｈ６Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３
）２Ｃ３Ｈ６− で示される構造単位を３個含有するポ
リプロピレングリコール１００ｇに、１０ｇのγ−アミ
ノプロピルトリエトキシシランを添加し、窒素気流下１
５０℃で４時間反応させた。反応終了後、反応溶液中の
揮発分を加熱減圧下に取り除くことにより、生成物を透
明感のある粘ちょうな液体として１０６ｇ（９６％）回
収した。Example 3 A polymer with a molecular weight of 11,000 was dehydrated by heating and vacuum drying, and the terminal end of the molecular chain was blocked with a structure represented by -OCH2COOC2H5, and -C3H6Si(CH3)2OSi(CH3
) 2C3H6- 10g of γ-aminopropyltriethoxysilane was added to 100g of polypropylene glycol containing three structural units represented by
The reaction was carried out at 50°C for 4 hours. After the reaction was completed, the volatile matter in the reaction solution was removed under reduced pressure under heating to recover 106 g (96%) of the product as a transparent viscous liquid.
【００２３】得られた生成物の分子量は１２，０００で
あった。また、核磁気共鳴スペクトル分析、赤外吸収ス
ペクトル分析及びアルカリ分解法によるＳｉ−ＯＣ２Ｈ
５基量測定分析により、γ−アミノプロピルトリエトキ
シシランのアミノ基とポリプロピレングリコールの末端
エチルエステル基が脱エタノール反応により化学量論的
にアミド結合を形成していることを確認した。また、生
成物１００重量部に対し、ジオクチルスズジメトキサイ
ド１重量部を添加した組成物からはゴム弾性を示す硬化
物が得られた。The molecular weight of the product obtained was 12,000. In addition, Si-OC2H by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and alkaline decomposition method
It was confirmed by five-base weight measurement analysis that the amino group of γ-aminopropyltriethoxysilane and the terminal ethyl ester group of polypropylene glycol stoichiometrically formed an amide bond through a deethanol reaction. Furthermore, a cured product exhibiting rubber elasticity was obtained from a composition in which 1 part by weight of dioctyltin dimethoxide was added to 100 parts by weight of the product.
【００２４】実施例４
加熱真空乾燥により脱水した、分子量１１，０００の分
子鎖末端が
−ＯＣＨ２ＣＯＯＣＨ３ で示される構造で封鎖されか
つ主鎖中に−Ｃ３Ｈ６Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３
）２Ｃ３Ｈ６− で示される構造単位を３個含有するポ
リプロピレングリコール１００ｇに、７ｇのＮ−（β−
アミノエチル）−γ−アミノプロピルトリメトキシシラ
ンを添加し、窒素気流下１５０℃で４時間反応させた。
反応終了後、反応溶液中の揮発分を加熱減圧下に取り除
くことにより、生成物を透明感のある粘ちょうな液体と
して１０３ｇ（９６％）回収した。Example 4 A polymer with a molecular weight of 11,000 was dehydrated by heating and vacuum drying, and the terminal end of the molecular chain was blocked with a structure represented by -OCH2COOCH3, and -C3H6Si(CH3)2OSi(CH3
)2C3H6- 7g of N-(β-
(aminoethyl)-γ-aminopropyltrimethoxysilane was added, and the mixture was reacted at 150° C. for 4 hours under a nitrogen stream. After the reaction was completed, volatile components in the reaction solution were removed under reduced pressure under heating to recover 103 g (96%) of the product as a transparent viscous liquid.
【００２５】得られた生成物の分子量は１２，０００で
あった。また、核磁気共鳴スペクトル分析、赤外吸収ス
ペクトル分析及びアルカリ分解法によるＳｉ−ＯＣＨ３
基量測定分析により、Ｎ−（β−アミノエチル）−γ
−アミノプロピルトリメトキシシランのアミノ基とポリ
プロピレングリコールの末端メチルエステル基が脱メタ
ノール反応により化学量論的にアミド結合を形成してい
ることを確認した。また、生成物１００重量部に対し、
ジオクチルスズジメトキサイド１重量部を添加した組成
物からはゴム弾性を示す硬化物が得られた。The molecular weight of the product obtained was 12,000. In addition, Si-OCH3 by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and alkaline decomposition method
By base measurement analysis, N-(β-aminoethyl)-γ
It was confirmed that the amino group of -aminopropyltrimethoxysilane and the terminal methyl ester group of polypropylene glycol stoichiometrically formed an amide bond through a demethanol reaction. Also, for 100 parts by weight of the product,
A cured product exhibiting rubber elasticity was obtained from a composition to which 1 part by weight of dioctyltin dimethoxide was added.
【００２６】[0026]
【発明の効果】本発明により新規なシラン架橋性アルキ
レンオキシド重合体の製造方法が提供された。本発明の
方法は、従来の技術と比較して容易に、即ち一段の反応
で収率よくしかも目的とする反応が化学量論的に定量的
に進行するものであり、生成物の回収も容易に行うこと
ができるものである。[Effects of the Invention] The present invention provides a novel method for producing a silane crosslinkable alkylene oxide polymer. The method of the present invention is easier than conventional techniques, that is, it is a one-step reaction with a high yield, and the desired reaction proceeds stoichiometrically and quantitatively, and the product can be easily recovered. This is something that can be done.
【化４】[C4]
Claims (1)
レンオキシド重合体のエステル結合部位と、一般式【化
１】 （式中、Ｒ１ は２価の有機基、Ｒ２、Ｒ３ は同一ま
たは異種の１価の有機基、ａは０または１）で示される
シラン化合物のアミノ基とを反応させることを特徴とす
る、シラン架橋性アルキレンオキシド重合体の製造方法
。Claim 1: An ester bonding site of an alkylene oxide polymer having an ester bond at the end of the molecular chain, and an ester bonding site of the general formula [Formula 1] (wherein R1 is a divalent organic group, R2 and R3 are the same or different 1 1. A method for producing a silane crosslinkable alkylene oxide polymer, which comprises reacting a valent organic group, a being 0 or 1) with an amino group of a silane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3160077A JP2554412B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing silane crosslinkable alkylene oxide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3160077A JP2554412B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing silane crosslinkable alkylene oxide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04359018A true JPH04359018A (en) | 1992-12-11 |
| JP2554412B2 JP2554412B2 (en) | 1996-11-13 |
Family
ID=15707378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3160077A Expired - Fee Related JP2554412B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing silane crosslinkable alkylene oxide polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2554412B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191723A (en) * | 1970-09-08 | 1984-10-30 | ミネソタ、マイニング、アンド、マニユフアクチユアリング、コンパニ− | Manufacture of bis-trialkoxysilane compound |
| JPH02228365A (en) * | 1989-03-01 | 1990-09-11 | Kanegafuchi Chem Ind Co Ltd | Two-component hardenable composition with improved storage stability |
| JPH03195768A (en) * | 1989-12-22 | 1991-08-27 | Dainippon Ink & Chem Inc | Moisture-curable composition |
-
1991
- 1991-06-03 JP JP3160077A patent/JP2554412B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191723A (en) * | 1970-09-08 | 1984-10-30 | ミネソタ、マイニング、アンド、マニユフアクチユアリング、コンパニ− | Manufacture of bis-trialkoxysilane compound |
| JPH02228365A (en) * | 1989-03-01 | 1990-09-11 | Kanegafuchi Chem Ind Co Ltd | Two-component hardenable composition with improved storage stability |
| JPH03195768A (en) * | 1989-12-22 | 1991-08-27 | Dainippon Ink & Chem Inc | Moisture-curable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2554412B2 (en) | 1996-11-13 |
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