JPH04334390A - New silane compound and production thereof - Google Patents
New silane compound and production thereofInfo
- Publication number
- JPH04334390A JPH04334390A JP13040091A JP13040091A JPH04334390A JP H04334390 A JPH04334390 A JP H04334390A JP 13040091 A JP13040091 A JP 13040091A JP 13040091 A JP13040091 A JP 13040091A JP H04334390 A JPH04334390 A JP H04334390A
- Authority
- JP
- Japan
- Prior art keywords
- silane compound
- ketene dimer
- compound
- silane
- dimer
- 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
- -1 silane compound Chemical class 0.000 title claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical class C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical class O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 8
- 239000000539 dimer Substances 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- SZPHJWIVTRIHBG-UHFFFAOYSA-N octadec-1-en-1-one Chemical class CCCCCCCCCCCCCCCCC=C=O SZPHJWIVTRIHBG-UHFFFAOYSA-N 0.000 description 6
- 125000000913 palmityl 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])C([H])([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 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000004798 β-ketoamides Chemical group 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001204 arachidyl 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])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])[H] 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- FZRKAZHKEDOPNN-UHFFFAOYSA-N Nitric oxide anion Chemical compound O=[N-] FZRKAZHKEDOPNN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 1
- 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 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 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 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GAPJZAHIPBLCCF-UHFFFAOYSA-N hexadec-1-en-1-one Chemical class CCCCCCCCCCCCCCC=C=O GAPJZAHIPBLCCF-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 125000002960 margaryl 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])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])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- VNRDAMBPFDPXSM-UHFFFAOYSA-N n'-[2-(3-triethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCNCCN VNRDAMBPFDPXSM-UHFFFAOYSA-N 0.000 description 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical group O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 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 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002958 pentadecyl 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])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 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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、シランカップリング剤
などとして有用である耐水性、密着性などの諸性能が優
れた安価なシラン化合物、およびその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inexpensive silane compound that is useful as a silane coupling agent and has excellent properties such as water resistance and adhesion, and a method for producing the same.
【０００２】0002
【従来の技術】シラン化合物は、一般的には耐水性、密
着性などの諸性能が良好である。そのため、例えばガラ
ス表面などの無機基材と、塗料、プラスチックなどの有
機基材との層間接着強度を改良する、いわゆるシランカ
ップリング剤として種々の用途に使用されている。近時
、これらの適用条件の多様化、高度化にともない、種々
の新規なシラン化合物の開発が進められている。BACKGROUND OF THE INVENTION Silane compounds generally have good properties such as water resistance and adhesion. Therefore, it is used in various applications as a so-called silane coupling agent, which improves the interlayer adhesive strength between inorganic substrates such as glass surfaces and organic substrates such as paints and plastics. Recently, as these application conditions have become more diverse and sophisticated, various new silane compounds have been developed.
【０００３】例えば、酸性雨によるコンクリ−ト、セメ
ントなどの劣化を有効に防止することのできる、特に耐
水性の優れたシランカップリング剤の開発が近時切望さ
れている。しかし、シラン化合物は、一般の有機化合物
に比べて製造方法が複雑であったり高価格であるなどの
問題があり、経済的かつ実用的なシランカップリング剤
は必ずしも見い出されていないのが現状である。For example, there has recently been a strong desire to develop a silane coupling agent that has particularly excellent water resistance and can effectively prevent deterioration of concrete, cement, etc. caused by acid rain. However, compared to general organic compounds, silane compounds have problems such as being more complicated to produce and being more expensive, so it is currently difficult to find an economical and practical silane coupling agent. be.
【０００４】0004
【発明が解決しようとする課題】本発明は、高価格であ
り、引火性の高い、従来の高級アルキルアルコキシシラ
ン化合物の持つ欠点を解消し、しかも無機質との密着性
などのシラン化合物本来の諸性能を高度に維持するとと
もに、特に耐水性の優れたシランカップリング剤として
好適なシラン化合物を提供することを目的とする。[Problems to be Solved by the Invention] The present invention solves the disadvantages of conventional higher alkyl alkoxysilane compounds, which are expensive and highly flammable, and also solves the inherent problems of silane compounds such as adhesion to inorganic materials. It is an object of the present invention to provide a silane compound suitable as a silane coupling agent that maintains high performance and particularly has excellent water resistance.
【０００５】[0005]
【課題を解決するための手段】本発明者は前記課題を解
決するために、アミノ基含有オルガノアルコキシシラン
化合物を改質しうる各種の疎水性化合物およびこれら化
合物の反応方法につき鋭意検討を行った。その結果、ア
ミノ基含有オルガノアルコキシシラン化合物と特定の疎
水性化合物たる置換ケテンダイマ−を反応させてなる特
定のシラン化合物を使用した場合に初めて前記目的を達
成しうることを見い出した。本発明はかかる知見に基づ
き完成されたものである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on various hydrophobic compounds that can modify amino group-containing organoalkoxysilane compounds and reaction methods for these compounds. . As a result, it was discovered that the above object could be achieved only when a specific silane compound formed by reacting an amino group-containing organoalkoxysilane compound with a specific hydrophobic compound, ie, a substituted ketene dimer, was used. The present invention was completed based on this knowledge.
【０００６】すなわち本発明は、アミノ基を有するオル
ガノアルコキシシラン化合物（Ａ）に置換ケテンダイマ
−（Ｂ）を反応させて得られるシラン化合物に関する。
更には、前記シラン化合物（Ａ）と前記ケテンダイマ−
（Ｂ）とを、シラン化合物（Ａ）に含有されるアミノ基
の全合計数Ｘに対してケテンダイマ−（Ｂ）に含有され
るβ−プロピオラクトン基が１〜Ｘとなる割合で反応さ
せることを特徴とするシラン化合物の製造法に関する。Specifically, the present invention relates to a silane compound obtained by reacting an organoalkoxysilane compound (A) having an amino group with a substituted ketene dimer (B). Furthermore, the silane compound (A) and the ketene dimer
(B) is reacted with the silane compound (A) in a ratio such that the number of β-propiolactone groups contained in the ketene dimer (B) is 1 to X with respect to the total number X of amino groups contained in the silane compound (A). The present invention relates to a method for producing a silane compound characterized by the following.
【０００７】本発明において用いる、アミノ基を有する
オルガノアルコキシシラン化合物（以下、シラン化合物
（Ａ）と称す）としては、例えば３−アミノプロピルト
リメトキシシラン、３−アミノプロピルトリエトキシシ
ラン、Ｎ−２−アミノエチル−３−アミノプロピルトリ
メトキシシラン、Ｎ−２−アミノエチル−３−アミノプ
ロピルトリエトキシシラン、トリメトキシシリルプロピ
ルジエチレントリアミン、トリエトキシシリルプロピル
ジエチレントリアミン、Ｎ−（２−アミノエチル）アミ
ノプロピルメチルジメトキシシラン、Ｎ−（２−アミノ
エチル）アミノプロピルメチルジエトキシシラン、３−
アミノプロピルメチルジメトキシシラン、３−アミノプ
ロピルメチルジエトキシシランなど各種公知の化合物を
挙げることができる。これらは単独使用の他、適宜に２
種以上を併用しても良い。Examples of the organoalkoxysilane compound having an amino group (hereinafter referred to as silane compound (A)) used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 -Aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, trimethoxysilylpropyldiethylenetriamine, triethoxysilylpropyldiethylenetriamine, N-(2-aminoethyl)aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)aminopropylmethyldiethoxysilane, 3-
Various known compounds such as aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane can be mentioned. In addition to using these alone, you can also use 2
You may use more than one species together.
【０００８】本発明において用いる置換ケテンダイマ−
（以下、ダイマ−（Ｂ）と称す）としては、特に制限は
されず、各種公知のものを任意に選択使用することがで
きる。原料の入手性などを考慮すれば、下記一般式で表
されるものが好適である。Substituted ketene dimer used in the present invention
The dimer (hereinafter referred to as dimer (B)) is not particularly limited, and various known dimers can be arbitrarily selected and used. Considering the availability of raw materials, those represented by the following general formula are preferred.
【０００９】[0009]
【化１】[Chemical formula 1]
【００１０】ダイマ−（Ｂ）の飽和または不飽和炭化水
素基であるＲ１、Ｒ２ としては、例えばオクチル、デ
シル、ウンデシル、ドデシル、トリデシル、テトラデシ
ル、ペンタデシル、ヘキサデシル、ヘプタデシル、オク
タデシル、エイコシル、トリアコンタニル基などのアル
キル基、デセニル、トリデセニル、ヘキサデセニル、オ
クタデセニル、エイコセニル基などのアルケニル基など
を例示しうる。これら置換ケテンダイマーは、単独また
は混合して使用できる。また、天然脂肪酸、牛脂油、硬
化牛脂油などから合成されるものであってもさしつかえ
ない。The saturated or unsaturated hydrocarbon groups R1 and R2 of dimer (B) include, for example, octyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, triacontanyl. Examples thereof include alkyl groups such as decenyl, tridecenyl, hexadecenyl, octadecenyl, and eicosenyl groups. These substituted ketene dimers can be used alone or in combination. Furthermore, it may be synthesized from natural fatty acids, beef tallow oil, hydrogenated beef tallow oil, etc.
【００１１】本発明のシラン化合物を製造するには、前
記シラン化合物（Ａ）とダイマ−（Ｂ）を特定割合で混
合撹拌しながら反応させれば良い。通常は、シラン化合
物（Ａ）の全アミノ基Ｘ当量に対してβ−プロピオラク
トン基が１〜Ｘ当量、好ましくは１級アミノ基１当量に
対しβ−プロピオラクトン基が１当量となる割合で、両
者を通常６０〜８０℃程度で滴下混合後５分〜１時間程
度反応させる事により容易に目的物を収得できる。なお
、反応時の発熱を考慮して、必要により冷却操作を行っ
ても良いし、トルエン、キシレンなどの適当な溶剤の存
在下に反応させても良い。In order to produce the silane compound of the present invention, the silane compound (A) and the dimer (B) may be mixed and reacted in a specific ratio while stirring. Usually, the β-propiolactone group is 1 to X equivalents relative to the total amino group X equivalents of the silane compound (A), and preferably the β-propiolactone group is 1 equivalent relative to 1 equivalent of the primary amino group. The desired product can be easily obtained by dropwise mixing the two at a ratio of about 60 to 80° C. and then reacting them for about 5 minutes to 1 hour. In addition, in consideration of heat generation during the reaction, a cooling operation may be performed if necessary, or the reaction may be carried out in the presence of an appropriate solvent such as toluene or xylene.
【００１２】上記方法により得られる本発明のシラン化
合物は、シラン化合物（Ａ）のアミノ基とダイマ−（Ｂ
）のβ−プロピオラクトン基の反応により生じたβ−ケ
トアミド基を有する化合物である。両者の反応は、例え
ば次式で表すことができる。The silane compound of the present invention obtained by the above method has the amino group of the silane compound (A) and the dimer (B
) is a compound having a β-ketoamide group produced by the reaction of the β-propiolactone group. Both reactions can be expressed, for example, by the following formula.
【００１３】[0013]
【化２】[Chemical 2]
【００１４】本発明のシラン化合物を適用するに当たり
、基材への塗布様式、塗布手段などは特に制限されるも
のではない。例えば該化合物をそのまま各種基材に塗布
しうるのはもとより、所望により溶剤に溶解させて塗布
しても良く、また適当な乳化剤を用いて水性分散状態に
して適用することもできる。更には、アルコキシ基の一
部を加水分解して使用しても良く、目的に応じて他の樹
脂または他のシラン化合物を併用しても良い。[0014] When applying the silane compound of the present invention, there are no particular restrictions on the manner of application to the substrate, the application means, etc. For example, the compound can be applied as it is to various substrates, or if desired, it can be dissolved in a solvent and applied, or it can be applied in an aqueous dispersion state using a suitable emulsifier. Furthermore, a part of the alkoxy group may be hydrolyzed and used, and other resins or other silane compounds may be used in combination depending on the purpose.
【００１５】[0015]
【発明の効果】本発明により、安価で、しかも耐水性、
密着性などの諸性能の良好なシラン化合物、ならびに該
化合物を容易に収得することのできる製造法を提供しう
るという多大な効果が奏せられる。[Effects of the invention] The present invention provides inexpensive, water-resistant,
This has the great effect of providing a silane compound with good properties such as adhesion, as well as a manufacturing method that allows the compound to be easily obtained.
【００１６】[0016]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明するが、本発明はこれら実施例に限定されるもので
はない。[Examples] The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
【００１７】実施例１
反応容器にヘキサデシルケテンダイマ−（化１において
Ｒ１ 、Ｒ２ がともにヘキサデシル基であり、融点が
６２℃のもの）５３０ｇ（１モル）を仕込み、加熱融解
したのち、系内温度７５℃で３−アミノプロピルトリエ
トキシシラン２２１ｇ（１モル）を１時間かけて滴下し
た。
なお、滴下時の発熱を除去するため適宜撹拌下に冷却を
行いながら系内温度を７５℃に維持した。滴下後、７０
℃〜８０℃で１５分撹拌した後、内容物を取り出した。
得られたシラン化合物は融点６９℃の淡黄色ワックス状
物であった。Example 1 530 g (1 mole) of hexadecyl ketene dimer (R1 and R2 in chemical formula 1 are both hexadecyl groups and the melting point is 62°C) was charged into a reaction vessel, and after melting by heating, At a temperature of 75°C, 221 g (1 mol) of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. In addition, in order to remove heat generated during the dropwise addition, the system temperature was maintained at 75° C. while cooling with appropriate stirring. After dripping, 70
After stirring for 15 minutes at ~80°C, the contents were removed. The obtained silane compound was a pale yellow waxy substance with a melting point of 69°C.
【００１８】ＩＲ（ｎｅａｔ）：アミド基：３２９０、
１６４２ｃｍ−１、β−ケト基：１７２０ｃｍ−１、ア
ルコキシシリル基：１０９０ｃｍ−１、上記より、β−
ケトアミドが生成していることおよび原料であるケテン
ダイマ−化合物由来のβ−プロピオラクトン基に基づく
吸収（１８５０ｃｍ−１）が消失していることが明確で
ある（図１および２参照）。IR (neat): amide group: 3290,
1642 cm-1, β-keto group: 1720 cm-1, alkoxysilyl group: 1090 cm-1, from the above, β-
It is clear that ketoamide has been produced and that the absorption (1850 cm-1) based on the β-propiolactone group derived from the ketene dimer compound as a raw material has disappeared (see Figures 1 and 2).
【００１９】ＨＬＣ：得られたシラン化合物はヘキサデ
シルケテンダイマ−より分子量が大きい単一成分である
ことが分かる（図３および４参照）。HLC: The obtained silane compound is found to be a single component having a larger molecular weight than the hexadecylketene dimer (see Figures 3 and 4).
【００２０】実施例２
エイコシルケテンダイマ−（化１においてＲ１ 、Ｒ２
がともにエイコシル基であり、融点が６５℃のもの）
６４１ｇ（１モル）を実施例１と同様に反応させた。得
られたシラン化合物は融点７０℃の淡黄色ワックス状物
であった。ＩＲは実施例１と同様の特性吸収を示し、β
−ケトアミド基の生成が認められた。Example 2 Eicosylketene dimer (R1, R2 in formula 1)
are both eicosyl groups and have a melting point of 65°C)
641 g (1 mol) was reacted in the same manner as in Example 1. The obtained silane compound was a pale yellow waxy substance with a melting point of 70°C. IR shows characteristic absorption similar to Example 1, and β
- Generation of ketoamide groups was observed.
【００２１】実施例３
テトラデシルケテンダイマ−（化１においてＲ１ 、Ｒ
２ がともにテトラデシル基であるもの）、ヘキサデシ
ルケテンダイマ−（化１においてＲ１ 、Ｒ２ がとも
にヘキサデシル基であるもの）、およびテトラデシルヘ
キサデシルケテンダイマ−（化１においてＲ１ 、Ｒ２
のいずれか一方がテトラデシル基であり、他方がヘキ
サデシル基であるもの）からなる混合物（硬化牛脂油よ
り得られた脂肪酸より誘導されたケテンダイマ−であり
、融点が５１℃のもの）５１０ｇ（１モル）を実施例１
と同様に反応させた。得られたシラン化合物は融点６３
℃の淡黄色ワックス状物であった。ＩＲは実施例１と同
様の特性吸収を示し、β−ケトアミド基の生成が認めら
れた。Example 3 Tetradecylketene dimer (R1, R
2 are both tetradecyl groups), hexadecyl ketene dimer (in formula 1, R1 and R2 are both hexadecyl groups), and tetradecylhexadecylketene dimer (in formula 1, R1 and R2 are both hexadecyl groups)
(one of which is a tetradecyl group and the other is a hexadecyl group) (a ketene dimer derived from a fatty acid obtained from hydrogenated tallow oil and has a melting point of 51°C) 510 g (1 mol) ) as Example 1
reacted in the same way. The obtained silane compound has a melting point of 63
It was a pale yellow wax-like substance at ℃. IR showed the same characteristic absorption as in Example 1, and the formation of a β-ketoamide group was observed.
【００２２】実施例４
ヘキサデシルケテンダイマ−５３０ｇ（１モル）と３−
アミノプロピルトリメトキシシラン１７９ｇ（１モル）
を実施例１と同様に反応させた。得られたシラン化合物
は融点５８℃の淡黄色ワックス状物であった。ＩＲは実
施例１と同様の特性吸収を示し、β−ケトアミド基の生
成が認められた。Example 4 530 g (1 mol) of hexadecylketene dimer and 3-
Aminopropyltrimethoxysilane 179g (1 mol)
were reacted in the same manner as in Example 1. The obtained silane compound was a pale yellow waxy substance with a melting point of 58°C. IR showed the same characteristic absorption as in Example 1, and formation of a β-ketoamide group was observed.
【００２３】実施例５
反応容器にＮ−２−アミノエチル−３−アミノプロピル
トリメトキシシラン２２２ｇ（１モル）を仕込み、系内
温度を７０℃にした後、加熱溶解したヘキサデシルケテ
ンダイマ−５３０ｇ（１モル）を滴下した。他は実施例
１と同様に行った。得られたシラン化合物は融点４６℃
の淡黄色ワックス状物であった。ＩＲは実施例１と同様
の特性を示し、β−ケトアミド基の生成が認められた。Example 5 222g (1 mol) of N-2-aminoethyl-3-aminopropyltrimethoxysilane was charged into a reaction vessel, and after the system temperature was brought to 70°C, 530g of hexadecylketene dimer was heated and dissolved. (1 mol) was added dropwise. The rest was carried out in the same manner as in Example 1. The obtained silane compound has a melting point of 46°C
It was a pale yellow waxy substance. IR showed the same characteristics as in Example 1, and formation of a β-ketoamide group was observed.
【００２４】比較例１〜３として、順にヘキサデシルケ
テンダイマ−（融点６２℃の淡黄色ワックス状物）、高
級アルキルアルコキシシランであるオクタデシルトリエ
トキシシラン（沸点１６５℃〜１６９℃の液体、危険物
第４類第３石油類）、および３−アミノプロピルトリエ
トキシシラン（沸点２１７℃の液体）を使用した。Comparative Examples 1 to 3 are, in order, hexadecylketene dimer (pale yellow waxy substance with a melting point of 62°C), octadecyltriethoxysilane which is a higher alkyl alkoxysilane (a liquid with a boiling point of 165°C to 169°C, and a dangerous substance). 4th class 3rd petroleum) and 3-aminopropyltriethoxysilane (liquid with a boiling point of 217°C) were used.
【００２５】（乳化液の調製）実施例１〜５の各種シラ
ン化合物および比較例１のケテンダイマーの各溶融物な
らびに比較例２〜３の各種種シラン化合物のそれぞれ４
５重量部に対し、リン酸エステル系乳化剤５部を混合し
、熱水９５０重量部を加え、高速ホモジナイザ−にて固
形分濃度５重量％の乳化液を調製した。この液を固形分
濃度０．５重量％となるまで希釈した後、該希釈液をア
プリケ−タ−（１．５ＭＩＬ）を使用してガラス板に塗
布した。その後、１１０℃の循風乾燥器内で３０分間乾
燥させ、供試基板を得た。(Preparation of emulsion) Each melt of the various silane compounds of Examples 1 to 5 and the ketene dimer of Comparative Example 1, and each of the various silane compounds of Comparative Examples 2 to 3
5 parts by weight of phosphoric acid ester emulsifier were mixed with 5 parts by weight, 950 parts by weight of hot water was added, and an emulsion having a solid content concentration of 5% by weight was prepared using a high-speed homogenizer. After diluting this liquid to a solid content concentration of 0.5% by weight, the diluted liquid was applied to a glass plate using an applicator (1.5 MIL). Thereafter, it was dried for 30 minutes in a circulating air dryer at 110° C. to obtain a test substrate.
【００２６】（性能評価方法）乳化性 固形分濃
度５重量％の前記各種の乳化液の乳化状態を目視観察し
、以下の基準で評価した。
○ 均一分散 × 分
離耐水性 前記供試基板に水滴を落とし、接触角
を測定した。また、供試基板をテトラヒドロフランで洗
浄した後、同様に接触角を測定し、以下の基準で評価し
た。
○ １００〜１１０度 △ ７０〜８０度
× ５０度以下
密着性 供試基板をセロハン粘着テープで剥離し
、以下の基準で評価した。
○ 剥離なし × 剥
離あり上記の評価結果は表１に示す。(Performance evaluation method) Emulsifying property The emulsifying state of each of the above-mentioned emulsions having a solid content concentration of 5% by weight was visually observed and evaluated according to the following criteria. ○ Uniform dispersion × Separation Water resistance Water droplets were dropped on the test substrate, and the contact angle was measured. Further, after cleaning the test substrate with tetrahydrofuran, the contact angle was similarly measured and evaluated based on the following criteria. ○ 100-110 degrees △ 70-80 degrees
× Adhesion below 50 degrees The test substrate was peeled off with cellophane adhesive tape, and evaluated based on the following criteria. ○ No peeling × Peeling The above evaluation results are shown in Table 1.
【００２７】[0027]
【表１】[Table 1]
【図１】実施例１で用いた置換ケテンダイマーのＩＲチ
ャートである。FIG. 1 is an IR chart of the substituted ketene dimer used in Example 1.
【図２】実施例１で得られたシラン化合物のＩＲチャー
トである。FIG. 2 is an IR chart of the silane compound obtained in Example 1.
【図３】実施例１で用いた置換ケテンダイマーのＨＬＣ
チャートである。FIG. 3: HLC of substituted ketene dimer used in Example 1
It is a chart.
【図４】実施例１で得られたシラン化合物のＨＬＣチャ
ートである。FIG. 4 is an HLC chart of the silane compound obtained in Example 1.
Claims (4)
シラン化合物（Ａ）に置換ケテンダイマ−（Ｂ）を反応
させて得られるシラン化合物。1. A silane compound obtained by reacting an organoalkoxysilane compound (A) having an amino group with a substituted ketene dimer (B).
ダイマ−（Ｂ）とを、シラン化合物（Ａ）に含有される
アミノ基の全合計数Ｘに対してケテンダイマ−（Ｂ）に
含有されるβ−プロピオラクトン基の数が１〜Ｘとなる
割合で反応させることを特徴とするシラン化合物の製造
法。[Claim 2] The silane compound (A) and the ketene dimer (B) are combined in such a manner that β contained in the ketene dimer (B) is - A method for producing a silane compound, characterized in that the reaction is carried out at a rate such that the number of propiolactone groups is 1 to X.
化１】 で表される置換ケテンダイマ−である請求項１記載のシ
ラン化合物。[Claim 3] The ketene dimer (B) has the following formula: [
The silane compound according to claim 1, which is a substituted ketene dimer represented by the following formula.
化１】で表される置換ケテンダイマ−である請求項２記
載の製造法。[Claim 4] The ketene dimer (B) has the following formula: [
3. The method according to claim 2, which is a substituted ketene dimer represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13040091A JPH04334390A (en) | 1991-05-02 | 1991-05-02 | New silane compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13040091A JPH04334390A (en) | 1991-05-02 | 1991-05-02 | New silane compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04334390A true JPH04334390A (en) | 1992-11-20 |
Family
ID=15033393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13040091A Pending JPH04334390A (en) | 1991-05-02 | 1991-05-02 | New silane compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04334390A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011516648A (en) * | 2008-04-02 | 2011-05-26 | ワッカー ケミー アクチエンゲゼルシャフト | Wax-like β-ketocarbonyl functional organosilicon compound |
-
1991
- 1991-05-02 JP JP13040091A patent/JPH04334390A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011516648A (en) * | 2008-04-02 | 2011-05-26 | ワッカー ケミー アクチエンゲゼルシャフト | Wax-like β-ketocarbonyl functional organosilicon compound |
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