JPH0474184A - Siloxane compound with di(meth)acryloxyalkyl group - Google Patents
Siloxane compound with di(meth)acryloxyalkyl groupInfo
- Publication number
- JPH0474184A JPH0474184A JP18569690A JP18569690A JPH0474184A JP H0474184 A JPH0474184 A JP H0474184A JP 18569690 A JP18569690 A JP 18569690A JP 18569690 A JP18569690 A JP 18569690A JP H0474184 A JPH0474184 A JP H0474184A
- Authority
- JP
- Japan
- Prior art keywords
- group
- meth
- reaction
- formula
- compound
- 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
- -1 Siloxane compound Chemical class 0.000 title claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 17
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003431 cross linking reagent Substances 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- URTNZUIDULVTHR-UHFFFAOYSA-N [2-(2-methylprop-2-enoyloxymethyl)-3-trimethoxysilylpropyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C[Si](OC)(OC)OC)COC(=O)C(C)=C URTNZUIDULVTHR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000000094 2-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 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
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 1
- AVDUEHWPPXIAEB-UHFFFAOYSA-N chloro-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)Cl AVDUEHWPPXIAEB-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([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
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004821 distillation 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
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001400 nonyl 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])[H] 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
- 239000012044 organic layer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は新規な有機官能性シロキサン化合物に関し、更
に詳しくは高酸素透過性コンタクトレンズ材料の架橋剤
として有用である、ジ（メり）アクリロキシアルキル基
を有するシロキサン化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to novel organofunctional siloxane compounds, and more particularly to di(mer)acryloxy compounds useful as crosslinking agents in highly oxygen permeable contact lens materials. The present invention relates to a siloxane compound having an alkyl group.
従来、高酸素透過性コンタクトレンズ材料の架橋剤のう
ち、シロキサンセグメントを含むもとしては１，３−ビ
ス（３−メタクリロキシプロピル） −１，１，３，３
−テトラメチルジシロキサン、α、ω−ビス（３−メタ
クリロキシプロピル）ポリジメチルシロキサン（平均重
合度２以上）が知られている。Conventionally, among crosslinking agents for contact lens materials with high oxygen permeability, 1,3-bis(3-methacryloxypropyl)-1,1,3,3 is used as a crosslinking agent containing a siloxane segment.
-Tetramethyldisiloxane and α,ω-bis(3-methacryloxypropyl)polydimethylsiloxane (average degree of polymerization of 2 or more) are known.
しかしながら、前者の化合物はシロキサンセグメントが
短すぎて酸素透過性が充分でないという欠点がある。一
方、後者の化合物は平均重合度即ちシロキサンセグメン
トの増加によって酸素透過性については改善されている
反面、長いシロキサンセグメントが主鎖骨格に導入され
ることにより、最終的に得られるコンタクトレンズの硬
さが低下するという新たな欠点がある。However, the former compound has the disadvantage that the siloxane segment is too short and oxygen permeability is insufficient. On the other hand, while the latter compound improves oxygen permeability by increasing the average degree of polymerization, that is, increasing the number of siloxane segments, the introduction of long siloxane segments into the main chain skeleton increases the hardness of the final contact lens. There is a new drawback that the amount of energy decreases.
このため、酸素透過性に優れ、しかも硬さの低下を起こ
さない架橋剤が望まれていた。本発明の目的は、高酸素
透過性コンタクトレンズ材料の架橋剤として有用である
、ジ（メタ）アクリロキシアルキル基を存する新規なシ
ロキサン化合物を提供することである。Therefore, a crosslinking agent that has excellent oxygen permeability and does not cause a decrease in hardness has been desired. It is an object of the present invention to provide novel siloxane compounds containing di(meth)acryloxyalkyl groups that are useful as crosslinking agents for high oxygen permeability contact lens materials.
即ち、本発明は一般式
％式％
（式中、ＲＩは水素原子またはメチル基、Ｒ２、Ｒ３、
Ｒ４およびＲ５は水素原子または置換または非置換の１
価の炭化水素基であり互いに同一でも相異なっていても
よい。ｎは１〜３の整数を示す。）で表されるジ（メタ
）アクリロキシアルキル基を有するシロキサン化合物で
ある。That is, the present invention is based on the general formula % (where RI is a hydrogen atom or a methyl group, R2, R3,
R4 and R5 are hydrogen atoms or substituted or unsubstituted 1
They are hydrocarbon groups with different valences and may be the same or different from each other. n represents an integer of 1 to 3. ) is a siloxane compound having a di(meth)acryloxyalkyl group.
本発明の化合物（Ｉ）において、「は水素原子またはメ
チル基であるが、化合物（１）をコンタクトレンズ材料
の架橋剤として使用する場合には、生体適合性を考慮す
ると、ＲＩはメチル基であることが望ましい。In compound (I) of the present invention, "is a hydrogen atom or a methyl group, but when compound (1) is used as a crosslinking agent for contact lens materials, in consideration of biocompatibility, RI is a methyl group. It is desirable that there be.
本発明の化合物（１）において、Ｒ２、Ｒ３、Ｒ“およ
びＲ５は水素原子または置換または非置換の１価の炭化
水素基であり互いに同一でも相異なっていてもよい。Ｒ
２、Ｒ３、Ｒ４およびＲ５としては、例えば、水素原子
；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、ヘプチル基、オクチル基、ノニル基
、デシル基、ドデシル基のようなアルキル基；シクロペ
ンチル基、シクロヘキシル基のようなシクロアルキル基
；２−フェニルエチル基、２−フェニルプロピル基のよ
うなアラルキル基；フェニ／Ｌ４、トリル基のような了
り−ル基；ビニル基、アリル基のようなアルケニル基；
およびこれらの１価の炭化水素基の炭素原子に結合した
水素原子が部分的にハロゲン原子、アミノ基、シアノ基
などで置換されたクロロメチル基、クロロフェニル基、
３．３．３−トリフルオロプロピル基、２−アミノエチ
ル基、２−シアノエチル基のような置換炭化水素基が例
示される。これらの中でも、原料の入手および合成が容
易なことから炭素数１〜４の飽和炭化水素基や３，３．
３− ）リフルオロプロピル基が望ましく、さらに生体
適合性の観点から、メチル基が特に好ましい。In the compound (1) of the present invention, R2, R3, R'' and R5 are hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups, and may be the same or different from each other.
2, R3, R4 and R5 include, for example, a hydrogen atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Alkyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; aralkyl group such as 2-phenylethyl group, 2-phenylpropyl group; oryl group such as phenyl/L4, tolyl group; vinyl group, Alkenyl groups such as allyl groups;
and chloromethyl groups, chlorophenyl groups, in which the hydrogen atoms bonded to the carbon atoms of these monovalent hydrocarbon groups are partially substituted with halogen atoms, amino groups, cyano groups, etc.
Examples include substituted hydrocarbon groups such as 3.3.3-trifluoropropyl group, 2-aminoethyl group, and 2-cyanoethyl group. Among these, saturated hydrocarbon groups having 1 to 4 carbon atoms and 3,3.
3-) A lifluoropropyl group is preferable, and a methyl group is particularly preferable from the viewpoint of biocompatibility.
本発明の化合物（Ｉ）において、ｎは１〜３の整数であ
るが、化合物（Ｉ）をコンタクトレンズ材料の架橋剤と
して使用する場合には、酸素透過性を考慮すると、ｎは
３であることが好ましい。In compound (I) of the present invention, n is an integer of 1 to 3, but when compound (I) is used as a crosslinking agent for contact lens materials, n is 3 in consideration of oxygen permeability. It is preferable.
本発明の化合物（Ｉ）の製法の一例を以下に説明する。An example of the method for producing compound (I) of the present invention will be explained below.
本発明の化合物（Ｉ）の製法としては、−最大
％式％
（式中、ＲＩ、Ｒ２およびれは前記と同じである）で表
されるジ（メタ）アクリロキシプロピル基を有するメト
キシシランと一般式
％式％
（式中、Ｒ３、Ｒ４およびＲ５は前記と同じである）で
表されるトリオルガノクロロシランとを共加水分解反応
させる方法が挙げられる。この化学反応式を反応式（１
）として示す。The method for producing the compound (I) of the present invention involves using a methoxysilane having a di(meth)acryloxypropyl group represented by -maximum % formula % (where RI, R2 and are the same as above). A method of cohydrolyzing a triorganochlorosilane represented by the general formula % (wherein R3, R4 and R5 are the same as above) can be mentioned. This chemical reaction formula is the reaction formula (1
).
ＲＩＲ２３−，１Ｒ３
（ＣＨｚ ＝ＣＣ０ＣＨｚ）ｚｃＨｃＨｚｓｉ （ＯＣ
Ｈ３）、＋ Ｒ’５ｉＣ１十０
Ｒ５（４） （１
［１）ＲＩ ＲＺ３□ ＲｆｆｎｃＨ
３０Ｈ＋ ｎＨｃｌ （１）（
式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびｎは前記と
同じである）
本発明の化合物（Ｉ）において、原料として使用される
ジ（メタ）アクリロキシプロピル基を有するメトキシシ
ラン（ｎ）は、例えば本発明者の提案した特願平１−３
３１０４０号明細書に記載された方法により合成するこ
とが可能である。RIR23-,1R3 (CHz = CC0CHz)zcHcHzsi (OC
H3), + R'5iC10
R5 (4) (1
[1) RI RZ3□ RffncH
30H+ nHcl (1) (
(In the formula, R1, R2, R3, R4, R5 and n are the same as above) Methoxysilane (n) having a di(meth)acryloxypropyl group used as a raw material in the compound (I) of the present invention For example, the patent application No. 1-3 proposed by the present inventor
It can be synthesized by the method described in No. 31040.
本発明の化合物（Ｉ）において、原料として使用される
トリオルガノクロロシラン（Ｉ［Ｉ）は公知物質である
。トリオルガノクロロシラン（Ｉ）としては、例えばト
リメチルクロロシラン、ジメチルクロロシラン、エチル
ジメチルクロロシラン、トリエチルクロロシラン、フエ
ニルジメチルクロロシラン、３，３．３−）リフルオロ
プロピルジメチルクロロシランが挙げられる。Triorganochlorosilane (I[I) used as a raw material in compound (I) of the present invention is a known substance. Examples of the triorganochlorosilane (I) include trimethylchlorosilane, dimethylchlorosilane, ethyldimethylchlorosilane, triethylchlorosilane, phenyldimethylchlorosilane, and 3,3.3-)lifluoropropyldimethylchlorosilane.
これらの中でも、入手の容易さ、反応性などの点でトリ
メチルクロロシランが特に好ましい。Among these, trimethylchlorosilane is particularly preferred in terms of availability, reactivity, and the like.
反応式（１）の共加水分解反応において、ジ（メタ）ア
クリロキシプロピル基を有するメトキシシラン（ＩＩ）
、）リオルガノクロロシラン（ＩＩＩ）および水の使用
割合は特に限定されるものではない。しかしながら、ジ
（メタ）アクリロキシプロピル基を有するメトキシシラ
ン（ＩＦ）のメトキシ基１モルあたり、１．５モル以上
、５．０モル未満のトリオルガノクロロシラン（ＩＩＩ
）を使用し反応させることが好ましい。１．５モル未満
では目的とする化合物（１）の反応選択率が低く、また
５、０モル以上用いても特に加えただけの効果がな（、
経済的にも不利である。一方、水の使用量はジ（メタ）
アクリロキシプロピル基を有するメトキシシラン（Ｉｆ
）とトリオルガノクロロシラン（ＩＩＩ）の合計量に対
して２０重量％以上、５００重量％未満の範囲とするこ
とが好ましい。２０重量％未満では反応が遅く、短時間
で良好な収率を上げることができない。５００重量％以
上でも特に加えただけの効果がなく、ポットイールドの
点でも不利である。In the cohydrolysis reaction of reaction formula (1), methoxysilane (II) having a di(meth)acryloxypropyl group
,) The proportions of liorganochlorosilane (III) and water used are not particularly limited. However, per mole of methoxy group in methoxysilane (IF) having di(meth)acryloxypropyl group, triorganochlorosilane (III
) is preferably used for the reaction. If it is less than 1.5 mol, the reaction selectivity of the target compound (1) will be low, and even if it is used in excess of 5.0 mol, it will not have the effect of adding it.
It is also economically disadvantageous. On the other hand, the amount of water used is
Methoxysilane with acryloxypropyl group (If
) and triorganochlorosilane (III) is preferably in the range of 20% by weight or more and less than 500% by weight. If it is less than 20% by weight, the reaction will be slow and it will not be possible to increase a good yield in a short time. Even if it is more than 500% by weight, there is no particular effect of adding it, and it is also disadvantageous in terms of pot yield.
反応式（１）の共加水分解反応において、有機溶媒は必
須とするものではないが、使用する場合はメチルアルコ
ール、エチルアルコールのようなアルコール類；アセト
ンのようなケトン類：ヘキサン、ヘプタンのような脂肪
族炭化水素；シクロヘキサンのような脂環式炭化水素；
ジエチルエーテルのようなエーテル類；ベンゼン、トル
エン、キシレンのような芳香族炭化水素；および１．２
−ジクロロエタンのようなハロゲン化炭化水素などが好
ましい。これらの有機溶媒は単独でも、２種類以上を混
合して使用してもよい。有機溶媒の使用量は特に限定さ
れないが、ジ（メタ）アクリロキシプロピル基を有する
メトキシシラン（ＩＩ）とトリオルガノクロロシラン（
ｎＩ）の合計量に対して、１０〜５００重量％の範囲と
することが好ましい。In the cohydrolysis reaction of reaction formula (1), organic solvents are not essential, but if used, alcohols such as methyl alcohol and ethyl alcohol; ketones such as acetone; and hexane and heptane. aliphatic hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane;
ethers such as diethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; and 1.2
-Halogenated hydrocarbons such as dichloroethane are preferred. These organic solvents may be used alone or in combination of two or more. The amount of organic solvent used is not particularly limited, but methoxysilane (II) having a di(meth)acryloxypropyl group and triorganochlorosilane (
It is preferably in the range of 10 to 500% by weight based on the total amount of nI).
また、本反応は、反応容器に水および必要に応じて有機
溶媒を仕込み、これにジ（メタ）アクリロキシプロピル
基を有するメトキシシラン（ＩＩ）とトリオルガノクロ
ロシラン（Ｉ［［）からなる混合溶液を滴下反応させる
方法によって行うことが、反応制御上好ましい。反応温
度は０〜８０℃の範囲が望ましく、さらに好ましくは０
〜５０°Ｃの範囲である。反応時間は温度、原料モル比
、反応スケールなどの反応条件によるが、通常０．５〜
１０時間で充分である。また、反応時の圧力は特に限定
されないが、通常は常圧で行われる。In addition, in this reaction, a reaction vessel is charged with water and an organic solvent as necessary, and a mixed solution consisting of methoxysilane (II) having a di(meth)acryloxypropyl group and triorganochlorosilane (I[[)] is added to the reaction vessel. In terms of reaction control, it is preferable to perform the reaction by dropping the reaction mixture. The reaction temperature is preferably in the range of 0 to 80°C, more preferably 0 to 80°C.
~50°C. The reaction time depends on reaction conditions such as temperature, raw material molar ratio, reaction scale, etc., but is usually 0.5~
10 hours is sufficient. Further, the pressure during the reaction is not particularly limited, but the reaction is usually carried out at normal pressure.
か（して得られた反応混合物からの本発明の化合物（Ｉ
）の単離および精製は、有機合成化学の分野で通常用い
られている手法によって行うことができる０例えば反応
後、分液、中和、乾燥を行い、さらに減圧蒸留で低沸点
成分を除去することによって化合物（１）が得られる。The compound of the present invention (I
) can be isolated and purified by methods commonly used in the field of organic synthetic chemistry. For example, after reaction, separation, neutralization, and drying are performed, and low-boiling components are further removed by vacuum distillation. Compound (1) is obtained by this.
本発明の化合物（Ｉ）は、分子内に複数のシロキサンセ
グメントとラジカル重合性の２つの（メタ）アクリロキ
シアルキル基を有し、しかもメタクリル酸メチル、３−
メタクリロキシプロピルトリス（トリメチルシロキシ）
シランなどのメタクリル基含有モノマーと共重合した場
合、シロキサンセグメントが主鎖でなく側鎖として導入
される構造であることから、高い酸素透過性と適当な硬
さが要求されるコンタクトレンズの架橋剤として有用で
ある。このほか、ポリスチレン、ポリアクリルアミド、
ポリアクリロニトリルなどの炭素−炭素二重結合の重合
反応性を応用した有機材料のシリコーン変性用原料とし
ても有用である。Compound (I) of the present invention has a plurality of siloxane segments and two radically polymerizable (meth)acryloxyalkyl groups in the molecule, and also has methyl methacrylate, 3-
Methacryloxypropyltris (trimethylsiloxy)
When copolymerized with a methacrylic group-containing monomer such as silane, the siloxane segment is introduced as a side chain rather than a main chain, so it is a crosslinking agent for contact lenses that requires high oxygen permeability and appropriate hardness. It is useful as In addition, polystyrene, polyacrylamide,
It is also useful as a raw material for silicone modification of organic materials such as polyacrylonitrile that utilizes the polymerization reactivity of carbon-carbon double bonds.
以下において、実施例を掲げ、本発明をさらに詳しく説
明する。なお、本発明の範囲は以下の実施例のみに限定
されるものではない。EXAMPLES Below, the present invention will be explained in more detail with reference to Examples. Note that the scope of the present invention is not limited only to the following examples.
実施例Ｉ
攪拌機、温度計、滴下漏斗、還流冷却器および氷バスを
備えた内容積ＩＡのフラスコに、ｎ−ヘキサ７１００ｇ
、メチルアルコール１００ｇおよび水１００ｇを仕込み
、攪拌を開始し、液温約５℃に冷却した。Example I In a flask with internal volume IA equipped with a stirrer, thermometer, addition funnel, reflux condenser and ice bath, 7100 g of n-hexane is added.
, 100 g of methyl alcohol and 100 g of water were charged, stirring was started, and the liquid temperature was cooled to about 5°C.
これに、２−メタクリロキシメチル−３−メタクリロキ
シプロピルトリメトキシシラン３４．６ｇ（０，１０モ
ル）とトリメチルクロロシラン９７．７ｇ （０゜９０
モル）からなる混合溶液を、滴下漏斗より液温５〜１５
℃となるように氷バスで適宜冷却しながら、１時間かけ
て滴下した。滴下終了後、２５〜３０℃で３時間攪拌し
、ガスクロマトグラフィー分析により２−メタクリロキ
シメチル−３−メタクリロキシプロピルトリメトキシシ
ランのピークが完全に消失していることを確認した。To this, 34.6 g (0.10 mol) of 2-methacryloxymethyl-3-methacryloxypropyltrimethoxysilane and 97.7 g (0.90 mol) of trimethylchlorosilane were added.
mol) from the dropping funnel at a liquid temperature of 5 to 15
The mixture was added dropwise over 1 hour while being appropriately cooled in an ice bath to a temperature of .degree. After the dropwise addition was completed, the mixture was stirred at 25 to 30°C for 3 hours, and gas chromatography analysis confirmed that the peak of 2-methacryloxymethyl-3-methacryloxypropyltrimethoxysilane had completely disappeared.
次いで、反応液の有機層を分液漏斗により分別し、それ
を中性になるまでよく水洗してから無水芒硝で乾燥した
。乾燥後、濾過により芒硝を分離し、さらに最高液温４
５°Ｃ，減圧度Ｉ Ｔｏｒｒの条件で低沸点留分を２時
間かけて除去した。Next, the organic layer of the reaction solution was separated using a separatory funnel, thoroughly washed with water until neutral, and then dried over anhydrous sodium sulfate. After drying, mirabilite is separated by filtration, and the maximum liquid temperature is 4.
The low boiling point fraction was removed over a period of 2 hours at 5°C and a reduced pressure of I Torr.
その結果、蒸留残液として無色透明液状の２メタクリロ
キシメチル−３−メタクリロキシプロピルトリス（トリ
メチルシロキシ）シラン４８．８ｇを得た。これは、原
料である２−メタクリロキシメチル−３−メタクリロキ
シプロピルトリメトキシシランに対して９４．０％の収
率であった。As a result, 48.8 g of 2methacryloxymethyl-3-methacryloxypropyltris(trimethylsiloxy)silane was obtained as a colorless transparent liquid as a distillation residue. This was a yield of 94.0% based on the raw material 2-methacryloxymethyl-3-methacryloxypropyltrimethoxysilane.
このもののガスクロマトグラフィー分析、赤外吸収スペ
クトル分析および１Ｈ核磁気共鳴吸収分析の結果は後記
の通りであり、次式の分子構造であることを確認した。The results of gas chromatography analysis, infrared absorption spectrum analysis, and 1H nuclear magnetic resonance absorption analysis of this product are as shown below, and it was confirmed that it had the molecular structure of the following formula.
ｃ
ＨＣＨ，ｄｅｆ ｇ
（ＨＣ＝ＣＣ０ＣＨ２） ｚｃＨｃＨｚｓｉ ［Ｏ５ｉ
（ＣＨ３） ３］ ３■
・ガスクロマトグラフィー分析： ９５．０％・赤外吸
収スペクトル分析（液膜法）：波数（Ｃ１伺） 帰属
２９５０ Ｃ−Ｈ
１７１５Ｃ＝０
１６３５ Ｃ＝Ｃ
１１００〜１０１０ ５ｉ−０−Ｓｉ・ＩＨ核磁気
共鳴吸収分析（９０ＭＨ２，ＣＤＣ１ｊ中）：位置 化
学シフトδ（ｐｐｍ） 積分強度 多重度ａ
６．２ ２Ｈｓｂ ５．６
２Ｈｓｃ ２．０
６Ｈｓｄ ３．９〜４．１ ４８
ｄｅ １．８〜２．２ １Ｈ
ｍｆ Ｏ０４〜０．６ ２Ｈｄｇ
−０，０２９Ｈｓc HCH, def g (HC=CC0CH2) zcHcHzsi [O5i
(CH3) 3] 3■ Gas chromatography analysis: 95.0% Infrared absorption spectrum analysis (liquid film method): Wave number (C1 range) Attribution 2950 C-H 1715C=0 1635 C=C 1100-1010 5i -0-Si IH nuclear magnetic resonance absorption analysis (90MH2, in CDC1j): Position Chemical shift δ (ppm) Integrated intensity Multiplicity a
6.2 2Hsb 5.6
2Hsc 2.0
6Hsd 3.9~4.1 48
de 1.8~2.2 1H
mf O04~0.6 2Hdg
-0,029Hs
Claims (1)
＾３、Ｒ＾４およびＲ＾５は水素原子または置換または
非置換の１価の炭化水素基であり互いに同一でも相異な
っていてもよい。ｎは１〜３の整数を示す。）で表され
るジ（メタ）アクリロキシアルキル基を有するシロキサ
ン化合物。[Claims] 1 General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom or a methyl group, R^2, R
^3, R^4 and R^5 are hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups, and may be the same or different from each other. n represents an integer of 1 to 3. ) A siloxane compound having a di(meth)acryloxyalkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18569690A JP2774362B2 (en) | 1990-07-13 | 1990-07-13 | Siloxane compound having di (meth) acryloxyalkyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18569690A JP2774362B2 (en) | 1990-07-13 | 1990-07-13 | Siloxane compound having di (meth) acryloxyalkyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0474184A true JPH0474184A (en) | 1992-03-09 |
| JP2774362B2 JP2774362B2 (en) | 1998-07-09 |
Family
ID=16175268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18569690A Expired - Lifetime JP2774362B2 (en) | 1990-07-13 | 1990-07-13 | Siloxane compound having di (meth) acryloxyalkyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2774362B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005132751A (en) * | 2003-10-29 | 2005-05-26 | Toray Ind Inc | Method for producing silicone compound |
| JP2006123582A (en) * | 2004-10-26 | 2006-05-18 | Nissan Motor Co Ltd | Ventilation structure for automobile |
-
1990
- 1990-07-13 JP JP18569690A patent/JP2774362B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005132751A (en) * | 2003-10-29 | 2005-05-26 | Toray Ind Inc | Method for producing silicone compound |
| JP4645016B2 (en) * | 2003-10-29 | 2011-03-09 | 東レ株式会社 | Method for producing silicone compound |
| JP2006123582A (en) * | 2004-10-26 | 2006-05-18 | Nissan Motor Co Ltd | Ventilation structure for automobile |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2774362B2 (en) | 1998-07-09 |
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