JPS62205045A - Fluorine-containing urethane di(meth)acrylate compound and production thereof - Google Patents
Fluorine-containing urethane di(meth)acrylate compound and production thereofInfo
- Publication number
- JPS62205045A JPS62205045A JP61047391A JP4739186A JPS62205045A JP S62205045 A JPS62205045 A JP S62205045A JP 61047391 A JP61047391 A JP 61047391A JP 4739186 A JP4739186 A JP 4739186A JP S62205045 A JPS62205045 A JP S62205045A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- meth
- fluorine
- acrylate
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- 239000011737 fluorine Substances 0.000 title claims abstract description 26
- -1 acrylate compound Chemical class 0.000 title claims abstract description 25
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000704 physical effect Effects 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 239000000057 synthetic resin Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- QPFYNOGVFGQCTI-UHFFFAOYSA-N [F].CCOC(N)=O Chemical compound [F].CCOC(N)=O QPFYNOGVFGQCTI-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- 239000012948 isocyanate Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009864 tensile test Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は２個の（メタ）アクリロイルオキシ基を有する
新規な含フッ素ウレタン系化合物。DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel fluorine-containing urethane compound having two (meth)acryloyloxy groups.
およびその製造法に関するものである。and its manufacturing method.
本発明において、 ”（メタ）アクリレート”とはメタ
クリレートと７クリレートの両者を意味する川＋ｉｆｉ
として使用する。同様に、 ”（メタ）アクリロイルオ
キシ基”や”（メタ）アクリル酸”笠も、それぞれ、メ
タクリロイルオキシ基と７クリロイルオキシ基の両者、
メタクリル酸とアクリル酸の両者１等を意味する。In the present invention, "(meth)acrylate" means both methacrylate and 7-acrylate.
Use as. Similarly, "(meth)acryloyloxy group" and "(meth)acrylic acid" are both methacryloyloxy group and 7-acryloyloxy group, respectively.
It means both methacrylic acid and acrylic acid.
２個以上の（メタ）アクリロイルオキシノふを有する多
官能性化合物は１合成樹脂の原料成分として広く知られ
ている。特に、中官能性の化合物と併用して、その架橋
成分として用いられることが多い、たとえば、巾官能性
の（メタ）アクリレート系化合物と併用し、その硬化物
の剛性１表面硬度、耐蝕性、その他の機械的化学的物性
を向トさせる。また、多官能性化合物のみから、塗膜や
成形品を得ることもできる。しかし、従来の多官能性化
合物を用いた硬化物においては、その要求物性が必ずし
も充分に満足し得ない場合があった。A polyfunctional compound having two or more (meth)acryloyloxy groups is widely known as a raw material component of a synthetic resin. In particular, it is often used in combination with a medium-functional compound as a crosslinking component. Improve other mechanical, chemical and physical properties. Furthermore, coating films and molded articles can also be obtained only from polyfunctional compounds. However, in cured products using conventional polyfunctional compounds, the required physical properties may not always be fully satisfied.
本発明者は、硬化物の高い要求物性を達成しうる多官能
性化合物を見い出すべく研究検討した結果、新規な含フ
ッ素ウレタンジ（メタ）アクリレート系化合物、および
その製造法を見い出すに至った。この化合物はパーフル
オロメチレンツ＾と２個の（メタ）アクリロイルオキシ
ノとを有するＦ記式（Ｉ）で表わされる含フッ素ウレタ
ンジ（メタ）アクリレート系化合物である。The present inventor conducted research to find a polyfunctional compound that can achieve the high required physical properties of a cured product, and as a result, discovered a new fluorine-containing urethane di(meth)acrylate compound and a method for producing the same. This compound is a fluorine-containing urethane di(meth)acrylate compound represented by formula (I) having perfluoromethylene and two (meth)acryloyloxinos.
−−−−−（Ｉ）
Ｒ：水素原子あるいはメチル基
Ｒ１：炭素数２〜６のフルキレン基
Ｘ：ウレタン結合
ｎ：２〜８の整数
ｍａｌあるいは２の整数
閤
ウレタン結合は、 −０ＣＮＨ−で表わされる結合であ
り、水酸基とインシアネート基の反応により生成する。-------(I) R: Hydrogen atom or methyl group R1: Fullylene group having 2 to 6 carbon atoms X: Urethane bond n: An integer of 2 to 8 mal or an integer of 2. This bond is produced by the reaction between a hydroxyl group and an incyanate group.
上記化合物において、このウレタン結合の向きは限定さ
れるものではない、即ち、上記式（Ｉ）の左方のＸは一
〇ａ＊Ｏ−であって輯
も−ＮＨＣＯ−であってもよい、しかし、通常下記式（
Ｉ）における左右２つのＸの向きはこの２つの向きの組
み合せからなる（即ち、両ウレタン結合の向きは異る）
、 ＲＩで表わされるアルキレン基は直鎖アルキレン
基であっても分岐アルキレン基であってもよい、好まし
いＲ１はエチレン基、プロピレン基、テトラメチレン基
、およびヘキサメチレン基であり、特にエチレン基とプ
ロピレン基が好ましい、ｎは４〜８の偶数が好ましく、
特に４が好ましい０ｍは特に１が好ましい。In the above compound, the direction of this urethane bond is not limited, that is, the left side X of the above formula (I) is 10a*O-, and the other side may also be -NHCO-. However, usually the following formula (
The two left and right X directions in I) are a combination of these two directions (that is, the directions of both urethane bonds are different)
, The alkylene group represented by RI may be a straight chain alkylene group or a branched alkylene group, and R1 is preferably an ethylene group, a propylene group, a tetramethylene group, and a hexamethylene group, and in particular, an ethylene group and a propylene group. group is preferable, n is preferably an even number of 4 to 8,
0m is particularly preferably 4, and 1 is particularly preferable.
Ｌ配合フッ素ウレタンジ（メタ）アクリレート化合物の
製造法は、たとえば下記（ａ）〜（Ｃ）の方法があるが
、これらに限定されるものではない、しかし、好ましく
は、（ａ）あるいは（ｂ）の方法で製造され、特に（ａ
）の方法で製造されることかに了ましい。Examples of methods for producing L-blended fluorine urethane di(meth)acrylate compounds include, but are not limited to, the following methods (a) to (C). However, preferably (a) or (b) In particular, (a
) is manufactured using this method.
（ａ） 下記〔ＩＩ〕で表わされる含フッ素ジイソシ
アネート化合物と下記式（ｍ）で表わされるヒドロキシ
アルキル（メタ）アクリレートとの反応。(a) A reaction between a fluorine-containing diisocyanate compound represented by the following [II] and a hydroxyalkyl (meth)acrylate represented by the following formula (m).
０ＣＮ４ＣＩｚｈ（ＣＦ２）ｎ（ＣＨ２）ＪＣＯ−−−
−−（ＩＩ ）（ｂ） 下記式（１７）で表わされ
る含フッ素ジヒドロキシ化合物と下記式（Ｖ）で表わＳ
れるイソシアネートアルキル（メタ）アクリレートとの
反応。0CN4CIzh(CF2)n(CH2)JCO---
--(II)(b) A fluorine-containing dihydroxy compound represented by the following formula (17) and S represented by the following formula (V)
Reaction with isocyanate alkyl (meth)acrylate.
ＨＯ（Ｃ１２）ｓ（ＣＦ２）ｎ（ＣＨ２）、ＯＨ−−−
−−（ｒＶ）（Ｃ） 下記式（９１）で表わされる含
フッ素ヒドロキシ末端ウレタン化合物と下記式〔■〕で
表わされる（メタ）アクリル酸あるいはその反応性誘導
体との反応。HO(C12)s(CF2)n(CH2), OH---
--(rV)(C) Reaction between a fluorine-containing hydroxy-terminated urethane compound represented by the following formula (91) and (meth)acrylic acid or its reactive derivative represented by the following formula [■].
ｌｏ−ＲＩ Ｘ（ＣＨ２）＠ （ＣＦ？＊ｎ （ＣＨ
２）＠ ＸＲＩ −ＯＨただし、上記各式において、
Ｒ，Ｒ１、Ｘ・ｎ、 ｍは前記式（Ｉ）におけるものと
同じものを表わし、Ｚは水素原子、ハロゲン、アルキル
基等の反応性の酸誘導体の残基を表わす。lo-RI X (CH2) @ (CF?*n (CH
2) @XRI -OH However, in each of the above formulas,
R, R1, X·n, and m are the same as those in formula (I) above, and Z represents a residue of a reactive acid derivative such as a hydrogen atom, halogen, or alkyl group.
を温式（ｎ）で表わされる含フッ素ジイソシアネート化
合物は公知であり、たとえば、特開昭５７−１０８０５
５号公報に記載されている。また、式（ＩＶ）で表わさ
れる含フッ素ジヒドロキシ化合物の水酸基をアミノ基に
変換後ホスゲン化して得ることもできる０式（ＩＶ）で
表わされる含フッ素ジヒドロキシ化合物も公知であり、
たとえば、特公昭５２−８８０７号公報記載の方法でＨ
Ｏ（ＯＨ２）？（ＣＦ２）ｎ（ＧＨ？）２０Ｈが製造さ
れる。また、このジヒドロキシ化合物を発煙硫酸等で酸
化してジカルボン酸としくたとえば、特開昭５７−９９
５５２号公報参照）、これを直接あるいはエステル化し
た後還元してｌｏ−ＣＴｏ （ＣＦ２）ｎ ＣＨ？ＯＨ
ルコールでエステル化した後還元して
ＨＯＣＨ７（ＣＦ？＊ｎ ＣＨ２０Ｈを得ることもでき
る０式（ＶＩ）で表わされる含フッ素ヒドロキシ末端ウ
レタン化合物は、１：温式〔ＩＩ〕で表わされる含フッ
素ジイソシアネート化合物１分子にＨＯ−Ｒ１−ＯＨで
表わされるジヒドロキシ化合物２分子を反応させて得る
ことができる０式〔ｍ３１式〔Ｖ〕、および式〔■〕で
表わされる（メタ）アクリロイルオキシ基を有する化合
物は周知の化合物である。具体的化合物としては、たと
えば以下のような化合物がある。The fluorine-containing diisocyanate compound represented by the warm formula (n) is known, for example, as disclosed in JP-A-57-10805.
It is described in Publication No. 5. Further, a fluorine-containing dihydroxy compound represented by the formula (IV) which can be obtained by converting the hydroxyl group of the fluorine-containing dihydroxy compound represented by the formula (IV) into an amino group and then phosgenating it is also known,
For example, H
O(OH2)? (CF2)n(GH?)20H is produced. In addition, this dihydroxy compound is oxidized with oleum or the like to form a dicarboxylic acid, for example, JP-A-57-99
552), directly or by reducing it after esterification to obtain lo-CTo (CF2)n CH? OH
The fluorine-containing hydroxy-terminated urethane compound represented by the formula (VI), which can be esterified with alcohol and then reduced to obtain HOCH7(CF?*n CH20H), is a fluorine-containing diisocyanate represented by the 1: warm formula [II]. A compound having a (meth)acryloyloxy group represented by the formula 0 [m31 formula [V] and the formula [■], which can be obtained by reacting one molecule of the compound with two molecules of a dihydroxy compound represented by HO-R1-OH is a well-known compound. Specific examples include the following compounds.
２−ヒドロキシエチル（メタ）アクリレート。2-Hydroxyethyl (meth)acrylate.
２−ヒドロキシプロピル（メタ）アクリレート、４−ヒ
ドロキシブチル（メタ）アクリレート、６−ヒドロキシ
ヘキシル（メタ）アクリレート、２−インシアネートエ
チル（メタ）アクリレート、２−インシアネートプロピ
ル（メタ）アクリレート、（メタ）アクリル酸。2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-incyanate ethyl (meth)acrylate, 2-incyanatepropyl (meth)acrylate, (meth) acrylic acid.
（メタ）アクリル酸クロライド、
上記（ａ）および（ｂ）の方法による含フッ素ウレタン
ジ（メタ）アクリレート系化合物の製造は２官能の化合
物（式（ＩＩ）および式（ＩＶ）で表わされる化合物）
１モル当りｌ官能の化合物（式（ｍ）および式（Ｖ）で
表わされる化合物）２モルを反応させることによって行
われる。製造時に一方が過剰量存在してもよいが、その
場合ヒドロキシ基を有する化合物を過剰に使用する方が
残存インシアネート基による副反応を防ぐ面で好ましい
０通常はほぼ７当に（前者１モルに対し後者２モル）〜
３倍当量を用いることが好ましい。反応は溶媒中で行っ
てもよく、無溶媒下に行うこともできる。溶媒としては
、インシアネート基やヒドロキシ基と反応性を有しない
ものである限り、種々のものを使用しうる。また、必要
によりウレタン化反応を促進する触媒の存在下で反応を
行ってもよい、触媒としては、たとえばジブチル錫ジラ
ウレートなどの有機錫系触媒や他の有機金属系触媒、ト
リエチレンジアミン、メチルモルホリン、その他の第３
級アミン触媒などがある１反応温度としては、常温〜
１５０℃を採用しうるが、副反応を抑制するために約８
０℃以下が適当である０反応の終了は通常インシアネー
ト基による赤外吸収が消失したことで確認される０反応
終了後、必要により未反応物などを除いて目的化合物を
得る。また、（Ｃ）の方法による製造の場合、式〔■〕
で表わされる化合物と式〔■〕で表わされる化合物の反
応は通常のエステル化反応に準じて行いうる。上記と同
様、この反応は溶媒中で行ってもよく、エステル化反応
を促進する触媒のイＣ在丁に行ってもよい。(Meth)acrylic acid chloride The production of fluorine-containing urethane di(meth)acrylate compounds by the methods (a) and (b) above is a bifunctional compound (compounds represented by formula (II) and formula (IV)).
The reaction is carried out by reacting 2 moles of a l-functional compound (compounds represented by formula (m) and formula (V)) per mole. One may be present in an excess amount during production, but in that case it is preferable to use an excess of the compound having a hydroxyl group in order to prevent side reactions caused by residual incyanate groups.Usually, approximately 7 equivalents (1 mol of the former) 2 moles of the latter) ~
Preferably, three equivalents are used. The reaction may be carried out in a solvent or without a solvent. Various solvents can be used as long as they do not have reactivity with incyanate groups or hydroxyl groups. In addition, the reaction may be carried out in the presence of a catalyst that promotes the urethanization reaction, if necessary. Examples of catalysts include organotin catalysts such as dibutyltin dilaurate, other organometallic catalysts, triethylenediamine, methylmorpholine, Other third
The reaction temperature for one reaction with a grade amine catalyst is room temperature to
150°C can be used, but the temperature is about 8°C to suppress side reactions.
The completion of the zero reaction, which is suitably at 0°C or lower, is usually confirmed by the disappearance of infrared absorption by the incyanate group.After the completion of the zero reaction, unreacted substances are removed if necessary to obtain the target compound. In addition, in the case of manufacturing by the method (C), the formula [■]
The reaction between the compound represented by the formula [■] and the compound represented by the formula [■] can be carried out according to a conventional esterification reaction. As above, this reaction may be carried out in a solvent or in the presence of a catalyst that promotes the esterification reaction.
Ｌ記製造方法の内、好ましい方法は（ａ）と（ｂ）の方
法であり、特に（ａ）の方法が好ましい、（Ｃ）の方法
では１式〔■〕で表わされる化合物の製造においてオリ
ゴマー状副生物が生成し易く、従って純度の高い目的化
合物を得ることが困難である。一方（ｂ）の方法は、（
ａ）の方法に比べて反応が遅く、そのため反応条件に制
約を受は易い、この原因は１式（ＩＴ）で表わされるジ
ヒドロキシ化合物のヒドロキシ基の反応性が式（ｍ）で
表わされる化合物のヒドロキシ基よりも低いためである
と考えられる。Among the production methods described in L, preferred methods are methods (a) and (b), with method (a) being particularly preferred.In method (C), the oligomer is used in the production of the compound represented by formula 1 [■] By-products are likely to be produced, and therefore it is difficult to obtain the target compound with high purity. On the other hand, method (b) is (
The reaction is slower than in method a), and therefore the reaction conditions are easily restricted.The reason for this is that the reactivity of the hydroxyl group of the dihydroxy compound represented by formula (IT) is lower than that of the compound represented by formula (m). This is thought to be because it is lower than the hydroxyl group.
本発明の含フッ素ウレタンジ（メタ）アクリレート系化
合物は、対応するフッ素原子不含のウレタンジ（メタ）
アクリレート系化合物に比較してその硬化物に対する物
性向上効果が憧れている。その例を下記参考例に示す。The fluorine-containing urethane di(meth)acrylate compound of the present invention is a corresponding fluorine-containing urethane di(meth)acrylate compound.
Compared to acrylate compounds, its effect on improving the physical properties of cured products is desired. An example of this is shown in the reference example below.
参考例
メチルメタクリレートとｖｋ述実施例１で製造した本発
明の含フッ素ウレタンジ（メタ）アクリレート化合物（
下記式（Ａ） ’） １０．４モル％とベンゾイルパー
オキシド０．５重量％とを含む混合物を製造し、５５℃
で２４時間、続いて １００℃で２４時間バルク重合を
行い、硬化物を得た。この硬化物を下記物性試験法で試
験した結果をド記ｉｉ表Ａ欄に示す。Reference Example Methyl methacrylate and vk The fluorine-containing urethane di(meth)acrylate compound of the present invention produced in Example 1 (
A mixture containing 10.4 mol% of the following formula (A)') and 0.5% by weight of benzoyl peroxide was prepared and heated at 55°C.
Bulk polymerization was then carried out at 100° C. for 24 hours to obtain a cured product. This cured product was tested using the following physical property test method, and the results are shown in column A of Table II.
一方、メチルメタクリレートに対応ウレタンジアクリレ
ート化合物（下記式ＣＢ） ） １０．４モル％とベン
ゾイルパーオキシド０．５ｉ［［，１％とを含む混合物
を製造し、上記と同じ条件でバルク重合して硬化物を得
た。この硬化物の物性試験結果をド記第１表Ｂ欄に示す
。On the other hand, a mixture containing 10.4 mol% of a urethane diacrylate compound (formula CB below) corresponding to methyl methacrylate and 0.5i[[,1%] of benzoyl peroxide was prepared, and bulk polymerized under the same conditions as above. A cured product was obtained. The physical property test results of this cured product are shown in column B of Table 1.
（ヘキサメチレンジイソシアネート１モルと２−ヒドロ
キシエチルメタクリレート２モルとの反応生成物）
物性試験方法
１） 圧縮試験：試験片の寸法は４φ×８■■とした。(Reaction product of 1 mole of hexamethylene diisocyanate and 2 moles of 2-hydroxyethyl methacrylate) Physical property test method 1) Compression test: The dimensions of the test piece were 4φ×8■■.
２） Ｄｉａｍｅｊｒａｌ法間接引張試験：試験片の
寸法は６φ×５１１層とした。2) Diamejral method indirect tensile test: The dimensions of the test piece were 6φ×511 layers.
以上の二つの試験片は３７℃、２４±２時間水中保存後
、島律製オートグラフＩＳ−５００を用いクロスヘッド
スピード２．５１１１口ｉｎで行った。The above two test pieces were stored in water at 37° C. for 24±2 hours, and then tested using an Autograph IS-500 manufactured by Shima Ritsu at a crosshead speed of 2.5111 in.
３） 曲げ試験：試験片の寸法は４φＸ ２５ｍ−とし
、支点間距離２０１園、３点曲げ試験法を採用した。な
お、試験片は３７℃、５０±２時間水中保存後、上記オ
ートグラ
フ、クロスヘッドスピード１鳳鳳１１ｎで行った。3) Bending test: The dimensions of the test piece were 4φ x 25m, the distance between the supports was 201 mm, and a 3-point bending test method was adopted. The test piece was stored in water at 37° C. for 50±2 hours, and then tested using the above-mentioned autograph and crosshead speed 1, 11n.
４） 吸水試験：試験片の寸法はｌＯφＸ１ｍｍとし、
ＡＤＡ規格に基き、３７℃、７日間水中保存後吸水量を
測定した。4) Water absorption test: The dimensions of the test piece are lOφ x 1mm,
Based on the ADA standard, the water absorption amount was measured after being stored in water at 37°C for 7 days.
５） ビッカース硬度試験：試験片はｌＯφ×１ｍｍと
し、３７℃、５０±２時間水中保存後、荷１１１１００
ｇ、荷重保持時間５秒とし。5) Vickers hardness test: The test piece was 1Oφ x 1mm, and after being stored in water at 37°C for 50±2 hours, the load was 111100.
g, load holding time is 5 seconds.
松沢精機製、マイクロハードネステス ターロＭＨ−２を用い、測定した。Made by Matsuzawa Seiki, Micro Hardness Test Measurement was performed using Taro MH-2.
６） ブラシ摩耗試験：試験片の１法は１０φ×２層園
とし、東京技研製摩耗試験＠ Ｋ１７２を用い、１スト
ロ一ク５ｃｍ、荷重１３２ｇ／個３００００回往復させ
、その玉；談減少を測定し、試料の比重を用い、摩耗体
積として算出した。6) Brush abrasion test: One method for the test piece is 10φ x 2 layers, using a Tokyo Giken abrasion test @ K172, one stroke of 5cm, a load of 132g/piece 30,000 times, and the ball; The wear volume was calculated using the specific gravity of the sample.
Ｌ記第１表に示すように１本発明の含フッ素ウレタンジ
（メタ）アクリレート系化合物は対応するフッ素直り不
含ウレタンジ（メタ）アクリレート系化合物に比較して
、測定物性のすべてにおて高い物性向上効果を与える。As shown in Table 1, the fluorine-containing urethane di(meth)acrylate compound of the present invention has higher physical properties in all measured physical properties than the corresponding fluorine-containing urethane di(meth)acrylate compound. Gives an improving effect.
特に、曲げ強度と吸水量において著しく優れた物性向上
効果がある。In particular, it has a remarkable effect of improving physical properties in terms of bending strength and water absorption.
以ドに、本発明を実施例により具体的に説明するが１本
発明はこれら実施例に限られるものではない。Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
実施例１
２００ｍＪ１のフラスコに２−ヒドロキシエチルメタク
リレート １７．０ｇ、ベンゼンＢｏｗ１． トリエ
チレンジアミン０．０８ｇをとり、１，１，８．８−テ
トラヒドロパーフルオロへキサメチレン−１，８−ジイ
ソシアネート（ＯＣＮ（：Ｔｏ （ＣＦｚｌａＣＨ２Ｎ
ＧＯ）１０−２ｇをベンゼン３０ｗｕに溶解した溶液を
全量適ドした。Example 1 In a 200 mJ flask, 17.0 g of 2-hydroxyethyl methacrylate and 1 benzene Bowl were placed. Take 0.08 g of triethylenediamine and add 1,1,8.8-tetrahydroperfluorohexamethylene-1,8-diisocyanate (OCN(:To(CFzlaCH2N)
A solution prepared by dissolving 10-2 g of GO) in 30 wu of benzene was added in its entirety.
滴Ｆ終了後４５℃で１昼夜撹拌した０反応混合物を温水
３ｆＬで洗浄し、ベンゼン層を無水Ｊｉ＆酸ナトリウム
で脱水後脱溶媒して白色粉末１８．５ｇを得た。この生
成物の融点は９８〜９９℃であったつＩＲおよびＮＭＲ
のスペクトルデーターは以ドの通りであり、前記Ａの式
で示される化合物であることを確認した。After the completion of the droplet F, the reaction mixture was stirred at 45° C. for one day and night and washed with 3 fL of warm water, and the benzene layer was dehydrated with anhydrous Ji and sodium chloride and the solvent was removed to obtain 18.5 g of white powder. The melting point of this product was 98-99°C. IR and NMR
The spectral data of is as shown below, and it was confirmed that it was a compound represented by the formula of A above.
ＩＲ：第１図
會 ヒドロキシ基の吸収（３４５０ｃｍ−’付近）およ
びインシアネート基の吸収（２２５０ＣＩ ’付近）は
ない。IR: Figure 1 There is no absorption of hydroxyl groups (near 3450 cm-') and absorption of incyanate groups (near 2250 CI').
・ ウレタン結合の＞ＮＨ基の吸収（３３２０Ｃ鵬１）
およびウレタン結合〉Ｃ＝０基の吸収（１７２０＋、ｓ
ｌ ）が認められる。・Absorption of >NH group in urethane bond (3320C Peng 1)
and urethane bond>C=0 group absorption (1720+, s
l) is accepted.
ＩＨＮＭＲニド記の吸収ピークが存在
１．９２ｐｐｍ −ＣＨ？、 ５．６２ｐｐａ
＋ ＞ＣＨ−３，９８ｐｐ−−〇Ｈ？−８，Ｏ８ｐｐ
ｍ ＞ＣＨ〜４．３２ｐｐ’■ −ＣＨ２ＣＨ２−８
，９３ｐｐｍ ＞ＮＯIHNMR absorption peak exists at 1.92 ppm -CH? , 5.62ppa
+ >CH-3,98pp--〇H? -8,O8pp
m>CH~4.32pp'■ -CH2CH2-8
,93ppm >NO
第１図は実施例１で製造した本発明含フッ素ウレタンジ
（メタ）アクリレート系化合物のＩＲチャートである。
＝、Ｐ−続−？ｔ１３ ｔｌＥ ；ｔ？１．゛１警件
の表示
昭和６１年特許願第４７３９１１３−
２、発明の名称
含フッ素ウレタンジ（メタ）アクリレート系化合物およ
びその製造法
３、補正をする者
事件との関係 特許出願人
住 所 東京都千代Ｉ１１区丸の内二丁目１番２号名
称 （００４）旭硝子株式会社
Ｂ、補正により増加する発明の数 なし７、補正の
対象
８、補正の内容
明細書第１６頁最終行の次に、以下の文章を種入する。
「実施例２
１００ａ＋９のフラスコに、２−インシアナートエチル
メタクリレート１３．４ｇ、ジエチルエーテル３０ｄ、
）リエチレンジアミン０．１４ｇをとり、 ３，３，４
，４，５，５，１３．８−オクタフルオロ オクタン−
１，８−ジオール（ＨＯＣＴｏＣＨ２（Ｃｄ５）ＣＨ２
ＣＴｏＯＨ） ｌｏ、Ｏｇをジエチルエーテル３０ａＱ
に溶解した溶液を全量滴下した０滴下終了後、−昼夜還
流した０反応終了後、溶液を大量のヘキサンに滴下し、
析出した白色粉末を１別し乾燥した（２０．３ｇ）、
この生成物の融点は５７〜５８℃であった。 ＩＲお
よびＮＭＨのスペクトルデータは以下の通りであり。
で表わされる化合物であることを確認した。
Ｉ Ｒ； ３３２０ｃｒｉ ウレタン結合ノ〕」基
１７２０ｃｒ Ｉ ｔｔ
：ｌ：Ｃ鳳０ ス（ＩＨＮＭＲ；下記の吸収ピーク
が存在
１．９２ｐｐｍ−ＣＩ： ４．１４〜４．４１ｐｐ
■−ＣＨ，’−，−ＣＨニー（多重線）
２．４１ｐｐ霞−ＣＨＦ−５，０３ｐｐｍ ）ＮＨ”３
．４８ｐｐ−−〇Ｈ２−５，５８ｐｐｍ 、：
ＣＨ’ＬＯ８ｐｐｍ ンＣＨ’ −Ｊ
以上FIG. 1 is an IR chart of the fluorine-containing urethane di(meth)acrylate compound of the present invention produced in Example 1. =, P-continued-? t13 tlE ;t? 1.゛1 Indication of the incident Patent Application No. 4739113-1988 2. Name of the invention Fluorine-containing urethane di(meth)acrylate compound and its manufacturing method 3. Relationship with the person making the amendment Patent applicant address Chiyo, Tokyo I11-ku Marunouchi 2-1-2 Name (004) Asahi Glass Co., Ltd. B, Number of inventions to be increased by amendment None 7, Subject of amendment 8, Next to the last line of page 16 of the specification of contents of the amendment, the following sentence: Seed. Example 2 In a 100a+9 flask, 13.4g of 2-incyanatoethyl methacrylate, 30d of diethyl ether,
) Take 0.14g of lyethylenediamine, 3,3,4
,4,5,5,13.8-octafluoro octane-
1,8-diol (HOCToCH2(Cd5)CH2
CToOH) lo, Og to diethyl ether 30aQ
After dropping the entire amount of the solution dissolved in the solution into a large amount of hexane,
The precipitated white powder was separated and dried (20.3 g),
The melting point of this product was 57-58°C. The IR and NMH spectral data are as follows. It was confirmed that it is a compound represented by I R; 3320cri urethane bond group 1720cr I tt
:l:C00S(IHNMR; The following absorption peak exists: 1.92ppm-CI: 4.14-4.41pp
■-CH,'-,-CH knee (multiplet) 2.41pp haze-CHF-5,03ppm)NH”3
．． 48pp --〇H2-5,58ppm, :
CH'LO8ppm -J or more
Claims (2)
（メタ）アクリレート系化合物。 ▲数式、化学式、表等があります▼−−−−−〔 I 〕 Ｒ：水素原子あるいはメチル基 Ｒ＾１：炭素数２〜６のアルキレン基 Ｘ：ウレタン結合 ｎ：２〜８の整数 ｍ：１あるいは２の整数(1) A fluorine-containing urethane di(meth)acrylate compound represented by the following formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼------ [I] R: Hydrogen atom or methyl group R^1: Alkylene group with 2 to 6 carbon atoms X: Urethane bond n: Integer from 2 to 8 m: an integer of 1 or 2
ート化合物と下記式〔III〕で表わされるヒドロキシア
ルキル（メタ）アクリレートとを反応させて下記式〔
I 〕で表わされる含フッ素ウレタンジ（メタ）アクリレ
ート系化合物を製造することを特徴とする含フッ素ウレ
タンジ（メタ）アクリレート系化合物の製造法。 ▲数式、化学式、表等があります▼−−−−−〔 I 〕 Ｒ：水素原子あるいはメチル基 Ｒ＾１：炭素数２〜６のアルキレン基 Ｘ：ウレタン結合 ｎ：２〜８の整数 ｍ：１あるいは２の整数 ＯＣＮ−（ＣＨ＿２）−＿ｍ−（ＣＨ＿２）−＿ｎ−（
ＣＨ＿２）−＿ｍＮＣＯ−−−−−〔II〕 ｎ、ｍ：前記〔 I 〕に同じ ▲数式、化学式、表等があります▼−−−−−〔III〕 Ｒ、Ｒ＾１：前記〔 I 〕に同じ(2) A fluorine-containing diisocyanate compound represented by the following formula [II] and a hydroxyalkyl (meth)acrylate represented by the following formula [III] are reacted to form the following formula [
A method for producing a fluorine-containing urethane di(meth)acrylate compound, the method comprising producing a fluorine-containing urethane di(meth)acrylate compound represented by [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼------ [I] R: Hydrogen atom or methyl group R^1: Alkylene group with 2 to 6 carbon atoms X: Urethane bond n: Integer from 2 to 8 m: Integer OCN-(CH_2)-_m-(CH_2)-_n-(
CH_2) -_mNCO------- [II] n, m: Same as [I] above ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ------- [III] R, R^1: Above [I] same as
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61047391A JPH0798789B2 (en) | 1986-03-06 | 1986-03-06 | Fluorine-containing urethane di (meth) acrylate compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61047391A JPH0798789B2 (en) | 1986-03-06 | 1986-03-06 | Fluorine-containing urethane di (meth) acrylate compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62205045A true JPS62205045A (en) | 1987-09-09 |
| JPH0798789B2 JPH0798789B2 (en) | 1995-10-25 |
Family
ID=12773810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61047391A Expired - Fee Related JPH0798789B2 (en) | 1986-03-06 | 1986-03-06 | Fluorine-containing urethane di (meth) acrylate compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798789B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308420A (en) * | 1988-06-07 | 1989-12-13 | Nippon Kayaku Co Ltd | Urethane (meth)acrylate mixture and resin composition and coating agent for optical fiber prepared by using same |
| JPH02255711A (en) * | 1989-03-30 | 1990-10-16 | Nippon Kayaku Co Ltd | Urethane acrylate mixture, resin composition and coating agent using the same for optical fiber |
| CN114773512A (en) * | 2022-06-21 | 2022-07-22 | 苏州易昇光学材料有限公司 | High-wear-resistance fluorocarbon resin and coating for solar backboard using same |
-
1986
- 1986-03-06 JP JP61047391A patent/JPH0798789B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308420A (en) * | 1988-06-07 | 1989-12-13 | Nippon Kayaku Co Ltd | Urethane (meth)acrylate mixture and resin composition and coating agent for optical fiber prepared by using same |
| JPH02255711A (en) * | 1989-03-30 | 1990-10-16 | Nippon Kayaku Co Ltd | Urethane acrylate mixture, resin composition and coating agent using the same for optical fiber |
| CN114773512A (en) * | 2022-06-21 | 2022-07-22 | 苏州易昇光学材料有限公司 | High-wear-resistance fluorocarbon resin and coating for solar backboard using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798789B2 (en) | 1995-10-25 |
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