JPH0442391B2 - - Google Patents
Info
- Publication number
- JPH0442391B2 JPH0442391B2 JP59258785A JP25878584A JPH0442391B2 JP H0442391 B2 JPH0442391 B2 JP H0442391B2 JP 59258785 A JP59258785 A JP 59258785A JP 25878584 A JP25878584 A JP 25878584A JP H0442391 B2 JPH0442391 B2 JP H0442391B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxymethyl
- parts
- present
- reaction
- cyclic acetal
- 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.)
- Expired
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- -1 cyclic acetal compound Chemical class 0.000 claims description 10
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- 238000006359 acetalization reaction Methods 0.000 description 3
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 3
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 1
- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分子中に反応性に富んだヒドロキシ
メチル基と、アリル基とを有し、さらにスピロ環
構造を有する下記一般式（）で示される新規な
多官能環状アセタール化合物に関する。Detailed Description of the Invention [Industrial Application Field] The present invention is directed to the following general formula (), which has a highly reactive hydroxymethyl group and an allyl group in its molecule, and further has a spiro ring structure. The present invention relates to a novel polyfunctional cyclic acetal compound.
一般式
（式中：ｎ＝１〜２）
本発明の多官能環状アセタール化合物は、１分
子内に二つの異なつた官能基を有しており、また
環状構造を有していることから、これらの特性を
利用した独特な性能を有する合成樹脂、塗料、接
着剤あるいは機能性分子材料に使用される原料と
して、また変性材として広汎に応用することがで
き、多彩な分子設計が可能であるなど実用上中間
体原料として有用な化合物である。 general formula (In the formula: n = 1 to 2) The polyfunctional cyclic acetal compound of the present invention has two different functional groups in one molecule and has a cyclic structure, so these characteristics It can be widely applied as a raw material for synthetic resins, paints, adhesives, and functional molecular materials that have unique properties, and as a modified material, making it possible to design a variety of molecules. It is a useful compound as an intermediate raw material.
従来、本発明に係る化合物のごときの環状アセ
タール化合物、たとえば、ヒドロキシピバルアル
デヒドとペンタエリスリトールとを反応させ、分
子末端にヒドロキシメチル基を有する環状グリコ
ール、すなわち、３，９−ビス（１，１−ジメチ
ル−２−ヒドロキシエチル）２，４，８，10−テ
トラオキサスピロ〔５，５〕ウンデカン（スピロ
グリコールと呼ぶ）が良く知られている。（たと
えば、usp 第2945008号）また、ペンタエリス
リトールとアクロレインとを反応させ、分子中に
スピロ環を有し、末端にアリル基を有する環状ア
セタール化合物が知られている。（たとえば、特
開昭51−59991号公報）
しかしながら、本発明の化合物のごとき、１分
子中に異つた多官能基、すなわち、ヒドロキシメ
チル基及びアリル基の両者を有し、環状構造を有
する化合物は、これまで報告されていない。
Conventionally, a cyclic acetal compound such as the compound according to the present invention, for example, hydroxypivalaldehyde, and pentaerythritol are reacted to form a cyclic glycol having a hydroxymethyl group at the molecular end, that is, 3,9-bis(1,1 -dimethyl-2-hydroxyethyl)2,4,8,10-tetraoxaspiro[5,5]undecane (called spiroglycol) is well known. (For example, USP No. 2945008) Furthermore, a cyclic acetal compound having a spiro ring in the molecule and an allyl group at the terminal is known by reacting pentaerythritol and acrolein. (For example, JP-A-51-59991) However, compounds such as the compound of the present invention that have different multifunctional groups in one molecule, that is, both a hydroxymethyl group and an allyl group, and have a cyclic structure. has not been reported so far.
本発明は、前記の一般式（）で示される多官
能環状アセタール化合物に関する。
The present invention relates to a polyfunctional cyclic acetal compound represented by the above general formula ().
本発明の多官能環状アセタール化合物は、２，
２−ジメチル−１，３−プロパナールとペンタエ
リスリトールとの等モルを反応させて、２−ヒド
ロキシピバル−５，５−ビス（ヒドロキシメチ
ル）１，３−ジオキサンを得、これにアクロレイ
ンまたはクロトンアルデヒドとをアセタール化反
応させることにより得る方法（下記式で示
す。）、または、ペンタエリスリトールとアクロレ
インまたはクロトンアルデヒドとの等モルを反応
させて、２−ビニル−５，５−ビス（ヒドロキシ
メチル）−１，３−ジオキサンまたは２−プロピ
ニル−５，５−ビス（ヒドロキシメチル）−１，
３−ジオキサンを得、これと２，２−ジメチル−
１，３−プロパナールとをアセタール化反応させ
て得る方法（下記式で示す。）により得ること
ができる。 The polyfunctional cyclic acetal compound of the present invention comprises 2,
Equimolar amounts of 2-dimethyl-1,3-propanal and pentaerythritol are reacted to obtain 2-hydroxypival-5,5-bis(hydroxymethyl)1,3-dioxane, which is treated with acrolein or croton. 2-vinyl-5,5-bis(hydroxymethyl) is obtained by acetalization reaction with aldehyde (as shown in the following formula), or by reacting equimolar amounts of pentaerythritol with acrolein or crotonaldehyde. -1,3-dioxane or 2-propynyl-5,5-bis(hydroxymethyl)-1,
3-dioxane was obtained, and 2,2-dimethyl-
It can be obtained by an acetalization reaction with 1,3-propanal (shown by the following formula).
本発明の環状アセタール化合物は上記のごとき
方法により容易に得ることができるが、工業的に
は、副反応生成物が少ない等の点から上記の方
法が有利である。また上記反応の場合、アクロ
レインまたはクロトンアルデヒドと２−ヒドロキ
シピバル−５，５−ビス（ヒドロキシメチル）
１，３−ジオキサンとの反応は、２−ヒドロキシ
ピバル−５，５−ビス（ヒドロキシメチル）１，
３−ジオキサンを理論量より若干過剰に用いるの
が好ましく、通常、1.0：1.01〜1.10、好ましくは
1.0：1.03〜1.05のモル比で用いられる。 Although the cyclic acetal compound of the present invention can be easily obtained by the method described above, the method described above is advantageous from the viewpoint of producing fewer side reaction products. In the case of the above reaction, acrolein or crotonaldehyde and 2-hydroxypival-5,5-bis(hydroxymethyl)
The reaction with 1,3-dioxane produces 2-hydroxypival-5,5-bis(hydroxymethyl)1,
It is preferable to use 3-dioxane in a slight excess of the theoretical amount, usually 1.0:1.01 to 1.10, preferably
It is used in a molar ratio of 1.0:1.03 to 1.05.
本発明の化合物は、１分子中に異なつた二種の
官能基を有しているので、種々の特性を持つた化
合物を得ることができる。
Since the compound of the present invention has two different types of functional groups in one molecule, compounds having various properties can be obtained.
すなわち、分子中のヒドロキシメチル基は１級
アルコールとして高い反応性を持つことから、こ
れを利用し、エステル化、アセタール化、ウレタ
ン化などによる変性反応や架橋反応ができる。ま
た一方の官能基であるアリルはラジカル重合性に
は乏しいが、活性水素を有する化合物と容易に付
加反応を起す性質があり、たとえば多価アルコー
ル、カルボン酸、フエノール類、さらには末端に
水酸基を有するポリエステル、ポリエーテルなど
と容易に反応させることができる。 That is, since the hydroxymethyl group in the molecule has high reactivity as a primary alcohol, it can be used to carry out modification reactions and crosslinking reactions such as esterification, acetalization, and urethanization. Furthermore, although allyl, one of the functional groups, has poor radical polymerizability, it has the property of easily causing an addition reaction with compounds having active hydrogen, such as polyhydric alcohols, carboxylic acids, phenols, and even terminal hydroxyl groups. It can be easily reacted with polyester, polyether, etc.
したがつて、本発明の環状アセタール化合物
は、合成樹脂、塗料、接着剤、あるいは機能性高
分子材料に使用される原料として、また変性材と
して広汎な応用ができ、目的に合つた多彩な分子
設計を行なうことができる。たとえば、塗料原料
の一つとして、または変性材として利用した場
合、架橋密度を高めることなく、耐熱性が良好で
硬度が高く、強靭な物性を示し、また耐候性、耐
薬品性にすぐれた塗膜を賦与することができる。 Therefore, the cyclic acetal compound of the present invention can be widely applied as a raw material for synthetic resins, paints, adhesives, or functional polymer materials, and as a modified material, and can be used as a material for a variety of molecules suitable for various purposes. Design can be done. For example, when used as a paint raw material or as a modified material, it can be used as a coating material that exhibits good heat resistance, high hardness, and strong physical properties without increasing crosslink density, and has excellent weather resistance and chemical resistance. A membrane can be provided.
つぎに、本発明の実施例を記す。 Next, examples of the present invention will be described.
実施例 １
内容量１(l)の４つの口フラスコに溶媒トルエン
500部、２−ヒドロキシピバル−５，５−ビス
（ヒドロキシメチル）−ｍ−ジオキサン76.5部と触
媒Ｐ−トルエンスルホン酸3.0部を採り撹拌しな
がら液温80〜90℃で溶解均一液とした後、ついで
液温90〜95℃で保持し、アクロレイン18.0部を１
時間かけて滴下した。滴下満了後、90〜95℃を保
持しながら２時間撹拌下で反応させた。Example 1 The solvent toluene was added to a four-necked flask with an internal capacity of 1 (l).
500 parts, 76.5 parts of 2-hydroxypival-5,5-bis(hydroxymethyl)-m-dioxane and 3.0 parts of catalyst P-toluenesulfonic acid were dissolved at a temperature of 80 to 90°C with stirring to form a homogeneous liquid. After that, the liquid temperature was maintained at 90 to 95℃, and 18.0 parts of acrolein was added to the
It dripped over time. After completion of the dropwise addition, the reaction was carried out under stirring for 2 hours while maintaining the temperature at 90 to 95°C.
つぎに、液温を30〜40℃に冷却した後、10wt
％の炭酸ナトリウム水溶液20部を加えて中和した
後、二相分離し、更に上相の有機相を200部の水
で水洗した。こうして得た反応液からトルエン
250部を300mmＨｇの減圧下で留去し、その留残液
を冷却したところ白色の結晶が析出した。この結
晶を過ケーキとして回収し、減圧下50〜60（℃）
で乾燥し白色結晶77.1部を得た。（収率93.0mol
％）、この結晶の元素分析、OH基当量、分子量
はそれぞれ下記の通りであり、これは３−ビニル
−９−ヒドロキシピバル−２，４，８，10−テト
ラオキサスピロ〔５，５〕ウンデカンであること
が確認された。 Next, after cooling the liquid temperature to 30-40℃, 10wt
After neutralizing by adding 20 parts of aqueous sodium carbonate solution, the two phases were separated, and the upper organic phase was washed with 200 parts of water. Toluene is extracted from the reaction solution thus obtained.
250 parts were distilled off under reduced pressure of 300 mmHg, and when the residual liquid was cooled, white crystals were precipitated. The crystals were collected as a supercake and heated to 50-60℃ under reduced pressure.
This was dried to obtain 77.1 parts of white crystals. (Yield 93.0mol
%), elemental analysis, OH group equivalent, and molecular weight of this crystal are as follows, and this is 3-vinyl-9-hydroxypival-2,4,8,10-tetraoxaspiro[5,5] It was confirmed that it was undecan.
(イ) 元素分析
C60.3％、H8.6％、O31.1％
（理論値C60.5％、H8.5％、O31.0％）
(ロ) OH基当量
6.51％ （理論値6.59％）
(ハ) 分子量
258.1
実施例 ２
実施例１においてはアクロレインの代りにクロ
トンデアルデヒド20.3部を使用し、滴下終了後、
90〜95℃で2.5時間反応させた外は実施例１と同
様に行ない、白色結晶74.4部を得た。（収率94.4
％）
この結晶の元素分析、OH基当量、分子量はそ
れぞれ下記の通りであり、これは３−プロピニル
−３−ヒドロキシピバル−２，４，８，10−テト
ラオキサスヒロ〔５，５〕ウンデカンであること
が確認された。
(a) Elemental analysis C60.3%, H8.6%, O31.1% (theoretical value C60.5%, H8.5%, O31.0%) (b) OH group equivalent 6.51% (theoretical value 6.59%) ) (c) Molecular weight 258.1 Example 2 In Example 1, 20.3 parts of crotonaldehyde was used instead of acrolein, and after completion of dropping,
The same procedure as in Example 1 was conducted except that the reaction was carried out at 90 to 95°C for 2.5 hours to obtain 74.4 parts of white crystals. (Yield 94.4
%) The elemental analysis, OH group equivalent, and molecular weight of this crystal are as follows, and this is 3-propynyl-3-hydroxypival-2,4,8,10-tetraoxashilo[5,5] It was confirmed that it was undecan.
(イ) 元素分析 C61.7％、H8.9％、O29.4％ （理論値C61.8％、H8.8％、O29.4％） (ロ) OH基当量 6.20％（理論値6.25％） (ハ) 分子量 271.8 (b) Elemental analysis C61.7%, H8.9%, O29.4% (Theoretical value C61.8%, H8.8%, O29.4%) (b) OH group equivalent 6.20% (theoretical value 6.25%) (c) Molecular weight 271.8
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59258785A JPS61137889A (en) | 1984-12-07 | 1984-12-07 | Polyfunctional cyclic acetal compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59258785A JPS61137889A (en) | 1984-12-07 | 1984-12-07 | Polyfunctional cyclic acetal compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61137889A JPS61137889A (en) | 1986-06-25 |
| JPH0442391B2 true JPH0442391B2 (en) | 1992-07-13 |
Family
ID=17325037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59258785A Granted JPS61137889A (en) | 1984-12-07 | 1984-12-07 | Polyfunctional cyclic acetal compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61137889A (en) |
-
1984
- 1984-12-07 JP JP59258785A patent/JPS61137889A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61137889A (en) | 1986-06-25 |
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