JPS59157074A - Preparation of modified tris(2-hydroxyethyl)isocyanurate - Google Patents
Preparation of modified tris(2-hydroxyethyl)isocyanurateInfo
- Publication number
- JPS59157074A JPS59157074A JP58032639A JP3263983A JPS59157074A JP S59157074 A JPS59157074 A JP S59157074A JP 58032639 A JP58032639 A JP 58032639A JP 3263983 A JP3263983 A JP 3263983A JP S59157074 A JPS59157074 A JP S59157074A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyethyl
- tris
- isocyanurate
- caprolactone
- reaction
- 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
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical class OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000007513 acids Chemical class 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007983 Tris buffer Substances 0.000 description 16
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- -1 2-hydroxyethyl isocyanurate Chemical compound 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical class CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- SZXKSDXHODZTFS-UHFFFAOYSA-N 4-[4,5-bis[4-(dimethylamino)phenyl]-1H-imidazol-2-yl]-2,6-dimethoxyphenol Chemical compound COC1=C(O)C(OC)=CC(C=2NC(=C(N=2)C=2C=CC(=CC=2)N(C)C)C=2C=CC(=CC=2)N(C)C)=C1 SZXKSDXHODZTFS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 102000010410 Nogo Proteins Human genes 0.000 description 1
- 108010077641 Nogo Proteins Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 239000000654 additive Substances 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はε−カプロラクトン類で変性されたトリス（２
−ヒドロキシエチル）イソシアヌレートの製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides tris (2
-Hydroxyethyl)isocyanurate.
トリス（２−ヒドロキシエチル）イソシアヌレートは剛
直な骨格を有し、更に骨格中にＮを含むため、ポリエス
テル、ポリウレタン、ウレタンアクリレート等のグリコ
ール成分の１つとして用いることにより、ポリエステル
、ポリウレタン、ウレタンアクリレート等に硬度を付与
するとともに密着性の改良も期待出来る。そのため、ト
リス（２−ヒドロキシエチル）イソがヌレートはウレタ
ンニジストマー分野、コーティング分野等で広く用いら
れているＮ要な化合物である。しカルながら、トリス（
２−ヒドロキシエチル）イソシアヌレートの第１級水酸
基は剛直な骨格のため酸、イソシアネート等との反応性
が悪いという欠点を狩っていた。Tris (2-hydroxyethyl) isocyanurate has a rigid skeleton and further contains N in the skeleton, so it can be used as one of the glycol components of polyester, polyurethane, urethane acrylate, etc. In addition to imparting hardness to materials such as the like, improvement in adhesion can also be expected. Therefore, tris(2-hydroxyethyl)isonurate is an essential compound widely used in the urethane distomer field, coating field, etc. Tris (
Since the primary hydroxyl group of 2-hydroxyethyl isocyanurate has a rigid skeleton, it has had the disadvantage of poor reactivity with acids, isocyanates, etc.
そこで本発明者等はこのようなトリス（２−ヒドロキシ
エチル）イソシアヌレートの欠点を改良しトリス（２−
ヒドロキンエチル）イソシアヌレートの利用可能性をさ
らに拡げんと鋭意研死した結果、トリス（２−ヒドロキ
シエチル）インシアヌレートの第１級水酸基の全部又は
一部にε−カプロラクトン類を重合することによつて、
剛直で反応性の悪いトリス（２−ヒドロキシエチル）イ
ンシアヌレートに適度な可撓性が伺与されるとともに、
固体であるトリス（２−とドロキシエチル少イソシアヌ
レートが液状になり作業性の改善がはかられ、更に剛直
なインシアヌレート環に近（立体障害等のために反応性
の悪い水酸基は、ε−カプロラクトン類の側鎖末端の反
応性の大きな第１級水酸基となり、しかも剛直なイソシ
アヌレート環から遠（離れたところに第１級水酸基が存
在するため酸、イソシアネート等との反応性が改善され
ることを見出し、本発明を完成させた。Therefore, the present inventors improved the drawbacks of tris(2-hydroxyethyl)isocyanurate and developed tris(2-hydroxyethyl)isocyanurate.
As a result of intensive research to further expand the usability of hydroquine ethyl isocyanurate, we discovered that ε-caprolactones were polymerized to all or part of the primary hydroxyl groups of tris(2-hydroxyethyl) in cyanurate. According to
Tris(2-hydroxyethyl)in cyanurate, which is rigid and has poor reactivity, is given appropriate flexibility, and
The solid tris(2-) and droxyethyl oligoisocyanurate become liquid, which improves workability. It is a highly reactive primary hydroxyl group at the end of the side chain of caprolactones, and is located far away from the rigid isocyanurate ring, improving reactivity with acids, isocyanates, etc. They discovered this and completed the present invention.
即ち、本発明はトリス（２−ヒドロキシエチル）インシ
アヌレート９５〜５重量％と、ε−カプロ２クトン類５
〜９５ｉ蛍％とを重合させることを特徴とする、６０℃
における粘度が５００．０００ ｃｐ 以下の流動状
を呈する変性トリス（２−ヒドロキシエチル）インシア
ヌレートの製造方法に係るものである。That is, the present invention contains 95 to 5% by weight of tris(2-hydroxyethyl)in cyanurate and 5% by weight of ε-caprodictones.
~60°C, characterized by polymerizing with ~95i%
The present invention relates to a method for producing modified tris(2-hydroxyethyl)in cyanurate which exhibits a fluid state with a viscosity of 500.000 cp or less.
従来、水酸基を有する物質とシフトン類とが重合反応し
て、それ等の重合体か生じることは知られていた。しか
し乍ら、本発明の対象とするトリス（２−ヒドロキシエ
チルラインシアヌレートについてはε−カプロラクトン
類との反応は知られておらす、これで変性されたトリス
（２−ヒドロキシエチルラインシアヌレートの流動性、
可撓性、反応性等の性質については知られるところがな
かった。It has been known that a substance having a hydroxyl group and a sifton undergo a polymerization reaction to form a polymer thereof. However, the reaction of tris (2-hydroxyethyl line cyanurate, which is the object of the present invention) with ε-caprolactones is known, and the reaction of tris (2-hydroxyethyl line cyanurate) modified with this is known. Liquidity,
Nothing was known about its properties such as flexibility and reactivity.
本発明に用いるε−カプロラクトン須としては例えば、
ε−カプロラクトン、ω−ヒドロキシカプロン酸、ω−
ヒドロキシカプロン酸エステル等が挙げられるが、特に
好ましいのは、６−カプロラクトンである。ε−カプロ
ラクトンはシクロヘキサノンを過酢酸でバイヤービリガ
ー反応によって酸化することにより工業的に製造されて
いる。Examples of the ε-caprolactone used in the present invention include:
ε-caprolactone, ω-hydroxycaproic acid, ω-
Examples include hydroxycaproic acid esters, but 6-caprolactone is particularly preferred. ε-caprolactone is produced industrially by oxidizing cyclohexanone with peracetic acid by the Bayer-Villiger reaction.
本発明の変性トリス（２−ヒドロキシエチル）インシア
ヌレートを製造する際のトリス（２−ヒドロキシエチル
ラインシアヌレートとｅ−カプロ２クト／胡との反応割
合は重量比で９５；５〜５：９５、好ましくは、８０：
２０〜２０：８０である。トリス（２−ヒドロキシエチ
ルラインシアヌレートが上記範囲より多すぎる場合は、
最終樹脂に、目的とする充分な可撓性を付与することか
出来す、又少な過ぎる場合はイー１脂が柔か（なり過ぎ
好才しくない。When producing the modified tris(2-hydroxyethyl)ine cyanurate of the present invention, the reaction ratio of tris(2-hydroxyethylline cyanurate and e-capro2cto/hu) is 95:5 to 5: 95, preferably 80:
20-20:80. If the amount of tris(2-hydroxyethyl line cyanurate is too much than the above range,
It is possible to impart the desired sufficient flexibility to the final resin, and if it is too small, the E1 fat is too soft (not too good).
本発明において、トリス（２−ヒドロキシエチル）イソ
シアヌレート１モルに対し、Ｅ−カプロラクトン腿１モ
ルを反応させた場合、トリス（２−ヒドロキシエチＡＩ
）インシアヌレートの水酸基へのε−カプロラクトン類
の（付加）反し＋Ｓ４度と生成物のカプロラクトン末端
の水敵基へのε−カプロラクトン類の（付加）反応速度
が殆んど変らず、且つ該反応はそれ等Ａり酸基の任意の
位置で起るため、実際には反応生成物は式
％式％）
（式中１１＋ １２１ ｎ ３ はそれぞれ０又は正
の畝）で表わされる化合物でｎｌ−ｎ２−ｎ３＝０ の
未反応物から、ｎ１＊ｎ２＋１５ が任意の数である
ホリカプロラクトンに到るまで杭計的に分布する混合物
である。In the present invention, when 1 mol of E-caprolactone is reacted with 1 mol of tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxyethyl)
) The (addition) reaction rate of ε-caprolactones to the hydroxyl group of incyanurate +S4 times and the (addition) reaction rate of ε-caprolactones to the water group at the caprolactone end of the product are almost unchanged, and Since the reaction occurs at any position of the acid group, the reaction product is actually a compound represented by the formula % (in which 11 + 121 n 3 is 0 or a positive ridge), nl -n2-n3=0 It is a mixture that is distributed systematically from unreacted substances to holicaprolactone where n1*n2+15 is an arbitrary number.
この混合物はさらに分離、梢製する必要はな（、混合物
のままで最終樹脂の合成に用いることができる。This mixture does not need to be further separated or refined (the mixture can be used as it is for the synthesis of the final resin.
本発明のトリス（２−ヒドロキシエチル）イソシアヌレ
ートの第１級Ｘ酸基へのε−カプロラクトン類の重合反
応は屋索雰囲気下、１００〜２４０℃、好ましくは１２
０〜２００℃の温度で行なわれる。１００℃より低い場
合は反応速度が小さく、また２４０℃より高い場合はε
−カプロラクトン類が沸騰し、反応系外に逃げてしまう
からである。The polymerization reaction of ε-caprolactones to the primary
It is carried out at a temperature of 0 to 200°C. If it is lower than 100℃, the reaction rate is small, and if it is higher than 240℃, ε
- This is because caprolactones boil and escape from the reaction system.
この反応には触媒を用いることが好ましい。It is preferable to use a catalyst for this reaction.
触媒としてはテトラブチルチタネート、テトラプロビル
チタ洋−ト、テトラエチルチタネート等のチタン化合物
、オクチル酸スズ、ジブチルスズオキシド、ジブチルス
ズジラウレート等の有イ幾スズ化合物、さらには塩化第
１スズ、臭化第１スズ、ヨウ化第１スズ等のハロゲン化
スズ化合物を用いることが出来る。使用量は全仕込量に
対し０．０１〜１０００ ｐｐｍ、好ましくは０．２〜
５００ ｐｐｍである。Examples of catalysts include titanium compounds such as tetrabutyl titanate, tetraprobyl titanate, and tetraethyl titanate, tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate, and stannous chloride and stannous bromide. Tin halide compounds such as tin and stannous iodide can be used. The amount used is 0.01 to 1000 ppm, preferably 0.2 to 1000 ppm based on the total amount of preparation.
500 ppm.
反応は無浴剤で行なってもよいし、トルエン、キシレン
、メチルエチルケトン、メチルイソブチルケトン等の活
性水巣を付たない溶剤中で行なっても良い。但しエステ
ル結合を有する浴剤は好ましくない。なぜなら、反応中
にポリカプロラクトンのエステル基とエステル交換反応
を起こし、トリス（２−ヒドロキシエチル）インシアヌ
レートに結合していないポリカプロラクトンが佑成する
恐れがあるからである。The reaction may be carried out without a bath agent, or in a solvent that does not form active water holes, such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone. However, bath additives having ester bonds are not preferred. This is because, during the reaction, a transesterification reaction may occur with the ester group of polycaprolactone, resulting in polycaprolactone not bonded to tris(2-hydroxyethyl)in cyanurate.
不発明のε−カプロラクトン頬で変性された）リス（２
−ヒドロキシエチルラインシアヌレートは、目的とする
樹脂を合成するに掘り、作業性が改善され、架橋剤等と
の反応性が優れ、それにより可焼性に冨んだ最終細面、
例えば、ポリエステル、ポリウレタン、ウレタンアクリ
レート等を提供することかできる。Squirrel (2) modified with uninvented ε-caprolactone cheeks
-Hydroxyethyl line cyanurate improves workability when synthesizing the desired resin, has excellent reactivity with crosslinking agents, etc., and has a fine final surface with high flammability.
For example, polyesters, polyurethanes, urethane acrylates, etc. can be provided.
以下実施例を挙げて本発明を更に詳細に説明するが、本
発明はこれらによって限定されるものではない。尚、物
中の部はＭ置部を意味する。EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. In addition, the part in the product means the M-place part.
実施例１
窒素導入管、温度計、冷却管、撹拌装置を備えた４ツロ
フラスコに、トリス（２−ヒドロキシエチル）イソシア
ヌレート７ ’３０８ ｍ （２８，０モル）及びε−
カプロラクトン３１９２ｉ１Ｓ（２８，０モル）、触媒
としてテトラブチルチタネー） ０．１０５部を仕込み
、窒素雰囲気下、１７０℃で約７時間反応させたところ
、未反応６−カプロラクトンは０．６％以下であった。Example 1 Tris(2-hydroxyethyl)isocyanurate 7'308 m (28.0 mol) and ε-
Caprolactone 3192i1S (28.0 mol) and 0.105 parts of tetrabutyl titanium (tetrabutyl titanium) as a catalyst were charged and reacted at 170°C for about 7 hours in a nitrogen atmosphere, resulting in less than 0.6% of unreacted 6-caprolactone. there were.
得られたラクトン変性トリス（２−ヒドロキシエチル）
インシアヌレートは以下忙示す性状を有していた。The resulting lactone-modified tris(2-hydroxyethyl)
Incyanurate had the following properties.
外 観（ガードナー） ５
酸 ブＩｆｌＪ Ｃ１り≦７ＫＯＨ／ｊ９ ）
ＣＩ、８ ２ ２ｏＨ価（Ｉｎｆ／ｘｏＨ／、
ｉ９ ） ４４０．４粘度（ｃｐ／ａｔ３０℃）
（Ｓ ５．（Ｓ ００実施例２〜４
トリス（２−ヒドロキシエチル）イソシアヌレート（Ｔ
ｌ（ＥユＣと略記）及びε−カプロラクトン（ｇ −Ｏ
Ｌ と略記）の仕込割合を変えた以外は実施例１と同
僚にして重合反応を行った。結果は表１に示す。Appearance (Gardner) 5 Acid IflJ C1ri≦7KOH/j9)
CI, 8 2 2oH titer (Inf/xoH/,
i9) 440.4 viscosity (cp/at 30℃)
(S 5. (S 00 Examples 2-4 Tris(2-hydroxyethyl)isocyanurate (T
l (abbreviated as EyuC) and ε-caprolactone (g -O
A polymerization reaction was carried out in the same manner as in Example 1 except that the charging ratio of L (abbreviated as L) was changed. The results are shown in Table 1.
表 １
応用例
（Ａ） 空気導入管、温度計、冷却管、攪拌装置、及
び滴下ロートを備えた５−ｅ５ツロフラスコに、インホ
ロンジイソシアネート２，２２０部（１０，０モル）お
よびジブチルスズオキシド−）９．０５部を加え、全気
雰囲気下６０″ｃｒｔｃ保った。ついで、反応温度Ｃ６
０℃以下少に保ちながら、２−ヒト目キシエチルアクリ
レ−） １．１６０部（ｉ ｏ、ｏモル〕を鉤下ロート
より約２時間で綱下し滴下終了後約５時間６０℃で反応
を枕り゛反応生成物中にはＩＲ分析より水酸基か存在し
ないことを確認して反応を停止した。生成物として、エ
チレン性不飽和モノインシアネー） ５，５８０部を得
た。Table 1 Application example (A) 2,220 parts (10,0 mol) of inphoron diisocyanate and dibutyltin oxide (2,220 parts (10,0 mol)) and dibutyltin oxide were placed in a 5-e5 Turow flask equipped with an air inlet tube, a thermometer, a cooling tube, a stirring device, and a dropping funnel. 9.05 parts was added and maintained at 60" crtc under a full atmosphere. Then, the reaction temperature was increased to C6.
While keeping the temperature below 0°C, 1.160 parts (io, o mol) of 2-human xyethyl acrylate was added through a hooked funnel over about 2 hours, and kept at 60°C for about 5 hours after the dropwise addition was completed. When the reaction stopped, it was confirmed by IR analysis that no hydroxyl group was present in the reaction product, and the reaction was stopped. 5,580 parts of ethylenically unsaturated monocyane was obtained as a product.
（Ｂ） 次に、同様な装胤に、実施例３で合成した６
−カプロラクトン変性のトリス（２−ヒドロキシエチル
〕イソシアヌレート１２０６部（２，０モルンを仕込み
８０℃に加温した。なお、この場合、反応混合物は適度
な流動性を持ち、溶媒メチルエチルケトンは使用しなか
った。さらに（Ａ）で合成したエチレン性不頗狽モノイ
ソシアネート２．７１２部（６，Ｄモル）を柴気雰囲気
下、反応温度（８０℃以下〕に保ちながら滴下ロートよ
り約４時間で滴下し鵬下終了仮約５時同８０℃で反応を
ぜじけた。(B) Next, the 6 synthesized in Example 3 was added to the same seed.
- 1206 parts (2.0 mol) of caprolactone-modified tris(2-hydroxyethyl)isocyanurate was charged and heated to 80°C.In this case, the reaction mixture had appropriate fluidity, and the solvent methyl ethyl ketone was not used. Furthermore, 2.712 parts (6, D mol) of the ethylenic monoisocyanate synthesized in (A) was added dropwise from the dropping funnel over about 4 hours while maintaining the reaction temperature (below 80°C) under a slag atmosphere. The reaction was terminated at 80°C at about 5 hours after completion of the test.
ＮＣｏ ％ が０．１％以下であることを５ｋ ｇし
て反応を停止した。生成物として光硬化性オリゴマー５
，９１８部を得た。この光鋭化性オリゴマー７０ＭＭ郡
を希釈剤テトラヒドロフルフリルアクリレー）３０重量
部に浴かした際の溶解粘度は２０，０００ｃｐ／ａｔ２
５℃であった。The reaction was stopped after checking that the NCo % was 0.1% or less using 5 kg. Photocurable oligomer 5 as product
, 918 copies were obtained. When 70 MM of this photo-sharpening oligomer was immersed in 30 parts by weight of diluent (tetrahydrofurfuryl acrylate), the dissolution viscosity was 20,000 cp/at2.
The temperature was 5°C.
対照例
応用例の（Ｂ）と同様にしてメチルエチルケトン５００
部に＃屏したトリス（２−ヒドロキシエチル）インシア
ヌレート５２２部（２，０モル）を応用例ＣＡ）で合成
したエチレン性不飽和モノインシアネー） ２．０２８
部（６，０モルつと反応させ光鋭化性オリゴマー２．５
５０部を得た。この光硬化性オリゴマーの上記と同じ溶
解粘度は２ Ｄ Ｏ，ＯＤ Ｄ ｃｐ／ａｔ ２５℃で
あった。In the same manner as in (B) of the control example application example, methyl ethyl ketone 500
522 parts (2.0 mol) of tris(2-hydroxyethyl)in cyanurate divided into 522 parts (2.0 mol) of ethylenically unsaturated monocyanate synthesized in Application Example CA) 2.028
part (6.0 mol) of photo-sharpening oligomer (2.5 mol)
Got 50 copies. The same dissolution viscosity as above for this photocurable oligomer was 2 D O,OD D cp/at 25°C.
次で上記応用例及び対照例で得た光硬化性オリゴマーに
希釈剤としてテトラヒドロフルフリルアクリレ−） （
ＴＨＦＡ ） 及び光増感剤としてイルガキュア６５
１（チバガイギー社Ｎ）１．９部を組合せ紫外線照射に
て硬化塗膜を得た。Next, the photocurable oligomers obtained in the above application examples and control examples were added as a diluent to tetrahydrofurfuryl acrylate) (
THFA) and Irgacure 65 as a photosensitizer
1 (Ciba Geigy Co., Ltd. N) were combined and irradiated with ultraviolet rays to obtain a cured coating film.
その結果を表−２に示す。The results are shown in Table-2.
衣−２
硬化条件
高圧水銀灯ラング ８０Ｗ／画
照射距離 ６ｃｍ
照射時間 １０ｓθ０
膜 ノ皐 約１００μ出願人代理人
古 谷 馨Clothes-2 Curing conditions High-pressure mercury lamp rung 80W/Image irradiation distance 6cm Irradiation time 10sθ0 Film Nogo Approximately 100μ Applicant's representative
Kaoru Furuya
Claims (1)
９５〜５重景％と、６−カプロラクトン類５〜９５重量
％とを重合さセることを特徴とする、６０℃におけるイ
′占度が５００，０００ｃｐ 以下の流動状を呈する変
性トリス（２−ヒドロキシエチル）イソシアヌレートの
製造方法 ２、 重合反応を蟹素雰囲気下１００〜２４０℃の温度
で行なう特許請求の範囲第１項記載の製造方法[Scope of Claims] 1. An i' at 60°C characterized by polymerizing 95 to 5% by weight of tris(2-hydroxyethyl)isocyanurate and 5 to 95% by weight of 6-caprolactones. Method 2 for producing modified tris(2-hydroxyethyl) isocyanurate exhibiting a fluid state with a density of 500,000 cp or less, claimed in claim 1, wherein the polymerization reaction is carried out at a temperature of 100 to 240°C in a crab atmosphere. manufacturing method
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58032639A JPS59157074A (en) | 1983-02-28 | 1983-02-28 | Preparation of modified tris(2-hydroxyethyl)isocyanurate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58032639A JPS59157074A (en) | 1983-02-28 | 1983-02-28 | Preparation of modified tris(2-hydroxyethyl)isocyanurate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59157074A true JPS59157074A (en) | 1984-09-06 |
| JPH0417951B2 JPH0417951B2 (en) | 1992-03-26 |
Family
ID=12364417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58032639A Granted JPS59157074A (en) | 1983-02-28 | 1983-02-28 | Preparation of modified tris(2-hydroxyethyl)isocyanurate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59157074A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010112179A1 (en) * | 2009-04-03 | 2010-10-07 | Cook Composites And Polymers Company | Thermosetting compositions containing isocyanurate rings |
| FR2951718A1 (en) * | 2009-10-22 | 2011-04-29 | Seppic Sa | New tris(hydroxyethyl) isocyanurate derivatives useful as flame retardant and a crosslinking agent in polyurethane foam/elastomer, and for manufacturing molded articles |
| FR2951719A1 (en) * | 2009-10-22 | 2011-04-29 | Seppic Sa | New tris(hydroxyethyl) isocyanurate compounds useful as flame retardant and a crosslinking agent in polyurethane foam/elastomer, and for manufacturing molded articles |
| US8546486B2 (en) | 2007-09-18 | 2013-10-01 | Ccp Composites Us Llc | Low VOC thermosetting polyester acrylic resin for gel coat |
| JP2014196470A (en) * | 2013-03-05 | 2014-10-16 | 株式会社Adeka | Trifunctional viscosity controlling agent |
| JP2015232111A (en) * | 2014-05-13 | 2015-12-24 | 日本化薬株式会社 | Polyfunctional acid anhydride, thermosetting resin composition using the same, and cured product of the composition |
| CN114402034A (en) * | 2019-09-17 | 2022-04-26 | 株式会社大赛璐 | Composition and cured product thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660327A (en) * | 1970-06-08 | 1972-05-02 | George Co P D | Lactone or lactam pre-esterified isocyanurate-containing resins |
| JPS48103594A (en) * | 1972-03-08 | 1973-12-25 |
-
1983
- 1983-02-28 JP JP58032639A patent/JPS59157074A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660327A (en) * | 1970-06-08 | 1972-05-02 | George Co P D | Lactone or lactam pre-esterified isocyanurate-containing resins |
| JPS48103594A (en) * | 1972-03-08 | 1973-12-25 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8546486B2 (en) | 2007-09-18 | 2013-10-01 | Ccp Composites Us Llc | Low VOC thermosetting polyester acrylic resin for gel coat |
| WO2010112179A1 (en) * | 2009-04-03 | 2010-10-07 | Cook Composites And Polymers Company | Thermosetting compositions containing isocyanurate rings |
| US8501877B2 (en) | 2009-04-03 | 2013-08-06 | Ccp Composites Us Llc | Thermosetting compositions containing isocyanurate rings |
| US8637612B2 (en) | 2009-04-03 | 2014-01-28 | Ccp Composites Us Llc | Thermosetting compositions containing isocyanurate ring |
| US9346909B2 (en) | 2009-04-03 | 2016-05-24 | Ccp Composites Us Llc | Thermosetting compositions containing isocyanurate rings |
| EA025765B1 (en) * | 2009-04-03 | 2017-01-30 | Ссп Композитс Юс Ллс | Thermosetting compositions containing isocyanurate rings |
| FR2951718A1 (en) * | 2009-10-22 | 2011-04-29 | Seppic Sa | New tris(hydroxyethyl) isocyanurate derivatives useful as flame retardant and a crosslinking agent in polyurethane foam/elastomer, and for manufacturing molded articles |
| FR2951719A1 (en) * | 2009-10-22 | 2011-04-29 | Seppic Sa | New tris(hydroxyethyl) isocyanurate compounds useful as flame retardant and a crosslinking agent in polyurethane foam/elastomer, and for manufacturing molded articles |
| JP2014196470A (en) * | 2013-03-05 | 2014-10-16 | 株式会社Adeka | Trifunctional viscosity controlling agent |
| JP2015232111A (en) * | 2014-05-13 | 2015-12-24 | 日本化薬株式会社 | Polyfunctional acid anhydride, thermosetting resin composition using the same, and cured product of the composition |
| CN114402034A (en) * | 2019-09-17 | 2022-04-26 | 株式会社大赛璐 | Composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0417951B2 (en) | 1992-03-26 |
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