JPH08302013A - Polythiourethane - Google Patents
PolythiourethaneInfo
- Publication number
- JPH08302013A JPH08302013A JP10970095A JP10970095A JPH08302013A JP H08302013 A JPH08302013 A JP H08302013A JP 10970095 A JP10970095 A JP 10970095A JP 10970095 A JP10970095 A JP 10970095A JP H08302013 A JPH08302013 A JP H08302013A
- Authority
- JP
- Japan
- Prior art keywords
- polythiourethane
- compound
- polymer
- formula
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002578 polythiourethane polymer Polymers 0.000 title claims abstract description 34
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 12
- 150000004985 diamines Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- BGPJLYIFDLICMR-UHFFFAOYSA-N 1,4,2,3-dioxadithiolan-5-one Chemical compound O=C1OSSO1 BGPJLYIFDLICMR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 16
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003287 optical effect Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 abstract description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 27
- 229940125782 compound 2 Drugs 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 125000003396 thiol group Chemical class [H]S* 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- -1 mercapto compound Chemical class 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 150000002540 isothiocyanates Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 150000007970 thio esters Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical compound O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、光学材料、架橋剤、
エポキシ樹脂硬化剤などとして利用される新規なポリチ
オウレタンおよびその製造方法に関するものである。This invention relates to an optical material, a crosslinking agent,
The present invention relates to a novel polythiourethane used as an epoxy resin curing agent and a method for producing the same.
【０００２】[0002]
【従来の技術】ポリチオウレタンは高屈折率の光学材料
（特開平５−２０８９５０号公報、特開平５−２０２３
４７号公報）、光学材料用の接着剤（特開平３−５６５
２５号公報）などの原料として有用な化合物であること
が知られている。このポリチオウレタンは、メルカプト
化合物とイソシアナートあるいはイソチオシアナートと
の反応により製造されている。これらのイソシアナー
ト、イソチオシアナートは極めて反応性が高いことか
ら、各種活性水素化合物との反応により、多種多様の構
造と物性とを有するポリチオウレタンを合成することが
できる。2. Description of the Related Art Polythiourethane is an optical material having a high refractive index (JP-A-5-208950 and JP-A-5-2023).
47), adhesives for optical materials (Japanese Patent Laid-Open No. 3-565).
It is known to be a compound useful as a raw material such as JP-A No. 25). This polythiourethane is produced by reacting a mercapto compound with an isocyanate or isothiocyanate. Since these isocyanates and isothiocyanates have extremely high reactivity, polythiourethanes having various structures and physical properties can be synthesized by reacting with various active hydrogen compounds.
【０００３】[0003]
【発明が解決しようとする課題】ところが、その反応性
の多様さ故に、他の活性水素化合物混在下でアミンとの
み選択的に反応させることは不可能であり、アルコー
ル、チオール、カルボン酸などの官能基を有する化合物
の共存下には、これらとの副反応なしにポリチオウレタ
ンを合成することはできないという問題があった。However, due to the variety of the reactivity, it is impossible to selectively react only with amine in the presence of other active hydrogen compounds, and alcohols, thiols, carboxylic acids, etc. In the presence of a compound having a functional group, there is a problem that polythiourethane cannot be synthesized without side reaction with these compounds.
【０００４】このため、これら官能基を自身に有するポ
リチオウレタンの自由な分子設計を妨げている。かかる
困難さのため、特定のポリチオウレタンは従来、合成さ
れていなかった。This hinders the free molecular design of polythiourethanes having these functional groups themselves. Due to such difficulties, certain polythiourethanes have not previously been synthesized.
【０００５】この発明は、上記のような従来技術の問題
に着目してなされたものである。その目的とするところ
は、優れた機械的物性や光学的物性を発揮でき、光学材
料や架橋剤などとして好適に利用できる新規なポリチオ
ウレタンを提供することにある。また、他の目的とする
ところは、イソシアナートやイソチオシアナートを使用
することなく、容易に得ることができるポリチオウレタ
ンの製造方法を提供することにある。The present invention has been made by paying attention to the problems of the prior art as described above. It is an object of the invention to provide a novel polythiourethane which can exhibit excellent mechanical properties and optical properties and can be suitably used as an optical material, a crosslinking agent and the like. Another object is to provide a method for producing polythiourethane which can be easily obtained without using isocyanate or isothiocyanate.
【０００６】[0006]
【課題を解決するための手段】この目的を達成するため
に、請求項１に記載の新規なポリチオウレタンの発明
は、前記一般式（１）で表される単位を有するものであ
る。To achieve this object, the invention of a novel polythiourethane described in claim 1 has a unit represented by the general formula (1).
【０００７】また、請求項２に記載のポリチオウレタン
の製造方法の発明では、前記化学式（２）で表される二
官能性５員環ジチオカーボナートと二官能性のジアミン
とを反応させるものである。Further, in the invention of the method for producing a polythiourethane according to claim 2, the bifunctional 5-membered ring dithiocarbonate represented by the chemical formula (2) is reacted with a bifunctional diamine. Is.
【０００８】以下に、この発明について詳細に説明す
る。この発明の新規なポリチオウレタンは、前記一般式
（１）で表される単位を有し、ビスフェノールＳ骨格と
キシリレンなどの二官能性のジアミンとがチオウレタン
結合により交互に連続してなる主鎖と、それに結合した
遊離または保護されたチオール基とから構成される。こ
のポリチオウレタンは、強度などの機械的性質に優れ、
また屈折率などの光学的性質にも優れ、さらに架橋によ
り溶媒不溶の硬化物を生じる等の性質を有している。The present invention will be described in detail below. The novel polythiourethane of the present invention has a unit represented by the general formula (1), and is mainly composed of a bisphenol S skeleton and a difunctional diamine such as xylylene, which are alternately continuous by a thiourethane bond. It is composed of a chain and a free or protected thiol group attached to it. This polythiourethane has excellent mechanical properties such as strength,
Further, it has excellent optical properties such as a refractive index, and further has a property of producing a cured product insoluble in a solvent by crosslinking.
【０００９】一般式（１）中、 Rは水素または-COCH3で
あり、これらは上記の優れた物性を発揮できるととも
に、ポリチオウレタンを容易に製造することができる。
そして、前記性質に基づいて、ポリチオウレタンは例え
ば、光学材料、架橋剤、エポキシ樹脂硬化剤、加硫剤、
重合調整剤、合成樹脂原料、酸化防止剤、金属錯体生成
剤、生化学的薬物、潤滑油添加剤、塗膜等の広範囲の用
途に使用される。In the general formula (1), R is hydrogen or --COCH 3 , which can exhibit the above-mentioned excellent physical properties and can easily produce polythiourethane.
Then, based on the above properties, polythiourethane is, for example, an optical material, a crosslinking agent, an epoxy resin curing agent, a vulcanizing agent,
It is used in a wide range of applications such as polymerization regulators, raw materials for synthetic resins, antioxidants, metal complex forming agents, biochemical drugs, lubricant additives, and coating films.
【００１０】次に、このポリチオウレタンの製造方法に
ついて説明する。ポリチオウレタンは、前記化学式
（２）で表される二官能性５員環ジチオカーボナート
（以下化合物２という）とキシリレンジアミンなどの二
官能性のジアミンとの反応によって得られる。Next, a method for producing this polythiourethane will be described. Polythiourethane is obtained by reacting a bifunctional 5-membered ring dithiocarbonate represented by the above chemical formula (2) (hereinafter referred to as compound 2) with a bifunctional diamine such as xylylenediamine.
【００１１】この化合物２は、二官能性エポキシ化合物
と二硫化炭素とをアルカリ金属塩、アルカリ土類金属
塩、第四アンモニウム塩などの適当な触媒の存在下に反
応させて容易に合成される。この場合、溶媒としては非
プロトン性溶媒を用いると化合物２を収率良く得ること
ができる（例えば、特開平５−２４７０２７号公報）。This compound 2 is easily synthesized by reacting a difunctional epoxy compound with carbon disulfide in the presence of a suitable catalyst such as an alkali metal salt, an alkaline earth metal salt or a quaternary ammonium salt. . In this case, when an aprotic solvent is used as the solvent, the compound 2 can be obtained in good yield (for example, JP-A-5-247027).
【００１２】二官能性のジアミンの量は、化合物２に対
し当量を反応させると、分子量の増大には好ましいが、
この発明はこれに限定されるものではない。また、反応
温度、反応時間および反応圧力のいずれも特に限定され
ないが、反応温度は 0〜120℃で、反応時間は 2〜30時
間で、圧力は常圧あるいはごくわずかな加圧であること
が望ましい。The amount of the difunctional diamine is preferably an amount equivalent to that of the compound 2 for increasing the molecular weight,
The present invention is not limited to this. The reaction temperature, reaction time, and reaction pressure are not particularly limited, but the reaction temperature is 0 to 120 ° C., the reaction time is 2 to 30 hours, and the pressure may be normal pressure or very slight pressurization. desirable.
【００１３】また、化合物２とジアミンとの反応は、溶
媒中または無溶媒で行うことができる。溶媒としては、
化合物２およびジアミンをよく溶解し、それらに不活性
なテトラヒドロフラン（ＴＨＦ）、クロロホルムなどが
使用される。さらに、通常のイソシアナート、イソチオ
シアナートを用いたポリチオウレタンの合成において
は、副反応を生じるアルコール、チオール、カルボン
酸、水などの化合物が共存していても、これらと副反応
を生ずることなく、可溶性の反応生成物（重合体）を得
ることが可能である。The reaction between compound 2 and diamine can be carried out in a solvent or without solvent. As the solvent,
Tetrahydrofuran (THF), chloroform and the like, which dissolve the compound 2 and the diamine well and are inert to them, are used. Furthermore, in the synthesis of polythiourethanes using usual isocyanates and isothiocyanates, even if compounds such as alcohols, thiols, carboxylic acids, and water that cause side reactions coexist, side reactions occur with these compounds. Without, it is possible to obtain a soluble reaction product (polymer).
【００１４】このように、この発明では、従来用いられ
ていたイソシアナートやイソチオシアナートを使用する
ことなく、ポリチオウレタンを容易に製造することがで
きる。As described above, according to the present invention, polythiourethane can be easily produced without using conventionally used isocyanate or isothiocyanate.
【００１５】加えて、化合物２とジアミンとを反応させ
ると同時または反応後に無水酢酸などのカルボン酸無水
物を加えると、チオール基をチオエステルとして保護し
たポリチオウレタンが得られる。これを加えない場合に
は、遊離のチオール基を有するポリチオウレタンが得ら
れる。In addition, when a carboxylic acid anhydride such as acetic anhydride is added simultaneously with or after the reaction of compound 2 with a diamine, a polythiourethane having a thiol group protected as a thioester can be obtained. If this is not added, a polythiourethane with free thiol groups is obtained.
【００１６】遊離のチオール基を有するチオウレタンは
溶液中では可溶性のポリマーであるが、空気中に放置す
ればチオール基が容易に空気酸化して重合体間で架橋を
生じ、溶媒不溶の硬化物が生じる。例えば、これを塗膜
原料として用いれば、塗布直後に酸化され、架橋、硬化
して強固な塗膜を形成することができる。Thiourethane having a free thiol group is a soluble polymer in a solution, but if left in the air, the thiol group is easily air-oxidized to cause cross-linking between polymers, and a solvent-insoluble cured product. Occurs. For example, if this is used as a coating material, it can be oxidized immediately after coating, crosslinked and cured to form a strong coating.
【００１７】[0017]
【実施例】以下に、参考例および実施例を挙げ、この発
明をさらに具体的に説明する。 （参考例１）ビスフェノールＳジグリシジルエーテル3
6.2g 、臭化リチウム0.44g 、テトラヒドロフラン30ml
を還流冷却器を取り付けたフラスコに入れ、二硫化炭素
7ml をこれらの混合溶液中に滴下し、室温下で反応させ
た。生じた二官能性５員環ジチオカーボナートをシリカ
ゲルカラムクロマトグラフィー( ヘキサン/ アセトン=1
/1) で分離し、化合物２を得た。EXAMPLES The present invention will be described more specifically below with reference to Examples and Examples. (Reference Example 1) Bisphenol S diglycidyl ether 3
6.2g, lithium bromide 0.44g, tetrahydrofuran 30ml
Place in a flask fitted with a reflux condenser and carbon disulfide.
7 ml was dropped into these mixed solutions and reacted at room temperature. The resulting bifunctional 5-membered ring dithiocarbonate was subjected to silica gel column chromatography (hexane / acetone = 1.
Separation by (1) gave compound 2.
【００１８】化合物２の分析値： 1H NMR (CDCl3,δppm): 3.72(d, 4H, CH2)、4.33(d, 4
H, CH2)、5.44(m, 2H,CH) 、7.00, 7.90(d, 8H, Ph) 、 IR (KBr,cm-1): 3067(Ph), 2928, 2874(CH2, CH)、1257
(Ph-O)、1190(C=S) 、 元素分析：C20H18O6S5, found(calcd.), C,46.30(46.6
9), H,3.68(3.50), S,30.88(31.13) （実施例１）アルゴン置換THF 中、参考例１で得た化合
物２を515mg とp-キシリレンジアミン136mg とを反応さ
せ、下記化学式（３）で表される単位を有する化合物
（重合体３という）を得た。Analysis value of compound 2: 1H NMR (CDCl 3 , δppm): 3.72 (d, 4H, CH 2 ), 4.33 (d, 4)
H, CH 2 ), 5.44 (m, 2H, CH), 7.00, 7.90 (d, 8H, Ph), IR (KBr, cm -1 ): 3067 (Ph), 2928, 2874 (CH 2 , CH), 1257
(Ph-O), 1190 ( C = S), elemental analysis: (. Calcd) C 20 H 18 O 6 S 5, found, C, 46.30 (46.6
9), H, 3.68 (3.50), S, 30.88 (31.13) (Example 1) Compound 2 obtained in Reference Example 1 was reacted with 515 mg and p-xylylenediamine 136 mg in argon-substituted THF to give the following chemical formula: A compound having a unit represented by (3) (referred to as polymer 3) was obtained.
【００１９】[0019]
【化３】 Embedded image
【００２０】重合体３の分析値： 1H NMR (CDCl3,δppm): 1.47(br, 2H, SH)、3.08(d, 4
H, CH2)、4.13(d, 4H,CH2)、4.2 〜4.8(d, 4H, CH2) 、
5.7 〜6.0(m, 2H, CH)、6.7(br, NH) 、6.7 〜7.4(m, 1
2H, Ph) 、 IR (KBr,cm-1): 3068(Ph) 、2928, 2868(CH2, CH) 、12
51(Ph-O)、1186(C=S) 重合体３をメタノールで再沈殿して精製、空気中で乾燥
し、下記化学式（４）で表される化合物（重合体４とい
う）を得た。このものはS-S 結合で重合体が架橋されい
るため溶媒に不溶であった。Analysis value of Polymer 3 : 1H NMR (CDCl 3 , δppm): 1.47 (br, 2H, SH), 3.08 (d, 4)
H, CH 2 ), 4.13 (d, 4H, CH 2 ), 4.2 to 4.8 (d, 4H, CH 2 ),
5.7 ~ 6.0 (m, 2H, CH), 6.7 (br, NH), 6.7 ~ 7.4 (m, 1
2H, Ph), IR (KBr, cm -1 ): 3068 (Ph), 2928, 2868 (CH 2 , CH), 12
51 (Ph-O), 1186 (C = S) Polymer 3 was reprecipitated with methanol, purified, and dried in air to obtain a compound represented by the following chemical formula (4) (referred to as Polymer 4). . This product was insoluble in the solvent because the polymer was cross-linked by SS bond.
【００２１】[0021]
【化４】 [Chemical 4]
【００２２】重合体４の分析値： IR (KBr,cm-1): 3064(Ph) 、2926, 2861(CH2, CH) 、12
54(Ph-O)、1185(C=S)、559(S-S) （実施例２）アルゴン置換THF 中、参考例１で得た化合
物２を515mg とm-キシリレンジアミン136mg とを反応さ
せ、下記化学式（５）で表される単位を有する化合物
（重合体５という）を得た。Analysis value of polymer 4: IR (KBr, cm -1 ): 3064 (Ph), 2926, 2861 (CH 2 , CH), 12
54 (Ph-O), 1185 (C = S), 559 (SS) (Example 2) The compound 2 obtained in Reference Example 1 was reacted with 515 mg and m-xylylenediamine 136 mg in argon-substituted THF, A compound having a unit represented by the following chemical formula (5) (referred to as polymer 5) was obtained.
【００２３】[0023]
【化５】 Embedded image
【００２４】重合体５の分析値： 1H NMR (CDCl3,δppm): 1.47(br, 2H, SH)、3.08(d, 4
H, CH2)、4.13(d, 4H,CH2)、4.2 〜4.8(d, 4H, CH2) 、
5.7 〜6.0(m, 2H, CH)、6.7(br, NH) 、6.7 〜7.4(m, 1
2H, Ph) 、 IR (KBr,cm-1): 3070(Ph) 、2928, 2868(CH2, CH) 、12
51(Ph-O)、1186(C=S) 重合体５をメタノールで再沈殿して精製、空気中で乾燥
し、下記化学式（６）で表される化合物（重合体６とい
う）を得た。このものはS-S 結合で重合体が架橋されい
るため溶媒に不溶であった。Analysis value of polymer 5: 1H NMR (CDCl 3 , δppm): 1.47 (br, 2H, SH), 3.08 (d, 4)
H, CH 2 ), 4.13 (d, 4H, CH 2 ), 4.2 to 4.8 (d, 4H, CH 2 ),
5.7 ~ 6.0 (m, 2H, CH), 6.7 (br, NH), 6.7 ~ 7.4 (m, 1
2H, Ph), IR (KBr, cm -1 ): 3070 (Ph), 2928, 2868 (CH 2 , CH), 12
51 (Ph-O), 1186 (C = S) Polymer 5 was reprecipitated with methanol, purified, and dried in air to obtain a compound represented by the following chemical formula (6) (referred to as Polymer 6). . This product was insoluble in the solvent because the polymer was cross-linked by SS bond.
【００２５】[0025]
【化６】 [Chemical 6]
【００２６】重合体６の分析値： IR (KBr,cm-1): 3062(Ph) 、2926, 2861(CH2, CH) 、12
54(Ph-O)、1185(C=S)、559(S-S) （実施例３）THF中で化合物２を515mg とp-キシリレン
ジアミン136mg とを反応させ、無水酢酸1ml とトリエチ
ルアミン101mg とを加えた。メタノールで再沈殿して精
製し、下記化学式（７）で表される単位を有する化合物
（重合体７という）を得た。Analysis value of polymer 6: IR (KBr, cm -1 ): 3062 (Ph), 2926, 2861 (CH 2 , CH), 12
54 (Ph-O), 1185 (C = S), 559 (SS) (Example 3) 515 mg of compound 2 was reacted with 136 mg of p-xylylenediamine in THF, and 1 ml of acetic anhydride and 101 mg of triethylamine were reacted. added. The product was reprecipitated with methanol and purified to obtain a compound having a unit represented by the following chemical formula (7) (referred to as polymer 7).
【００２７】[0027]
【化７】 [Chemical 7]
【００２８】重合体７の分析値： 1H NMR (CDCl3,δppm): 1.69(s, 6H, CH3)、2.29(s, 6
H, CH3)、3.35(d, 4H,CH2)、4.13(d, 4H, CH2)、4.2 〜
4.8(d, 4H, CH2) 、5.7 〜6.0(m, 2H, CH)、6.7(br, N
H) 、6.7 〜7.4(m, 12H, Ph) 、 IR (KBr,cm-1): 3059(Ph) 、2925, 2878(CH2, CH) 、16
94 (C=O)、1246(Ph-O)、1165(C=S) （実施例４）化合物２を515mg とm-キシリレンジアミン
136mg とを反応させ、無水酢酸1mlとトリエチルアミン1
01mg とを加えた。メタノールで再沈殿して精製し、下
記化学式（８）で表される単位を有する化合物（重合体
８という）を得た。Analysis value of polymer 7: 1H NMR (CDCl 3 , δppm): 1.69 (s, 6H, CH 3 ), 2.29 (s, 6)
H, CH 3 ), 3.35 (d, 4H, CH 2 ), 4.13 (d, 4H, CH 2 ), 4.2 ~
4.8 (d, 4H, CH 2 ), 5.7 ~ 6.0 (m, 2H, CH), 6.7 (br, N
H), 6.7 to 7.4 (m, 12H, Ph), IR (KBr, cm -1 ): 3059 (Ph), 2925, 2878 (CH 2 , CH), 16
94 (C = O), 1246 (Ph-O), 1165 (C = S) (Example 4) 515 mg of compound 2 and m-xylylenediamine
React with 136 mg, 1 ml of acetic anhydride and triethylamine 1
01 mg was added. Reprecipitation with methanol and purification were performed to obtain a compound having a unit represented by the following chemical formula (8) (referred to as polymer 8).
【００２９】[0029]
【化８】 Embedded image
【００３０】重合体８の分析値： 1H NMR (CDCl3,δppm): 1.69(s, 6H, CH3)、2.29(s, 6
H, CH3)、3.35(d, 4H,CH2)、4.13(d, 4H, CH2)、4.2 〜
4.7(d, 4H, CH2) 、5.7 〜6.0(m, 2H, CH)、6.7(br, N
H) 、6.7 〜7.4(m, 12H, Ph) 、 IR (KBr,cm-1): 3034(Ph) 、2965, 2928(CH2, CH) 、16
94 (C=O)、1244(Ph-O)、1162(C=S) 重合体７、８の物性値を下記に示す。Analysis value of polymer 8: 1H NMR (CDCl 3 , δppm): 1.69 (s, 6H, CH 3 ), 2.29 (s, 6)
H, CH 3 ), 3.35 (d, 4H, CH 2 ), 4.13 (d, 4H, CH 2 ), 4.2 ~
4.7 (d, 4H, CH 2 ), 5.7 ~ 6.0 (m, 2H, CH), 6.7 (br, N
H), 6.7 to 7.4 (m, 12H, Ph), IR (KBr, cm -1 ): 3034 (Ph), 2965, 2928 (CH 2 , CH), 16
The physical properties of the 94 (C = O), 1244 (Ph-O), 1162 (C = S) polymers 7 and 8 are shown below.
【００３１】数平均分子量〔ポリスチレン換算ＧＰＣ
（ゲルパーミエーションクロマトグラフ）分析値〕：重
合体７は５０００、重合体８は６０００ １０％重量減少温度〔ＴＧＡ（熱重量分析法）分析
値〕：重合体７は２２５℃、重合体８は２３８℃ ガラス転移点〔ＤＳＣ（示差走査熱量測定法）分析
値〕：重合体７は６６℃、重合体８は４５℃ （参考例２）参考例１で得た化合物２を515mg とp-キシ
リレンジアミン136mg とを均一に混合し、重合体３を得
た。そこにビスフェノールA340mgを加え、均一とした
後、ガラスモールドとガスケットよりなるモールド型に
注入し、次いで加熱硬化させて透明樹脂を得た。この透
明樹脂は、屈折率Nd=1.61 、アッベ数νD=32で、光学材
料などとして利用可能なものであった。 （１）二官能性のジアミンは、キシリレンジアミンであ
る請求項２に記載のポリチオウレタンの製造方法。この
製造方法によれば、前記一般式（１）で表される単位を
有するポリチオウレタンを効率良く製造することができ
る。 （２）二官能性５員環ジチオカーボナートは、二官能性
エポキシ化合物と二硫化炭素とを触媒の存在下に反応さ
せて得られるものである請求項２に記載のポリチオウレ
タンの製造方法。この方法によれば、二官能性５員環ジ
チオカーボナートを容易に製造することができる。 （３）触媒は、アルカリ金属、アルカリ土類金属塩また
は第四アンモニウム塩である上記（２）に記載のポリチ
オウレタンの製造方法。この製造方法によれば、二官能
性エポキシ化合物と二硫化炭素との反応を促進させるこ
とができる。 （４）二官能性５員環ジチオカーボナートと、二官能性
のジアミンと、カルボン酸無水物とを反応させ、チオー
ル基をチオエステルとした請求項２に記載のポリチオウ
レタンの製造方法。この製造方法によれば、ポリチオウ
レタン中のチオール基をチオエステルとして保護するこ
とができる。Number average molecular weight [polystyrene conversion GPC
(Gel permeation chromatograph) analysis value]: Polymer 7 is 5000, Polymer 8 is 6000 10% weight loss temperature [TGA (Thermogravimetric analysis) analysis value]: Polymer 7 is 225 ° C., Polymer 8 is 238 ° C. glass transition point [DSC (differential scanning calorimetry) analysis value]: Polymer 7 was 66 ° C., Polymer 8 was 45 ° C. (Reference Example 2) 515 mg of compound 2 obtained in Reference Example 1 and p-xylyl Polymer 3 was obtained by uniformly mixing with 136 mg of diamine. After adding 340 mg of bisphenol A thereto and homogenizing it, it was poured into a mold composed of a glass mold and a gasket, and then cured by heating to obtain a transparent resin. This transparent resin had a refractive index Nd = 1.61 and an Abbe number νD = 32 and was usable as an optical material. (1) The method for producing a polythiourethane according to claim 2, wherein the difunctional diamine is xylylenediamine. According to this production method, the polythiourethane having the unit represented by the general formula (1) can be efficiently produced. (2) The bifunctional 5-membered ring dithiocarbonate is obtained by reacting a bifunctional epoxy compound with carbon disulfide in the presence of a catalyst. . According to this method, a bifunctional 5-membered ring dithiocarbonate can be easily produced. (3) The method for producing a polythiourethane according to (2) above, wherein the catalyst is an alkali metal salt, an alkaline earth metal salt or a quaternary ammonium salt. According to this production method, the reaction between the difunctional epoxy compound and carbon disulfide can be promoted. (4) The method for producing a polythiourethane according to claim 2, wherein the bifunctional 5-membered ring dithiocarbonate, the bifunctional diamine and the carboxylic acid anhydride are reacted to form a thioester as the thiol group. According to this production method, the thiol group in polythiourethane can be protected as a thioester.
【００３２】[0032]
【発明の効果】以上詳述したように、請求項１に記載の
発明によれば、チオウレタン結合を有する主鎖と、それ
に結合した遊離または保護されたチオール基とを有し、
優れた機械的物性や光学的物性を発揮でき、光学材料や
架橋剤などとして好適に利用できる新規なポリチオウレ
タンを提供することができる。As described in detail above, according to the invention described in claim 1, it has a main chain having a thiourethane bond and a free or protected thiol group bonded thereto,
It is possible to provide a novel polythiourethane which can exhibit excellent mechanical properties and optical properties and can be suitably used as an optical material, a cross-linking agent and the like.
【００３３】また、請求項２に記載の発明によれば、イ
ソシアナートやチオイソシアナートを使用することな
く、容易かつ確実にポリチオウレタンを製造することが
できる。According to the second aspect of the invention, the polythiourethane can be easily and reliably produced without using isocyanate or thioisocyanate.
Claims (2)
るポリチオウレタン。 【化１】 (式中 Rは水素または-COCH3を表す。)1. A polythiourethane having a unit represented by the following general formula (1). Embedded image (In the formula, R represents hydrogen or -COCH 3. )
員環ジチオカーボナートと二官能性のジアミンとを反応
させる請求項１に記載の一般式（１）で表される単位を
有するポリチオウレタンの製造方法。 【化２】 2. A bifunctional 5 represented by the following chemical formula (2):
The method for producing a polythiourethane having a unit represented by the general formula (1) according to claim 1, wherein a membered ring dithiocarbonate is reacted with a difunctional diamine. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10970095A JPH08302013A (en) | 1995-05-08 | 1995-05-08 | Polythiourethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10970095A JPH08302013A (en) | 1995-05-08 | 1995-05-08 | Polythiourethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08302013A true JPH08302013A (en) | 1996-11-19 |
Family
ID=14517000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10970095A Pending JPH08302013A (en) | 1995-05-08 | 1995-05-08 | Polythiourethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08302013A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023447A1 (en) * | 1999-09-30 | 2001-04-05 | Kyowa Yuka Co., Ltd. | Method of diminishing odor emission |
| US7518001B2 (en) | 2004-09-21 | 2009-04-14 | Showa Denko K.K. | Radically polymerizable sulfur-containing compound and radically polymerizable sulfur-containing polymer |
| JP2011236154A (en) * | 2010-05-10 | 2011-11-24 | Yamagata Univ | Metal complex by polycondensation reaction of polyfunctional thiol and metal compound and organic-inorganic hybrid material |
| JP2012007067A (en) * | 2010-06-24 | 2012-01-12 | Dainichiseika Color & Chem Mfg Co Ltd | Self-crosslinkable polyhydroxy polyurethane resin, and method of manufacturing the same |
| CN104877525A (en) * | 2015-05-12 | 2015-09-02 | 上海乘鹰新材料有限公司 | Self-repair lustering paint composition |
-
1995
- 1995-05-08 JP JP10970095A patent/JPH08302013A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023447A1 (en) * | 1999-09-30 | 2001-04-05 | Kyowa Yuka Co., Ltd. | Method of diminishing odor emission |
| US6759484B1 (en) | 1999-09-30 | 2004-07-06 | Kyowa Yuka Co., Ltd. | Method of diminishing odor emission |
| US7518001B2 (en) | 2004-09-21 | 2009-04-14 | Showa Denko K.K. | Radically polymerizable sulfur-containing compound and radically polymerizable sulfur-containing polymer |
| JP2011236154A (en) * | 2010-05-10 | 2011-11-24 | Yamagata Univ | Metal complex by polycondensation reaction of polyfunctional thiol and metal compound and organic-inorganic hybrid material |
| JP2012007067A (en) * | 2010-06-24 | 2012-01-12 | Dainichiseika Color & Chem Mfg Co Ltd | Self-crosslinkable polyhydroxy polyurethane resin, and method of manufacturing the same |
| CN104877525A (en) * | 2015-05-12 | 2015-09-02 | 上海乘鹰新材料有限公司 | Self-repair lustering paint composition |
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