JPS6263596A - Siloxane oligomer - Google Patents
Siloxane oligomerInfo
- Publication number
- JPS6263596A JPS6263596A JP60204781A JP20478185A JPS6263596A JP S6263596 A JPS6263596 A JP S6263596A JP 60204781 A JP60204781 A JP 60204781A JP 20478185 A JP20478185 A JP 20478185A JP S6263596 A JPS6263596 A JP S6263596A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- expressed
- halogen
- siloxane oligomer
- compound expressed
- 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title description 10
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000012044 organic layer Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- -1 contact lenses Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000007818 Grignard reagent Substances 0.000 abstract description 2
- 150000004795 grignard reagents Chemical class 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 125000005375 organosiloxane group Chemical group 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 230000002785 anti-thrombosis Effects 0.000 abstract 1
- 239000003146 anticoagulant agent Substances 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 description 1
- GIWOHOUNSAJDGH-UHFFFAOYSA-N 3-tris[[dimethyl(3,3,3-trifluoropropyl)silyl]oxy]silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)CCC(F)(F)F)(O[Si](C)(C)CCC(F)(F)F)O[Si](C)(C)CCC(F)(F)F GIWOHOUNSAJDGH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000001732 thrombotic effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は文献未載の新規なシロキサンオリゴマー、とく
には機能的高分子の中間体またはシリコーン変成高分子
用として有用とされるシロキサンオリゴマーに関するも
のある。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel siloxane oligomer that has not been published in any literature, and particularly to a siloxane oligomer that is useful as an intermediate for functional polymers or for use in silicone-modified polymers. be.
（発明の構成） 本発明は一般式 （こ＼にＹは水素原子、ＣＱＣＨ，、 ＣＨ。(Structure of the invention) The present invention is based on the general formula (Here, Y is a hydrogen atom, CQCH, CH.
ＣＨ２＝ＣＣ０○（ＣＨ２） −”示される基から選択
される原子または基）で示される文献未載の新規なシロ
キサンオリゴマーに関するものである。The present invention relates to a novel siloxane oligomer represented by CH2=CC0○(CH2) - "an atom or group selected from the groups shown" which has not been described in any literature.
上記した式（１）におけるＹは水素原子、ＣＨ。Y in the above formula (1) is a hydrogen atom, CH.
ＣＱＣＨ２、ＣＨ，＝ＣＣ００（ＣＨ，）。CQCH2,CH,=CC00(CH,).
で示される基から選択される原子または基であり、した
がってこれにはつぎの３種のものが例示される。It is an atom or group selected from the groups represented by, and therefore, the following three types are exemplified.
ＣＨ。CH.
ＣＨ２＝ＣＣＯＯ（ＣＨ２）、Ｓｉ−
このシロキサンオリゴマーは例えば
ＣＨ３
Ｘ−Ｍｇ−〇−５Ｌ−ＣＨ，ＣＨ，ＣＦ３ ・・・
（２）ＣＨ。CH2=CCOO(CH2), Si- This siloxane oligomer is, for example, CH3X-Mg-〇-5L-CH,CH,CF3...
(2) CH.
（ニーにＸはハロゲン原子）で示される有機けい素ハロ
マグネシウム塩に一般式
％式％（３）
（こ＼にＹは前記に同じ、２はハロゲン原子または低級
アルコキシ基）で示されるハロシランまたはアルコキシ
シランを反応させると、この反応が次式
％式％
によって進行するので、反応終了後これらを水中に注ぎ
有機層を蒸溜すれば目的とするシロキサンオリゴマーを
高純度、高収率で得ることができるが、この反応は０℃
〜還流温度の範囲、好ましくは３０〜８０℃で行わせれ
ばよい。(wherein, When alkoxysilanes are reacted, this reaction proceeds according to the following formula % formula %, so if the reaction is completed and the organic layer is poured into water and the organic layer is distilled, the desired siloxane oligomer can be obtained with high purity and high yield. Yes, but this reaction takes place at 0°C.
to reflux temperature, preferably 30 to 80°C.
なお、上記した一般式（２）で示される有機けい素ハロ
マグネシウム塩は常法で製造したＲＭｇＸ （Ｒは一
価炭化水素基）で示されるグリニヤール試薬に式
で示されるオルガノシロキサンを滴下し５０〜１２０℃
で反応させることによって得ることかできる。また、こ
の有機けい素ハロマグネシウム塩に添加される上記した
一般式（３）で示されるオルガノシランとしては Ｈ８
１ＣＱ、、
Ｈ８１（○ＣＨ３）３、ＣＱ ＣＨ２ＳｉＣＱ□。The organosilicon halomagnesium salt represented by the above general formula (2) is obtained by adding dropwise an organosiloxane represented by the formula to a Grignard reagent represented by RMgX (R is a monovalent hydrocarbon group) prepared by a conventional method. ~120℃
It can be obtained by reacting with In addition, the organosilane represented by the above general formula (3) added to this organosilicon halomagnesium salt is H8
1CQ,, H81(○CH3)3,CQ CH2SiCQ□.
ＣＨ。CH.
ＣＨ２＝ＣＣ００（ＣＨ，）、５ｉＣＬなどが例示され
る。Examples include CH2=CC00(CH,) and 5iCL.
本発明のシロキサンオリゴマーは種々の用途に使用され
るが、これは特にはガス透過性や撥水性の機能を有する
機能高分子化合物、シリコ−変性高分子化合物となるの
で、コンタクトレンズ、包帯、抗血栓性材料などのよう
な医療用高分子物質として有用とされるほか、透湿性防
水布などの分野にも有用とされる。The siloxane oligomer of the present invention can be used for various purposes, and in particular, it can be used as a functional polymer compound with gas permeability or water repellency, or as a silico-modified polymer compound, so it can be used in contact lenses, bandages, anti-inflammatory materials, etc. It is said to be useful as a medical polymer substance such as a thrombotic material, and also in fields such as moisture-permeable waterproof fabric.
つぎに本発明の実施例をあげる。Next, examples of the present invention will be given.
実施例１
反応器中に金属マグネシウム２４．３ ｇ （１モル）
とテトラハイドロフラン３００ｗＱを仕込んだのち、こ
れにメチルクロライドを吹き込んでメチルマグネシウム
クロライドのテトラハイドロフラン溶液を作り、これに
還流下でトリフルオロプロピルメチルシロキサントリマ
ー
テトラハイドロフラン２００ｍＭにとかして液を２時間
で滴下して反応させ、さらに２時間還流させてから、こ
の反応液にトリクロロシラン（ＨＳ ｉＣＱ 、） ４
５ ｇ （０，３３モル）を還流温度で滴下して反応さ
せたのち、これを水ＩＱ中に注ぎ込み、分離した有機層
を減圧蒸溜したところ、４ｒｍＨｇ、１２５℃の留分（
ＧＣ純度９９．２％）のものが１４６ｇ得られた。Example 1 24.3 g (1 mol) of magnesium metal in the reactor
After charging 300 wQ of tetrahydrofuran with methyl chloride, a solution of methylmagnesium chloride in tetrahydrofuran was prepared by blowing methyl chloride into the solution, and 200 mM of trifluoropropylmethylsiloxane trimer in tetrahydrofuran was dissolved in this under reflux, and the solution was stirred for 2 hours. After refluxing for another 2 hours, trichlorosilane (HS iCQ, ) 4 was added to the reaction solution.
After dropping 5 g (0.33 mol) at reflux temperature to react, it was poured into water IQ and the separated organic layer was distilled under reduced pressure.
146 g of a product with a GC purity of 99.2% was obtained.
ついてＩＲｌＮＭＲおよび元素分析を行ったところ、こ
れらについて
エＲ：第１図
ＮＭＲ： δ ０．１７ｐｐｍ −５ｉＣＨ３１８
Ｈδ ０．７７ｐｐｍ −Ｓ ｉＣＨ２Ｓ Ｈδ ２
．Ｏｐｐｍ −ＣＨ２ＣＦ、 ６ Ｈδ ５．２５
ｐｐｍ −ＳｉＨＩ Ｈ元素分析：
０％ Ｈ％ Ｓｉｘ
計算値 ３３．１９ ５．７６ ２０．７０実測
値 ３３，１６ ５．７６ ２０．７４が得られ
たので、これは次式
で示されるシロキサンオリゴマーであることが確認され
た。When IRlNMR and elemental analysis were performed on these, the following results were obtained: Figure 1 NMR: δ 0.17ppm -5iCH318
Hδ 0.77ppm -S iCH2S Hδ 2
．． Oppm -CH2CF, 6 Hδ 5.25
ppm -SiHI H elemental analysis: 0% H% Six Calculated value 33.19 5.76 20.70 Actual value 33,16 5.76 20.74 was obtained, so this is a siloxane oligomer represented by the following formula. It was confirmed that there is.
実施例２
実施例１におけるトリクロロシラン４５ｇの代りにクロ
ロメチルトリクロロシラン
（ＣＱＣＨ２ＳｉＣＯ３）６１ ｇを使用したほかは実
施例１と同様に処理したところ、４ｍＨｇ、１３９℃の
留分（ＧＣ，純度９６％）のものが１５６ｇ得られた。Example 2 The same procedure as in Example 1 was performed except that 61 g of chloromethyltrichlorosilane (CQCH2SiCO3) was used instead of 45 g of trichlorosilane in Example 1. As a result, a fraction of 4 mHg and 139°C (GC, purity 96%) was obtained. ) was obtained.
このものは屈折率 ２５が１．３８５０であり、そのＩ
Ｒ，ＮＭＲおよび元素分析結果が
工Ｒ：第２図
ＮＭＲ：δＯ，１７ｐｐｍ −ＳｉＣＨｆｆｌ ８
Ｈ３Ｏ，７７ｐｐｍ−８ｉＣＨ２６Ｈ
δ ２．０ρｐｍ −ＣＨ，ＣＦ、 ６Ｈδ ２．
５５ｐｐｍ −８ｉＣＨ，ＣＩ２ ２Ｈ元素分析：
０％ Ｈ％ Ｓｉｘ
計算値 ３２，５６ ５．４６ １９．００実測
値 ３２，５９ ５．４７ １８．９６であるこ
とから、これは次式
で示されるクロロメチルトリス（トリフルオロジメチル
シロキシ）シランであることが確認された。The refractive index 25 of this one is 1.3850, and its I
R, NMR and elemental analysis results are shown.
H3O, 77ppm-8iCH26Hδ 2.0ρpm -CH,CF, 6Hδ 2.
55ppm -8iCH,CI2 2H elemental analysis: 0% H% Six Calculated value 32,56 5.46 19.00 Actual value 32,59 5.47 18.96, so this is chloromethyl expressed by the following formula It was confirmed to be tris(trifluorodimethylsiloxy)silane.
実施例３
実施例１におけるトリクロロシラン４５ｇの代りに３−
メタクリロキシプロピルトリクロロシラン
８６ｇを使用したほかは実施例１と同様に処理したとこ
ろ、 ｌｎｍＨｇ 、 １５６℃の留分（ＧＣ純度９６
％）のものが１６１ｇ得られた。Example 3 Instead of 45 g of trichlorosilane in Example 1, 3-
When treated in the same manner as in Example 1 except that 86 g of methacryloxypropyltrichlorosilane was used, the fraction at lnmHg and 156°C (GC purity 96
%) was obtained.
このものは屈折率ｎＤが１．４００５であり、このＩＲ
，ＮＭＲおよび元素分析結果が
工Ｒ：第３図
ＮＭＲ：δ０．１７ｐｐｎ＋ −８ｉＣＨ，１８Ｈδ
０．７７ｐｐｍ −Ｓ ｉＣＨ２Ｓ Ｈδ４．Ｏ４ｐ
ｐｍ −Ｃ○○ＣＨ２−２Ｈδ ５．４５ρｐｆｆｌ
ＩＨδ ６．９９ｐｐ
ｍ −ＣＨ，＝Ｃ−Ｉ Ｈ元素分析：
０％ Ｈ％ Ｓｉｘ
計算値 ３９．５０ ６．１８ １６．８０実測
値 ３９．４４ ６．１８ １６．８２であるこ
とから、これは次式
で示される３−メタクリロキシプロピルトリス（トリフ
ルオロプロピルジメチルシロキシ）シランであることが
確認された。This material has a refractive index nD of 1.4005, and this IR
, NMR and elemental analysis results are shown in Figure 3. NMR: δ0.17ppn+ -8iCH, 18Hδ
0.77ppm -S iCH2S Hδ4. O4p
pm -C○○CH2-2Hδ 5.45ρpffl
IHδ 6.99pp
m -CH,=C-I H elemental analysis: 0% H% Six Calculated value 39.50 6.18 16.80 Actual value 39.44 6.18 16.82, so this is shown by the following formula. It was confirmed that it was 3-methacryloxypropyltris(trifluoropropyldimethylsiloxy)silane.
図はいずれも本発明のシロキサンオリゴマーの赤外線吸
収スペクトル（ＩＲ）を示したものであり、第１図〜第
３図はそれぞれ実施例１〜３で得られたシロキサンオリ
ゴマーのＩＲを図示したものである。Each figure shows the infrared absorption spectrum (IR) of the siloxane oligomer of the present invention, and Figures 1 to 3 illustrate the IR of the siloxane oligomer obtained in Examples 1 to 3, respectively. be.
Claims (1)
択 される原子または基）で示されるシロキサンオリゴマー
。[Claims] 1. An atom selected from the groups represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, Y is a hydrogen atom, ClCH_2, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or group).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204781A JPS6263596A (en) | 1985-09-17 | 1985-09-17 | Siloxane oligomer |
| US06/905,576 US4727172A (en) | 1985-09-12 | 1986-09-09 | Method for the preparation of an organosiloxane oligomer and a novel organosiloxane oligomer thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204781A JPS6263596A (en) | 1985-09-17 | 1985-09-17 | Siloxane oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6263596A true JPS6263596A (en) | 1987-03-20 |
| JPH0255439B2 JPH0255439B2 (en) | 1990-11-27 |
Family
ID=16496238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60204781A Granted JPS6263596A (en) | 1985-09-12 | 1985-09-17 | Siloxane oligomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6263596A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0211588A (en) * | 1988-06-30 | 1990-01-16 | Chisso Corp | Organosiloxane compound |
| CN1058760C (en) * | 1996-03-22 | 2000-11-22 | 株式会社村田制作所 | Cerium-containing magnetic garnet single crystal and production method therefor |
| US6973805B2 (en) | 2001-03-14 | 2005-12-13 | Showa Denko K.K. | Layered heat exchanger, layered evaporator for motor vehicle air conditioners and refrigeration system |
| JP2017510637A (en) * | 2014-03-17 | 2017-04-13 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Fluorinated compound, curable composition containing the compound, and cured product |
-
1985
- 1985-09-17 JP JP60204781A patent/JPS6263596A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0211588A (en) * | 1988-06-30 | 1990-01-16 | Chisso Corp | Organosiloxane compound |
| CN1058760C (en) * | 1996-03-22 | 2000-11-22 | 株式会社村田制作所 | Cerium-containing magnetic garnet single crystal and production method therefor |
| US6973805B2 (en) | 2001-03-14 | 2005-12-13 | Showa Denko K.K. | Layered heat exchanger, layered evaporator for motor vehicle air conditioners and refrigeration system |
| JP2017510637A (en) * | 2014-03-17 | 2017-04-13 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Fluorinated compound, curable composition containing the compound, and cured product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0255439B2 (en) | 1990-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5115729B2 (en) | Organosilicon compound containing acetoacetate group protected with trialkylsilyl group and process for producing the same | |
| US5508369A (en) | Organopolysiloxanes having a silanol group and process of making them | |
| JPS609759B2 (en) | hydroalkenyloxysilane | |
| JPS61263986A (en) | Organic silicon compound | |
| JPS6263596A (en) | Siloxane oligomer | |
| US4727172A (en) | Method for the preparation of an organosiloxane oligomer and a novel organosiloxane oligomer thereby | |
| US4469881A (en) | [2-(p-t-Butylphenyl)ethyl]silanes and method of making the same | |
| EP0499409A1 (en) | Olefinic and acetylenic azasilacyclopentanes | |
| US4814475A (en) | Vinyl silane compounds | |
| EP0392509B1 (en) | 3-(2-Oxo-1-pyrrolidinyl)-propyl-silanes and method for preparing the silane compounds | |
| Ishikawa et al. | Synthesis of Chlorosilanes from (Fluoroalkyl) silanes, Bis (silyl) benzenes, and. alpha.,. omega.-Dihydropolysiloxanes | |
| JPS59524B2 (en) | Method for producing silicone-modified polyoxyalkylene | |
| JPH0436292A (en) | Alkoxysilane | |
| JPH029888A (en) | 3-(3,4-dimethoxyphenyl)propyltrichlorosilane | |
| EP0578185B1 (en) | 1-aza-2-silacyclobutane compounds and method for their preparation | |
| Luderer et al. | Preparation and Synthetic Utility of 1‐Trimethylsiloxyalkyl‐bis (trimethylsilyl) silanes,(Me3Si) 2SiH–C (OSiMe3) R1R2 | |
| JPS63253090A (en) | Silyl (meth)acrylate having trimethylsiloxy group | |
| JP2501064B2 (en) | Organic silicon compounds | |
| EP0499408B1 (en) | Allyl cyclosilalactams | |
| US7932412B2 (en) | Method of manufacturing an aminoaryl-containing organosilicon compound and method of manufacturing an intermediate product of the aforementioned compound | |
| JPH06107671A (en) | Organosilicon compound and its production | |
| US3686252A (en) | Preparation of organosilicon compounds with silylphenyl groups | |
| US3419592A (en) | Method for making organosiloxane hydrides | |
| US5914419A (en) | Organosilicon compound | |
| JPS6261988A (en) | Production of siloxane oligomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |