JPH0625420A - Sulfonated silicone - Google Patents
Sulfonated siliconeInfo
- Publication number
- JPH0625420A JPH0625420A JP4301530A JP30153092A JPH0625420A JP H0625420 A JPH0625420 A JP H0625420A JP 4301530 A JP4301530 A JP 4301530A JP 30153092 A JP30153092 A JP 30153092A JP H0625420 A JPH0625420 A JP H0625420A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silicone
- sulfonic acid
- reaction
- weight
- 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
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 229920001400 block copolymer Polymers 0.000 claims abstract description 6
- 229920005604 random copolymer Polymers 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 125000000732 arylene group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 28
- -1 (substituted)phenyl Chemical group 0.000 abstract description 12
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000000126 substance Substances 0.000 description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000006459 hydrosilylation reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical group C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WMJRPJZQQSSDBU-UHFFFAOYSA-L disodium;sulfite;heptahydrate Chemical compound O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])=O WMJRPJZQQSSDBU-UHFFFAOYSA-L 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、界面活性剤及び塗膜の
改質剤等として有用なスルホン酸変性シリコーンに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfonic acid-modified silicone useful as a surfactant and a coating film modifier.
【０００２】[0002]
【従来の技術】ジメチルシリコーンのいくつかのメチル
基をアミノアルキル基、エポキシ基、ポリエーテル基等
の親水性基で置き換えたシリコーンは、従来より界面活
性剤として用いられてきた。例えば、ポリエーテル変性
シリコーンはシリコーン界面活性剤として、有機系の界
面活性剤と比べてレベリング効果、柔軟効果、湿潤効
果、乳化効果、分散効果等に優れた特徴を持っているこ
とがよく知られている。2. Description of the Related Art Silicone in which some methyl groups of dimethyl silicone are replaced with hydrophilic groups such as aminoalkyl group, epoxy group and polyether group has been used as a surfactant. For example, it is well known that polyether-modified silicone has excellent characteristics as a silicone surfactant in leveling effect, softening effect, wetting effect, emulsifying effect, dispersing effect, etc. as compared with organic surfactants. ing.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、スルホン酸
変性シリコーンを提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a sulfonic acid modified silicone.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は、次式で
示されるスルホン酸変性シリコーンであるMeans for Solving the Problems That is, the present invention is a sulfonic acid-modified silicone represented by the following formula.
【０００５】[0005]
【化２】 （ここで、各Ｒ1 は独立に低級アルキル基又は非置換も
しくは置換フェニル基を示し、ｍ及びｎは整数であっ
て、ｎ／ｍは１〜１００であり、Ａは一価の金属、水素
原子又は−Ｈ・Ｘ1 （ここで、Ｘ1 はアンモニア又はア
ミンを示す）を示し、Ｒはアリーレン基、直鎖又は分岐
のアルキレン基、アルカリーレン基又はアラルキレン基
を示し、該シリコーンはランダム共重合体でもブロック
共重合体でもよい）。[Chemical 2] (Here, each R 1 independently represents a lower alkyl group or an unsubstituted or substituted phenyl group, m and n are integers, n / m is 1 to 100, and A is a monovalent metal or hydrogen. Atom or —H · X 1 (wherein X 1 represents ammonia or amine), R represents an arylene group, a linear or branched alkylene group, an alkali-ylene group or an aralkylene group, and the silicone is a random copolymer. It may be a polymer or a block copolymer).
【０００６】ここで、低級アルキル基とは、好ましくは
メチル基、エチル基、プロピル基を示す。ｍ及びｎの値
は、それぞれｍ＝１０〜２００、ｎ＝５０〜２０００で
あり、好ましくはｍ＝３０〜１００、ｎ＝３００〜１０
００である。またｎ／ｍ＝１〜１００であり、好ましく
は５〜５０である。Ａで表される１価の金属としては、
好ましくはＬｉ、Ｎａ、Ｋが挙げられる。また、式−Ｈ
・Ｘ1 中のＸ1 がアミンである場合、これは、一般式Ｎ
Ｒ3 3 で示され、ここで、Ｒ3 は、それぞれ独立して、
水素原子、好ましくは１〜５個の炭素原子を有する直鎖
又は分岐のアルキル基、あるいは好ましくは１〜５個の
炭素原子を有し、好ましくは３個以下のヒドロキシル基
を有する直鎖又は分岐のヒドロキシアルキル基を示す。
該アミンとしては、例えばトリエタノールアミン、２‐
アミノ‐２‐メチル‐１‐プロパノール、２‐アミノ‐
２‐メチル‐１，３‐プロパンジオール、モノエタノー
ルアミン等が挙げられる。Ｒは、好ましくはフェニレン
基、炭素数１〜４の低級アルキル基で置換されたフェニ
レン基、炭素数１〜５のアルキレン基及びHere, the lower alkyl group is preferably a methyl group, an ethyl group or a propyl group. The values of m and n are respectively m = 10 to 200 and n = 50 to 2000, preferably m = 30 to 100 and n = 300 to 10.
00. Further, n / m = 1 to 100, preferably 5 to 50. As the monovalent metal represented by A,
Li, Na, and K are preferable. Also, the formula −H
When X 1 in X 1 is an amine, it has the general formula N
R 3 3 , wherein R 3 are each independently
Hydrogen atom, preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, or preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms and preferably 3 or less hydroxyl groups Is a hydroxyalkyl group.
Examples of the amine include triethanolamine and 2-
Amino-2-methyl-1-propanol, 2-amino-
2-Methyl-1,3-propanediol, monoethanolamine and the like can be mentioned. R is preferably a phenylene group, a phenylene group substituted with a lower alkyl group having 1 to 4 carbon atoms, an alkylene group having 1 to 5 carbon atoms, and
【０００７】[0007]
【化３】 である。また、該スルホン酸変性シリコーンはブロック
共重合体でもランダム共重合体でもよく、その数平均分
子量（Ｍｎ）は好ましくは３万〜１０万、特に好ましく
は５万〜６万である。[Chemical 3] Is. The sulfonic acid-modified silicone may be a block copolymer or a random copolymer, and its number average molecular weight (Mn) is preferably 30,000 to 100,000, particularly preferably 50,000 to 60,000.
【０００８】本発明のスルホン酸変性シリコーンは、側
鎖にスルホン化剤と反応しうる基を持つシリコーンを合
成し、続いて該シリコーンをスルホン化することにより
製造することができる。The sulfonic acid-modified silicone of the present invention can be produced by synthesizing a silicone having a group having a side chain capable of reacting with a sulfonating agent, and then sulfonating the silicone.
【０００９】ここで、側鎖にスルホン化剤と反応しうる
基を持つシリコーンは、次式で示される。Here, the silicone having a group capable of reacting with a sulfonating agent in the side chain is represented by the following formula.
【００１０】[0010]
【化４】 ここで、Ｒ、Ｒ1 、ｍ、ｎは上記と同じであり、Ｘはス
ルホン化剤と反応する基、例えばハロゲン原子、ビニル
基、又は芳香環に結合した水素原子等であり、また該シ
リコーンはブロック共重合体でもランダム共重合体でも
よい。[Chemical 4] Here, R, R 1 , m, and n are the same as above, and X is a group that reacts with a sulfonating agent, such as a halogen atom, a vinyl group, or a hydrogen atom bonded to an aromatic ring. May be a block copolymer or a random copolymer.
【００１１】側鎖にスルホン化剤と反応しうる基を持つ
シリコーンは、ｍ個のＳｉに結合した水素を持つシリコ
ーンと、スルホン化剤と反応しうる基及びビニル基を持
つ化合物（ヒドロシリル化剤）とを白金系触媒の存在下
に付加反応させるヒドロシリル化反応により製造する。The silicone having a group capable of reacting with a sulfonating agent in the side chain is a silicone having a hydrogen bonded to m Si and a compound having a group capable of reacting with a sulfonating agent and a vinyl group (hydrosilylating agent). ) And are added to each other in the presence of a platinum-based catalyst to produce a hydrosilylation reaction.
【００１２】ヒドロシリル化反応の原料として使用する
上記Ｓｉに結合した水素を持つシリコーンは、次式で示
される。The silicone having Si-bonded hydrogen used as a raw material for the hydrosilylation reaction is represented by the following formula.
【００１３】[0013]
【化５】 ここで、Ｒ1 、ｍ、ｎは上記と同じであり、また該シリ
コーンはブロック共重合体でもランダム共重合体でもよ
い。[Chemical 5] Here, R 1 , m, and n are the same as above, and the silicone may be a block copolymer or a random copolymer.
【００１４】該Ｓｉに結合した水素を持つシリコーンは
公知の方法によって製造される。例えば該シリコーンと
してのポリメチルポリハイドロジェンポリシロキサン
は、オクタメチルシクロテトラシロキサンと１，３，
５，７−テトラメチルシクロテトラシロキサン及びエン
ドキャップとしてヘキサメチルジシロキサンの平衡化反
応で製造される。好ましくは該平衡化反応は、窒素等の
不活性ガス雰囲気下で、ヘキサン等の炭化水素系溶媒の
存在下に、反応温度０〜１００℃、反応時間２４〜１０
０時間で終了する。また、原料として使用されるオクタ
メチルシクロテトラシロキサンと１，３，５，７−テト
ラメチルシクロテトラシロキサン及びヘキサメチルジシ
ロキサンのモル比は、所望の目的物の分子量及びｎ／ｍ
比により適宜調節される。The silicone having hydrogen bonded to the Si is produced by a known method. For example, polymethylpolyhydrogenpolysiloxane as the silicone is octamethylcyclotetrasiloxane and 1,3,3.
It is prepared by an equilibration reaction of 5,7-tetramethylcyclotetrasiloxane and hexamethyldisiloxane as an end cap. Preferably, the equilibration reaction is carried out under an atmosphere of an inert gas such as nitrogen in the presence of a hydrocarbon solvent such as hexane at a reaction temperature of 0 to 100 ° C. for a reaction time of 24 to 10
It ends in 0 hours. The molar ratio of octamethylcyclotetrasiloxane used as a raw material to 1,3,5,7-tetramethylcyclotetrasiloxane and hexamethyldisiloxane is the molecular weight of the desired target substance and n / m.
It is adjusted appropriately by the ratio.
【００１５】一方、スルホン化剤と反応しうる基及びビ
ニル基を持つヒドロシリル化剤は次の一般式で示されOn the other hand, a hydrosilylating agent having a vinyl group and a group capable of reacting with a sulfonating agent is represented by the following general formula.
【００１６】[0016]
【化６】 （ここで、Ｒは上記と同じであり、Ｒ2 はアリール基、
アルカリール基又はアラルキル基である。）、例えば[Chemical 6] (Wherein R is the same as above, R 2 is an aryl group,
It is an alkaryl group or an aralkyl group. ), For example
【００１７】[0017]
【化７】 （ここで、ｐは、整数であり好ましくは１〜５であ
る。）等が挙げられる。該ヒドロシリル化剤の使用量
は、化学式（３）中のｍ個のＳｉに結合した水素に対し
当量比で１．０〜１．３が好ましい。[Chemical 7] (Here, p is an integer and preferably 1 to 5) and the like. The amount of the hydrosilylation agent used is preferably 1.0 to 1.3 in terms of an equivalent ratio with respect to hydrogen bonded to m Si in the chemical formula (3).
【００１８】また、白金系触媒としては、例えば塩化白
金酸のイソプロピルアルコール（ＩＰＡ）溶液等が使用
され、その添加量はヒドロシリル化剤に対して１×１０
-4〜１×１０-5当量が好ましい。また、該ヒドロシリル
化反応に際しては、好ましくは、溶媒として例えばヘキ
サン、ベンゼン等の脂肪族炭化水素あるいは芳香族炭化
水素が使用される。該ヒドロシリル化反応の好ましい例
を挙げれば、該反応は、反応系を窒素等の不活性ガス雰
囲気下に置き、反応温度を０〜１００℃として、反応時
間が１時間〜２４時間程度で終了する。As the platinum catalyst, for example, a solution of chloroplatinic acid in isopropyl alcohol (IPA) or the like is used, and the addition amount thereof is 1 × 10 with respect to the hydrosilylation agent.
-4 to 1 x 10 -5 equivalents are preferred. Further, in the hydrosilylation reaction, it is preferable to use, for example, an aliphatic hydrocarbon such as hexane or benzene or an aromatic hydrocarbon as a solvent. As a preferred example of the hydrosilylation reaction, the reaction is completed by placing the reaction system in an atmosphere of an inert gas such as nitrogen and setting the reaction temperature to 0 to 100 ° C. and the reaction time in about 1 to 24 hours. .
【００１９】次に、上記ヒドロシリル化反応によって製
造された側鎖にスルホン化剤と反応しうる基を持つシリ
コーンをスルホン化してスルホン酸変性シリコーンを製
造する。Next, a sulfonic acid-modified silicone is produced by sulfonating a silicone having a side chain produced by the above hydrosilylation reaction and having a group capable of reacting with a sulfonating agent.
【００２０】ここで使用するスルホン化剤は、ヒドロシ
リル化反応で使用したヒドロシリル化剤の種類によって
異なり、スルホン化剤と反応する基としてハロゲン原子
を有するヒドロシリル化剤、例えば、化学式（４）又は
化学式（５）の化合物を使用した場合には、例えばＮａ
2 ＳＯ3 、ＮａＨＳＯ3 等が好ましい。スルホン化剤と
反応する基としてビニル基を有するヒドロシリル化剤、
例えば、化学式（６）又は化学式（７）の化合物を使用
した場合には、例えばＮａＨＳＯ3 等が好ましい。スル
ホン化剤と反応する基としてフェニル基を有するヒドロ
シリル化剤、例えば、化学式（８）又は化学式（９）の
化合物を使用した場合には、例えばＨ2ＳＯ4 、ＨＳＯ
3 Ｃｌ等が好ましい。該スルホン化剤の使用量は、化学
式（２）中のスルホン化剤と反応する基Ｘに対して当量
比で１〜５が好ましい。The sulfonating agent used here depends on the kind of the hydrosilylating agent used in the hydrosilylation reaction, and is a hydrosilylating agent having a halogen atom as a group which reacts with the sulfonating agent, for example, chemical formula (4) or chemical formula When the compound of (5) is used, for example, Na
2 SO 3 , NaHSO 3 and the like are preferable. A hydrosilylating agent having a vinyl group as a group which reacts with a sulfonating agent,
For example, when the compound of the chemical formula (6) or the chemical formula (7) is used, NaHSO 3 or the like is preferable. When a hydrosilylating agent having a phenyl group as a group which reacts with a sulfonating agent, for example, a compound represented by the chemical formula (8) or the chemical formula (9) is used, for example, H 2 SO 4 , HSO
3 Cl and the like are preferable. The amount of the sulfonating agent used is preferably 1 to 5 in an equivalent ratio to the group X which reacts with the sulfonating agent in the chemical formula (2).
【００２１】スルホン化反応に際しては、溶媒として例
えば１，４−ジオキサン、ジメトキシエタン、ジエチル
エーテル、テトラヒドロフラン又は炭素数５〜８の炭化
水素系溶媒（例えばヘキサン等）等、又はこれらの二種
類以上を混合して使用してもよい。好ましい反応条件を
例示すると、反応系を窒素等の不活性ガス雰囲気下に置
き、スルホン化剤と反応する基としてハロゲン原子を有
するヒドロシリル化剤を使用した場合は反応温度は５０
〜３００℃、反応時間は５〜３０時間程度である。ビニ
ル基を有するヒドロシリル化剤あるいはフェニル基を有
するヒドロシリル化剤を使用した場合は共に反応温度は
０〜１００℃、反応時間は５〜３０時間程度である。In the sulfonation reaction, as a solvent, for example, 1,4-dioxane, dimethoxyethane, diethyl ether, tetrahydrofuran or a hydrocarbon solvent having 5 to 8 carbon atoms (such as hexane) or the like, or two or more kinds thereof are used. You may mix and use. As an example of preferable reaction conditions, when the reaction system is placed in an atmosphere of an inert gas such as nitrogen and a hydrosilylating agent having a halogen atom as a group which reacts with a sulfonating agent is used, the reaction temperature is 50.
The reaction time is about 5 to 30 hours. When a hydrosilylating agent having a vinyl group or a hydrosilylating agent having a phenyl group is used, the reaction temperature is 0 to 100 ° C. and the reaction time is about 5 to 30 hours.
【００２２】あるいは、本発明のスルホン酸変性シリコ
ーンは、化学式（３）のｍ個のＳｉに結合した水素を持
つシリコーンを一工程でヒドロシリル化することにより
製造することもできる。このためのヒドロシリル化剤は
次の一般式で示されAlternatively, the sulfonic acid-modified silicone of the present invention can be produced by hydrosilylating silicone having hydrogen bonded to m Si of the chemical formula (3) in one step. The hydrosilylating agent for this has the general formula:
【００２３】[0023]
【化８】 （ここで、Ｒは上記と同じである。）、例えば[Chemical 8] (Where R is the same as above), for example
【００２４】[0024]
【化９】 等が挙げられる。また、該化合物の使用量は、化学式
（３）中のｍ個のＳｉに結合した水素に対し当量比で１
〜１．１が好ましい。白金系触媒としては、例えば塩化
白金酸のイソプロピルアルコール（ＩＰＡ）溶液等が使
用され、その添加量は上記ヒドロシリル化剤に対して１
×１０-4〜１×１０-5当量が好ましい。該反応において
も、好ましくは、溶媒として例えば１，４−ジオキサ
ン、ジメトキシエタン、ジエチルエーテル、テトラヒド
ロフラン、炭素数５〜８の脂肪族炭化水素（例えばヘキ
サン等）又は芳香族炭化水素等が使用され、これら二種
類以上を混合して使用してもよい。また、好ましい反応
条件を例示すれば、反応系を窒素等の不活性ガス雰囲気
下に置き、反応温度を０〜１００℃とし、反応時間を１
〜１０時間程度とする。[Chemical 9] Etc. The amount of the compound used is 1 in an equivalent ratio with respect to hydrogen bonded to m Si in the chemical formula (3).
~ 1.1 is preferable. As the platinum-based catalyst, for example, a solution of chloroplatinic acid in isopropyl alcohol (IPA) is used, and the addition amount is 1 with respect to the hydrosilylation agent.
X10-4 to 1x10-5 equivalents are preferable. Also in the reaction, preferably, for example, 1,4-dioxane, dimethoxyethane, diethyl ether, tetrahydrofuran, an aliphatic hydrocarbon having 5 to 8 carbon atoms (such as hexane) or an aromatic hydrocarbon is used as a solvent, You may use these 2 or more types in mixture. As an example of preferable reaction conditions, the reaction system is placed under an atmosphere of an inert gas such as nitrogen, the reaction temperature is set to 0 to 100 ° C., and the reaction time is set to 1
Approximately 10 hours.
【００２５】スルホン酸基をアンモニウム塩又はアミン
塩にする方法は公知である。例えば、上記のようにして
製造した化学式（１）のＡが一価の金属であるスルホン
酸変性シリコーンをヘキサン又はヘプタンに溶解し、こ
れに塩酸又は硫酸の水溶液を加えて、好ましくは反応温
度０〜５０℃、好ましくは反応時間５分〜１時間で酸性
加水分解した後、シリコーン相を取り出し、これに上記
のアミンを加えるとアミン塩の形のスルホン酸変性シリ
コーンが生成する。A method for converting a sulfonic acid group into an ammonium salt or an amine salt is known. For example, the sulfonic acid-modified silicone in which A of the chemical formula (1) is a monovalent metal prepared as described above is dissolved in hexane or heptane, and an aqueous solution of hydrochloric acid or sulfuric acid is added thereto, preferably at a reaction temperature of 0. After acidic hydrolysis at -50 ° C, preferably for a reaction time of 5 minutes to 1 hour, the silicone phase is removed and the amine is added to it to produce a sulfonic acid-modified silicone in the form of an amine salt.
【００２６】本発明で製造されたスルホン酸変性シリコ
ーンは界面活性剤及び塗膜の改質剤等として有用であ
る。The sulfonic acid-modified silicone produced according to the present invention is useful as a surfactant and a modifier for a coating film.
【００２７】以下、本発明を実施例により更に詳細に説
明するが、本発明はこれら実施例に限定されるものでは
ない。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００２８】[0028]
【００２９】[0029]
【実施例１】１リットルの丸底フラスコにオクタメチル
シクロテトラシロキサン５４４重量部、１，３，５，７
−テトラメチルシクロテトラシロキサン４４重量部、ヘ
キサメチルジシロキサン１重量部、濃硫酸１２重量部お
よびヘキサン５００重量部を収め、窒素雰囲気下、室温
で７０時間撹拌後、炭酸水素ナトリウムで中和し、低沸
点物を蒸留によって除き、ポリメチルポリハイドロジェ
ンポリシロキサン４９６ｇ（収率８４％）を得た。Example 1 In a 1 liter round bottom flask, 544 parts by weight of octamethylcyclotetrasiloxane, 1,3,5,7
Containing 44 parts by weight of tetramethylcyclotetrasiloxane, 1 part by weight of hexamethyldisiloxane, 12 parts by weight of concentrated sulfuric acid and 500 parts by weight of hexane, stirred under a nitrogen atmosphere at room temperature for 70 hours, and then neutralized with sodium hydrogen carbonate, The low boiling substances were removed by distillation to obtain 496 g (yield 84%) of polymethylpolyhydrogenpolysiloxane.
【００３０】次に、このポリメチルポリハイドロジェン
ポリシロキサン２００重量部をヘキサン２００重量部に
溶解し、ｐ−クロロメチルスチレン４９重量部（ポリメ
チルポリハイドロジェンポリシロキサン中のＳｉに結合
した水素に対して当量比は１．３である）と塩化白金酸
のＩＰＡ溶液（２×１０-4モル／ｃｃ）０．０２ｍｌ
（ｐ‐クロロメチルスチレンに対して当量比は１．３×
１０-5である）を収めた丸底フラスコに窒素雰囲気下、
７０℃で攪拌しながら滴下した。１０時間撹拌後、濾過
し、続いて低沸点物を蒸留によって除き、クロロメチル
フェネチル基を有するシリコーン１８７ｇ（収率７６
％）を得た。Next, 200 parts by weight of this polymethyl polyhydrogen polysiloxane was dissolved in 200 parts by weight of hexane, and 49 parts by weight of p-chloromethylstyrene (to hydrogen bonded to Si in polymethyl polyhydrogen polysiloxane) was dissolved. Equivalent ratio is 1.3) and 0.02 ml of an IPA solution of chloroplatinic acid (2 × 10 -4 mol / cc)
(Equivalent ratio to p-chloromethylstyrene is 1.3 x
10 −5 ) in a round bottom flask under a nitrogen atmosphere,
The mixture was added dropwise with stirring at 70 ° C. After stirring for 10 hours, the mixture was filtered, and then low-boiling substances were removed by distillation to give 187 g of a silicone having a chloromethylphenethyl group (yield: 76
%) Was obtained.
【００３１】更に、得られたクロロメチルフェネチル基
を有するシリコーン１００重量部をヘキサン２００重量
部に溶解し、亜硫酸ナトリウム・７水和物４３重量部
（クロロメチルフェネチル基に対して当量比は１．７で
ある）を窒素雰囲気下オートクレーブ中に仕込み、２０
０℃で２４時間攪拌しながら反応させた。冷却後、生成
した塩及び未反応の亜硫酸ナトリウムを濾別、溶媒を蒸
留して除き乳白色のオイル８５ｇを得た。このオイルは
ＩＲスペクトル（図１に示す）上の１１８０ｃｍ-1のス
ルホン酸基に帰属される吸収によりスルホン酸変性シリ
コーンであることが確認された（化学式（１）のＲがFurther, 100 parts by weight of the obtained silicone having a chloromethylphenethyl group was dissolved in 200 parts by weight of hexane, and 43 parts by weight of sodium sulfite heptahydrate (equivalent ratio to chloromethylphenethyl group was 1. 7) was charged in an autoclave under a nitrogen atmosphere, and 20
The reaction was carried out at 0 ° C. for 24 hours with stirring. After cooling, the produced salt and unreacted sodium sulfite were filtered off and the solvent was distilled off to obtain 85 g of milky white oil. This oil was confirmed to be a sulfonic acid-modified silicone by absorption attributed to the sulfonic acid group at 1180 cm -1 on the IR spectrum (shown in FIG. 1) (R in chemical formula (1) is
【００３２】[0032]
【化１０】 であり、ＡがＮａであり、Ｒ1 がメチル基であり、ｍ＝
９７、ｎ＝８１８であった）。[Chemical 10] , A is Na, R 1 is a methyl group, and m =
97, n = 818).
【００３３】[0033]
【実施例２】オクタメチルシクロテトラシロキサン２０
０重量部、１，３，５，７−テトラメチルシクロテトラ
シロキサン５．４重量部、ヘキサメチルジシロキサン
０．３３重量部、濃硫酸５重量部から、実施例１と同様
な操作でポリメチルポリハイドロジェンポリシロキサン
を得た。Example 2 Octamethylcyclotetrasiloxane 20
From 0 parts by weight, 5.4 parts by weight of 1,3,5,7-tetramethylcyclotetrasiloxane, 0.33 parts by weight of hexamethyldisiloxane and 5 parts by weight of concentrated sulfuric acid, a polymethyl ester was prepared in the same manner as in Example 1. Polyhydrogen polysiloxane was obtained.
【００３４】次に、トルエンとテトラヒドロフランの
１：１混合溶液１００重量部とｐ‐スチレンスルホン酸
ナトリウム１０重量部（ポリメチルポリハイドロジェン
ポリシロキサン中のＳｉに結合した水素に対して当量比
は１．１である）及び塩化白金酸のＩＰＡ溶液（２×１
０-4モル／ｃｃ）０．０２ｍｌ（ｐ‐スチレンスルホン
酸ナトリウムに対して当量比は８×１０-5である）を収
めた丸底フラスコに、上記得られたポリメチルポリハイ
ドロジェンポリシロキサン１００重量部とヘキサン１０
０重量部の混合物を窒素雰囲気下５０℃で攪拌しながら
滴下した。１０時間攪拌後、濾過し、続いて低沸点物を
蒸留によって除き乳白色のオイル９０ｇを得た。このオ
イルは実施例１と同様にしてスルホン酸変性シリコーン
であることが確認された（化学式（１）のＲがｐ‐フェ
ニレンであり、ＡがＮａであり、Ｒ1 がメチル基であ
り、ｍ＝４４、ｎ＝７９０であった）。Next, 100 parts by weight of a 1: 1 mixed solution of toluene and tetrahydrofuran and 10 parts by weight of sodium p-styrenesulfonate (equivalent ratio to hydrogen bonded to Si in polymethylpolyhydrogenpolysiloxane is 1 .1) and an IPA solution of chloroplatinic acid (2 × 1)
(0 -4 mol / cc) 0.02 ml (equivalent ratio to sodium p-styrenesulfonate is 8 × 10 -5 ) was placed in a round bottom flask, and the polymethyl polyhydrogen polysiloxane obtained above was placed in the round bottom flask. 100 parts by weight and 10 parts of hexane
0 parts by weight of the mixture was added dropwise with stirring under a nitrogen atmosphere at 50 ° C. After stirring for 10 hours, the mixture was filtered, and then low-boiling substances were removed by distillation to obtain 90 g of a milky white oil. This oil was confirmed to be a sulfonic acid-modified silicone in the same manner as in Example 1 (R in the chemical formula (1) is p-phenylene, A is Na, R 1 is a methyl group, and m is = 44, n = 790).
【００３５】[0035]
【実施例３】実施例１で製造したスルホン酸変性シリコ
ーン５０ｇをヘキサン５０ｍｌに溶解し、１Ｎ ＨＣｌ
水溶液５０ｍｌと攪拌しながら室温で２０分間反応させ
た。反応後シリコーン相を取り出し、トリエタノールア
ミン５．０ｇを加えて攪拌しながら３０分間反応させた
後、未反応部分を留去して乳白色のオイル４６ｇを得
た。このオイルはＩＲスペクトル（図２に示す）上の３
３５０ｃｍ-1付近にヒドロキシエチル基に帰属される吸
収帯を示すので、生成物がスルホン酸トリエタノールア
ミンとの塩の形のスルホン酸変性シリコーンであること
が確認された。Example 3 50 g of the sulfonic acid-modified silicone prepared in Example 1 was dissolved in 50 ml of hexane to prepare 1N HCl.
The reaction was carried out at room temperature for 20 minutes while stirring with 50 ml of an aqueous solution. After the reaction, the silicone phase was taken out, 5.0 g of triethanolamine was added and the mixture was reacted for 30 minutes while stirring, and then the unreacted portion was distilled off to obtain 46 g of a milky white oil. This oil has 3 IR spectra (shown in FIG. 2).
Since an absorption band attributed to the hydroxyethyl group is shown near 350 cm -1 , it was confirmed that the product was a sulfonic acid-modified silicone in the form of a salt with triethanolamine sulfonate.
【００３６】[0036]
【発明の効果】以上のように本発明により、界面活性剤
及び塗膜の改質剤等として有用な新規なスルホン酸変性
シリコーンが提供される。INDUSTRIAL APPLICABILITY As described above, the present invention provides a novel sulfonic acid-modified silicone which is useful as a surfactant, a coating film modifier and the like.
【図１】実施例１で得られたスルホン酸変性シリコーン
の水洗後のＩＲスペクトルのチャート。FIG. 1 is an IR spectrum chart of the sulfonic acid-modified silicone obtained in Example 1 after washing with water.
【図２】実施例３で得られたスルホン酸変性シリコーン
の水洗後のＩＲスペクトルのチャート。FIG. 2 is an IR spectrum chart of the sulfonic acid-modified silicone obtained in Example 3 after washing with water.
Claims (1)
ン 【化１】 （ここで、各Ｒ1 は独立に低級アルキル基又は非置換も
しくは置換フェニル基を示し、ｍ及びｎは整数であっ
て、ｎ／ｍは１〜１００であり、Ａは一価の金属、水素
原子又は−Ｈ・Ｘ1 （ここで、Ｘ1 はアンモニア又はア
ミンを示す）を示し、Ｒはアリーレン基、直鎖又は分岐
のアルキレン基、アルカリーレン基又はアラルキレン基
を示し、該シリコーンはランダム共重合体でもブロック
共重合体でもよい）。1. A sulfonic acid-modified silicone represented by the following formula: (Here, each R 1 independently represents a lower alkyl group or an unsubstituted or substituted phenyl group, m and n are integers, n / m is 1 to 100, and A is a monovalent metal or hydrogen. Atom or —H · X 1 (wherein X 1 represents ammonia or amine), R represents an arylene group, a linear or branched alkylene group, an alkali-ylene group or an aralkylene group, and the silicone is a random copolymer. It may be a polymer or a block copolymer).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4301530A JP2864196B2 (en) | 1992-05-15 | 1992-10-15 | Sulfonic acid-modified silicone |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14792792 | 1992-05-15 | ||
| JP4-147927 | 1992-05-15 | ||
| JP4301530A JP2864196B2 (en) | 1992-05-15 | 1992-10-15 | Sulfonic acid-modified silicone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0625420A true JPH0625420A (en) | 1994-02-01 |
| JP2864196B2 JP2864196B2 (en) | 1999-03-03 |
Family
ID=26478318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4301530A Expired - Lifetime JP2864196B2 (en) | 1992-05-15 | 1992-10-15 | Sulfonic acid-modified silicone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2864196B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0693470A1 (en) * | 1994-07-21 | 1996-01-24 | MITSUI TOATSU CHEMICALS, Inc. | Process for preparing bisphenol A and polysiloxane catalyst therefor |
| US5608123A (en) * | 1994-07-05 | 1997-03-04 | Mitsui Toatsu Chemicals, Inc. | Process for catalytic hydration of olefins |
| JP2003331645A (en) * | 2002-05-17 | 2003-11-21 | Toyota Motor Corp | Proton conductive material |
| JP2003335818A (en) * | 2002-05-17 | 2003-11-28 | Toyota Motor Corp | Proton conductive material |
| JP2005190813A (en) * | 2003-12-25 | 2005-07-14 | Toyota Motor Corp | Electrolyte material for fuel cell electrode |
| JP2007224299A (en) * | 2006-02-21 | 2007-09-06 | Samsung Sdi Co Ltd | Polysiloxane compound and production method thereof, polymer electrolyte membrane, membrane electrode assembly, and fuel cell |
| EP2283064A4 (en) * | 2008-05-23 | 2012-02-01 | Univ Ontario Inst Of Technology | POLYMER ELECTROLYTE MEMBRANES OF POLY 2- (PHENYL ETHYL) SILOXANE SULFONATE |
| US20130172510A1 (en) * | 2012-01-04 | 2013-07-04 | Momentive Performance Materials Inc. | Process for the manufacture of silicone ionomer |
| WO2013103536A1 (en) * | 2012-01-04 | 2013-07-11 | Momentive Performance Materials Inc. | Polymer composites of silicone ionomers |
| CN116333318A (en) * | 2023-02-20 | 2023-06-27 | 上海锦湖日丽塑料有限公司 | Modified polymethylphenylsiloxane flame retardant, transparent flame-retardant polycarbonate composition and preparation method thereof |
-
1992
- 1992-10-15 JP JP4301530A patent/JP2864196B2/en not_active Expired - Lifetime
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5608123A (en) * | 1994-07-05 | 1997-03-04 | Mitsui Toatsu Chemicals, Inc. | Process for catalytic hydration of olefins |
| EP0693470A1 (en) * | 1994-07-21 | 1996-01-24 | MITSUI TOATSU CHEMICALS, Inc. | Process for preparing bisphenol A and polysiloxane catalyst therefor |
| CN1113076C (en) * | 1994-07-21 | 2003-07-02 | 三井化学株式会社 | Polyorganosiloxane simultaneously contg sulfoacid group and alkyl group with mercapto |
| JP2003331645A (en) * | 2002-05-17 | 2003-11-21 | Toyota Motor Corp | Proton conductive material |
| JP2003335818A (en) * | 2002-05-17 | 2003-11-28 | Toyota Motor Corp | Proton conductive material |
| JP2005190813A (en) * | 2003-12-25 | 2005-07-14 | Toyota Motor Corp | Electrolyte material for fuel cell electrode |
| JP2007224299A (en) * | 2006-02-21 | 2007-09-06 | Samsung Sdi Co Ltd | Polysiloxane compound and production method thereof, polymer electrolyte membrane, membrane electrode assembly, and fuel cell |
| US7833665B2 (en) | 2006-02-21 | 2010-11-16 | Samsung Sdi Co., Ltd. | Polysiloxane compound containing sulfonic acid groups, method of preparing the same and fuel cell including the same |
| EP2283064A4 (en) * | 2008-05-23 | 2012-02-01 | Univ Ontario Inst Of Technology | POLYMER ELECTROLYTE MEMBRANES OF POLY 2- (PHENYL ETHYL) SILOXANE SULFONATE |
| WO2013103498A1 (en) * | 2012-01-04 | 2013-07-11 | Momentive Performance Materials Inc. | Process for the manufacture of silicone ionomer |
| US20130172510A1 (en) * | 2012-01-04 | 2013-07-04 | Momentive Performance Materials Inc. | Process for the manufacture of silicone ionomer |
| WO2013103536A1 (en) * | 2012-01-04 | 2013-07-11 | Momentive Performance Materials Inc. | Polymer composites of silicone ionomers |
| US8697829B2 (en) | 2012-01-04 | 2014-04-15 | Momentive Performance Materials Inc. | Process for the manufacture of silicone ionomer |
| US8772422B2 (en) | 2012-01-04 | 2014-07-08 | Momentive Performance Materials Inc. | Polymer composites of silicone ionomers |
| KR20140116905A (en) * | 2012-01-04 | 2014-10-06 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Polymer composites of silicone ionomers |
| CN104136500A (en) * | 2012-01-04 | 2014-11-05 | 莫门蒂夫性能材料股份有限公司 | Polymer composites of silicone ionomers |
| CN104136495A (en) * | 2012-01-04 | 2014-11-05 | 莫门蒂夫性能材料股份有限公司 | Process for the manufacture of silicone ionomer |
| JP2015512956A (en) * | 2012-01-04 | 2015-04-30 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silicone ionomer polymer composite |
| CN104136500B (en) * | 2012-01-04 | 2017-03-22 | 莫门蒂夫性能材料股份有限公司 | The ionomeric polymer composites of organosilicon |
| CN116333318A (en) * | 2023-02-20 | 2023-06-27 | 上海锦湖日丽塑料有限公司 | Modified polymethylphenylsiloxane flame retardant, transparent flame-retardant polycarbonate composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2864196B2 (en) | 1999-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2293745C2 (en) | Method for formation of polyhedral oligomer silsesquioxanes | |
| US4417068A (en) | Process for the addition of organic silicon compounds with SiH groups to compounds with olefinic double bonds | |
| JPS61148184A (en) | Siloxane compound containing carboxyl group | |
| EP0419076A1 (en) | Process for the synthesis of soluble, condensed hydridosilicon resins containing low levels of silanol | |
| JP2003073477A (en) | Organopolysiloxane with quaternary ammonium group and method for producing the same | |
| EP0629648A2 (en) | Method for preparation of carbinol-functional siloxanes | |
| US5880305A (en) | Process for preparation of SioH-functional carbosilane dendrimers | |
| JPH0525879B2 (en) | ||
| JP2864196B2 (en) | Sulfonic acid-modified silicone | |
| JPH03170530A (en) | Organopolysiloxane having one branched molecular terminal and blocked by aminoalkyl group, and its preparation | |
| JPS63243089A (en) | Organosilicone sulfosuccinate and manufacture | |
| US3700715A (en) | Polyaminoalkylthioalkyl silanes | |
| KR950011769B1 (en) | Anionic silicone surfacant and method of its manufacture | |
| JPH1017579A (en) | N, N-bis (trimethylsilyl) aminopropylsilane compound and method for producing the same | |
| KR100242750B1 (en) | Inorganic acid catalyzed silylation reactions | |
| JP2635990B2 (en) | Method for producing sulfonated organosilicone compound | |
| US6495708B1 (en) | Aluminosiloxane compound and process for preparing the same | |
| JP2864191B2 (en) | Sulfonic acid-modified silicone | |
| US5532399A (en) | Process for the preparation or organosilicon compounds carrying sulfur-containing organic radicals | |
| JPH02290880A (en) | Method for synthesizing acylaminoorganosilicon compound | |
| JPH0291083A (en) | One-end reactive siloxane compound | |
| JP5252761B2 (en) | Diacetylene-based polyorganosiloxane, intermediate thereof and cured composition thereof | |
| Ready et al. | Facile and Effective Synthesis of Siloxane‐Based Polyamines | |
| JP2799806B2 (en) | Sulfonic acid-modified silicone | |
| JPH04193886A (en) | N,n-dialkylaminoalkyl-n',n'-dialkylaminodimethylsilane |