JPH0426609B2 - - Google Patents
Info
- Publication number
- JPH0426609B2 JPH0426609B2 JP62091594A JP9159487A JPH0426609B2 JP H0426609 B2 JPH0426609 B2 JP H0426609B2 JP 62091594 A JP62091594 A JP 62091594A JP 9159487 A JP9159487 A JP 9159487A JP H0426609 B2 JPH0426609 B2 JP H0426609B2
- Authority
- JP
- Japan
- Prior art keywords
- units
- organopolysiloxane
- sio
- added
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001296 polysiloxane Polymers 0.000 claims description 40
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- -1 alkyl silicate Chemical compound 0.000 claims description 16
- 125000005375 organosiloxane group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical group C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000001282 organosilanes Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- 125000003944 tolyl group Chemical group 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZDQGUEHIMBQNFU-UHFFFAOYSA-N [dimethyl(silyloxy)silyl]oxy-dimethyl-silyloxysilane Chemical compound [SiH3]O[Si](C)(C)O[Si](C)(C)O[SiH3] ZDQGUEHIMBQNFU-UHFFFAOYSA-N 0.000 description 1
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013138 pruning Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Description
(産業上の利用分野)
本発明はオルガノポリシロキサンの製造方法、
特にはSiO2単位を含有するオルガノポリシロキ
サンをそのSiO2単位の含有比を容易に調整する
ことができて、しかも塩酸やアルコールなどの副
生なしで製造する方法に関するものである。
(従来の技術)
R3SiO0.5単位(Rは水素原子または1価炭化水
素基(M単位)とSiO2単位(Q単位)とからな
るベンゼン可溶性のオルガノポリシロキサンはシ
リコーン業界において多くの分野で使用されてお
り、これは通常、水ガラス、オルソけい酸ナトリ
ウムのような水に可溶な塩基性けい酸塩に、塩酸
または硫酸を添加してけい酸オリゴマーとしたの
ち、トリアルキルクロロシランと反応させる方法
(米国特許第2676182、2814601号明細書参照)で
作られている。
しかし、この方法は中間体としてのオリゴマー
が不安定な物質であるために得られるオルガノポ
リシロキサンの分子量分布の調整が難しいし、M
単位とQ単位の構成比も目的とするものが得られ
がたく、また、中和のために使用する多量の酸や
トリアルキルクロロシランから副生する塩酸が排
水中に廃棄され、反応系を安定化させるために添
加される多量のアルコールも排水中に流出される
ためにこの排水の浄化処理が必要とされるという
不利があり、特にこの塩酸については揮発する塩
化水素が刺激臭の強い人体に有害なものである
し、製造装置、配管およびその他の付帯機器を著
しく腐触するものであるために、装置を高価な耐
腐食性の材質のものとしたり、補修費などに多く
の人手と費用が必要とされるという問題点があ
る。
他方、この種のオルガノポリシロキサンの製造
については、アルキルシリケートとトリアルキル
クロロシランとを塩酸の共存下で共加水分解する
方法(米国特許第2857356号明細書参照)、ヘキサ
アルキルジシロキサンまたはトリアルキルクロロ
シランにアルキルシリケートまたはその部分加水
分解物を塩酸水の共存下に滴下して反応させる方
法(特開昭61−195129号公報参照)も知らせてお
り、これらの方法には前記した方法にくらべると
目的とするM/Q比や分子量分布の調整が比較的
容易であるという利点があるが、反応系中に大量
の塩酸が添加されるか反応中に塩酸が発生する
し、原料から大量のアルコールが発生したり、ア
ルコールの添加が必要とされるために上記と同様
の排水処理、塩酸対策が必要とされる不利があ
る。
したがつて、従来公知の方法にはいずれも排水
処理が必要であるし、多量の有機溶剤が加水分解
補助剤などとして使用されるので単位反応器当
り、のオルガノポリシロキサンの収量が少なく生
産効率がわるい不利があり、Q単位を多く含むも
の、特にM単位/Q単位のモル比が2以上の組成
のものは反応の制御や特定のM/Q比の含有量、
分子量分布をもつオルガノシロキサンの取得が難
しく、さらにはシラノール基やアルコキシ基を有
するオルガノポリシロキサンレジンを再現性よく
製造することも難しいという欠点がある。
(発明の構成)
本発明は従来法におけるこのような不利を解決
したオルガノポリシロキサンの製造方法に関する
ものであり、これは一般式RaSiX4-a
(こゝにRは水素原子または同一あるいは異種の
非置換または置換一価炭化水素基、Xはハロゲン
原子、アルコキシ基または水酸基、aは1、2ま
たは3)で示されるオルガノシランおよび/また
は一般式
(Industrial Application Field) The present invention relates to a method for producing organopolysiloxane,
In particular, the present invention relates to a method for producing an organopolysiloxane containing SiO 2 units in which the content ratio of SiO 2 units can be easily adjusted and without by-products such as hydrochloric acid or alcohol. (Prior art) Benzene-soluble organopolysiloxane consisting of R 3 SiO 0.5 units (R is a hydrogen atom or a monovalent hydrocarbon group (M units) and SiO 2 units (Q units) is used in many fields in the silicone industry. This is usually done by adding hydrochloric acid or sulfuric acid to water glass or a water-soluble basic silicate such as sodium orthosilicate to form a silicic acid oligomer, which is then reacted with trialkylchlorosilane. However, since the oligomer as an intermediate is an unstable substance, it is difficult to adjust the molecular weight distribution of the resulting organopolysiloxane. It's difficult, M
It is difficult to obtain the desired composition ratio of units and Q units, and a large amount of acid used for neutralization and hydrochloric acid by-produced from trialkylchlorosilane are disposed of in the waste water, making it difficult to stabilize the reaction system. The disadvantage is that a large amount of alcohol that is added to the water is also washed out into the wastewater, which requires purification treatment.In particular, with regard to hydrochloric acid, the volatilized hydrogen chloride has a strong odor and is harmful to the human body. It is harmful and significantly corrodes manufacturing equipment, piping, and other ancillary equipment, so the equipment must be made of expensive corrosion-resistant materials and require a lot of manpower and expense to repair. The problem is that it requires On the other hand, for the production of this type of organopolysiloxane, a method of co-hydrolyzing an alkyl silicate and a trialkylchlorosilane in the presence of hydrochloric acid (see US Pat. No. 2,857,356), a method of co-hydrolyzing an alkyl silicate and a trialkylchlorosilane, a method of co-hydrolyzing an alkyl silicate and a trialkylchlorosilane, a method of co-hydrolyzing an alkyl silicate and a trialkylchlorosilane, etc. A method of reacting an alkyl silicate or its partial hydrolyzate by dropping it in the coexistence of hydrochloric acid (see Japanese Patent Application Laid-open No. 61-195129) has also been reported, and compared to the above-mentioned method, these methods have a different purpose. The advantage is that it is relatively easy to adjust the M/Q ratio and molecular weight distribution, but a large amount of hydrochloric acid is added to the reaction system or generated during the reaction, and a large amount of alcohol is removed from the raw materials. There is a disadvantage that wastewater treatment and hydrochloric acid countermeasures similar to those described above are required because of the waste water generated and the addition of alcohol. Therefore, all of the conventionally known methods require wastewater treatment, and a large amount of organic solvent is used as a hydrolysis aid, resulting in a low yield of organopolysiloxane per unit reactor, resulting in poor production efficiency. However, those containing a large amount of Q units, especially those with a molar ratio of M units/Q units of 2 or more, have the disadvantage of controlling the reaction and controlling the content at a specific M/Q ratio.
It has the disadvantage that it is difficult to obtain an organosiloxane with a molecular weight distribution, and furthermore, it is difficult to produce an organopolysiloxane resin having a silanol group or an alkoxy group with good reproducibility. (Structure of the Invention) The present invention relates to a method for producing an organopolysiloxane that solves the disadvantages of conventional methods, and is based on the general formula R a SiX 4-a (where R is a hydrogen atom or the same or Different types of unsubstituted or substituted monovalent hydrocarbon groups, X is a halogen atom, an alkoxy group or a hydroxyl group, a is an organosilane represented by 1, 2 or 3) and/or the general formula
【式】(こゝにRは前記に同
じ、bは1、2または3)単位を含有するオルガ
ノシロキサンを、アルキルシリケートまたはその
部分加水分解物とスルホン酸基含有化合物、ホス
ホニトリルクロライドから選択される少なくとも
1種の触媒の存在下に反応させて、SiO2単位を
含有するオルガノポリシロキサンとすることを特
徴とするものである。
すなわち、本発明者らはSiO2単位を含有する
オルガノポリシロキサン、例えばM単位とQ単位
とからなるオルガノポリシロキサン、M単位とD
単位(R2SiO単位)およびQ単位とからなるオル
ガノポリシロキサン、M単位とT単位(RSiO1.5
単位)およびQ単位とからなるオルガノポリシロ
キサン、D単位とQ単位とからなるオルガノポリ
シロキサンなどの効率のよい製造方法について
種々検討した結果、上記した一般式で示されるオ
ルガノシラン、オルガノシロキサンとアルキルシ
リケートとの反応をスルホン酸基含有化合物、ホ
スホニトリルクロライドから選択される触媒の存
在下で反応させると目的とするSiO2単位含有オ
ルガノポリシロキサンのM単位/Q単位の含有モ
ル比、分子量分布の調整を容易に行なわせること
ができること、またこれによれば製造時に塩酸の
発生がなく、アルコールなどの添加も必要でない
ので排水処理や反応装置の腐触のおそれもなくな
るということを見出し、こゝに使用する各成分の
種類、配合量、反応条件などについての研究を進
めて本発明を完成させた。
本発明の方法で始発剤として使用されるオルガ
ノシランは一般式RaSiX4-aで示され、Rは水素
原子またはメチル基、エチル基、プロピル基、ブ
チル基などのアルキル基、シクロヘキシル基など
のシクロアルキル基、ビニル基、アリル基などの
アルケニル基、フエニル基、トリル基などのアリ
ール基またはこれらの基の炭素原子に結合した水
素原子の一部または全部をハロゲン原子、シアノ
基などで置換したクロロメチル基、トリフルオロ
プロピル基、シアノエチル基などから選択される
同一または異種の非置換または置換1価炭化水素
基、Xはハロゲン原子、アルコキシ基または水酸
基から選択される原子または基、aは1、2また
は3であるものとされ、またこゝに使用されるオ
ルガノシロキサンは一般式[Formula] (where R is the same as above, b is 1, 2 or 3) The organosiloxane containing the unit is selected from alkyl silicate or its partial hydrolyzate, a sulfonic acid group-containing compound, and phosphonitrile chloride. The organopolysiloxane containing SiO 2 units is produced by the reaction in the presence of at least one catalyst containing SiO 2 units. That is, the present inventors have discovered that organopolysiloxanes containing SiO 2 units, such as organopolysiloxanes consisting of M units and Q units, M units and D
Organopolysiloxane consisting of units (R 2 SiO units) and Q units, M units and T units (RSiO 1.5
As a result of various studies on efficient production methods for organopolysiloxanes consisting of D units and Q units, and organopolysiloxanes consisting of D units and Q units, we found that organosilanes represented by the above general formula, organosiloxanes and alkyl When the reaction with silicate is carried out in the presence of a catalyst selected from sulfonic acid group-containing compounds and phosphonitrile chloride, the content molar ratio of M units/Q units and molecular weight distribution of the target organopolysiloxane containing SiO 2 units can be changed. We discovered that it is easy to adjust, and that this method does not generate hydrochloric acid during production and does not require the addition of alcohol, so there is no risk of corrosion in wastewater treatment or reaction equipment. The present invention was completed by conducting research on the types, amounts, and reaction conditions of each component used in the process. The organosilane used as an initiator in the method of the present invention is represented by the general formula R a SiX 4-a , where R is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, etc. Cycloalkyl groups, alkenyl groups such as vinyl groups, allyl groups, aryl groups such as phenyl groups, tolyl groups, or some or all of the hydrogen atoms bonded to carbon atoms of these groups are replaced with halogen atoms, cyano groups, etc. the same or different unsubstituted or substituted monovalent hydrocarbon group selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc., X is an atom or group selected from halogen atom, alkoxy group or hydroxyl group, a is 1, 2 or 3, and the organosiloxane used here has the general formula
【式】単位を含有するオルガノポリシロ
キサンであり、(Rは前記と同じ水素原子または
同一あるいは異種の非置換または置換一価炭化水
素基、bは1、2または3である)これらはいず
れも公知のものでよく、これにはヘキサメチルシ
ロキサン、テトラメチルシロキサン1,1,3,
3−テトラメチルジシロキサン、オクタメチルシ
クロシロキサン、メチルトリクロロシラン、ジメ
チルジクロロシラン、トリメチルクロロシランお
よびこりれに混合物が例示される。
また、このオルガノシランまたはオルガノシロ
キサンと反応させるアルキルシリケートまたはそ
の部分加水分解物も公知のものでよく、これには
オルソメチルシリケート、ポリメチルシリケー
ト、オルソエチルシリケート、ポリエチルシリケ
ート、オルソプロピルシリケート、ポリプロピル
シリケートおよびこれらの部分加水分解物が例示
される。なお、このアルキルシリケートまたはそ
の部分加水分解物の上記したオルガノシランまた
はオルガノシロキサンに対する添加量は目的とす
るSiO2単位を有するオルガノポリシロキサン中
のM単位/Q単位の含有モル比、分子量分布に応
じて適宜に調整すればよい。
つぎにこの反応に使用される触媒は上記したよ
うにスルホン酸基含有化合物、ホスホニトリルク
ロライドから選択される1種または2種以上の混
合物とされるが、このスルホン酸基含有化合物と
しては硫酸、亜硫酸、発煙硫酸、パラトルエンス
ルホン酸、酸性白土、活性白土、トリフルオロメ
タンスルホン、固体超強酸などが例示される。な
お、この触媒の添加量は少量でよく、これは従来
法における塩酸にくらべてはるかに少ない量でよ
いが、通常は前記したオルガノシラン、オルガノ
シロキサン、アルシリケートまたはその部分加水
分解物の総量に対して0.001〜3重量%の範囲で
ある。
本発明の方法は上記したオルガノシラン、オル
ガノシロキサン、アルキルシリケートまたはその
部分加水分解物と触媒とを反応器中に収容して反
応させればよく、この反応温度は−30℃〜200℃
の範囲とすればよいが、好ましい温度は−20℃〜
100℃とされる。また、この反応は水の存在下で
行なわせてもよいが、この場合、水の量が少なす
ぎるとアルキルシリケート中のアルコキシ基が多
量に残留するようになり、多すぎると残存するア
ルコキシ基、水酸基、分子量に対する影響が低下
するので、この水量はアルキルシリケート中のア
ルコキシ基に対してモル比で0.6〜1.5の範囲とす
ることがよく、目的とするSiO2単位を有するオ
ルガノポリシロキサン中に残存するアルコキシ基
量、水酸基量、分子量はこの水の量、反応温度、
反応時間によつて調整することができる。なお、
この反応は有機溶剤の添加を必ずしも必要としな
いが、添加することは任意とされる。
本発明の方法は上記したようにオルガノシラン
および/またはオルガノシロキサンとアルキルシ
リケートまたはその部分加水分解物をスルホン酸
基含有化合物、ホスホニトリルクロライドを触媒
として反応させるものであるが、配合されるアル
キルシリケート、オルガノシラン、オルガノシロ
キサンのM/Q比に反応後のM/Q比が完全に一
致するし、特にM/Qが2以上のときは即存の各
処方にくらべてはるかに高収率(M単位のロスが
少ない)で配合どおりのM/Q比のオルガノポリ
シロキサンを得ることができる。
また、こゝに配合されるアルキルシリケートま
たはその部分加水分解物の添加量、触媒の添加
量、反応温度、反応時間を調整することによつて
残存アルコシキ基量、水酸基量、分子量分布を調
整することができるので、各種のオルガノポリシ
ロキサンを容易に得ることができるほか、これに
よる場合は塩酸の副生、アルコール類の添加副生
もないので反応装置の腐食に対する措置、排水処
理の難点がなくなるという有利性が与えられる。
つぎに本発明の実施例をあげる。
実施例 1
ヘキサンメチルジシロキサン162.4g(1.0モ
ル)にエチルシリケート40〔多摩化学工業(株)製商
品名、SiO2分40%〕150.0g(SiO2単位として1
モル)と濃度98%の濃硫酸2gを添加し、この混
合物を撹拌しながら0〜20℃に保つたのち、こゝ
に水24gを1時間かけて滴下下し、滴下終了1時
間後に水16gを投入し、還流下(80℃)で5時間
撹拌してから重炭素ソーダで中和してオルガノシ
ロキサンのエタノール溶液を得た。この溶剤をト
ルエンで置換後別してオルガノシロキサンの50
重量%のトルエン溶液を調製したところ、この溶
液中にはオルガノポリシロキサン211g(収率95
%)が含有されていた。
ついで、このオルガノポリシロキサンを分析ち
たところ、このものは〔(CH3)3SiO0.5〕単位と
SiO2とを2:1のモル比で含有するものが得ら
れた。この反応では塩酸、アルコールの発生は全
くなかつた。
実施例 2
1,3−ジビニル−1,1,3,3−テトラメ
チルジシロキサン46.6g(0.25モル)とヘキサメ
チルジシロキサン40.6g(0.25モル%)に、エチ
ルシリケート40(前出)150g(SiO2単位として
1モル)とp−トルエンスルホン酸5gを添加
し、この混合物を0〜15℃に冷却し、撹拌しなが
らこれに水9gを1時間かけて適下し、滴下終了
1時間後に水35gを投入したのち実施例1と同様
に後処理をしたところ、オルガノポリシロキサン
134.5g(収率91%)が得られた。
ついで、このオルガノポリシロキサンを分析し
たところ、このものは
〔(CH2=CH)(CH3)2SiO0.5〕、
〔(CH3)3SiO0.5〕単位およびSiO2単位をモル比
0.5:0.5:1で含有するものであつた。
実施例 3
ヘキサメチルジシロキサン324.8g(2.0モル)
にオルソメチルシリケート152.2g(1.0モル)と
濃度98%の濃硫酸4.0gを添加し、この混合物を
0〜10℃に冷却し、撹拌しながら0〜15℃の温度
で水45g(2.5モル)を1時間かけて滴下し、20
〜30℃で5時間撹拌したのち中性になるまで水洗
し、別したところ、オルガノポリシロキサン
363g(収率94%)が得られた。
ついで、このオルガノポリシロキサンを分析し
たところ、ものものは〔(CH3)3SiO0.5〕単位4.0
モルとSiO2単位1モルとからなるものであつた。
実施例 4
1,1,3,3−テトラメチルジシロキサン
142.0g(1.0モル)に正けい酸エチル208g、エ
チルシリケート40(前出)150gとp−トルエンス
ルホン酸5gを添加し、この混合物を0〜20℃に
冷却し、これに撹拌しながら水40gを1時間かけ
て滴下し、滴下終了1時間後に水110gを投入し
30℃で5時間撹拌してから炭酸ソーダ3.0gを加
えて中和し、この溶液をトルエンで置換したのち
別したところ、オルガノポリシロキサン196g
(収率97%)が得られた。
ついで、このオルガノポリシロキサンを分析し
たところ、このものは〔H(CH3)2SiO0.5〕単位
2.0モルとSiO2単位1モル比とからなるものであ
つた。
実施例 5
デカメチルテトラシロキサン155.3g(0.5モ
ル)にエチルシリケート40(前出)150g(SiO2
単位として1モル)と濃度98%の硫酸5gを添加
し、この混合物を0〜10℃に冷却し、これに撹拌
しながら水26gを1時間かけて滴下し、滴下終了
3時間後に水105gを投入して還流下に5時間撹
拌したのち重炭酸ソーダ8.6gを加えて中和し、
この溶液をトルエンで置換後別したところ、オ
ルガノポリシロキサン202g(収率94%)が得ら
れ、このものは〔(CH3)3SiOSi(CH3)2O0.5〕単位
1.0モルとSiO2単位1モルとからなるものであつ
た。
実施例 6
1,1,3,3−テトラメチルジシロキサン
35.5g(0.5モル)、ヘキサメチルジシロキサン41
g(0.5モル)に、メチルシリケート−51(SiO2単
位として1.0モル)〔多摩化学工業(株)製、SiO2分51
%〕117.6gとホスホニトリルクロライド
(PNCl)43gとを添加し、この混合物を撹拌しな
がら−5〜5℃に保ち、ここに水12gを1時間か
けて滴下し、滴下終了2時間後に水30gを投入し
10〜20℃で5時間撹拌してから重炭酸ソーダで中
和し、この溶液をトルエンで置換後別したとこ
ろ、式
〔H(CH3)2SiO0.5〕0.5
〔(CH3)3SiO0.5〕0.5〔SiO2〕
で示されるオルガノポリシロキサン124.2g(収
率91%)が得られた。
実施例 7
テトラメチルテトラシロキサン74g(0.25モ
ル)にエチルシリケート40(前出)150g(1モ
ル)と濃度98%の硫酸5gを添加し、この混合物
を−10〜−5℃に冷却し、これに撹拌しながら水
26gを1時間かけて滴下し、滴下終了3時間後に
水105gを投入して還流下に5時間撹拌した後、
重炭酸ソーダで中和し、この溶液をトルエンで置
換し、ろ別したところ、〔HO・(CH3)2SiO〕単
位0.85モルとSiO2単位1モルとからなるオルガノ
ポリシロキサン180g(収率80.4%)が得られた。
実施例 8
メチルトリメトキシシラン136g(1モル)に
エチルシリケート40(前出)150g(1モル)とp
−トルエンスルホン酸5gを添加し、この混合物
を−10〜−5℃に冷却し、これに撹拌しながら水
42gを1時間かけて滴下し、滴下終了5時間後に
水89gを投入して還流下に5時間撹拌したのち、
炭酸ソーダ6gを加えて中和し、この溶液をトル
エンで置換し、ろ別したところ、〔CH3
(CH3O)2SiO0.5〕単位0.73モルとSiO2単位1モル
からなるオルガノポリシロキサン71g(収率64.5
%)が得られた。
実施例 9
トリメチルクロロシラン108.5gにメチルシリ
ケート(前出)117.6gとp−トルエンスルホン
酸5gを添加し、この混合物を−10〜−5℃に冷
却し、撹拌下に冷却しながら水20gを1時間かけ
て滴下し、摘下終了3時間後に水30gを投入して
10〜20℃で5時間撹拌してから炭酸ソーダで中和
し、この溶液をトルエンで置換後、ろ別したとこ
ろ、〔(CH3)3SiO0.5〕単位1モルとSiO2単位1モ
ルとからなるオルガノポリシロキサン133g(収
率94.3%)が得られた。
実施例 10
実施例9におけるトリメチルクロロシランの代
わりにトリエチルクロロシラン150.5gを使用し
たほかは実施例9と同様に処理したところ、
〔(C2H5)SiO0.5〕単位1モルとSiO2単位1モル
とよりオルガノポリシロキサン136g(収率96.4
%)が得られた。[Formula] is an organopolysiloxane containing the unit (R is the same hydrogen atom as above or the same or different unsubstituted or substituted monovalent hydrocarbon group, b is 1, 2 or 3). Any known one may be used, including hexamethylsiloxane, tetramethylsiloxane 1,1,3,
Mixtures are exemplified by 3-tetramethyldisiloxane, octamethylcyclosiloxane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and korire. Further, the alkyl silicate or its partial hydrolyzate to be reacted with the organosilane or organosiloxane may be a known alkyl silicate, and examples thereof include orthomethyl silicate, polymethyl silicate, orthoethyl silicate, polyethyl silicate, orthopropyl silicate, and polysilicate. Examples include propyl silicate and partially hydrolyzed products thereof. The amount of this alkyl silicate or its partial hydrolyzate added to the above-mentioned organosilane or organosiloxane depends on the molar ratio of M units/Q units contained in the target organopolysiloxane having SiO 2 units and the molecular weight distribution. You can adjust it as appropriate. Next, the catalyst used in this reaction is one or a mixture of two or more selected from sulfonic acid group-containing compounds and phosphonitrile chloride, as described above, and the sulfonic acid group-containing compounds include sulfuric acid, Examples include sulfurous acid, fuming sulfuric acid, paratoluenesulfonic acid, acid clay, activated clay, trifluoromethanesulfone, and solid super strong acids. Note that the amount of this catalyst added may be small, which is much smaller than the amount of hydrochloric acid used in the conventional method, but it is usually added to the total amount of the organosilane, organosiloxane, alsilicate, or partial hydrolyzate thereof. The range is 0.001 to 3% by weight. In the method of the present invention, the above-described organosilane, organosiloxane, alkyl silicate, or a partial hydrolyzate thereof and a catalyst may be placed in a reactor and reacted, and the reaction temperature is -30°C to 200°C.
The preferred temperature is -20℃~
It is said to be 100℃. Further, this reaction may be carried out in the presence of water, but in this case, if the amount of water is too small, a large amount of alkoxy groups in the alkyl silicate will remain; if it is too large, the remaining alkoxy groups, Since the effect on hydroxyl groups and molecular weight is reduced, the amount of water is preferably in the range of 0.6 to 1.5 in terms of molar ratio to the alkoxy groups in the alkyl silicate, and the amount of water remaining in the organopolysiloxane having the target SiO 2 units is The amount of alkoxy groups, amount of hydroxyl groups, and molecular weight depend on the amount of water, reaction temperature,
It can be adjusted by the reaction time. In addition,
This reaction does not necessarily require the addition of an organic solvent, but its addition is optional. As described above, the method of the present invention involves reacting an organosilane and/or organosiloxane with an alkyl silicate or a partial hydrolyzate thereof using a sulfonic acid group-containing compound and phosphonitrile chloride as a catalyst. The M/Q ratio after reaction completely matches the M/Q ratio of , organosilane, and organosiloxane, and especially when M/Q is 2 or more, the yield is much higher than that of each existing formulation ( (with less loss of M units), an organopolysiloxane having the M/Q ratio as formulated can be obtained. In addition, the amount of residual alkoxy groups, the amount of hydroxyl groups, and the molecular weight distribution can be adjusted by adjusting the amount of alkyl silicate or its partial hydrolyzate added, the amount of catalyst added, reaction temperature, and reaction time. Not only can various organopolysiloxanes be easily obtained, but also there is no by-product of hydrochloric acid or added by-product of alcohols, so there is no need to take measures to prevent corrosion of reaction equipment or problems with wastewater treatment. This gives you an advantage. Next, examples of the present invention will be given. Example 1 162.4 g (1.0 mol) of hexanemethyldisiloxane was mixed with 150.0 g of ethyl silicate (trade name, manufactured by Tama Chemical Industry Co., Ltd., SiO 2 min 40%) (150.0 g as SiO 2 units).
mol) and 2 g of concentrated sulfuric acid with a concentration of 98% were added, and after stirring the mixture and keeping it at 0 to 20°C, 24 g of water was added dropwise over 1 hour, and 1 hour after the completion of the addition, 16 g of water was added. was added, stirred under reflux (80°C) for 5 hours, and then neutralized with heavy carbon soda to obtain an ethanol solution of organosiloxane. After replacing this solvent with toluene, 50% of the organosiloxane was separated.
When a wt% toluene solution was prepared, 211 g of organopolysiloxane (yield: 95
%) was contained. Next, when this organopolysiloxane was analyzed, it was found to have units of [(CH 3 ) 3 SiO 0.5 ].
A product containing SiO 2 in a molar ratio of 2:1 was obtained. In this reaction, no hydrochloric acid or alcohol was generated. Example 2 To 46.6 g (0.25 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 40.6 g (0.25 mol%) of hexamethyldisiloxane, 150 g of ethyl silicate 40 (described above) ( 1 mol of SiO 2 units) and 5 g of p-toluenesulfonic acid were added, the mixture was cooled to 0 to 15°C, and 9 g of water was dropped over 1 hour while stirring, and 1 hour after the completion of the dropwise addition, After adding 35 g of water and post-treatment in the same manner as in Example 1, organopolysiloxane
134.5g (yield 91%) was obtained. Then, when this organopolysiloxane was analyzed, it was found that the molar ratio of [(CH 2 = CH) (CH 3 ) 2 SiO 0.5 ], [(CH 3 ) 3 SiO 0.5 ] units and SiO 2 units was
The content was 0.5:0.5:1. Example 3 Hexamethyldisiloxane 324.8g (2.0mol)
152.2 g (1.0 mol) of orthomethylsilicate and 4.0 g of concentrated sulfuric acid with a concentration of 98% are added to the mixture, the mixture is cooled to 0-10°C, and 45 g (2.5 mol) of water is added at a temperature of 0-15°C with stirring. Drip over 1 hour, 20
After stirring at ~30°C for 5 hours, the organopolysiloxane was washed with water until neutral and separated.
363 g (yield 94%) was obtained. Then, when this organopolysiloxane was analyzed, it was found that the [(CH 3 ) 3 SiO 0.5 ] unit was 4.0.
mol and 1 mol of SiO 2 units. Example 4 1,1,3,3-tetramethyldisiloxane
To 142.0 g (1.0 mol) were added 208 g of ethyl orthosilicate, 150 g of ethyl silicate 40 (above), and 5 g of p-toluenesulfonic acid, and the mixture was cooled to 0 to 20°C, and 40 g of water was added to it with stirring. was dripped over an hour, and 1 hour after the dripping was finished, 110g of water was added.
After stirring at 30°C for 5 hours, 3.0 g of sodium carbonate was added to neutralize the solution, which was replaced with toluene and separated, resulting in 196 g of organopolysiloxane.
(yield 97%) was obtained. Then, when this organopolysiloxane was analyzed, it was found that it had units of [H(CH 3 ) 2 SiO 0.5 ].
It consisted of 2.0 mol and 1 mol ratio of SiO 2 units. Example 5 155.3 g (0.5 mol) of decamethyltetrasiloxane and 150 g (SiO 2
1 mole) and 5 g of sulfuric acid with a concentration of 98% were added, the mixture was cooled to 0 to 10°C, 26 g of water was added dropwise to it over 1 hour while stirring, and 105 g of water was added 3 hours after the completion of the dropwise addition. After charging and stirring under reflux for 5 hours, 8.6 g of bicarbonate of soda was added to neutralize.
When this solution was replaced with toluene and separated, 202 g (yield 94%) of organopolysiloxane was obtained, which contained [(CH 3 ) 3 SiOSi(CH 3 ) 2 O 0.5 ] units.
It consisted of 1.0 mol and 1 mol of SiO 2 units. Example 6 1,1,3,3-tetramethyldisiloxane
35.5g (0.5 mole), hexamethyldisiloxane 41
g (0.5 mol), methyl silicate-51 (1.0 mol as SiO 2 unit) [manufactured by Tama Chemical Industry Co., Ltd., SiO 2 min 51
%] and 43 g of phosphonitrile chloride (PNCl), the mixture was kept at -5 to 5°C with stirring, and 12 g of water was added dropwise over 1 hour, and 2 hours after the completion of the addition, water was added. Add 30g
After stirring at 10 to 20 ° C for 5 hours, the solution was neutralized with sodium bicarbonate, replaced with toluene , and separated . 124.2 g (yield 91%) of organopolysiloxane represented by [SiO 2 ] was obtained. Example 7 To 74 g (0.25 mol) of tetramethyltetrasiloxane, 150 g (1 mol) of ethyl silicate 40 (mentioned above) and 5 g of sulfuric acid with a concentration of 98% were added, and the mixture was cooled to -10 to -5°C. water while stirring
26g was added dropwise over 1 hour, and 3 hours after the addition was completed, 105g of water was added and stirred under reflux for 5 hours.
When the solution was neutralized with sodium bicarbonate and replaced with toluene and filtered, 180 g of organopolysiloxane (yield 80.4%) consisting of 0.85 mol of [HO・(CH 3 ) 2 SiO] units and 1 mol of 2 units of SiO was obtained. )was gotten. Example 8 136 g (1 mol) of methyltrimethoxysilane, 150 g (1 mol) of ethyl silicate 40 (mentioned above) and p
- Add 5 g of toluenesulfonic acid, cool the mixture to -10 to -5°C and add water to it with stirring.
42g was added dropwise over 1 hour, and 5 hours after the addition was completed, 89g of water was added and stirred under reflux for 5 hours.
When 6 g of soda carbonate was added to neutralize, this solution was replaced with toluene, and filtered, [CH 3
71 g of organopolysiloxane (yield: 64.5
%)was gotten. Example 9 To 108.5 g of trimethylchlorosilane, 117.6 g of methyl silicate (previously described) and 5 g of p-toluenesulfonic acid were added, the mixture was cooled to -10 to -5°C, and 20 g of water was added with stirring while cooling. Drop it over time and add 30g of water 3 hours after the pruning is finished.
After stirring at 10 to 20°C for 5 hours, the solution was neutralized with sodium carbonate, replaced with toluene, and filtered, resulting in 1 mol of [(CH 3 ) 3 SiO 0.5 ] unit and 1 mol of SiO 2 unit. 133 g (yield 94.3%) of organopolysiloxane consisting of Example 10 The same procedure as in Example 9 was performed except that 150.5 g of triethylchlorosilane was used instead of trimethylchlorosilane in Example 9.
From 1 mol of [(C 2 H 5 )SiO 0.5 ] unit and 1 mol of SiO 2 unit, 136 g of organopolysiloxane (yield 96.4
%)was gotten.
Claims (1)
非置換または置換一価炭化水素基、Xはハロゲン
原子、アルコキシ基または水酸基、aは1、2ま
たは3)で示されるオルガノシラン、および/ま
たは一般式【式】 (こゝにRは前記に同じ、bは1、2または3)
単位を含有するオルガノシロキサンを、アルキル
シリケートまたはその部分加水分解物とスルホン
酸基含有化合物、ホスホニトリルクロライドから
選択される少なくとも1種の触媒の存在下に反応
させて、SiO2単位を含有するオルガノポリシロ
キサンとすることを特徴とするオルガノポリシロ
キサンの製造方法。 2 オルガノシロキサンがヘキサメチルジシロキ
サンである特許請求の範囲第1項記載のオルガノ
ポリシロキサンの製造方法。 3 オルガノシロキサンがテトラメチルジビニル
ジシロキサンである特許請求の範囲第1項記載の
オルガノポリシロキサンの製造方法。 4 オルガノシロキサンがオクタメチルシクロテ
トラポリシロキサンとヘキサメチルジシロキサン
との混合物である特許請求の範囲第1項記載のオ
ルガノポリシロキサンの製造方法。[Claims] 1 General formula R a SiX 4-a (where R is a hydrogen atom or the same or different unsubstituted or substituted monovalent hydrocarbon group, X is a halogen atom, an alkoxy group or a hydroxyl group, and a is a 1, 2 or 3) and/or the general formula [Formula] (where R is the same as above, b is 1, 2 or 3)
The organosiloxane containing the SiO 2 unit is reacted with an alkyl silicate or a partial hydrolyzate thereof in the presence of at least one catalyst selected from a sulfonic acid group-containing compound and phosphonitrile chloride. A method for producing an organopolysiloxane, characterized in that it is a polysiloxane. 2. The method for producing an organopolysiloxane according to claim 1, wherein the organosiloxane is hexamethyldisiloxane. 3. The method for producing an organopolysiloxane according to claim 1, wherein the organosiloxane is tetramethyldivinyldisiloxane. 4. The method for producing organopolysiloxane according to claim 1, wherein the organosiloxane is a mixture of octamethylcyclotetrapolysiloxane and hexamethyldisiloxane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9159487A JPS63256628A (en) | 1987-04-14 | 1987-04-14 | Production of organopolysiloxane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9159487A JPS63256628A (en) | 1987-04-14 | 1987-04-14 | Production of organopolysiloxane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63256628A JPS63256628A (en) | 1988-10-24 |
JPH0426609B2 true JPH0426609B2 (en) | 1992-05-07 |
Family
ID=14030879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9159487A Granted JPS63256628A (en) | 1987-04-14 | 1987-04-14 | Production of organopolysiloxane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63256628A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2739222B2 (en) * | 1988-05-25 | 1998-04-15 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane for curing high energy rays and method for producing the same |
JP2580348B2 (en) * | 1989-11-20 | 1997-02-12 | 信越化学工業 株式会社 | Grease composition for heat radiation |
JP3772258B2 (en) | 2002-01-25 | 2006-05-10 | 信越化学工業株式会社 | Method for producing organopolysiloxane |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5415999A (en) * | 1977-07-07 | 1979-02-06 | Central Glass Co Ltd | Production of organosilicon polymer |
JPS5455100A (en) * | 1977-10-12 | 1979-05-01 | Central Glass Co Ltd | Preparation of organosilicon polymer |
JPS5867728A (en) * | 1981-10-20 | 1983-04-22 | Nippon Yunikaa Kk | Organopolysiloxane and preparation thereof |
JPS61195129A (en) * | 1985-02-22 | 1986-08-29 | Toray Silicone Co Ltd | Production of organosilicon polymer |
-
1987
- 1987-04-14 JP JP9159487A patent/JPS63256628A/en active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5415999A (en) * | 1977-07-07 | 1979-02-06 | Central Glass Co Ltd | Production of organosilicon polymer |
JPS5455100A (en) * | 1977-10-12 | 1979-05-01 | Central Glass Co Ltd | Preparation of organosilicon polymer |
JPS5867728A (en) * | 1981-10-20 | 1983-04-22 | Nippon Yunikaa Kk | Organopolysiloxane and preparation thereof |
JPS61195129A (en) * | 1985-02-22 | 1986-08-29 | Toray Silicone Co Ltd | Production of organosilicon polymer |
Also Published As
Publication number | Publication date |
---|---|
JPS63256628A (en) | 1988-10-24 |
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