JPH0912724A - Production of diorganopolysiloxane - Google Patents
Production of diorganopolysiloxaneInfo
- Publication number
- JPH0912724A JPH0912724A JP7187729A JP18772995A JPH0912724A JP H0912724 A JPH0912724 A JP H0912724A JP 7187729 A JP7187729 A JP 7187729A JP 18772995 A JP18772995 A JP 18772995A JP H0912724 A JPH0912724 A JP H0912724A
- Authority
- JP
- Japan
- Prior art keywords
- group
- diorganopolysiloxane
- reaction
- formula
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- -1 polysiloxane Polymers 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 14
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 24
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000007086 side reaction Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229920001296 polysiloxane Polymers 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 19
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 19
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000011146 sterile filtration Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- LXWJIZILSYLRND-UHFFFAOYSA-N 1,2,2,4-tetramethylazasilolidine Chemical compound CC1CN(C)[Si](C)(C)C1 LXWJIZILSYLRND-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- CHDKQNHKDMEASZ-UHFFFAOYSA-N n-prop-2-enoylprop-2-enamide Chemical compound C=CC(=O)NC(=O)C=C CHDKQNHKDMEASZ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 238000006227 trimethylsilylation reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、片末端アクリルアミド
基またはメタクリルアミド基官能性ジオルガノポリシロ
キサンの新規な製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a diorganopolysiloxane functionalized with acrylamide or methacrylamide at one end.
【０００２】[0002]
【従来の技術】有機官能基を有するオルガノポリシロキ
サンは、有機樹脂にオルガノポリシロキサンの特性であ
る耐候性、表面撥水性、潤滑性、生体適合性、気体透過
性等を付与するための改質剤として使用されている。こ
れらの中でも分子鎖片末端のみに有機官能基を有するジ
オルガノポリシロキサンは、その改質効果が大きく、現
在まで種々の官能基を有するジオルガノポリシロキサン
が提案されている。従来、このような片末端有機官能性
ジオルガノポリシロキサンのうち、片末端アクリルアミ
ド基またはメタクリルアミド基官能性ジオルガノポリシ
ロキサンは、片末端アミノ基官能性ジオルガノポリシロ
キサンに酸塩化物等のアクリル酸またはメタクリル酸の
誘導体を反応させる方法か、または、片末端ケイ素原子
結合水素原子官能性ジオルガノポリシロキサンに、アク
リルアミド基またはメタクリルアミド基と脂肪族二重結
合を有する化合物をヒドロシリル化反応させる方法によ
り製造されていた（例えば、特開平５−１７５７７号公
報参照）。しかしながら、前者の方法は、反応時に発生
する塩化水素を補足し、反応を円滑に促進させるために
トリエチルアミンなどの三級アミンを添加することが必
須とされており、このとき生成する三級アミンの塩酸塩
を生成物から完全に除去することが非常に難しいという
問題点があった。また、往々にしてアクリルアミド基ま
たはメタクリルアミド基の単独重合反応により、目的と
するポリマーの純度が低下するという問題点があった。
さらに、アクリル酸クロリドを使用した場合には片末端
アミノ基官能性ジオルガノポリシロキサン中の未反応の
アミノ基とアクリル酸クロリドまたは生成物であるアク
リルアミド基官能性ジオルガノポリシロキサン中のアク
リル基とのマイケル付加型の副反応により目的とするポ
リマーの純度が低下するという問題点があった。後者の
方法は、反応を促進させるために加熱条件下で行われる
が、この反応条件下で往々にしてアクリルアミド基また
はメタクリルアミド基の単独重合反応が起こって得られ
るポリマーの純度が低下するという問題点があった。こ
れらの問題を解決するために、三級アミン塩酸塩などの
不純物の混入がなく、アクリルアミド基またはメタクリ
ルアミド基の単独重合反応およびマイケル付加型の副反
応を起こさず、高純度の片末端アクリルアミド基または
メタクリルアミド基官能性ジオルガノポリシロキサンを
生産性良く製造できる方法が求められていた。2. Description of the Related Art Organopolysiloxanes having organic functional groups are modified to give organic resins the characteristics of organopolysiloxanes such as weather resistance, surface water repellency, lubricity, biocompatibility and gas permeability. Used as an agent. Among these, the diorganopolysiloxane having an organic functional group only at one end of the molecular chain has a large modifying effect, and up to now, diorganopolysiloxane having various functional groups has been proposed. Conventionally, among such one-terminal organofunctional diorganopolysiloxanes, one-terminal acrylamide group- or methacrylamide group-functional diorganopolysiloxane is one-terminal amino group-functional diorganopolysiloxane and acrylic acid such as acid chloride. Method of reacting an acid or a derivative of methacrylic acid, or a method of hydrosilylating a compound having an acrylamide group or a methacrylamide group and an aliphatic double bond with a silicon atom-bonded hydrogen atom functional diorganopolysiloxane having one terminal (See, for example, Japanese Patent Laid-Open No. 5-17577). However, in the former method, it is essential to add a tertiary amine such as triethylamine in order to capture hydrogen chloride generated during the reaction and to accelerate the reaction smoothly. There is a problem that it is very difficult to completely remove the hydrochloride from the product. Further, there has been a problem that the purity of a target polymer is often lowered due to a homopolymerization reaction of an acrylamide group or a methacrylamide group.
Further, in the case of using acrylic acid chloride, an unreacted amino group in the amino-functional diorganopolysiloxane having one terminal and an acrylic group in the acrylic acid chloride or the acrylamide-functional diorganopolysiloxane as a product are used. However, there is a problem in that the purity of the target polymer is reduced by the side reaction of Michael addition type. The latter method is carried out under heating conditions in order to accelerate the reaction, but under this reaction condition, a homopolymerization reaction of an acrylamide group or a methacrylamide group often occurs, resulting in a decrease in the purity of the obtained polymer. There was a point. In order to solve these problems, impurities such as tertiary amine hydrochloride are not mixed, homopolymerization reaction of acrylamide group or methacrylamide group and Michael addition type side reaction do not occur, and highly pure one-end acrylamide group Further, there has been a demand for a method capable of producing a methacrylamide group-functional diorganopolysiloxane with high productivity.
【０００３】[0003]
【発明が解決しようとする課題】本発明者は、上記問題
点を解消するために研究した結果、本発明に至った。即
ち、本発明の目的は、副反応を起こさず、高純度の片末
端アクリルアミド基またはメタクリルアミド基官能性ジ
オルガノポリシロキサンを生産性よく製造できる方法を
提供することにある。The present inventor has arrived at the present invention as a result of research for solving the above problems. That is, an object of the present invention is to provide a method capable of producing a highly pure diorganopolysiloxane functionalized with an acrylamide group or a methacrylamide group at one end with high productivity without causing a side reaction.
【０００４】[0004]
【課題の解決手段とその作用】本発明は、一般式：(Ａ)The present invention has the general formula: (A)
【化４】 （式中、ＲおよびＲ1は同種または異種の一価炭化水素
基、Ｒ2は二価有機基、Ｒ3は水素原子または一価炭化水
素基、ｎは０〜１０００の整数である。）で表される片
末端アミノ基官能性ジオルガノポリシロキサンと、一般
式：(Ｂ)Embedded image (In the formula, R and R 1 are the same or different monovalent hydrocarbon groups, R 2 is a divalent organic group, R 3 is a hydrogen atom or a monovalent hydrocarbon group, and n is an integer of 0 to 1000.) A diorganopolysiloxane functionalized at one end with an amino group and represented by the general formula: (B)
【化５】 （式中、Ｒ4は水素原子またはメチル基であり、Ｘはハ
ロゲン原子である。）で表されるアクリル酸ハライドま
たはメタクリル酸ハライドとをアルカリ性物質の水溶液
の存在下に反応させることを特徴とする、一般式：(Ｃ)Embedded image (In the formula, R 4 is a hydrogen atom or a methyl group, and X is a halogen atom.) An acrylic acid halide or a methacrylic acid halide represented by the formula is reacted in the presence of an aqueous solution of an alkaline substance. Yes, general formula: (C)
【化６】 （式中、Ｒ，Ｒ1，Ｒ2，Ｒ3およびＲ4は前記と同じであ
る。）で表される片末端アクリルアミド基またはメタク
リルアミド基官能性ジオルガノポリシロキサンの製造方
法に関する。[Chemical 6] (In the formula, R, R 1 , R 2 , R 3 and R 4 are the same as described above.) The present invention relates to a method for producing a diorganopolysiloxane functionalized with an acrylamide group or a methacrylamide group at one end.
【０００５】以下、本発明を詳細に説明する。本発明に
使用される(Ａ)成分の式Hereinafter, the present invention will be described in detail. Formula of component (A) used in the present invention
【化７】 で示される片末端アミノ基官能性ジオルガノポリシロキ
サンは、アミノ基含有有機基を有するジオルガノポリシ
ロキサンの１種として公知とされるものである。ここ
で、上式中、ＲおよびＲ1はメチル基，エチル基，プロ
ピル基，ブチル基のようなアルキル基、ビニル基，アリ
ル基，ヘキセニル基のようなアルケニル基、フェニル
基，トリル基のようなアリール基、ベンジル基，フェネ
チル基のようなアラルキル基で例示される一価炭化水素
基であり、Ｒ2はメチレン基，エチレン基，プロピレン
基のようなアルキレン基、フェニレン基のようなアリー
レン基で例示される二価有機基であり、Ｒ3は水素原子
または上記Ｒ1およびＲ2と同様な一価炭化水素基であ
る。ｎは０〜１０００の整数である。このようなジオル
ガノポリシロキサンは、例えば、分子鎖片末端にケイ素
原子結合水素原子を有するジオルガノポリシロキサンと
トリメチルシリルアリルアミンを白金系触媒の存在下で
付加反応した後、メタノール等で処理して脱トリメチル
シリル化を行うことにより容易に得られる。また、分子
鎖片末端にシラノール基を有するジオルガノポリシロキ
サンを環状シラザンと反応させる方法により容易に得ら
れる（特開平１−１９３２７６号公報参照）。これらの
方法において原料として使用される分子鎖片末端にシラ
ノール基を有するジオルガノポリシロキサンは環状オル
ガノトリシロキサンを非平衡重合した後、この反応を酸
で停止させることよって得られる。また、分子鎖片末端
にケイ素原子結合水素原子を有するジオルガノポリシロ
キサンは、上記のようにして得られた分子鎖片末端にシ
ラノール基を有するジオルガノポリシロキサンとジメチ
ルクロロシランを反応させることにより容易に製造され
る。尚、これらのジオルガノポリシロキサンを得るため
には、本発明者らが先に特願平６−１１３９５１号およ
び特開平６−３４０７４３号で提案した方法に従って製
造した方法が好ましい。Embedded image The one-terminal amino group-functional diorganopolysiloxane represented by is known as one kind of diorganopolysiloxane having an amino group-containing organic group. Here, in the above formula, R and R 1 are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkenyl groups such as vinyl group, allyl group and hexenyl group, phenyl group and tolyl group. Are monovalent hydrocarbon groups exemplified by aralkyl groups such as aryl group, benzyl group and phenethyl group, R 2 is alkylene group such as methylene group, ethylene group and propylene group, and arylene group such as phenylene group Is a divalent organic group, and R 3 is a hydrogen atom or a monovalent hydrocarbon group similar to R 1 and R 2 above. n is an integer of 0 to 1000. Such a diorganopolysiloxane is obtained by, for example, subjecting a diorganopolysiloxane having a silicon-bonded hydrogen atom at one end of a molecular chain and trimethylsilylallylamine to an addition reaction in the presence of a platinum-based catalyst, and then treating with methanol or the like to remove it. It is easily obtained by performing trimethylsilylation. Further, it can be easily obtained by a method of reacting a diorganopolysiloxane having a silanol group at one end of a molecular chain with a cyclic silazane (see JP-A-1-193276). The diorganopolysiloxane having a silanol group at one end of the molecular chain used as a raw material in these methods is obtained by nonequilibrium polymerization of a cyclic organotrisiloxane and then terminating this reaction with an acid. Further, the diorganopolysiloxane having a silicon atom-bonded hydrogen atom at one end of the molecular chain can be easily prepared by reacting the diorganopolysiloxane having a silanol group at one end of the molecular chain with dimethylchlorosilane. Manufactured to. In order to obtain these diorganopolysiloxanes, the method produced by the present inventors according to the methods previously proposed in Japanese Patent Application No. 6-113951 and Japanese Patent Application Laid-Open No. 6-340743 is preferable.
【０００６】本発明に使用される(Ｂ)成分の式Formula of component (B) used in the present invention
【化８】 で表されるアクリル酸ハライドまたはメタクリル酸ハラ
イドは、上記(Ａ)成分にアクリルアミド基またはメタク
リルアミド基を導入するための成分である。ここで、上
式中、Ｒ4は水素原子またはメチル基であり、Ｘは臭素
原子，塩素原子で例示されるハロゲン原子である。この
ような化合物は、市販されており、容易に入手できる。Embedded image The acrylic acid halide or methacrylic acid halide represented by is a component for introducing an acrylamide group or a methacrylamide group into the component (A). Here, in the above formula, R 4 is a hydrogen atom or a methyl group, and X is a halogen atom exemplified by a bromine atom and a chlorine atom. Such compounds are commercially available and are easily available.
【０００７】本発明の方法は、上記のような(Ａ)成分と
(Ｂ)成分をアルカリ性物質の水溶液存在下で反応させる
のであるが、アルカリ性物質の水溶液存在下で反応させ
ることにより、反応の結果副生する塩が水相に移るた
め、これらの混入のない高純度の目的ポリマーを得るこ
とができる。このようなアルカリ性物質としては、水溶
性であり、片末端アミノ基官能性ジオルガノポリシロキ
サン中のアミノ基のＰＫbより大きいＰＫbを有する物質
であれば、その種類は特に制限はない。推奨されるのは
水酸化ナトリウム、水酸化カリウム等のアルカリ金属水
酸化物である。(Ａ)成分の片末端アミノ基官能性ジオル
ガノポリシロキサンに対する(Ｂ)成分のアクリル酸また
はメタクリル酸ハライドの仕込比は１.０〜１.５当量の
範囲が好ましい。これは１.０当量未満では反応が完結
せず未反応のアミノ基が残存し、特にアクリル酸ハライ
ドの場合マイケル付加型の副反応を起こすからであり、
１.５当量を越えると未反応のアクリル酸またはメタク
リル酸ハライドが大量に残存し、経済的に不利になるか
らである。また、アルカリ性物質の使用量は、副生する
ハロゲン化水素の中和量以上が必要であり、通常はアク
リル酸またはメタクリル酸ハライドに対し、１.０〜２.
０当量の範囲内で用いられる。この反応は通常、(Ａ)成
分の片末端アミノ基官能性ジオルガノポリシロキサンと
アルカリ性物質の水溶液との混合物に(Ｂ)成分のアクリ
ル酸またはメタクリル酸ハライドを滴下することにより
行われる。The method of the present invention comprises the above component (A)
The component (B) is reacted in the presence of an aqueous solution of an alkaline substance, but by reacting in the presence of an aqueous solution of an alkaline substance, the salt produced as a result of the reaction is transferred to the aqueous phase, so that there is no contamination of these components. It is possible to obtain a target polymer having a purity. Such an alkaline substance is not particularly limited in its kind as long as it is water-soluble and has a PK b larger than PK b of the amino group in the diorganopolysiloxane functionalized with an amino group at one end. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are recommended. The charge ratio of the acrylic acid or methacrylic acid halide of the component (B) to the diorganopolysiloxane having a terminal amino group functional component (A) is preferably in the range of 1.0 to 1.5 equivalents. This is because if the amount is less than 1.0 equivalent, the reaction is not completed and unreacted amino groups remain, and particularly in the case of acrylic acid halide, a Michael addition type side reaction occurs.
If it exceeds 1.5 equivalents, a large amount of unreacted acrylic acid or methacrylic acid halide remains, which is economically disadvantageous. Further, the amount of the alkaline substance used is required to be equal to or more than the neutralization amount of hydrogen halide produced as a by-product, and usually 1.0 to 2.0 with respect to acrylic acid or methacrylic acid halide.
Used within the range of 0 equivalents. This reaction is usually carried out by dropping the acrylic acid or methacrylic acid halide of the component (B) into a mixture of the component (A) diaminopolysiloxane having one terminal amino group functional group and an aqueous solution of an alkaline substance.
【０００８】この反応は無溶剤下でも行い得るが、温度
制御を容易にしたり、攪拌を行い易くするため、および
片末端アミノ基官能性ジオルガノポリシロキサンと水相
との相分離を容易にし、乳化を防ぐために有機溶媒を使
用することが推奨される。使用できる有機溶媒は片末端
アミノ基官能性ジオルガノポリシロキサンと相溶し、こ
の反応で用いられる各種成分と反応しないものであれば
特に制限はない。これらの有機溶媒としては、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素、ヘキサ
ン、ヘプタン等の脂肪族炭化水素、四塩化炭素、クロロ
ホルム、トリクロロエタン等の塩素化炭化水素、ジエチ
ルエーテル、テトラヒドロフラン等のエーテル類が例示
される。This reaction can be carried out in the absence of a solvent, but for facilitating temperature control and facilitating stirring, and facilitating phase separation of the diorganopolysiloxane functionalized at the amino group at one end with the aqueous phase, It is recommended to use organic solvents to prevent emulsification. The organic solvent that can be used is not particularly limited as long as it is compatible with the amino-functional diorganopolysiloxane having one terminal and does not react with the various components used in this reaction. Examples of these organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, chlorinated hydrocarbons such as carbon tetrachloride, chloroform and trichloroethane, and ethers such as diethyl ether and tetrahydrofuran. The kind is illustrated.
【０００９】反応温度は、副反応が起こるのを防ぐため
に水相が凍らない程度で、なるべく低い温度が好まし
い。従って好ましい反応温度として推奨されるのは、０
〜２０℃であり、さらに好ましくは０〜１０℃である。
この反応は一般に不均一二相系で行われるため、有機相
と水相とが十分に接触するように激しく攪拌して行う必
要がある。反応終了後、水相を除去し、必要に応じて有
機相を水洗し、有機相から低沸点物を加熱減圧留去する
ことにより、目的とする片末端アクリルアミド基または
メタクリルアミド基官能性ジオルガノポリシロキサンを
得ることができる。尚、反応中または低沸点物を除く際
に、副反応として起こるアクリル酸ハライドまたはメタ
クリル酸ハライドの重合反応、あるいは反応生成物中の
アクリルアミド基またはメタクリルアミド基の重合反応
を防ぐために通常ラジカル重合反応の禁止剤として知ら
れている化合物を添加するのが好ましい。このような化
合物としてフェノチアジン、ヒドロキノンモノメチルエ
ーテル、２,６−ジ−ｔ−ブチル−ｐ−クレゾール等が
例示される。The reaction temperature is preferably as low as possible so that the aqueous phase does not freeze in order to prevent side reactions from occurring. Therefore, the recommended reaction temperature is 0
It is -20 degreeC, More preferably, it is 0-10 degreeC.
Since this reaction is generally carried out in a heterogeneous two-phase system, it is necessary to carry out vigorous stirring so that the organic phase and the aqueous phase are sufficiently in contact with each other. After completion of the reaction, the aqueous phase is removed, the organic phase is washed with water as necessary, and the low boiling point substances are distilled off under reduced pressure by heating from the organic phase to obtain the desired diacrylamide containing acrylamide group or methacrylamide group functionalized at one end. Polysiloxane can be obtained. In addition, in order to prevent the polymerization reaction of acrylic acid halide or methacrylic acid halide which occurs as a side reaction during the reaction or when removing low-boiling substances, or the polymerization reaction of acrylamide group or methacrylamide group in the reaction product, a normal radical polymerization reaction It is preferable to add a compound known as an inhibitor of Examples of such compounds include phenothiazine, hydroquinone monomethyl ether, and 2,6-di-t-butyl-p-cresol.
【００１０】[0010]
【実施例】以下、本発明を実施例によって詳細に説明す
る。尚、実施例中、ＧＰＣ（ゲルパーミェーションクロ
マトグラフィー）による数平均分子量と分散度は標準ジ
メチルポリシロキサン換算の値である。また、トリメチ
ルシラノール、ジメチルホルムアミド、アセトニトリル
は予め適当な手段で脱水したものを使用した。The present invention will be described below in detail with reference to examples. In the examples, the number average molecular weight and polydispersity by GPC (gel permeation chromatography) are values in terms of standard dimethylpolysiloxane. In addition, trimethylsilanol, dimethylformamide, and acetonitrile were used after being dehydrated by an appropriate means.
【００１１】[0011]
【合成例１】攪拌機，還流冷却管，滴下ロート，温度計
を備えた四つ口フラスコに、ヘキサメチルシクロトリシ
ロキサン（Ｄ3）４００グラム（１７９８.０ミリモル）
とトルエン３００グラムを入れて混合し、１時間共沸脱
水を行った。反応系の温度を室温まで冷却した後、ｎ−
ブチルリチウムの１.７１Ｎヘキサン溶液８.０ミリリッ
トル（１３.７ミリモル）を投入し、室温下で１０分間
攪拌した。次いで、トリメチルクロロシラン１.４１９
グラム（１３.０ミリモル）を投入し、室温で５分間攪
拌した後、トリメチルシラノール２.９０８グラム（３
２.２ミリモル）、ジメチルホルムアミド３２.０グラム
およびアセトニトリル１００.０グラムの混合物を投入
すると、白色沈澱物が生成し反応が開始した。反応混合
物をサンプリングし、このサンプルに酢酸１滴を加えて
反応を停止させた後、ＧＬＣ（ガスクロマトグラフィ
ー）にてその転化率をモニターした。４時間５０分後、
転化率が７９.２％になったところで酢酸０.１４ｇを添
加して反応を停止させた。副生した塩をろ別し、低沸点
物を加熱減圧留去し、冷却後析出した塩をさらにろ別す
ることにより、片末端シラノール基封鎖ジメチルポリシ
ロキサンを得た。このジメチルポリシロキサンはＧＰＣ
による数平均分子量が１０,０６８であり、分散度が１.
０６であり、シラノール基含有率が０.１９重量％であ
った。[Synthesis Example 1] 400 g (1798.0 mmol) of hexamethylcyclotrisiloxane (D 3 ) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
And 300 g of toluene were added and mixed, and azeotropic dehydration was performed for 1 hour. After cooling the temperature of the reaction system to room temperature, n-
8.0 ml (13.7 mmol) of 1.71N hexane solution of butyllithium was added, and the mixture was stirred at room temperature for 10 minutes. Then trimethylchlorosilane 1.419
After adding gram (13.0 mmol) and stirring at room temperature for 5 minutes, 2.908 g (3
2.2 mmol), 32.0 g of dimethylformamide and 100.0 g of acetonitrile were added thereto, and a white precipitate was formed to start the reaction. The reaction mixture was sampled, 1 drop of acetic acid was added to this sample to stop the reaction, and its conversion rate was monitored by GLC (gas chromatography). 4 hours and 50 minutes later,
When the conversion reached 79.2%, 0.14 g of acetic acid was added to stop the reaction. By-produced salts were filtered off, low-boiling substances were removed by heating under reduced pressure, and after cooling, the precipitated salts were filtered off to obtain dimethylpolysiloxane capped with silanol groups at one end. This dimethyl polysiloxane is GPC
Has a number average molecular weight of 10,068 and a dispersity of 1.
And the silanol group content was 0.19% by weight.
【００１２】[0012]
【合成例２】合成例１で得られた片末端シラノール基封
鎖ジメチルポリシロキサン２９０グラムとｎ−ヘキサン
２００ミリリットルの混合物に、攪拌しながら１,２,
２,４−テトラメチル−１−アザ−２−シラシクロペン
タン５.６４グラム（３９.４ミリモル）とｎ−ヘキサン
１００ミリリットルの混合溶液を滴下した。滴下終了
後、１時間加熱還流を行った。ｎ−ヘキサンと未反応の
１,２,２,４−テトラメチル−１−アザ−２−シラシク
ロペンタンを加熱減圧留去し、片末端メチルアミノ基封
鎖ジメチルポリシロキサンを得た。ＮＨＭｅ基の含有率
を測定したところ、原料のシラノール基含有率より求め
られる計算値０.３３３重量％に対して実測値は０.３５
０重量％であった。[Synthesis Example 2] A mixture of 290 g of dimethylpolysiloxane having a silanol group blocked at one end obtained in Synthesis Example 1 and 200 ml of n-hexane was stirred for 1,2,
A mixed solution of 5.64 g (39.4 mmol) of 2,4-tetramethyl-1-aza-2-silacyclopentane and 100 ml of n-hexane was added dropwise. After the completion of the dropwise addition, the mixture was heated under reflux for 1 hour. n-Hexane and unreacted 1,2,2,4-tetramethyl-1-aza-2-silacyclopentane were removed by heating under reduced pressure to obtain a dimethylpolysiloxane capped with a methylamino group at one end. The NHMe group content was measured, and the calculated value was 0.33% by weight, which was calculated from the silanol group content of the raw material, and the measured value was 0.35.
It was 0% by weight.
【００１３】[0013]
【実施例１】攪拌機，還流冷却管，滴下ロート，温度計
を備えた四つ口フラスコに、合成例２で得られた片末端
メチルアミノ基封鎖ジメチルポリシロキサン３０グラム
（３.５ミリモル）、クロロホルム１２０ミリリットル
および水酸化ナトリウム０.２２グラム（５.２３ミリモ
ル）の水（３０ミリリットル）溶液を投入した。氷水で
冷却した後、０℃でアクリル酸クロリド０.３９グラム
（４.３６ミリモル）とクロロホルム１ミリリットルの
混合物を滴下した。滴下終了後、０℃で５分間攪拌し、
さらに１０℃で１０分間攪拌した。静置して有機相と水
相を分離させ、水相を除去し、有機相を水洗後、硫酸ナ
トリウムを加えて乾燥させた。次いで、ヒドロキノンモ
ノメチルエーテル０.００３グラムを添加し、４０℃以
下で低沸点物を加熱減圧留去した。得られた反応生成物
を滅菌濾過し、無色透明の反応生成物２８.４グラムを
得た。このものは13Ｃ−ＮＭＲ（核磁気共鳴分析）、Ｉ
Ｒ（赤外分光分析）より、分子鎖片末端にアクリルアミ
ド基を有するジメチルポリシロキサンであることが判明
した。このジメチルポリシロキサンは、ＧＰＣによる数
平均分子量は１０,０６８であり、分散度は１.０６であ
った。Example 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 30 g (3.5 mmol) of dimethylpolysiloxane blocked with a methylamino group at one end obtained in Synthesis Example 2 was added. A solution of 120 ml of chloroform and 0.22 g (5.23 mmol) of sodium hydroxide in water (30 ml) was added. After cooling with ice water, a mixture of 0.39 g (4.36 mmol) of acrylic acid chloride and 1 ml of chloroform was added dropwise at 0 ° C. After the dropping, stir at 0 ° C for 5 minutes,
The mixture was further stirred at 10 ° C for 10 minutes. The mixture was allowed to stand to separate the organic phase from the aqueous phase, the aqueous phase was removed, the organic phase was washed with water, and sodium sulfate was added to dry the organic phase. Next, 0.003 g of hydroquinone monomethyl ether was added, and low-boiling substances were distilled off under reduced pressure by heating at 40 ° C. or lower. The obtained reaction product was sterilized by filtration to obtain 28.4 g of a colorless and transparent reaction product. This product has 13 C-NMR (nuclear magnetic resonance analysis), I
From R (infrared spectroscopic analysis), it was found to be dimethylpolysiloxane having an acrylamide group at one end of the molecular chain. The dimethylpolysiloxane had a number average molecular weight by GPC of 10,068 and a dispersity of 1.06.
【００１４】[0014]
【実施例２】攪拌機，還流冷却管，滴下ロート，温度計
を備えた四つ口フラスコに、合成例２で得られた片末端
メチルアミノ基封鎖ジメチルポリシロキサン１２０グラ
ム（１４.０ミリモル）、クロロホルム４８０ミリリッ
トルおよび水酸化ナトリウム０.８５グラム（２０.５７
ミリモル）の水（１２０ミリリットル）溶液を投入し
た。氷水で冷却した後、０℃でアクリル酸クロリド１.
５５グラム（１７.１５ミリモル）とクロロホルム１ミ
リリットルの混合物を滴下した。滴下終了後、０℃で５
分間攪拌し、さらに１０℃で１０分間攪拌した。静置し
て有機相と水相を分離させ、水相を除去し、有機相を水
洗後、硫酸ナトリウムを加えて乾燥させた。次いで、ヒ
ドロキノンモノメチルエーテル０.０１２グラムを添加
し、４０℃以下で低沸点物を加熱減圧留去した。得られ
た反応生成物を滅菌濾過し、無色透明の反応生成物２
８.４グラムを得た。このものは13Ｃ−ＮＭＲ（核磁気
共鳴分析）、ＩＲ（赤外分光分析）より、分子鎖片末端
にアクリルアミド基を有するジメチルポリシロキサンで
あることが判明した。このジメチルポリシロキサンは、
ＧＰＣによる数平均分子量は９,８６９であり、分散度
は１.０６であった。Example 2 In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 120 g (14.0 mmol) of dimethylpolysiloxane capped with a methylamino group at one end obtained in Synthesis Example 2, Chloroform 480 ml and sodium hydroxide 0.85 g (20.57
A solution of water (120 milliliters) was added. After cooling with ice water, acrylic acid chloride 1.
A mixture of 55 grams (17.15 mmol) and 1 ml of chloroform was added dropwise. After the dropping, 5 at 0 ℃
The mixture was stirred for 1 minute and further at 10 ° C. for 10 minutes. The mixture was allowed to stand to separate the organic phase from the aqueous phase, the aqueous phase was removed, the organic phase was washed with water, and sodium sulfate was added to dry the organic phase. Next, 0.012 g of hydroquinone monomethyl ether was added, and low-boiling substances were distilled off under reduced pressure by heating at 40 ° C. or lower. The obtained reaction product is sterilized by filtration to give a colorless and transparent reaction product 2
8.4 grams were obtained. It was found from 13 C-NMR (nuclear magnetic resonance analysis) and IR (infrared spectroscopic analysis) that this product was a dimethylpolysiloxane having an acrylamide group at one end of the molecular chain. This dimethylpolysiloxane is
The number average molecular weight by GPC was 9,869, and the dispersity was 1.06.
【００１５】[0015]
【比較例１】攪拌機，還流冷却管，滴下ロート，温度計
を備えた四つ口フラスコに、合成例２で得られた片末端
メチルアミノ基封鎖ジメチルポリシロキサン３０グラム
（３.５ミリモル）、トリエチルアミン０.６６グラム
（６.５４ミリモル）、ヒドロキノンモノメチルエーテ
ル０.００３グラムおよびｎ−ヘキサン３０ミリリット
ルの混合物を投入した。氷水で冷却した後、０℃でアク
リル酸クロリド０.３９グラム（４.３６ミリモル）とｎ
−ヘキサン１ミリリットルの混合物を滴下した。滴下終
了後、１０℃以下で１０分間攪拌し、さらに室温で１晩
攪拌した。メタノール０.２６グラム（８.０ミリモル）
を加えて３０分間攪拌し過剰のアクリル酸クロリドをア
クリル酸メチルに変換した後、副生した塩を滅菌濾過に
よりろ別した。ろ液からｎ−ヘキサンとメタクリル酸メ
チルを加熱減圧留去し、さらに滅菌濾過を行った。得ら
れた反応生成物は無色透明のポリマーではなく、淡黄色
で白濁したポリマーであった。このものをＧＰＣにより
分析したところ、数平均分子量は１０,３９９であり、
分散度は１.０７であった。主ピークの高分子量側に肩
が生成していたが、このものは生成物中のアクリルアミ
ド基の単独反応物または片末端メチルアミノ基封鎖ジメ
チルポリシロキサン中の未反応のメチルアミノ基と片末
端アクリルアミド官能性ジメチルポリシロキサン中のア
クリルアミド基とのマイケル付加型の副反応により生成
したものと思われた。[Comparative Example 1] In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 30 g (3.5 mmol) of dimethylpolysiloxane capped with a methylamino group at one end obtained in Synthesis Example 2 was added. A mixture of 0.66 g (6.54 mmol) triethylamine, 0.003 g hydroquinone monomethyl ether and 30 ml n-hexane was charged. After cooling with ice water, 0.39 g (4.36 mmol) of acrylic acid chloride and n were added at 0 ° C.
-A mixture of 1 ml of hexane was added dropwise. After the dropping was completed, the mixture was stirred at 10 ° C. or lower for 10 minutes and further at room temperature overnight. 0.26 g (8.0 mmol) of methanol
Was added and the mixture was stirred for 30 minutes to convert excess acrylic acid chloride into methyl acrylate, and then the by-produced salt was filtered off by sterile filtration. N-Hexane and methyl methacrylate were distilled off from the filtrate by heating under reduced pressure, and sterile filtration was performed. The obtained reaction product was not a colorless and transparent polymer but a pale yellow and cloudy polymer. When this product was analyzed by GPC, the number average molecular weight was 10,399,
The dispersity was 1.07. A shoulder was formed on the high molecular weight side of the main peak, but this was a single reaction product of the acrylamide group in the product or the unreacted methylamino group and the one terminal acrylamide in the dimethylpolysiloxane blocked with a methylamino group at one end. It was suspected to have been formed by a Michael addition-type side reaction with the acrylamide group in the functional dimethylpolysiloxane.
【００１６】[0016]
【発明の効果】本発明の製造方法によれば、高純度の片
末端アクリルアミド基またはメタクリルアミド基官能性
ジオルガノポリシロキサンを生産性よく製造することが
できる。According to the production method of the present invention, a highly pure diorganopolysiloxane functionalized with an acrylamide group or a methacrylamide group at one end can be produced with high productivity.
【図１】実施例１で得られた分子鎖片末端にアクリルア
ミド基を有するジメチルポリシロキサンのＧＰＣチャー
トである。FIG. 1 is a GPC chart of dimethylpolysiloxane having an acrylamide group at one end of a molecular chain obtained in Example 1.
【図２】実施例２で得られた分子鎖片末端にアクリルア
ミド基を有するジメチルポリシロキサンのＧＰＣチャー
トである。FIG. 2 is a GPC chart of dimethylpolysiloxane having an acrylamide group at one end of a molecular chain obtained in Example 2.
【図３】実施例２で得られた分子鎖片末端にアクリルア
ミド基を有するジメチルポリシロキサンの13Ｃ−ＮＭＲ
チャートである。[3] 13 C-NMR of dimethylpolysiloxane having an acrylamide group at a molecular chain terminal obtained in Example 2
It is a chart.
【図４】実施例２で得られた分子鎖片末端にアクリルア
ミド基を有するジメチルポリシロキサンのＩＲチャート
である。FIG. 4 is an IR chart of dimethylpolysiloxane having an acrylamide group at one end of the molecular chain obtained in Example 2.
【図５】比較例１で得られた分子鎖片末端にアクリルア
ミド基を有するジメチルポリシロキサンのＧＰＣチャー
トである。5 is a GPC chart of dimethylpolysiloxane having an acrylamide group at one end of the molecular chain obtained in Comparative Example 1. FIG.
Claims (1)
基、Ｒ2は二価有機基、Ｒ3は水素原子または一価炭化水
素基、ｎは０〜１０００の整数である。）で表される片
末端アミノ基官能性ジオルガノポリシロキサンと、一般
式：(Ｂ) 【化２】 （式中、Ｒ4は水素原子またはメチル基であり、Ｘはハ
ロゲン原子である。）で表されるアクリル酸ハライドま
たはメタクリル酸ハライドとをアルカリ性物質の水溶液
の存在下に反応させることを特徴とする、一般式：(Ｃ) 【化３】 （式中、Ｒ，Ｒ1，Ｒ2，Ｒ3およびＲ4は前記と同じであ
る。）で表される片末端アクリルアミド基またはメタク
リルアミド基官能性ジオルガノポリシロキサンの製造方
法。1. The general formula: (A) (In the formula, R and R 1 are the same or different monovalent hydrocarbon groups, R 2 is a divalent organic group, R 3 is a hydrogen atom or a monovalent hydrocarbon group, and n is an integer of 0 to 1000.) A diorganopolysiloxane functionalized at one end with an amino group and represented by the general formula: (B) (In the formula, R 4 is a hydrogen atom or a methyl group, and X is a halogen atom.) An acrylic acid halide or a methacrylic acid halide represented by the formula is reacted in the presence of an aqueous solution of an alkaline substance. The general formula: (C) (In the formula, R, R 1 , R 2 , R 3 and R 4 are the same as described above.) A method for producing a diorganopolysiloxane functionalized at one end with an acrylamide group or a methacrylamide group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7187729A JPH0912724A (en) | 1995-06-30 | 1995-06-30 | Production of diorganopolysiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7187729A JPH0912724A (en) | 1995-06-30 | 1995-06-30 | Production of diorganopolysiloxane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0912724A true JPH0912724A (en) | 1997-01-14 |
Family
ID=16211165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7187729A Pending JPH0912724A (en) | 1995-06-30 | 1995-06-30 | Production of diorganopolysiloxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0912724A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7622539B2 (en) | 2004-12-16 | 2009-11-24 | Dow Corning Toray Company, Ltd. | Organopolysiloxane and silicone composition |
| US7648766B2 (en) | 2005-01-05 | 2010-01-19 | Dow Corning Toray Company, Ltd. | Composite silicone rubber powder coated with inorganic microfines and an organic silicon compound, method of its manufacture, and use thereof |
| JP2013525512A (en) * | 2010-03-18 | 2013-06-20 | 東レ株式会社 | Silicone (meth) acrylamide monomers, polymers, ophthalmic lenses and contact lenses |
| JP2018193492A (en) * | 2017-05-18 | 2018-12-06 | 信越化学工業株式会社 | Method for producing polymerizable group-containing organopolysiloxane |
-
1995
- 1995-06-30 JP JP7187729A patent/JPH0912724A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7622539B2 (en) | 2004-12-16 | 2009-11-24 | Dow Corning Toray Company, Ltd. | Organopolysiloxane and silicone composition |
| US7648766B2 (en) | 2005-01-05 | 2010-01-19 | Dow Corning Toray Company, Ltd. | Composite silicone rubber powder coated with inorganic microfines and an organic silicon compound, method of its manufacture, and use thereof |
| JP2013525512A (en) * | 2010-03-18 | 2013-06-20 | 東レ株式会社 | Silicone (meth) acrylamide monomers, polymers, ophthalmic lenses and contact lenses |
| JP2018193492A (en) * | 2017-05-18 | 2018-12-06 | 信越化学工業株式会社 | Method for producing polymerizable group-containing organopolysiloxane |
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