CN1329631A - 有机聚硅氧烷树脂 - Google Patents
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 28
- 239000011347 resin Substances 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
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- 229920002554 vinyl polymer Polymers 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
本发明涉及有机聚硅氧烷树脂,其玻璃化转变温度(Tg)超过60℃,且其羟基含量至少为1wt.%。
Description
本发明涉及有机聚硅氧烷树脂及其制备方法。
玻璃化转变温度(Tg)高达约55℃的有机聚硅氧烷树脂是已知的。但是,在该温度或更高温度下的环境内这些有机聚硅氧烷树脂不稳定,因为在此情况下,它们软化且其进一步被加工的能力是不确定的。Tg高于55℃的有机聚硅氧烷树脂也是已知的。但是,这种树脂的羟基含量远低于1%(重量),因此该树脂的反应性大幅降低。
所以,本发明的目的是改进已有技术以及特别是提供具有相对高的玻璃化转变温度(Tg)同时保持高度反应性的有机聚硅氧烷。
本发明提供有机聚硅氧烷树脂,其玻璃化转变温度(Tg)高达约60℃且其羟基含量至少为1%(重量),以有机聚硅氧烷树脂为基准。
所讨论的有机聚硅氧烷树脂是根据下述方法制备的常规有机聚硅氧烷树脂。本发明的有机聚硅氧烷树脂,其玻璃化转变温度(Tg)为60℃以上至高达优选200℃,其羟基含量为至少1%(重量)至高达优选8%(重量),其分子量优选为500至10000克/摩尔,特别优选为1000至8000克/摩尔。
本发明另外提供制备有机聚硅氧烷树脂的方法,在该方法中,在酸、水及沸点高于水的有机溶剂的存在下,使下列通式(I)的相同或不同的烷氧基硅烷反应,
RxSi(OR′)y (I)其中R可相同或不同,且代表氢原子或有机基,且R′的定义与R的相同,X等于0至3,及Y等于4至1,终了时,通过蒸馏除去所用的酸。
R基优选为具有l至18个碳原子的直链烷基;特别优选是如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基,己基,如正己基,庚基,如正庚基,辛基,如正辛基及异辛基,如2,2,4—三甲基戊基,壬基,如正壬基,癸基,如正癸基,十二烷基,如正十二烷基,十八烷基,如正十八烷基;烷基可能被取代,优选被巯基、环氧官能基、羧基、氨基如氨基乙基氨基、异氰酸基、丙烯酰氧基、甲基丙烯酰氧基、和/或羟基取代;链烯基,如乙烯基及烯丙基;环烷基,如环戊基、环己基、环庚基及甲基环己基;芳烃基,如苯基、萘基及蒽基及菲基;烷芳基,如邻—、间—及对—甲苯基、二甲苯基及乙苯基;芳烷基,如苯甲基、α—及β—苯乙基;特别优选是甲基至丙基及苯基。R′的定义与R基的一致。
可以相同或不同的烷氧基硅烷优选以化学计量摩尔数被采用。关于这点,优选的烷氧基硅烷RSi(OR′)3比例为50mol%是R为苯基且R′为乙基的烷氧基硅烷。其它的烷氧基硅烷可以是通式(I)所述的任何烷氧基硅烷。
可以使用的酸优选是无机酸,如盐酸、硫酸、硝酸或磷酸,优选为盐酸,多元酸,如多磷酸、聚丙烯酸及聚乙烯基硫酸;羧酸,如甲酸、乙酸、丙酸、乙二酸、丙二酸、丁二酸、己二酸、苯甲酸、邻苯二甲酸、及柠檬酸也可优选地被使用,用量为1ppm至1%(重量),优选低于0.1%(重量),以组合物的总重量为基准。
根据待水解的烷氧基,使用的水的摩尔数为0.1至10,优选为0.5至2。
作为沸点高于水的有机溶剂,优选使用芳香烃如甲苯、二甲苯及苯,或直链和/或支链的取代或未取代的烃类的混合物,所述烃类如辛烷、壬烷及癸烷,或戊酮、己酮、庚酮,或其异构体,其用量为1至1000%(重量),优选为10至100%(重量),以组合物的重量为基准。
制备本发明的有机聚硅氧烷树脂的温度优选为20至190℃,更优选为40至150℃,压力优选为500至10000百帕斯卡(绝对),更优选为950至6000百帕斯卡(绝对),特别优选为约950百帕斯卡(绝对)的略微减压。
本发明的有机聚硅氧烷树脂的制备优选连续进行或优选依照分批法进行:在分批法的情况下,所形成的醇在第一步骤中用水蒸馏除去,并在第二阶段中将沸点高于水的有机溶剂添加进去,随后通过蒸馏除去酸。
在连续制备的情况下,用水的水解作用和通式(I)的有机聚硅氧烷的缩合同时进行。反应混合物优选通过泵在闭路系统内循环。连续供以新鲜水、有机烷氧基硅烷以及酸性催化剂。包括上述通式(I)的有机聚硅氧烷及反应形成的醇、以及水与酸性催化剂的适当部分的反应混合物同样连续地自该过程中移出。在部分共沸物(醇及水)经蒸馏除去之后,添加足量的有机溶剂,将反应混合物内剩余的醇连同初始引入的水及酸性水解催化剂一起自反应混合物蒸馏除去。如此形成高分子质量的有机聚硅氧烷在有机溶剂中的溶液。如果需要,可通过蒸馏或喷雾干燥将有机溶剂随后完全除去。
在分批制备的情况下,将水加入优选的有机烷氧基硅烷混合物中并将此混合物作为初始进料连同酸性水解催化剂一起引入。随后,将反应混合物加热至足以反应的温度。稍后,反应开始并将反应期间形成的醇连同初始引入的水一起以共沸方式蒸馏除去。在部分共沸物被蒸馏除去之后,添加足量的有机溶剂,并将反应混合物中剩余的醇连同初始引入的水及酸性水解催化剂一起自反应混合物蒸馏除去。如此形成高分子质量的有机聚硅氧烷在有机溶剂中的溶液。如果需要,可以通过蒸馏或喷雾干燥将有机溶剂完全除去。
本发明的有机聚硅氧烷树脂,或依照本发明制备的有机聚硅氧烷树脂,可用于迄今有机聚硅氧烷树脂已应用的任何目的:例如,用作制造涂料或涂层材料(粉末涂层材料)的粘合剂,因其反应性高而非常适于加工。由于本发明的有机聚硅氧烷树脂不聚结,所以其优点是纵使在超过55℃的环境温度下它们仍可被加工。尤其因为没有盐形成,本发明的方法的优点是无需过滤。
实施例
用以分批制备本发明的有机聚硅氧烷树脂的装置由装有内部温度计的2升四颈圆底烧瓶、回流冷凝器及装有蒸馏液接受器的蒸馏桥及搅拌器组成。该烧瓶用加热套加热。反应进行后,(如果需要)在旋转蒸发仪中减压下将反应混合物从溶剂中完全分离出。实施例1
将1120克苯基三乙氧基硅烷、300克水及4.2克20%浓度的盐酸置入上述的装置内。随后,将反应混合物加热至回流温度并将水解/缩合反应所生醇的一部分连同初始引入的水的一部分蒸馏除去。添加400克甲苯,然后继续蒸馏至塔顶温度达到110℃。随后在旋转蒸发仪中在温度150℃及压力10毫巴下将所得粗产物从溶剂中完全分离出。其它实施例
表内所列的其它实施例通过类似上述的过程制得,但所用初始烷氧基硅烷或对应的烷氧基硅烷混合物不同,表内所示烷氧基硅烷的比例是指采用的摩尔数。另外,所用的溶剂不是甲苯,且同样酸性催化剂的用量也不同。
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
烷氧基硅烷 | PTEO | PTEO | PTEO | PTEO | PTEO | PTEO | PTEO | PTEO |
- | - | - | - | PrTEO | MTEO | MTEO | TES | |
- | - | - | - | - | M2DEO | - | ||
比例 | - | - | - | - | 8∶2 | 9∶1 | 5∶4∶1 | 9∶1 |
水 | 300克 | 300克 | 300克 | 300克 | 320克 | 300克 | 450克 | 450克 |
盐酸(20%) | 4.3克 | 2.1克 | 4.3克 | 4.2克 | 4.3克 | 4.2克 | 0.7克 | 2.4克 |
有机溶剂 | 甲苯 | 甲苯 | 二甲苯 | MIBK | 二甲苯 | 甲苯 | 甲苯 | 甲苯 |
羟基含量 | 3.4% | 3.8% | 3.6% | 3.5% | 3.2% | 3.1% | 4.9% | 5.9% |
Tg | 80℃ | 74℃ | 83℃ | 79℃ | 62℃ | 75℃ | 71℃ | 96℃ |
Mw(克/摩尔) | 1298 | 1197 | 1296 | 1267 | - | 1232 | 1143 | 4036 |
Mn(克/摩尔) | 1961 | 1653 | 1966 | 1898 | - | 1827 | 1679 | 1608 |
Mw/Mn | 1.51 | 1.38 | 1.52 | 1.50 | - | 1.48 | 1.47 | 2.51 |
注解:
* =通过Zerewitinov法测得
—IPTEO=苯基三乙氧基硅烷
—MTEO =甲基三乙氧基硅烷
—PrTEO=丙基三乙氧基硅烷
—M2DEO=二甲基二乙氧基硅烷
—TES =四乙氧基硅烷
—MIBK =甲基异丁基酮
Claims (3)
1.一种玻璃化转变温度(Tg)超过60℃,且羟基含量至少为1%(重量)的有机聚硅氧烷树脂。
2.一种用以制备有机聚硅氧烷树脂的方法,所述方法包括:在酸、水及沸点高于水的有机溶剂的存在下,使下列通式(I)的相同或不同的烷氧基硅烷反应,
RxSi(OR′)y (I)其中R可相同或不同,且代表氢原子或有机基,且R′的定义与R的相同,x等于0至3,及y等于4至1,所用的酸在终了时通过蒸馏除去。
3.一种用以制备如权利要求1的有机聚硅氧烷树脂的方法,所述方法包括:在第一步骤中,用水将所形成的醇蒸馏除去,在第二阶段中,添加沸点高于水的有机溶剂,随后通过蒸馏将酸除去。
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DE19857348.0 | 1998-12-11 | ||
DE19857348A DE19857348A1 (de) | 1998-12-11 | 1998-12-11 | Organopolysiloxanharze |
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US (1) | US6552151B1 (zh) |
EP (1) | EP1137691B1 (zh) |
JP (1) | JP4125873B2 (zh) |
KR (1) | KR100483449B1 (zh) |
CN (1) | CN1149249C (zh) |
DE (2) | DE19857348A1 (zh) |
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CN109553772A (zh) * | 2018-10-26 | 2019-04-02 | 广州嘉睿复合材料有限公司 | 一种聚硅氧烷树脂及其制备方法 |
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JP2006526668A (ja) | 2003-04-07 | 2006-11-24 | コンゾルテイウム フユール エレクトロケミツシエ インヅストリー ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | オルガノシリル官能化された粒子およびその製造 |
DE102004022400A1 (de) * | 2004-05-06 | 2005-12-15 | Consortium für elektrochemische Industrie GmbH | Feuchtigkeitsvernetzbare alkoxysilyfunktionelle Partikel enthaltende Zusammensetzung |
DE602005008226D1 (de) * | 2005-07-28 | 2008-08-28 | Eastman Kodak Co | Zweischichtige infrarotempfindliche Bildaufzeichnungselemente mit Polysiloxanüberschicht. |
DE602005007887D1 (de) * | 2005-07-28 | 2008-08-14 | Eastman Kodak Co | Infrarotempfindlicher positivarbeitender Litographiedruckplattenvorläufer. |
JP5161875B2 (ja) | 2006-06-09 | 2013-03-13 | ダウ・コーニング・コーポレイション | 無溶媒固体mq樹脂の調製方法 |
US8828648B2 (en) | 2010-02-17 | 2014-09-09 | Fujifilm Corporation | Method for producing a planographic printing plate |
KR100967759B1 (ko) * | 2010-03-02 | 2010-07-05 | 윤기영 | 링겔팩 안착결합부가 구비된 다기능 모자 |
US8846300B2 (en) | 2010-03-31 | 2014-09-30 | Fujifilm Corporation | Developer for processing lithographic printing plate precursor, method for manufacturing lithographic printing plate by using the developer, and printing method |
RU2456308C2 (ru) * | 2010-07-23 | 2012-07-20 | Учреждение Российской академии наук Институт синтетических полимерных материалов им. Н.С. Ениколопова (ИСПМ РАН) | Способ получения линейных полидиметилсилоксанов с концевыми гидроксильными группами поликонденсацией диметилдиалкоксисиланов в активной среде |
WO2023099017A1 (de) | 2021-12-03 | 2023-06-08 | Wacker Chemie Ag | Verfahren zur herstellung von verzweigten organopolysiloxanen |
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DE2415331A1 (de) | 1974-03-29 | 1975-10-16 | Bayer Ag | Verfahren zur herstellung silanolgruppen enthaltender organopolysiloxanharze |
US4877837A (en) | 1988-10-07 | 1989-10-31 | The Glidden Company | Epoxy functional and silicone thermosetting powder coatings |
JP2604498B2 (ja) * | 1990-11-09 | 1997-04-30 | 東芝シリコーン株式会社 | 非反応性シリコーン樹脂及び艶出し剤 |
JP3150731B2 (ja) * | 1991-09-30 | 2001-03-26 | 東レ・ダウコーニング・シリコーン株式会社 | シリコーン樹脂の製造方法 |
DE4243895A1 (de) | 1992-12-23 | 1994-06-30 | Wacker Chemie Gmbh | Verfahren zur Herstellung von Organopolysiloxanharz |
JP3024473B2 (ja) * | 1993-12-07 | 2000-03-21 | 信越化学工業株式会社 | 熱可塑性フルオロシリコーン樹脂及びその製造方法 |
JP3445831B2 (ja) * | 1994-06-28 | 2003-09-08 | ジーイー東芝シリコーン株式会社 | シリコーン樹脂組成物 |
JP3541075B2 (ja) * | 1995-03-01 | 2004-07-07 | ジーイー東芝シリコーン株式会社 | ポリメチルシロキサン樹脂の製造法 |
US5962568A (en) * | 1998-03-31 | 1999-10-05 | Morton International, Inc. | Coating powder for high temperature resistant coatings |
US6034178A (en) * | 1998-09-30 | 2000-03-07 | Morton International, Inc. | Coating powder for high temperature resistant coatings |
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CN109553772A (zh) * | 2018-10-26 | 2019-04-02 | 广州嘉睿复合材料有限公司 | 一种聚硅氧烷树脂及其制备方法 |
CN109553772B (zh) * | 2018-10-26 | 2021-07-20 | 广州嘉睿复合材料有限公司 | 一种聚硅氧烷树脂及其制备方法 |
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DE19857348A1 (de) | 2000-06-15 |
CN1149249C (zh) | 2004-05-12 |
DE59910307D1 (de) | 2004-09-23 |
TW526226B (en) | 2003-04-01 |
US6552151B1 (en) | 2003-04-22 |
WO2000035994A1 (de) | 2000-06-22 |
JP2002532595A (ja) | 2002-10-02 |
EP1137691A1 (de) | 2001-10-04 |
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