CN109438501A - 一种γ异氰酸酯丙基硅烷及其制备方法 - Google Patents
一种γ异氰酸酯丙基硅烷及其制备方法 Download PDFInfo
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 title claims abstract 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- -1 allyl iso cyanurate Chemical compound 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 2
- KATWWKLDOOVHTO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3].CCC[SiH3] KATWWKLDOOVHTO-UHFFFAOYSA-N 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- WCSKRHCGELNDFV-UHFFFAOYSA-N ethoxy-methoxy-oxosilane Chemical compound CCO[Si](=O)OC WCSKRHCGELNDFV-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MBOOMFWIUMKSNA-UHFFFAOYSA-N isocyanatomethylsilane Chemical compound [SiH3]CN=C=O MBOOMFWIUMKSNA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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Abstract
本发明公开了一种γ异氰酸酯丙基硅烷及其制备方法,本发明利用含氢硅烷偶联剂和烯丙基异氰酸酯之间的硅氢加成反应,制得γ异氰酸酯丙基硅烷。该方法操作简单,环境友好,产率高,反应温和:适合制备高纯度的γ异氰酸酯丙基硅烷。
Description
技术领域
本发明涉及硅烷偶联剂领域,具体涉及一种γ异氰酸酯丙基硅烷及其制备方法。
背景技术
异氰酸酯硅烷含有可以参与反应的异氰酸酯基团和可以进行湿气固化的硅氧烷基团。因此越来越多地应用于高分子领域,以提高涂料、胶粘剂等产品对墙体、汽车等界面的粘接能力。随着环保要求的日益提高,引入该类型硅烷的树脂甚至可以不添加额外的催化剂,便可以完成固化。硅烷封端的聚醚树脂、聚氨酯树脂就是很好的例子。
在传统的制备方法中,异氰酸酯硅烷主要采用光气法和热裂解法进行合成。但是,光气过于活泼,危险性高,而且一般硅烷厂家很难涉及光气这种原料;而热裂解法主要采用氨基硅烷和碳酸二酯、碳酸二胺之间的反应,该过程中需要采用高温裂解氨基甲酸酯的方式进行,因此耗能较大,且对生产装置和生产工艺要求苛刻。
发明内容
为解决现有技术中存在的问题,本发明提供一种γ异氰酸酯丙基硅烷及其制备方法。
一种γ异氰酸酯丙基硅烷,包括下述步骤:将烯丙基异氰酸酯和催化剂混合后,加热到25~40℃,缓慢滴加含氢硅烷偶联剂,反应24~72h;在50~100℃的条件下,减压蒸馏,除去未反应的含氢硅烷偶联剂后,制得γ异氰酸酯丙基硅烷。
此外,所述烯丙基异氰酸酯与所述含氢硅烷偶联剂的物质的量之比为1: (1~1.2);所述催化剂的质量占所述烯丙基异氰酸酯质量的0.1~5%。
此外,所述催化剂为氯铂酸催化剂和卡斯特催化剂中的一种。
此外,所述所述氯铂酸催化剂为2%浓度的异丙醇溶剂。
此外,所述含氢硅烷偶联剂的化学通式为:
其中,R1、R2、R3分别为CnH2n+1和OCmH2m+1中的一种,n≥1,m≥1。
本发明还包括一种如上述的γ异氰酸酯丙基硅烷的制备方法制得的γ异氰酸酯丙基硅烷。
本发明采用含氢硅烷偶联剂和烯丙基异氰酸酯之间的硅氢加成反应,制得γ异氰酸酯丙基硅烷。该方法操作简单,耗能低,不采用溶剂,产物易于分离,催化剂的使用量少,产率高,反应温和,未反应的含氢硅烷可以重复利用。因此,对于中小型硅烷偶联剂厂家,该种方法是制备异氰酸酯硅烷更为合适的路径。
具体实施方式
下结合各实施方式对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
本发明的原料均为市场可得品。作为一种示例,本发明中卡斯特催化剂采用道康宁SYL-OFF 4000催化剂。
实施例1
将83.089g(1mol)烯丙基异氰酸酯和0.83g氯铂酸催化剂混合后,加热到25℃,缓慢滴加164.28g(1mol)含氢硅烷偶联剂为三乙氧基硅烷,反应24h;在100℃的条件下,减压蒸馏,除去未反应的三乙氧基硅烷后,收集280~300℃的产物,制得γ异氰酸酯丙基三乙氧基硅烷。
实施例2
将83.089g(1mol)烯丙基异氰酸酯和4.15g卡斯特催化剂混合后,加热到40℃,缓慢滴加146.4(1.2mol)含氢硅烷偶联剂为三甲氧基硅烷,反应72h;在90℃的条件下,减压蒸馏,除去未反应的三甲氧基硅烷后,收集 95-110℃的产物,制得γ异氰酸酯丙基三甲氧基硅烷。
实施例3
将83.089g(1mol)烯丙基异氰酸酯和0.83g卡斯特催化剂混合后,加热到40℃,缓慢滴加116.8(1.1mol)含氢硅烷偶联剂为甲基二甲氧硅烷,反应72h;在50℃的条件下,减压蒸馏,除去未反应的甲基二甲氧硅烷后,收集70-90℃的产物,制得γ异氰酸酯丙基甲基二甲氧硅烷。
三种异氰酸酯甲基硅烷的产率与纯度如下:
产率=产物实际质量/产物理论质量
纯度:CG-MS,以庚烷作溶剂,温度为120℃
从实施例产率与纯度结果可以看出,使用本发明的γ异氰酸酯丙基硅烷的制备方法制得的γ异氰酸酯丙基硅烷的产率高达98%,纯度高达99%。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种γ异氰酸酯丙基硅烷的制备方法,其特征在于,包括下述步骤:将烯丙基异氰酸酯和催化剂混合后,加热到25~40℃,缓慢滴加含氢硅烷偶联剂,反应24~72h;在50~100℃的条件下,减压蒸馏,除去未反应的含氢硅烷偶联剂后,制得γ异氰酸酯丙基硅烷。
2.根据权利要求1所述的γ异氰酸酯丙基硅烷的制备方法,其特征在于,所述烯丙基异氰酸酯与所述含氢硅烷偶联剂的物质的量之比为1:(1~1.2);所述催化剂的质量占所述烯丙基异氰酸酯质量的0.1~5%。
3.根据权利要求1所述的γ异氰酸酯丙基硅烷的制备方法,其特征在于,所述催化剂为氯铂酸催化剂和卡斯特催化剂中的一种。
4.根据权利要求3所述的γ异氰酸酯丙基硅烷的制备方法,其特征在于,所述氯铂酸催化剂为2%浓度的异丙醇溶剂。
5.根据权利要求1所述的γ异氰酸酯丙基硅烷的制备方法,其特征在于,所述含氢硅烷偶联剂的化学通式为:
其中,R1、R2、R3分别为CnH2n+1和OCmH2m+1中的一种,n≥1,m≥1。
6.一种根据权利要求1-5任一项所述的γ异氰酸酯丙基硅烷的制备方法制得的γ异氰酸酯丙基硅烷。
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CN110128465A (zh) * | 2019-06-25 | 2019-08-16 | 荆州市江汉精细化工有限公司 | 一种用硅氢加成反应制备异氰酸酯基硅烷的方法 |
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WO2002050000A1 (en) * | 2000-12-19 | 2002-06-27 | General Electric Company | Amine modified catalysts for bisphenol production |
WO2015009841A2 (en) * | 2013-07-16 | 2015-01-22 | Blend Therapeutics | Platinum compounds having a heterocycle ligand, nanoparticles, and uses thereof |
CN109071574A (zh) * | 2016-04-27 | 2018-12-21 | 美国陶氏有机硅公司 | 亲水性硅烷 |
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WO2002050000A1 (en) * | 2000-12-19 | 2002-06-27 | General Electric Company | Amine modified catalysts for bisphenol production |
WO2015009841A2 (en) * | 2013-07-16 | 2015-01-22 | Blend Therapeutics | Platinum compounds having a heterocycle ligand, nanoparticles, and uses thereof |
CN109071574A (zh) * | 2016-04-27 | 2018-12-21 | 美国陶氏有机硅公司 | 亲水性硅烷 |
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CN110128465A (zh) * | 2019-06-25 | 2019-08-16 | 荆州市江汉精细化工有限公司 | 一种用硅氢加成反应制备异氰酸酯基硅烷的方法 |
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