Process for the preparation of urea-functionalized siloxanes

一种脲官能、聚硅氧烷的技术，应用在有机聚硅氧烷领域，能够解决大苯氧基-Si基团比例、反应性小、致突变等问题

Active Publication Date: 2022-02-11
WACKER CHEM GMBH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the reported examples are based only on the reaction of aminoalkylsilanes with alkyl carbamates (such as the toxic O-ethyl carbamate), which are substantially less reactive and require the presence of tin catalyst
[0005] Although the direct reaction of amino-functionalized polysiloxanes with phenyl carbamates leads to the desired urea-functionalized polysiloxanes, it has the disadvantage of the presence of a large proportion of phenoxy-Si groups and the subsequent possible release of toxic phenols due to hydrolysis (CMR2 substances (CMR = carcinogenic, mutagenic and toxic to reproduction), H341 "suspected to cause genetic defects")

Method used

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  • Process for the preparation of urea-functionalized siloxanes
  • Process for the preparation of urea-functionalized siloxanes
  • Process for the preparation of urea-functionalized siloxanes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0137]In a manner similar to Comparative Example 1, 90 g of aminopolysiloxane (0.026 mol amine) was mixed with 4.5 g (0.027 mol) of 2-methoxyphenyl carbamate (prepared from guaiacol and chlorosulfonyl isocyanate) , as described by Singh, R. et al., ACSCatalysis 6(10), 6520-6524 (2016)) at 80°C and 1 hPa for 2 hours. According to CDCl 3 middle 1 H-NMR spectrum (reference signal of undeuterated part: 7.24ppm), the conversion of ammonia functional group is quantitative (corresponding CH 2 Comparison of signals of -N groups: amine: 2.63 ppm, urea 3.12 ppm). Oil pump vacuum (4 hPa) was then applied and the residue was heated at 130° C. for 30 minutes while passing a nitrogen stream (2-5 l / h) through it. 82.7 g of a colorless clear oil and 3.8 g of a liquid distillate were isolated as a residue, in which 1 In the H-NMR spectrum, 2-methoxyphenol (=guaiacol) was detected as a main component (D6-acetone, signal groups at 7.5 ppm, 6.8 ppm, 6.9 ppm). remnants 1 H-NMR spectrum indic...

Embodiment 2

[0141] In a manner similar to Example 1, 90 g (0.11 mol of amine) were given the average formula Me 3 SiO 1 / 2 : Me 2 SiO 2 / 2 :MeSi(CH 2 CH 2 CH 2 -NH-CH 2 CH 2 -NH 2 )O 2 / 2 =2:17.8:1.1 The amino-functional polysiloxane was reacted with 22.1 g (=0.13 mol) of 2-methoxyphenyl carbamate and treated with heat. The complete conversion of the amine functional group to the corresponding urea functional group can be achieved by the 1 H-NMR spectrum (CDCl 3 ) between 2.5 and 2.9 ppm was confirmed by the absence of a signal and a new signal between 3.0 and 3.5 ppm.

Embodiment 3

[0143] In a manner similar to Example 2, 90 g (0.11 mol of amine) were given the average formula Me 3 SiO 1 / 2 :Me 2 SiO 2 / 2 :MeSi(CH 2 CH 2 CH 2 -NH-CH 2 CH 2 -NH 2 )O 2 / 2 =2:17.8:1.1 The amino-functional polysiloxane was reacted with 11 g (=0.065 mol) of 2-methoxyphenyl carbamate and treated with heat. The 48% conversion of amine functional groups into the corresponding urea functional groups can be determined by the 1 H-NMR spectrum (CDCl 3 ) is confirmed by the integration ratio of the signal between 2.5 and 2.9 ppm and the new signal between 3.0 and 3.5 ppm.

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Abstract

The present invention relates to be used for preparing by formula R n SiO (4‑n) / 2 (I) A method of urea-functionalized organopolysiloxanes consisting of units wherein R and n are as defined in claim 1 by making the formula R' n SiO (4‑n) / 2 (IV) An amino-functional organopolysiloxane consisting of units wherein R' and n are as defined in claim 1, with the formula R 7 ‑Ar‑O‑C(=O)‑NH 2 (VI) Ortho-substituted aryl carbamate reaction, where Ar and R 7 as defined in claim 1.

Description

technical field [0001] The present invention relates to the preparation of NH 2 Method for urea-functionalized organopolysiloxanes with -C(O)-N-groups. Background technique [0002] In contrast to amino-functional siloxanes, siloxanes with polar urea functions have a neutral reaction in aqueous environments and are therefore ideal as surface-active or hydrophobizing substances in physiological environments, for example as ingredients in cosmetics. Interesting. The extremely polar urea groups are capable of forming strong hydrogen bonds, for which reason the corresponding functionalized (poly)siloxanes, in contrast to analogous amino-functionalized representatives, lead to stronger interactions with the surface, and This results in a greater persistence as an additive. [0003] Due to the high polarity of the urea functional group, the introduction of such functional groups from polar precursors such as urea into siloxane frameworks with low polarity, as described in US 37...

Claims

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Application Information

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Patent Type & AuthorityPatents(China)
IPC IPC(8): C08G77/388
CPCC08G77/388
Inventor迈克尔·斯特普比吉特·佩沙内尔
OwnerWACKER CHEM GMBH