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Active hydrogen tolerant catalyst, preparation method thereof and ultralow-molecular-weight poly(carbonate-ether) polyol

A catalyst and active hydrogen technology, applied in the field of polymers, can solve the problems of catalyst deactivation, uncontrollable polymerization reaction, poor catalyst proton tolerance, etc., and achieve the effect of high proton tolerance

Active Publication Date: 2020-07-31
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The proton tolerance of the catalyst is not strong. In the presence of active protons such as hydroxyl groups and carboxyl groups at high concentrations, the catalyst is deactivated due to irreversible coordination, and the polymerization reaction is uncontrollable, making it difficult to synthesize ultra-low molecular weight polyols.
Chinese patent CN102617844A discloses a method for preparing polycarbonate-ether polyols. The catalyst used in the method is a rare earth-doped modified double metal cyanide catalyst (Re-DMC). At high initiator dosage (propylene oxide / initiator = 5-10, molar ratio), the catalyst has been deactivated

Method used

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  • Active hydrogen tolerant catalyst, preparation method thereof and ultralow-molecular-weight poly(carbonate-ether) polyol
  • Active hydrogen tolerant catalyst, preparation method thereof and ultralow-molecular-weight poly(carbonate-ether) polyol
  • Active hydrogen tolerant catalyst, preparation method thereof and ultralow-molecular-weight poly(carbonate-ether) polyol

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preparation example Construction

[0063] The present invention provides a preparation method of the active hydrogen tolerant catalyst shown in the formula (I), comprising:

[0064] A) react p-hydroxybenzaldehyde, substituted benzaldehyde, and pyrrole under the condition of propionic acid reflux, and separate by column chromatography to obtain a monohydroxyl-substituted asymmetric porphyrin;

[0065] Maleimide and halogenated alkyl alcohol carry out dehydration reaction under the condition of diisopropyl azodicarboxylate and triphenylphosphine to obtain the maleimide substituted by halogenated alkyl chain,

[0066] B) reacting the maleimide substituted with the haloalkyl chain and the monohydroxyl-substituted porphyrin to synthesize an ether under alkaline conditions to prepare a maleimide-based porphyrin monomer;

[0067] C) asymmetric addition reaction of divinyl ether and hydrogen bromide to obtain an intermediate of formula (h), and then react with TBD or quaternize to obtain vinyl ether monomer;

[0068] ...

Embodiment 1

[0108]

[0109] Triphenylphosphine (1.35 g, 5.15 mmol) was dissolved in 20 ml of dehydrated THF solution, and the reaction system was set to -78°C using a dry ice / acetone bath. Add diisopropyl azodicarboxylate DIAD (1.01ml, 5.15mmol) dropwise for about 2 minutes, and the solution turns yellow after the dropwise addition. After stirring for 10 minutes, 6-chloro-1-hexanol (1.16g, 8.5mmol) was added dropwise, and after 5 minutes, maleimide (0.5g, 5.15mmol) was added, and after returning to room temperature, it was reacted for 10h, and the reaction system was dark gray. After rotary evaporation of the solvent, the crude product was separated by silica gel column chromatography (eluent n-hexane / ethyl acetate=2 / 1), and the product EL1 was a light yellow solid with a yield of 66%. 1 HNMR (300MHz, CDCl 3 )δ=6.72, 3.68, 3.37, 2.15~2.07, 1.75~1.71MS (ESI):[C10H14ClNO2], m / z=215.7[M+H] + (calcd. 215.7).

[0110] Add p-hydroxybenzaldehyde (13.2g, 108mmol), p-bromobenzaldehyde (59.7...

Embodiment 2

[0116]

[0117] Add p-hydroxybenzaldehyde (13.2g, 108mmol), 2,4-dichlorobenzaldehyde (56.8g, 324mmol) and 500mL propionic acid, heat up to 130°C, add pyrrole (30mL, 432mmol) dropwise, continue Raise the temperature to 160°C for reflux reaction for 2 hours, cool to room temperature after the reaction, add methanol and cool in the refrigerator overnight, filter the resulting product through silica gel column chromatography (CHCl 3 / CH 3 OH) Purify and collect the second color band to obtain the product EL6 with a yield of about 9%. 1 H NMR (300MHz, CDCl 3 )δ=8.89,8.13,7.92,7.10,-2.82MS (MALDI-ToF):[C44H24Br6N4O], m / z=837.4[M+H] + (calcd. 837.4).

[0118] Under nitrogen protection, EL1 (0.26g, 1.2mmol), EL6 (0.84g, 1mmol), anhydrous potassium carbonate (0.28g, 2mmol) and catalytic amount of potassium iodide (10mg) were dissolved in 50ml of dehydrated DMF, 100 Reaction at ℃ for 12h. After the reaction, the potassium salt was removed by filtration, and the DMF was rotary ev...

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Abstract

The invention provides an active hydrogen tolerant catalyst shown as a formula (I). The invention also provides a preparation method of ultralow-molecular-weight poly(carbonate-ether) polyol, which comprises: carrying out chain transfer polymerization reaction on carbon dioxide, an epoxy compound and an initiator under the action of the active hydrogen tolerant catalyst or the active hydrogen tolerant catalyst prepared by the preparation method to obtain the ultralow-molecular-weight poly(carbonate-ether) polyol. The active hydrogen tolerant catalyst provided by the invention is an alternatingmulti-center Lewis acid-base pair catalyst; the catalyst has high proton tolerance, so that the catalyst is not limited by the concentration of the initiator any more and can be used for preparing the ultralow-molecular-weight carbon dioxide polyol. The molecular weight of the ultralow-molecular-weight poly(carbonate-ether) polyol is 500-1000 g / mol, and the molecular weight distribution is 1.07-1.15; a carbonate segment and an ether segment exist on a main chain at the same time, and the functionality is 2-10; and the content of byproduct cyclic carbonate is lower than 1%.

Description

technical field [0001] The invention relates to the technical field of polymers, in particular to an active hydrogen resistant catalyst and a preparation method thereof and an ultra-low molecular weight poly(carbonate-ether) polyol. Background technique [0002] Polyether polyol is one of the important raw materials for the preparation of polyurethane. Due to the huge amount of polyurethane used, polyol production has brought a large increase in carbon footprint. In recent years, the route of preparing polycarbonate-ether polyols by substituting some petroleum-based monomers with carbon dioxide has greatly slowed down the environmental pressure on the polyurethane industry. At the same time, Chinese patent CN105566597A reports the technology of water-based polyurethane prepared from carbon dioxide polyol. Compared with polyether-based polyurethane, carbon dioxide-based polyurethane has more comprehensive hydrolysis / oxidation resistance. However, researchers found that with ...

Claims

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Application Information

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IPC IPC(8): C08F222/40C08F216/14C08F8/32C08F8/42C08G64/34C08G65/26
CPCC08F8/32C08F8/42C08F216/1408C08F216/1458C08F222/40C08G64/34C08G65/26C08G65/2654
Inventor 曹瀚张若禹周庆海王献红
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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