CN107513156A - The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration - Google Patents

The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration Download PDF

Info

Publication number
CN107513156A
CN107513156A CN201710788713.2A CN201710788713A CN107513156A CN 107513156 A CN107513156 A CN 107513156A CN 201710788713 A CN201710788713 A CN 201710788713A CN 107513156 A CN107513156 A CN 107513156A
Authority
CN
China
Prior art keywords
catalyst
polyether polyol
reduced
catalytic oxidation
photochemical catalytic
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
Application number
CN201710788713.2A
Other languages
Chinese (zh)
Inventor
翟洪金
应珏
倪小明
郑磊
于文超
王飞
任翠环
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jurong Ningwu New Material Co Ltd
Original Assignee
Jurong Ningwu New Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jurong Ningwu New Material Co Ltd filed Critical Jurong Ningwu New Material Co Ltd
Priority to CN201710788713.2A priority Critical patent/CN107513156A/en
Publication of CN107513156A publication Critical patent/CN107513156A/en
Pending legal-status Critical Current

Links

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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2648—Alkali metals or compounds thereof
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of method for reducing polyether polyol odor by binary composite catalyst and photochemical catalytic oxidation collaboration.This method uses specific binary composite catalyst " potassium ethoxide and glutaric acid zinc " synthesizing polyether glycol first, improves chemical reaction rate.Meanwhile in the last handling process of product, aldehyde material is aoxidized using optically catalytic TiO 2, collaboration reduces the concentration of low molecule aldehyde material, to reach the purpose for reducing polyether polyol odor.The content of the low molecule aldehydes such as PPG prepared by the present invention, its free formaldehyde, acetaldehyde is low, and product quality is stable, and performance is good.

Description

The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration
Technical field
It is specifically a kind of to be urged by binary composite catalyst and light the invention belongs to the preparation method of high-molecular compound Change the method that oxidation collaboration reduces polyether polyol odor.
Background technology
PPG extensive application, such as manufacturing polyurethane high-elastic cushion, direction in the automotive industry Disk etc..With the increasingly enhancing of people's environmental consciousness, have become limit the problems such as volatility, high smell existing for polyurethane product An important factor for making its application.Country issued Air Quality Evaluation guide in passenger car on March 1st, 2012（GB/T 27630—2011）, it is specified that the content of the volatilization aldehyde material such as in-car formaldehyde in air, acetaldehyde.From synthesis material and technical process Analyzed, the smell of Contents In Polyether Polyol is mainly unreacted propylene oxide monomer, and low molecular aldehyde material produces 's.This not only have impact on the comfortableness that automotive trim uses, and also health is formed and endangered.Therefore, PPG is found out The reason for producing smell is simultaneously effectively solved, and just turns into the key of lifting product quality.At present, studies in China personnel and correlation Enterprise is all explored constantly.Such as utility model patent (application number：201220436842.8) " vaporizing extract process removes PPG Peculiar smell device ", it is reduced the effect of polyether polyol odor；Patent of invention (application number：201410383509.9) " reduce polyethers The method of polyol amount ", reach the poly- ammonia of improvement by adding the volatile organic matter in hydrogen peroxide oxidation PPG The purpose of ester articles smell.Good brightness of the Qin of Qingdao University of Science and Technology et al. report " hydrogen peroxide reduce PPG in volatility The technical study of aldehyde material " [contemporary chemical industry, 2015,44 (1):49-50], they think the technique：(1) both can be notable PPG volatile aldehyde material is removed, while polyether polyol odor can be reduced again；(2) simple and easy, cost is low It is honest and clean, both it can be widely applied to without scrap build in PPG batch production.What the above method was directed to is all to product Post-processed to reduce the smell of PPG.Wherein vaporizing extract process is physical process, required although technique is simple Temperature is higher, and energy consumption is big；Hydrogen peroxide oxidation process is chemical process, although reducing, product odour effect is good, and control is reacted Condition is relatively harsh.
The content of the invention
For the problems of prior art and deficiency, it is an object of the invention to provide one kind to pass through binary composite catalyzing The method that agent and photochemical catalytic oxidation collaboration reduce polyether polyol odor.This method post-processes two sides for synthetic reaction and product Face carries out technological innovation, makes every effort to solve the subject matter that PPG produces smell.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration, it is characterised in that：With amine Material, using binary composite catalyst synthesizing polyether glycol, improves chemical reaction rate as initiator；Meanwhile in product Last handling process in, using titanium dioxide optical catalyst catalysis oxidation aldehyde material；Above-mentioned two steps synergy, effectively Reduce low molecule aldehydes formaldehyde, the content of acetaldehyde in PPG.
Heretofore described binary composite catalyst is potassium ethoxide and glutaric acid zinc, and its mass ratio is 1 ~ 5:1.Described Amine substance is ethylenediamine；Its dosage of the titanium dioxide optical catalyst is the 1 ~ 5% of PPG, and controlling reaction temperature is 30~80oC。
The content of the low molecule aldehydes such as PPG prepared by the present invention, its free formaldehyde, acetaldehyde is low, and product quality is steady Fixed, performance is good.
Beneficial effects of the present invention：
(1) composite catalyst is made with potassium ethoxide and glutaric acid zinc, the basicity of reaction system, and can telo merization can be controlled Activity, reach the target for reducing product color and smell caused by side reaction.
(2) due to using composite catalyst, reducing the temperature of polymerisation to a certain extent, improving selectivity.
(3) titanium dioxide aoxidizes as photochemical catalyst to low molecule aldehyde material, reduce further low molecule aldehyde The content of class material, it can preferably meet the requirement of polyurethane material production, it is good applied to auto industry environment protecting.
Embodiment
Embodiment 1
A kind of method that polyether polyol odor is reduced by binary composite catalyst and photochemical catalytic oxidation collaboration：
Using ethylenediamine as initiator, using specific binary composite catalyst：Potassium ethoxide and glutaric acid zinc, its mass ratio are 1: 1, controlling reaction temperature 90oC synthesizing polyether glycols.Meanwhile in the last handling process of product, using optically catalytic TiO 2 Agent catalysis oxidation aldehyde material, the dosage of catalyst are the 1% of PPG, controlling reaction temperature 50oC。
The conventional method synthesizing polyether of subordinate list 1 is compared with aldehyde matter content in this example polyethers
Embodiment 2
A kind of method that polyether polyol odor is reduced by binary composite catalyst and photochemical catalytic oxidation collaboration：
Using ethylenediamine as initiator, using specific binary composite catalyst：Potassium ethoxide and glutaric acid zinc, its mass ratio are 2: 1, controlling reaction temperature 110oC synthesizing polyether glycols.Meanwhile in the last handling process of product, urged using titanium-dioxide photo Agent catalysis oxidation aldehyde material, the dosage of catalyst are the 3% of PPG, controlling reaction temperature 70oC。。
The conventional method synthesizing polyether of subordinate list 2 is compared with aldehyde matter content in this example polyethers
。

Claims (4)

  1. A kind of 1. method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration, it is characterised in that：With amine Class material, using binary composite catalyst synthesizing polyether glycol, improves chemical reaction rate as initiator；Meanwhile producing In the last handling process of product, using titanium dioxide optical catalyst catalysis oxidation aldehyde material；Above-mentioned two steps synergy, effectively Ground reduces low molecule aldehydes formaldehyde, the content of acetaldehyde in PPG.
  2. 2. the method according to claim 1 that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration, It is characterized in that：Binary composite catalyst is potassium ethoxide and glutaric acid zinc, and its mass ratio is 1 ~ 5:1, its dosage is reaction mass The 0.5 ~ 3% of gross mass.
  3. 3. the method according to claim 1 that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration, It is characterized in that：Described amine substance is ethylenediamine.
  4. 4. the method according to claim 1 that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration, It is characterized in that：Using titanium dioxide optical catalyst catalysis oxidation aldehyde material, the dosage of catalyst is PPG quality 1 ~ 5%, controlling reaction temperature be 30 ~ 80oC。
CN201710788713.2A 2017-09-05 2017-09-05 The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration Pending CN107513156A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710788713.2A CN107513156A (en) 2017-09-05 2017-09-05 The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710788713.2A CN107513156A (en) 2017-09-05 2017-09-05 The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration

Publications (1)

Publication Number Publication Date
CN107513156A true CN107513156A (en) 2017-12-26

Family

ID=60724433

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710788713.2A Pending CN107513156A (en) 2017-09-05 2017-09-05 The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration

Country Status (1)

Country Link
CN (1) CN107513156A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113908834A (en) * 2021-08-11 2022-01-11 万华化学集团股份有限公司 Preparation method of aldehyde-removing catalyst and refining method of polyether polyol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554472A (en) * 2013-10-31 2014-02-05 淄博德信联邦化学工业有限公司 Preparation method of unsaturated high-activity polyether polyol
CN104710609A (en) * 2015-04-02 2015-06-17 山西凯迪建材有限公司 Method for generating polyether by virtue of ethoxylation reaction under photocatalysis conditions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554472A (en) * 2013-10-31 2014-02-05 淄博德信联邦化学工业有限公司 Preparation method of unsaturated high-activity polyether polyol
CN104710609A (en) * 2015-04-02 2015-06-17 山西凯迪建材有限公司 Method for generating polyether by virtue of ethoxylation reaction under photocatalysis conditions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张人佶: "《先进成形制造实用技术》", 31 August 2009, 清华大学出版社 *
李玉宝: "《纳米材料研究与应用》", 31 January 2005, 电子科技大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113908834A (en) * 2021-08-11 2022-01-11 万华化学集团股份有限公司 Preparation method of aldehyde-removing catalyst and refining method of polyether polyol
CN113908834B (en) * 2021-08-11 2023-03-03 万华化学集团股份有限公司 Preparation method of aldehyde-removing catalyst and refining method of polyether polyol

Similar Documents

Publication Publication Date Title
i Xamena et al. An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions
CN101747150B (en) Method for producing 1,3-propanediol
US20140024861A1 (en) Catalyst For Reducing Selectively Saturated Aldehyde And A Process For Preparing The Catalyst
CN104923209B (en) A kind of solid catalyst for acetone self-condensation reaction and its preparation method and application
CN103702963A (en) Improved process of dehydration reactions
CN102040505A (en) Method for preparing unsaturated acid by oxidation of unsaturated aldehyde
CN107513156A (en) The method that polyether polyol odor is reduced by catalyst and photochemical catalytic oxidation collaboration
CN108883366A (en) The carbon monoxide-olefin polymeric directly prepared and method for the hydrogen cyanide in acrylonitrile reactor feeding logistics
CN102989459B (en) Catalyst for preparing epsilon-caprolactone by oxidizing cyclohexanone/oxygen under aldehyde-assisted oxidizing action
CN101811042A (en) Selective hydrogenation catalyst and preparation method and application thereof
CN110227481A (en) A kind of catalyst for hydroprocessing of heavy oil and preparation method thereof
CN107446123A (en) The method that polyether polyol odor is reduced by catalyst and the collaboration of aldehydes trapping agent
CN100402142C (en) Catalyst for synthesizing allyl alcohol by reduction of acrolein and preparation method thereof
CN1428190A (en) Catalyst for preparing 1,3-propanediol by hydrogenation of lactic aldehyde
EP2618929B1 (en) An improved process for the epoxidation of fatty acids, their esters and mixtures thereof
CN111253256B (en) Method for preparing olefin by catalyzing biomass polyol and polybasic alcohol acid to deoxidize and dehydrate by using heteropoly acid containing molybdenum
CN102173977B (en) Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol
CN107522855A (en) The method that polyether polyol odor is reduced by trapping agent and catalysis oxidation collaboration
CN107088438A (en) The method for preparing lactic acid with the selective conversion of catalyzing glycerol containing molybdenum heteropolyacid
Liu et al. Direct epoxidation of propylene by molecular oxygen over Pd (OAc) 2–[(C6H13) 4N] 3 {PO4 [W (O)(O2) 2] 4}–CH3OH catalytic system
CN107474237A (en) A kind of method by ternary complex catalyst synthesizing polyether glycol
CN110721693B (en) ZnO-CuO x /SiO 2 Catalyst, composite catalyst, and preparation method and application thereof
CN100575328C (en) Process for preparing dichloroacetyl chloride
CN106582744A (en) Preparation method of catalyst capable of increasing yield of maleic anhydride prepared through n-butane oxidation
WO2016078673A1 (en) Process for reducing the oxygen content of biomass using molybdenum-based catalysts

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20171226

RJ01 Rejection of invention patent application after publication