CN111072949A - High-functionality alkyl-terminated polyether for foam stabilizer and preparation method thereof - Google Patents

High-functionality alkyl-terminated polyether for foam stabilizer and preparation method thereof Download PDF

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CN111072949A
CN111072949A CN201911372122.2A CN201911372122A CN111072949A CN 111072949 A CN111072949 A CN 111072949A CN 201911372122 A CN201911372122 A CN 201911372122A CN 111072949 A CN111072949 A CN 111072949A
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foam
parts
polyether
functionality
initiator
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荆晓东
邹瑞
孙言丛
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    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
    • C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Abstract

The invention belongs to the technical field of polyether preparation, and particularly relates to high-functionality alkyl-terminated polyether for a foam stabilizer and a preparation method thereof. Is prepared from 100-500 parts of initiator, 5-15 parts of catalyst and 20-80 parts of chlorobutene, wherein the initiator is polyether polyol, the functionality is 6-8, the hydroxyl value is 20-40mgKOH/g, and the molecular weight is 10000-20000; the catalyst is one of cesium hydride, sodium hydroxide or sodium methoxide. The high-functionality alkyl-terminated polyether for the foam stabilizer disclosed by the invention is reacted with a catalyst to generate sodium alkoxide by adopting the high-functionality polyether as an initiator, and then reacted with chlorobutene to prepare the alkyl-terminated polyether.

Description

High-functionality alkyl-terminated polyether for foam stabilizer and preparation method thereof
Technical Field
The invention belongs to the technical field of polyether preparation, and particularly relates to high-functionality alkyl-terminated polyether for a foam stabilizer and a preparation method thereof.
Background
The polyurethane foam stabilizer is one of the essential raw materials for foaming, has the function of stabilizing the foaming process, enables various reactions in the foaming process to be smoothly carried out, supports the foam, has fine and uniform foam holes, and avoids the adverse phenomena of collapse, coarse holes, cracking and the like. The existing commercially available foam stabilizer mainly comprises L-580, Y-10366 and the like, and although the foam stabilizer has good foam stabilizing performance and air permeability, the formula adjusting range is narrow, so that foam falls back greatly and even collapses easily.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides high-functionality alkyl terminated polyether for a foam stabilizer; when the polyether is applied to preparation of polyurethane products, the debugging width of a foam formula is increased, the surface tension of various raw materials is improved, the intersolubility of the raw materials is increased, and the foaming process is stabilized. The invention also provides a preparation method thereof.
The high-functionality alkyl terminated polyether for the foam stabilizer is prepared from the following raw materials in parts by weight:
100 portions of initiator
5-15 parts of catalyst
20-80 parts of chlorobutene;
wherein:
the initiator is polyether polyol with the functionality of 6-8, the hydroxyl value of 20-40mgKOH/g and the molecular weight of 10000-; DX-12000 produced by Zibodegen Federal chemical industries, Ltd is preferred, having a functionality of 6, a hydroxyl value of 28mgKOH/g and a molecular weight of 12000.
The catalyst is one of cesium hydride, sodium hydroxide or sodium methoxide, preferably cesium hydride.
Preferably, the high-functionality alkyl-terminated polyether for the foam stabilizer is prepared from the following raw materials in parts by mass:
initiator 350 parts
Catalyst 6.5 parts
23.5 parts of chlorobutene.
The preparation method of the high-functionality alkyl-terminated polyether for the foam stabilizer comprises the steps of putting an initiator and a catalyst into a reaction kettle, replacing the initiator and the catalyst with nitrogen, heating to 65-77 ℃, and degassing for 2-8 hours until no bubbles are generated; and then cooling to 55-61 ℃, dropwise adding chlorobutene for polymerization reaction, curing for 5-10h, removing monomers for 1-3h to obtain a crude product, and then washing, neutralizing, adsorbing, drying and filtering to obtain the high-functionality alkyl terminated polyether for the foam stabilizer.
Preferably, the preparation method of the high-functionality alkyl-terminated polyether for the foam homogenizing agent comprises the steps of putting DX-12000 and cesium hydride into a reaction kettle, replacing with nitrogen, heating to 70 ℃, and degassing for 5 hours until no bubbles are generated; and then cooling to 60 ℃, dropwise adding chlorobutene for polymerization reaction, curing for 7h, removing monomers for 2h to obtain a crude product, and then washing, neutralizing, adsorbing, drying and filtering to obtain the high-functionality alkyl-terminated polyether for the foam stabilizer.
Wherein:
the polymerization reaction time is 8-12 hours, and the reaction temperature is 30-80 ℃.
The curing temperature is 40-90 ℃.
Adding pure water at 50-100 deg.C, stirring for 0.5-2 hr, and washing with water.
Adding phosphoric acid to neutralize the pH value to 4.5-6, and stirring for 1-3 h.
And after the neutralization is finished, adding a silicate adsorbent for adsorption.
Drying at 119-125 deg.c for 4-8 hr in vacuum until the water content is less than or equal to 0.10.
Vacuum decompression filtration is adopted, the temperature is 100-130 ℃, and the vacuum degree is 0.05-0.1 MPa.
The invention adopts high-functional polyether polyol as an initiator, reacts with catalyst cesium hydride and the like to generate sodium alkoxide, and then reacts with chlorobutene to prepare the alkyl-terminated polyether.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-functionality alkyl terminated polyether for the foam stabilizer disclosed by the invention is reacted with a catalyst to generate sodium alkoxide by adopting the high-functionality polyether as an initiator, and then reacted with chlorobutene to prepare the alkyl terminated polyether, so that the foam hardness and the comfort degree can be obviously improved when the alkyl terminated polyether is used for preparing polyurethane.
(2) When the foam stabilizer prepared from the high-functionality alkyl-terminated polyether for the foam stabilizer is applied to polyurethane preparation, the surface tension of various raw materials can be obviously improved, the intersolubility of the raw materials is increased, and the foaming process is stabilized.
(3) The preparation method of the high-functionality alkyl-terminated polyether for the foam stabilizer is scientific, reasonable, simple and feasible.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The high-functionality alkyl-terminated polyether for the foam stabilizer in the embodiment 1 is prepared from the following raw materials in parts by mass:
DX-12000350 parts
Cesium hydride 8.5 parts
33.5 parts of chlorobutene.
Wherein: DX-12000 is a high functional polyether polyol, the manufacturer is ZibodeXin Federal chemical industry Co., Ltd., functionality 6, hydroxyl value 28mgKOH/g, molecular weight 12000.
In the preparation method of the polyether with high functionality and alkyl end capping for the foam stabilizer described in this embodiment 1, DX-12000 and cesium hydride are put into a reaction kettle, replaced with nitrogen, heated to 65 ℃, and degassed for 5 hours until no bubbles are generated. Then cooling to 55 ℃, dropwise adding chlorobutene, curing for 7h, and removing monomers for 2h to obtain a crude product. Adding pure water at 68 ℃, stirring for 2.0h for water washing, then adding phosphoric acid for neutralization until the pH is 5.18, stirring for 1 h, adding silicate for adsorption, heating to 125 ℃, drying for 6 h, and finally carrying out vacuum reduced pressure filtration to obtain the high-functionality alkyl-terminated polyether for the foam stabilizer.
Example 2
The high-functionality alkyl-terminated polyether for the foam stabilizer in the embodiment 2 is prepared from the following raw materials in parts by mass:
DX-12000500 parts
Sodium methoxide 9 parts
29.5 parts of chlorobutene.
In the preparation method of the polyether capped with the high-functionality alkyl group for the foam stabilizer described in this embodiment 2, DX-12000 and sodium methoxide are put into a reaction kettle, replaced with nitrogen, heated to 71 ℃, and degassed for 5 hours until no bubbles are generated. Then cooling to 61 ℃, dropwise adding chlorobutene, curing for 7h, and removing monomers for 2h to obtain a crude product. Adding pure water at 93 ℃, stirring for 0.5h for water washing, then adding phosphoric acid for neutralization until the pH is 4.98, stirring for 1 h, adding silicate for adsorption, heating to 119 ℃, vacuum drum nitrogen drying for 6 h, and finally vacuum decompressing and filtering to obtain the high-functionality alkyl-terminated polyether for the foam stabilizer.
Example 3
The high-functionality alkyl-terminated polyether for the foam stabilizer in this embodiment 3 is prepared from the following raw materials in parts by mass:
DX-12000150 parts
5.5 parts of sodium hydroxide
28.7 parts of chlorobutene.
In the preparation method of the high-functionality alkyl-terminated polyether for the foam stabilizer in this embodiment 3, DX-12000 and sodium hydroxide are put into a reaction kettle, replaced with nitrogen, heated to 77 ℃, and degassed for 5 hours until no bubbles are generated; then cooling to 58 ℃, dropwise adding chlorobutene, curing for 7h, and removing monomers for 2h to obtain a crude product. And (2) cooling to 81 ℃, adding pure water, stirring for 1.5h for washing, then adding phosphoric acid for neutralizing until the pH value is 5.01, stirring for 2h, adding silicate for adsorption, heating to 120 ℃, carrying out vacuum nitrogen blowing for 6 h for drying, and finally carrying out vacuum pressure reduction and filtration to obtain the high-functionality alkyl-terminated polyether for the foam stabilizer.
Comparative example 1 is a commercial foam leveler L-580.
The foam homogenizers of examples 1-3 and comparative example 1 were used to prepare high density sponges with the following raw material composition:
the component A comprises:
Figure BDA0002339949000000031
Figure BDA0002339949000000041
and B component:
modified black material 100LL 35 Kg.
Polyether polyol DEP-505S is polyether polyol with functionality of 3 and molecular weight of 3500, and is produced by Zibodexin Federal chemical industry Co.
Polyether polyol DEP-330N is polyether polyol with functionality of 3 and molecular weight of 4800, and is produced by Zibodexin Federal chemical industries, Inc.
The foam stabilizer is the foam stabilizer described in examples 1-3 and comparative example 1.
The preparation method of the high-density sponge comprises the following steps:
adding the component A into a stirrer, adjusting the constant material temperature to 25 +/-2 ℃, and adjusting the rotating speed of the stirrer to 4300r/min to uniformly mix the raw materials; preheating to 25 +/-2 ℃, pouring the component B into the uniformly mixed component A, stirring for 5s, pouring the mixed material into a mold preheated to 40 +/-5 ℃, and demolding after 8min to obtain the product.
The results of the performance tests on the high density sponges prepared in examples 1-3 and comparative example 1 are shown in table 1.
Table 1 results of performance test of high density sponges prepared in examples 1-3 and comparative example 1
Numbering Time to spit foam Rate of fall back Hardness of Density of Ratio of indentation
Example 1 1 is divided into 31 7.1％ 53F 42.3 2.760
Example 2 1 in 28 7.3％ 55F 42.6 2.790
Example 3 1 is divided into 23 6.8％ 56F 41.9 2.740
Comparative example 1 1 is divided into 30 8.5％ 55F 42.0 2.750

Claims (10)

1. A high-functionality alkyl-terminated polyether for a foam stabilizer is characterized in that: the feed is prepared from the following raw materials in parts by mass:
100 portions of initiator
5-15 parts of catalyst
20-80 parts of chlorobutene;
wherein:
the initiator is polyether polyol, the functionality is 6-8, the hydroxyl value is 20-40mgKOH/g, and the molecular weight is 10000-;
the catalyst is one of cesium hydride, sodium hydroxide or sodium methoxide.
2. The foam stabilizer capped with high functionality alkyl polyether of claim 1, wherein: the feed is prepared from the following raw materials in parts by mass:
initiator 350 parts
Catalyst 6.5 parts
23.5 parts of chlorobutene;
wherein:
the initiator is DX-12000 produced by Zibodexin Federal chemical industry Co., Ltd, the functionality is 6, the hydroxyl value is 28mgKOH/g, and the molecular weight is 12000;
the catalyst is cesium hydride.
3. A process for preparing a high functionality alkyl terminated polyether for a suds leveler as defined in claim 1, wherein: putting an initiator and a catalyst into a reaction kettle, replacing with nitrogen, heating to 65-77 ℃, and degassing for 2-8 hours until no bubbles are generated; and then cooling to 55-61 ℃, dropwise adding chlorobutene for polymerization reaction, curing for 5-10h, removing monomers for 1-3h to obtain a crude product, and then washing, neutralizing, adsorbing, drying and filtering to obtain the high-functionality alkyl terminated polyether for the foam stabilizer.
4. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: the polymerization reaction time is 8-12 hours, and the reaction temperature is 30-80 ℃.
5. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: the curing temperature is 40-90 ℃.
6. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: adding pure water at 50-100 deg.C, stirring for 0.5-2 hr, and washing with water.
7. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: adding phosphoric acid to neutralize the pH value to 4.5-6, and stirring for 1-3 h.
8. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: and after the neutralization is finished, adding a silicate adsorbent for adsorption.
9. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: drying at 119-125 deg.c for 4-8 hr in vacuum until the water content is less than or equal to 0.10.
10. The process for preparing high functionality alkyl terminated polyethers for foam levelers according to claim 3 characterized by: vacuum decompression filtration is adopted, the temperature is 100-130 ℃, and the vacuum degree is 0.05-0.1 MPa.
CN201911372122.2A 2019-12-27 2019-12-27 High-functionality alkyl-terminated polyether for foam stabilizer and preparation method thereof Withdrawn CN111072949A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341617A (en) * 2020-11-26 2021-02-09 荆晓东 Refining method of oxa-cycloalkyl terminated polyether polyol

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341617A (en) * 2020-11-26 2021-02-09 荆晓东 Refining method of oxa-cycloalkyl terminated polyether polyol
CN112341617B (en) * 2020-11-26 2023-10-17 山东尚正新材料科技股份有限公司 Refining method of oxacycloalkanyl end-capped polyether polyol

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