CN112708124A - Preparation method and application of high-functionality polyether polyol - Google Patents
Preparation method and application of high-functionality polyether polyol Download PDFInfo
- Publication number
- CN112708124A CN112708124A CN201911019038.2A CN201911019038A CN112708124A CN 112708124 A CN112708124 A CN 112708124A CN 201911019038 A CN201911019038 A CN 201911019038A CN 112708124 A CN112708124 A CN 112708124A
- Authority
- CN
- China
- Prior art keywords
- polyether polyol
- polyol
- catalyst
- initiator
- functionality
- 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.)
- Granted
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
- C08G65/2603—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 oxygen
- C08G65/2606—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 oxygen containing hydroxyl groups
- C08G65/2609—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 oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
-
- 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
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for synthesizing high-functionality multi-branched polyether polyol, which comprises the step of reacting polyol with alkylene oxide and alkanol oxide under the action of a catalyst to generate polyether polyol. The polyether polyols produced by the process possess more functionality and more branching than the starters used therein. The novel macromonomer synthesized by using the high-functionality multi-branched polyether polyol has higher functionality and more branched chains, the macromonomer obviously improves the stability of polymer polyol, and the prepared polymer polyol has higher solid content and lower viscosity.
Description
Technical Field
The invention relates to a preparation method and application of high-functionality polyether polyol.
Background
Polymer polyols are obtained by grafting vinyl monomers onto a base polyether polyol by free radical in situ polymerization. Polymer polyols are mainly used for the production of polyurethane flexible foams. Polyurethane flexible foam materials made from polymer polyols are largely classified into slabstock flexible foams and molded foams. Polyurethane slabstock foams are used in carpets, furniture and bedding. Polyurethane molded foams are used primarily in the automotive and aircraft industries. Polyurethanes prepared using polymer polyols can improve the properties of flexible polyurethane foams, particularly hardness and load-bearing capacity.
A problem generally encountered in the manufacture of polymer polyols, i.e. systems in which the polymer is stably dispersed in the base polyol, is to obtain a polymer polyol having both a relatively high solid polymer content and a sufficiently low viscosity for easy handling. Polymer polyols having this combination of properties are advantageous for the properties of any polyurethane foam produced from the polymer polyol. In order to stably disperse the polymer particles in the liquid polyol medium, a dispersion stabilizer precursor is generally required.
The polymeric polyol is made using a macromer which contains in the molecule at least one or more polymerizable double bonds which are copolymerizable with the ethylenically unsaturated monomer to form part of the polymer segment and one or more polyether polyol segments, the polymer extending polyol segment being compatible with the liquid polyol medium in which it is dispersed, thereby stabilizing the dispersion. The concept of synthesizing similar macromers is known, and references disclosing stabilizer precursors (or macromers) for polymer polyols include, for example, U.S. Pat. nos. 4,550,194, 4,652,589, and 4,997,857. The stabilizer precursors of U.S. Pat. No. 4,997,857 are characterized by these four features: (1) they are prepared from starting polyols having a functionality of greater than 4; (2) they have at least 60% of remaining unsaturated bonds; (3) they have a viscosity of greater than 2000 centipoise at 25 ℃; and (4) the starting polyol is capped with ethylene oxide and/or the adduct formed between the starting polyol and the reactive unsaturated compound is capped with ethylene oxide.
CN1143874A describes reacting a polyol with a cyclic dicarboxylic acid anhydride not containing any polymerizable double bond and then reacting the adduct thus obtained with an epoxide compound containing a polymerizable double bond. The resulting macromers have a nominal molecular weight of at least 4000 and are useful for preparing polymer polyols by polymerizing at least one ethylenically unsaturated monomer in a base polyol in the presence of a polymerization initiator and a macromer, the resulting polymer polyols having good stability.
There are many ways to reduce the viscosity of polymer polyols, such as: the preformed stabilizer (PFS) is particularly useful for preparing polymer polyols having lower viscosities at high solids contents. In the preformed stabilizer process, a macromer is reacted with monomers to form a copolymer consisting of macromer and monomers. These copolymers comprising macromers and monomers are commonly referred to as pre-formed stabilizers (PFS). The reaction conditions may be controlled such that a portion of the copolymer may precipitate out of solution to form a solid. In many applications, dispersions having a low solids content (e.g., 3 to 15% by weight) are obtained. The reaction conditions are preferably controlled to produce small particle sizes, thereby enabling the particles to act as "seeds" in the polymer polyol reaction.
When high-solid content polymeric polyols are prepared, improvements are often made on the macromers to improve the dispersion effect and reduce the viscosity of the system. In the prior patents, the polyether polyol for synthesizing the macromonomer is mainly screened according to an initiator for synthesizing the polyether polyol so as to meet the effect of multi-branching and have good stabilizing effect in the final dispersion system. While high functionality starters tend to be relatively limited, as is conventional: glycerol, pentaerythritol, sorbitol, sucrose, amine starters, etc., but cannot be broken through by their fixed functionality.
Disclosure of Invention
In order to solve the technical problems in the prior art, the first aspect of the present invention provides a method for preparing a high functionality polyether polyol, which method produces a polyether polyol having more functionality and more branching than the initiator used therein.
According to the second aspect of the invention, the method for preparing the macromonomer enables the prepared macromonomer to have higher functionality and more branched chains by adopting the polyether polyol with high functionality and high branched chains provided by the first aspect, and the stability of the macromonomer on the polymer polyol is obviously improved.
In a third aspect of the present invention, a method for preparing a polymer polyol is provided.
According to a first aspect of the present invention, the process for the preparation of the high functionality polyether polyol comprises reacting a polyol with an alkylene oxide and an alkanol oxide in the presence of a catalyst to form the polyether polyol.
According to some embodiments of the invention, the molar ratio of the epoxyalkanol to the polyol is (0.1-10):1, e.g., 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4: 1. 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, and any value in between.
According to some embodiments of the invention, the molar ratio of the epoxyalkanol to the polyol is (0.5-8): 1.
According to some embodiments of the invention, the molar ratio of the epoxyalkanol to the polyol is (2-5): 1.
According to some embodiments of the present invention, the addition of the epoxyalkanol can form more branched monomers to achieve chain extension, thereby increasing the inherent functionality and number of branches of the polyether polyol.
According to some embodiments of the invention, the alkylene oxide may be added simultaneously with the alkylene oxide during the initial reaction, or may be added during the late stage of the reaction.
According to some embodiments of the invention, the temperature of the reaction is between 80 and 150 ℃, preferably between 90 and 140 ℃, more preferably between 110 and 130 ℃.
According to some embodiments of the invention, the polyol is selected from one or more of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose and glycerol.
According to some embodiments of the invention, the alkylene oxide is selected from C2-C6One or more of the alkylene oxides of (a).
According to some embodiments of the invention, the alkylene oxide is selected from one or more of ethylene oxide, propylene oxide and butylene oxide.
According to some embodiments of the invention, the alkylene oxides are ethylene oxide and propylene oxide, wherein the ethylene oxide is 5-20% by mass.
According to some embodiments of the invention, the alkylene oxide is selected from C3-C8One or more of the epoxyalkanols of (a).
According to some embodiments of the invention, the epoxyalkanol is selected from one or more of epoxypropanol, epoxybutanol and epoxypentanol.
According to some embodiments of the invention, the catalyst is selected from one or more of a base catalyst, a DMC catalyst and a phosphazene catalyst.
According to some embodiments of the invention, the base catalyst comprises potassium hydroxide, cesium hydroxide, sodium hydroxide, potassium methoxide, and the like.
According to some embodiments of the invention, the catalyst concentration when base catalysis is used is the mass ratio of polyether polyols: 0.1-0.4%, preferably 0.15-0.3%. The concentration of the catalyst in the DMC catalytic synthesis is the mass ratio of polyether polyol: 20 to 200ppm, preferably 25 to 100 ppm. When the phosphazene catalyst is used for synthesis, the concentration of the catalyst is the mass ratio of polyether polyol: 0.1 to 0.4%, preferably 0.1 to 0.3%.
According to some embodiments of the invention, the process further comprises a post-treatment step comprising refining with an acid, preferably an organic acid and a mineral acid, such that the potassium ion in the final product is 10ppm or less, preferably less than 5 ppm.
According to some embodiments of the present invention, the polyether polyol has a number average molecular weight of 3000-.
According to some embodiments of the invention, the polyether polyol has an average functionality of greater than or equal to 3.0, preferably from 4 to 11.
According to some embodiments of the invention, the length of each branch of the polyether polyol is the same or different, preferably the longest branch length is 10-1, more preferably 4-1, compared to the shortest branch length.
According to some embodiments of the invention, the primary hydroxyl content of the polyether polyol is from 10 to 90% of the total hydroxyl content.
According to some embodiments of the invention, the acid is selected from the group consisting of carboxylic acid, sulfonic acid, thiocarboxylic acid, hydrochloric acid, sulfuric acid, phosphoric acid, and the like.
According to a second aspect of the present invention, the method for preparing the macromonomer comprises preparing the macromonomer using the polyether polyol prepared by the method of the first aspect.
According to some embodiments of the invention, the method comprises introducing unsaturated double bonds in the polyether polyol to produce the macromer.
According to some embodiments of the invention, introducing unsaturated double bonds in the polyether polyol comprises: introducing double bonds using an esterification reaction of a polyether polyol with an acid or an anhydride, wherein the anhydride is selected from one or more of maleic anhydride, methacrylic acid, acrylic acid and itaconic acid.
According to some embodiments of the invention, introducing unsaturated double bonds in the polyether polyol comprises: introducing double bonds using a polyether polyol by reacting with an isocyanate containing double bonds, wherein the isocyanate containing double bonds is selected from one or more of isopropenyl-alpha, alpha-dimethylbenzyl isocyanate and Isocyanatoethylmethacrylate (IEM).
According to some embodiments of the invention, introducing unsaturated double bonds in the polyether polyol comprises: introducing double bonds by coupling a double bond containing molecule with an isocyanate using a polyether polyol, wherein the double bond containing molecule is selected from one or more of 2-hydroxymethyl acrylate and hydroxypropyl methacrylate.
According to some embodiments of the invention, introducing unsaturated double bonds in the polyether polyol comprises: the double bond is introduced by reacting a polyether polyol with an acid anhydride to form a carboxylic acid group and then reacting the carboxylic acid group with a glycidyl ester containing a double bond.
According to some embodiments of the present invention, the macromonomer can be obtained by reacting a polyether polyol with a cyclic dicarboxylic anhydride not containing any polymerizable double bond, and then using this adduct to react with an epoxide compound containing a polymerizable double bond, as described in patent CN 1354764. Reference may also be made to U.S. Pat. No. 4,550,194 for reacting a polyol with maleic anhydride in the presence of calcium naphthenate and cobalt naphthenate as catalysts, and reacting the resulting carboxylic acid structure with an alkylene oxide such as ethylene oxide or propylene oxide. And polyether polyol and micromolecules containing unsaturated double bonds can be connected into the polyether chain segment by using isocyanate such as MDI or TDI in CN101809086, and 2-hydroxymethyl acrylate reacts with TDI and then reacts with polyether to obtain the macromonomer. The macromolecular monomer can also be prepared by reacting polyether with isocyanate containing unsaturated double bond in CN100500736 to achieve the effect of introducing double bond.
According to some embodiments of the present invention, in order to further increase the functionality and the number of branches of the macromonomer, a polyfunctional isocyanate or epoxy condensation reaction, such as a condensation reaction of the macromonomer using a bisphenol a epoxy resin, or a condensation reaction of isocyanate in MDI with hydroxyl in the macromonomer, may be used to further increase the molecular weight and further increase the branching degree.
According to some embodiments of the invention, the condensation may be performed before or after the introduction of the double bond.
Compared with the conventional prepared macromonomer, the macromonomer with high functionality and high branched chain synthesized by the invention has better space volume and achieves better dispersion effect.
According to a third aspect of the present invention, the method for producing a polymer polyol comprises the steps of:
s1: pre-reacting a macromonomer prepared according to claim 5 or 6 with an unsaturated monomer in a solvent in the presence of a first initiator and a chain transfer agent to form a pre-reactant;
s2: reacting the pre-reactant of step S1 with a base polyether polyol and an unsaturated monomer in the presence of a second initiator to form the polymer polyol.
According to some embodiments of the invention, the first initiator and the second initiator are the same or different and are each independently selected from one or more of alkyl and aryl hydroperoxides, persulfates, perborates, percarbonates and azo compounds.
According to some embodiments of the invention, the first initiator and the second initiator comprise, for example: hydrogen peroxide, di (tert-butyl) peroxide, tert-butyl peroxydiethylacetate, tert-butyl peroctoate, tert-butyl peroxyisobutyrate, tert-butyl peroxide, tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, dimethyl azobisisobutyrate and the like. Preference is given in the context of the present invention to azobisisobutyronitrile, dimethyl azobisisobutyrate and tert-butylperoxy-2-ethylhexanoate.
According to some embodiments of the invention, the unsaturated monomer is selected from one or more of aliphatic conjugated dienes, vinylidene aromatic monomers, ethylenically unsaturated nitriles, and ethylenically unsaturated amides.
According to some embodiments of the invention, the unsaturated monomer comprises an aliphatic conjugated diene, such as butadiene, isoprene; monovinylidene aromatic monomers such as styrene, alpha-methylstyrene, (tert-butyl) styrene chlorostyrene, cyanostyrene and bromostyrene; α, β -ethylenically unsaturated nitriles and amides such as baccarat, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide and the like; vinyl esters such as ethyl acetate; vinyl ethers, vinyl ketones, vinyl and vinylidene halides, and various other ethylenically unsaturated materials copolymerizable with the above-described monomeric adducts or reactive monomers.
According to some embodiments of the invention, the unsaturated monomer is selected from one or more of a vinylidene aromatic monomer and an ethylenically unsaturated nitrile.
According to some embodiments of the present invention, the unsaturated monomers are acrylonitrile and styrene, wherein the mass ratio of acrylonitrile to styrene is 1 (0.5-3), preferably 1 (1.5-2.5).
According to some embodiments of the invention, the amount of acrylonitrile and the comonomer of styrene, acrylonitrile, is about 20-50%, preferably 30-50% of the comonomer mixture, and the corresponding styrene is 50-80%, preferably 70-60% of the mixture.
According to some embodiments of the invention, the ratio of acrylonitrile to styrene in the monomer mixture is about 25: 75 to 55:45, more particularly 30:70 to 40: 60.
According to some embodiments of the invention, the chain transfer agent is selected from one or more of methanol, ethanol, butanol, isopropanol, and mercaptans.
According to some embodiments of the invention, the initiator is selected from one or more of alkyl and aryl hydroperoxides, persulfates, perborates, percarbonates and azo compounds.
According to some embodiments of the present invention, the azo-based initiator may be used to synthesize a polymer having a low viscosity and a stable product quality, and the polymer polyol may have a high viscosity using a peroxide-based initiator, but the peroxide-based initiator may be used in a smaller amount than the azo-based initiator.
According to some embodiments of the invention, the preparation of the polymer polyol is carried out in a solvent that does not dissolve the polymer polyol. Solvents include, but are not limited to: benzene, toluene, ethylbenzene, xylene, hexane, ethyl acetate, butyl acetate, and the like.
According to some embodiments of the present invention, the base polyether polyol is initiated with glycerol and has a molecular weight of 2000-4000.
According to some embodiments of the present invention, in step S1, the pre-reaction temperature is 80 to 140 ℃, preferably 90 to 120 ℃, and the reaction time is 1 to 5 hours, preferably 1.5 to 3 hours.
According to some embodiments of the present invention, in step S2, the reaction temperature is 80-140 deg.C, preferably 90-140 deg.C, more preferably 115-135 deg.C, and the reaction time is 1-5h, preferably 1.5-3.
According to some embodiments of the present invention, the macromer is present in an amount of 1 to 8%, preferably 2 to 6%, based on the total weight of the reactants.
According to some embodiments of the present invention, the unsaturated monomer is present in an amount of 20 to 50%, preferably 30 to 45%, based on the total weight of the reactants.
According to some embodiments of the present invention, the base polyether polyol is present in an amount of from 40 to 80%, preferably from 50 to 60%, based on the total weight of the reactants.
According to some embodiments of the present invention, the first initiator is present in an amount of 0.1 to 1 wt%, preferably 0.1 to 0.6 wt%, and more preferably 0.1 to 0.4 wt%, based on the total weight of the reactants, and the conversion rate decreases due to the low initiator concentration, and increases with the increase in initiator concentration, but does not increase after the increase in initiator concentration.
According to some embodiments of the present invention, the second initiator is present in an amount of 0.1 to 1 wt%, preferably 0.1 to 0.6 wt%, and more preferably 0.1 to 0.4 wt%, based on the total weight of the reactants, wherein an excessively low initiator concentration results in a decrease in conversion, and an increase in initiator concentration increases conversion, but no increase in conversion occurs after the increase in initiator concentration.
According to some embodiments of the present invention, the mass fraction of the chain transfer agent is 0.1 to 20%, preferably 0.1 to 10%, based on the total weight of the reactants.
According to some embodiments of the invention, the polymer polyol has a solids content of greater than or equal to 40% and a viscosity of less than 6000 centipoise at 25 ℃.
The polymer polyol provided by the invention is synthesized by adopting a continuous method, the solid content of the polymer polyol with polymerization degree is more than 40%, the viscosity is less than 6000 centipoise at 25 ℃, and the polymer polyol has better stability and lower viscosity compared with the conventional polymer polyol.
Detailed Description
The invention is further illustrated by the following examples. It is to be noted that the following examples are only for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention.
[ example 1 ] polyether polyol A
Sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 18.97mol propylene oxide, 2.27mol ethylene oxide and 2mol propylene oxide in the presence of 0.08mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol had a hydroxyl number of about 293, a number average molecular weight of about 1532 and a functionality of about 8.
The above polyether polyol was further obtained by using 224mol of propylene oxide and 34mol of ethylene oxide in the presence of a DMC catalyst (tert-butyl alcohol coordinated zinc hexacyanocobaltate complex) to give a hydroxyl number of about: 28, number average molecular weight of about: 16028 and a functionality of about 8.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 279:1, and the molar ratio of propylene oxide to sorbitol was 2: 1.
[ example 2 ] polyether polyol B
A sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 224mol propylene oxide, 13mol ethylene oxide and 3mol propylene oxide in the presence of 0.08mol potassium methoxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol had a hydroxyl number of about 36, a number average molecular weight of about 14025, and a functionality of about 9.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 237:1, and the molar ratio of propylene oxide to sorbitol was 3: 1.
[ example 3 ] polyether polyol C
Sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 18.9mol propylene oxide, 2.27mol ethylene oxide and 2mol propylene oxide in the presence of 0.08mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol has a hydroxyl number of about 300, a number average molecular weight of about 1496 and a functionality of about 8.
The above polyether polyol was further subjected to DMC catalyst (tert-butyl alcohol coordinated zinc hexacyanocobaltate complex) using 167mol of propylene oxide and 27mol of ethylene oxide to give a hydroxyl number of about: 36, number average molecular weight of about: 12466 and a functionality of about 8.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 215:1, and the molar ratio of propylene oxide to sorbitol was 2: 1.
[ example 4 ] polyether polyol D
Sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 18.9mol propylene oxide, 2.27mol ethylene oxide and 0.5mol propylene oxide in the presence of 0.08mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol has a hydroxyl number of about 300, a number average molecular weight of about 1496 and a functionality of about 8.
The above polyether polyol was further subjected to DMC catalyst (tert-butyl alcohol coordinated zinc hexacyanocobaltate complex) using 167mol of propylene oxide and 27mol of ethylene oxide to give a hydroxyl number of about: 33.8, number average molecular weight about: 12319, functionality of about 6.5.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 215:1, and the molar ratio of propylene oxide to sorbitol was 0.5: 1.
[ example 5 ] polyether polyol E
Sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 18.9mol propylene oxide, 2.27mol ethylene oxide and 10mol propylene oxide in the presence of 0.08mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol had a hydroxyl number of about 423, a number average molecular weight of about 2122, and a functionality of about 8.
The above polyether polyol was further subjected to DMC catalyst (tert-butyl alcohol coordinated zinc hexacyanocobaltate complex) using 167mol of propylene oxide and 27mol of ethylene oxide to give a hydroxyl number of about: 47.8, number average molecular weight about: 13022 and a functionality of about 16.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 215:1, and the molar ratio of propylene oxide to sorbitol was 10: 1.
[ example 6 ] polyether polyol F
Sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 18.9mol propylene oxide, 2.27mol ethylene oxide and 2.5mol propylene oxide in the presence of 0.08mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol had a hydroxyl number of about 304, a number average molecular weight of about 1567, and a functionality of about 8.5.
The above polyether polyol was further prepared by using 167mol of propylene oxide and 27.mol of ethylene oxide in the presence of a DMC catalyst (tert-butyl alcohol coordinated zinc hexacyanocobaltate complex) to give a hydroxyl number of about: 28, number average molecular weight of about: 12467 and a functionality of about 8.5.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 215:1, and the molar ratio of propylene oxide to sorbitol was 2.5: 1.
[ example 7 ] polyether polyol G
Sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 18.9mol propylene oxide, 2.27mol ethylene oxide and 3.5mol propylene oxide in the presence of 0.08mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol had a hydroxyl number of about 324, a number average molecular weight of about 1641, and a functionality of about 9.5.
The above polyether polyol was further subjected to DMC catalyst (tert-butyl alcohol coordinated zinc hexacyanocobaltate complex) using 167mol of propylene oxide and 27mol of ethylene oxide to give a hydroxyl number of about: 28, number average molecular weight of about: 12541 and a functionality of about 9.5.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide to sorbitol as raw materials was 215:1, and the molar ratio of propylene oxide to sorbitol was 3.5: 1.
[ COMPARATIVE EXAMPLE 1 ] POLYETHER POLYOL H
A sorbitol-initiated polyether polyol was prepared by reacting 1mol sorbitol, 172mol propylene oxide and 42mol ethylene oxide in the presence of 0.64mol potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol had a hydroxyl number of about 28, a number average molecular weight of about 12020, and a functionality of about 6.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide as raw materials to sorbitol was 214: 1.
Comparative example 2 polyether polyol I
1mol of glycerol, 68.97mol of propylene oxide and 15.9mol of ethylene oxide are reacted at 115 ℃ in the presence of 0.25mol of potassium hydroxide catalyst to give a polyether polyol which is started with glycerol and purified to remove the catalyst. The resulting polyol has a hydroxyl number of about 36, a number average molecular weight of about 4675, and a functionality of about 3.
In this example, the molar ratio of the sum of the moles of propylene oxide and ethylene oxide as raw materials to glycerol was 85: 1.
[ example 8 ] macromonomer A
Prepared by heating polyol a (100 parts), isopropenyl-alpha, alpha-dimethylbenzyl isocyanate (TMI, 0.5 parts), diphenylmethane diisocyanate (MDI, 0.5 parts), and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 9 ] macromonomer B
Prepared by heating polyol B (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 10 ] macromonomer C
Prepared by heating polyol C (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 11 ] macromonomer D
Prepared by heating polyol D (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 12 ] macromonomer E
Prepared by heating polyol E (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 13 ] macromonomer F
Prepared by heating polyol F (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 14 ] macromonomer G
Prepared by heating polyol G (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 15 ] macromonomer H
Prepared by heating polyol H (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ example 16 ] macromonomer I
Prepared by heating polyol I (100 parts), TMI (0.5 parts), MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
Example 11: preparation of Polymer polyol
(1) Preparation of the prereactate:
the preparation of the pre-reactants was carried out using a two-stage reaction system comprising a continuous stirred tank reactor equipped with an impeller (first stage) and a plug flow reactor (second stage).
The macromonomers A, B, C, D, E, F, G, H and I prepared in examples 8 to 16 were each charged into a feed tank together with isopropanol, a mixture of Styrene (SM) and Acrylonitrile (AN), and the initiator ABIN azobisisobutyronitrile, and were passed from the feed tank through a series of static mixers in a continuously pumped manner, and then sequentially fed through feed pipes into a first reactor (continuous stirred tank reactor) and a second reactor (plug flow reactor) in series to allow thorough mixing reaction of the components, wherein the mixing reaction temperature of the two reactors was 120. + -. 1 ℃ and the residence time in the two reactors was 60 minutes. The pre-reactants PA, PB, PC, PD, PE, PF, PG, PH and PI from the second stage reactor were then passed through a cooler into a collection vessel.
The percentages of macromer, isopropanol, mixture of Styrene (SM) and Acrylonitrile (AN), and initiator are listed in table 1.
(2) Preparation of Polymer polyol:
the preparation of polymeric polyol was carried out using a two-stage reaction system comprising a continuous stirred tank reactor equipped with an impeller (first stage) and a plug flow reactor (second stage).
Respectively adding pre-reactants PA, PB, PC, PD, PE, PF, PG, PH and PI, base polyether polyol, a mixture of Styrene (SM) and Acrylonitrile (AN) and AN initiator AIBN azobisisobutyronitrile into a feed tank, passing the feed tank through a series of static mixers in a continuous pumping mode, then sequentially entering a first reactor (a continuous stirred tank reactor) and a second reactor (a plug flow reactor) in series through feed pipes to fully mix and react the components, wherein the mixing reaction temperature of the two reactors is 115 +/-1 ℃, the residence time of the two reactors in the reactors is 60 minutes, and passing the product polymer polyol from a second-stage reactor through a cooler to a collection container. The crude product was vacuum stripped to remove volatiles. The total weight% of polymer in the product was calculated by the monomer concentration measured in the vapor lead crude polymer polyol.
Wherein the percentages of the pre-reactants, the base polyether polyol G, the mixture of Styrene (SM) and Acrylonitrile (AN), and the initiator are listed in table 2.
Wherein the base polyether polyol G is a glycerol-initiated polyether polyol prepared by reacting 1mol of glycerol, 43mol of propylene oxide and 9mol of ethylene oxide in the presence of 0.16mol of potassium hydroxide catalyst at 115 ℃ and purified to remove the catalyst. The resulting polyol has a hydroxyl number of about 56, a number average molecular weight of about 3000, and a functionality of about 3.
Table 1:
| prereactants | PA | PB | PC | PD | PE | PF | PG | PH | P1 |
| Amount of isopropyl alcohol,% | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| Macromonomer A,%) | 24 | ||||||||
| Macromonomer B% | 24 | ||||||||
| Macromonomer C% | 24 | ||||||||
| Macromonomer D% | 24 | ||||||||
| Macromonomer E% | 24 | ||||||||
| Macromonomer F% | 24 | ||||||||
| Macromonomer G% | 24 | ||||||||
| Macromonomer H% | 24 | ||||||||
| Macromonomer I,% | 24 | ||||||||
| Monomer amount% | 15.9 | 15.9 | 15.9 | 15.9 | 15.9 | 15.9 | 15.9 | 15.9 | 15.9 |
| SM/AN (molar ratio) | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 |
| Initiator concentration% | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
Table 2:
it should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A process for preparing high-functionality polyether polyol includes reaction of polyol with alkylene oxide and alkanol under the action of catalyst to obtain polyether polyol.
2. The process according to claim 1, wherein the molar ratio of the epoxyalkanol to the polyol is (0.1-10) to 1, preferably (0.5-8) to 1, more preferably (2-5) to 1;
and/or the molar ratio of the alkylene oxide to the polyol is (200- & lt300) & gt 1;
and/or the temperature of the reaction is 80-150 ℃, preferably 90-140 ℃, more preferably 110-130 ℃.
3. The method according to claim 1 or 2, wherein the polyol is selected from one or more of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose and glycerol;
and/or the alkylene oxide is selected from C2-C6Preferably one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, more preferably ethylene oxide and propylene oxide, wherein the ethylene oxide is 5 to 20% by mass;
and/or the epoxyalkanol is selected from C3-C8Preferably selected from the group consisting of epoxypropanol, epoxybutanol and epoxypentanolOne or more of;
and/or the catalyst is selected from one or more of a base catalyst, a DMC catalyst and a phosphazene catalyst.
4. The process according to any one of claims 1 to 3, characterized in that the polyether polyol has a number average molecular weight of 3000-25000, preferably 4000-24000;
and/or the polyether polyol has an average functionality of greater than or equal to 3.0, preferably from 4 to 11;
and/or the length of each branch of the polyether polyol is the same or different, preferably the longest branch length is 10-1, more preferably 4-1, compared to the shortest branch length;
and/or the primary hydroxyl content of the polyether polyol is 10 to 90% of the total hydroxyl content.
5. A process for the preparation of a macromer comprising using the polyether polyol prepared according to the process of any one of claims 1 to 4 to form the macromer, preferably by introducing unsaturated double bonds in the polyether polyol to form the macromer.
6. The method of claim 5, wherein introducing unsaturated double bonds in the polyether polyol comprises: introducing double bonds using an esterification reaction of a polyether polyol with an acid or an anhydride, wherein the anhydride is selected from one or more of maleic anhydride, methacrylic acid, acrylic acid, and itaconic acid;
or introducing double bonds by reacting a polyether polyol with an isocyanate containing double bonds, wherein the isocyanate containing double bonds is selected from one or more of isopropenyl-alpha, alpha-dimethylbenzyl isocyanate and isocyanatoethylmethacrylate;
or introducing double bonds by coupling a double bond-containing molecule with an isocyanate using a polyether polyol, wherein the double bond-containing molecule is selected from one or more of 2-hydroxymethyl acrylate and hydroxypropyl methacrylate;
or the double bond is introduced by reacting polyether polyol with acid anhydride to form carboxylic acid group and then reacting with glycidyl ester containing double bond.
7. A method of preparing a polymer polyol, comprising the steps of:
s1: pre-reacting a macromonomer prepared according to claim 5 or 6 with an unsaturated monomer in a solvent in the presence of a first initiator and a chain transfer agent to form a pre-reactant;
s2: reacting the pre-reactant of step S1 with a base polyether polyol and an unsaturated monomer in the presence of a second initiator to form the polymer polyol.
8. The method of claim 7, wherein the first and second initiators are the same or different and are each independently selected from one or more of alkyl and aryl hydroperoxides, persulfates, perborates, percarbonates, and azo compounds;
and/or the unsaturated monomer is selected from one or more of aliphatic conjugated diene, vinylidene aromatic monomer, ethylenically unsaturated nitrile and ethylenically unsaturated amide, preferably from one or more of vinylidene aromatic monomer and ethylenically unsaturated nitrile, more preferably acrylonitrile and styrene, wherein the mass ratio of acrylonitrile to styrene is 1 (0.5-3), preferably 1 (1.5-2.5);
and/or the chain transfer agent is selected from one or more of methanol, ethanol, butanol, isopropanol and mercaptan;
and/or the solvent is selected from one or more of benzene, toluene, ethylbenzene, xylene, hexane, ethyl acetate and butyl acetate;
and/or the base polyether polyol takes glycerol as an initiator and has a molecular weight of 2000-4000.
9. The process according to claim 7 or 8, wherein in step S1, the pre-reaction temperature is 80-140 ℃, preferably 90-120 ℃, and the reaction time is 1-5h, preferably 1.5-3 h;
and/or in step S2, the reaction temperature is 80-140 ℃, preferably 90-140 ℃, more preferably 115-135 ℃, and the reaction time is 1-5h, preferably 1-1.5 h;
and/or the content of the macromonomer is 1-8%, preferably 2-6% based on the total weight of the reactants; the content of the unsaturated monomer is 20-50%, preferably 30-45%; the content of the basic polyether polyol is 40-80%, preferably 50-60%; the mass fraction of the first initiator is 0.1-1%, preferably 0.1-0.6%, more preferably 0.1-0.4%, the mass fraction of the second initiator is 0.1-1%, preferably 0.1-0.6%, more preferably 0.1-0.4%, and the mass fraction of the chain transfer agent is 0.1-20%, preferably 0.1-10%.
10. The process of any one of claims 7-9, wherein the polymer polyol has a solids content of greater than or equal to 40% and a viscosity of less than 6000 centipoise at 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911019038.2A CN112708124B (en) | 2019-10-24 | 2019-10-24 | Preparation method and application of high-functionality polyether polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911019038.2A CN112708124B (en) | 2019-10-24 | 2019-10-24 | Preparation method and application of high-functionality polyether polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112708124A true CN112708124A (en) | 2021-04-27 |
| CN112708124B CN112708124B (en) | 2022-12-09 |
Family
ID=75540341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911019038.2A Active CN112708124B (en) | 2019-10-24 | 2019-10-24 | Preparation method and application of high-functionality polyether polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112708124B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106041A (en) * | 2022-06-07 | 2022-09-27 | 万华化学集团股份有限公司 | Reaction system for preparing polymer polyol and method for preparing polymer polyol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3823201A (en) * | 1972-12-04 | 1974-07-09 | Basf Wyandotte Corp | Highly-stable graft copolymer dispersions in polyols containing unsaturation and polyurethanes prepared therefrom |
| CN103539932A (en) * | 2013-09-11 | 2014-01-29 | 江苏雅克科技股份有限公司 | Preparation method and applications of reaction type Mannich polyether polyol with permanent flame retardant effect |
| CN105026452A (en) * | 2013-03-04 | 2015-11-04 | 拜耳材料科学有限公司 | High functionality isocyanates as polymer polyol stabilizers and the polymer polyols prepared from these stabilizers |
-
2019
- 2019-10-24 CN CN201911019038.2A patent/CN112708124B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3823201A (en) * | 1972-12-04 | 1974-07-09 | Basf Wyandotte Corp | Highly-stable graft copolymer dispersions in polyols containing unsaturation and polyurethanes prepared therefrom |
| CN105026452A (en) * | 2013-03-04 | 2015-11-04 | 拜耳材料科学有限公司 | High functionality isocyanates as polymer polyol stabilizers and the polymer polyols prepared from these stabilizers |
| CN103539932A (en) * | 2013-09-11 | 2014-01-29 | 江苏雅克科技股份有限公司 | Preparation method and applications of reaction type Mannich polyether polyol with permanent flame retardant effect |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106041A (en) * | 2022-06-07 | 2022-09-27 | 万华化学集团股份有限公司 | Reaction system for preparing polymer polyol and method for preparing polymer polyol |
| CN115106041B (en) * | 2022-06-07 | 2023-12-29 | 万华化学集团股份有限公司 | Reaction system for preparing polymer polyol and method for preparing polymer polyol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112708124B (en) | 2022-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101215139B1 (en) | Methacrylates as stabilizers for polymer polyols | |
| US8383733B2 (en) | Low-viscosity polymer polyols characterized by a high hydroxyl number | |
| KR100550881B1 (en) | Polymer Polyol and Stabilizer Systems | |
| JP6258358B2 (en) | High functionality isocyanates as polymer polyol stabilizers and polymer polyols prepared from these stabilizers | |
| KR101985046B1 (en) | Hybrid phd/pmpo polyols for polyurethane foam applications | |
| EP1675885B1 (en) | Unsaturated macromers for preparing preformed stabilizers and polymer polyols | |
| EP3512888B1 (en) | Improved polymer polyol quality | |
| EP2622011A2 (en) | Polymer polyols prepared from nitrile-free azo-initiators | |
| CN112708037B (en) | Polymer polyol with wide particle size distribution, and preparation method and application thereof | |
| CN113557251B (en) | Process for preparing polymer polyols | |
| CN112708124B (en) | Preparation method and application of high-functionality polyether polyol | |
| CN114479050B (en) | Stabilizer precursor and preparation method and application thereof | |
| CN115232257B (en) | Preparation method of low-viscosity polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol | |
| US11319401B1 (en) | Process for preparing polymer polyols | |
| CN117964892A (en) | Modified macromer, preparation method thereof and application thereof in polymer polyol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |