Bio-based haplotype dispersant as well as preparation method and application thereof

Abstract

The invention provides a bio-based haplotype dispersant as well as a preparation method and application thereof, and the method comprises the following steps: carrying out transesterification on a compound A as shown in a formula 1 and a polyhydroxy compound to generate a compound B as shown in a formula 2; and carrying out addition reaction on the compound B as shown in the formula 2 and allyl glycidyl ether to generate the bio-based haplotype dispersant as shown in a formula 3. The invention provides a dispersant with high activity, low viscosity, high dispersion efficiency and flexibly controllable reaction activity by taking renewable resources as raw materials.

Description

Technical Field

[0001] This application relates to the field of green polymer materials, and more specifically to a bio-based monomeric dispersant and its preparation method, as well as to a polymeric polyol prepared using the monomeric dispersant, and the use of the polymeric polyol in polyurethane synthesis. Background Technology

[0002] Polymer-grafted polyether polyols (POPs) are a class of polymeric materials with special structures. They are typically produced by the free radical polymerization of unsaturated monomers containing carbon-carbon double bonds in a polyether polyol system containing a polymeric dispersant stabilizer. Polymer polyols (POPs) are key materials in the polyurethane industry, widely used in the production of high-resilience foams, flexible foams, elastomers, and other products. Their main function is as an organic filler in flexible polyurethane foam systems to improve the mechanical properties of the final product, such as hardness, load-bearing capacity, and tensile strength. Currently, the industrial production of high-solids-content (typically exceeding 40 wt%) POPs faces a critical challenge: as the content of vinyl polymer particles (such as styrene-acrylonitrile copolymers) in the system increases, the viscosity of the system rises sharply, leading to a severe deterioration in the product's processing performance. To resolve this "high solids-high viscosity" contradiction, macromolecular monomer dispersant stabilizer technology has become the mainstream solution in the industry. These dispersants are typically polymers with reactive unsaturated double bonds and a polyether-loving polyol structure. They effectively prevent particle aggregation by forming a stable interfacial film at the interface between the continuous phase (polyether polyol) and the dispersed phase (polymer particles), thus maintaining the low viscosity of the system at high solids content. The reactivity of the unsaturated double bonds determines the strength of their binding with the polymer particles, while hydrophilicity (i.e., the number of hydroxyl groups) affects their compatibility with the bulk polyether polyol.

[0003] Existing macromonomer dispersants mainly include two types: maleic anhydride-type macromonomers and isocyanate-type macromonomers. The former utilizes the ring-opening reaction of polyether with maleic anhydride to form macromonomers with unsaturated double bond structures and polyol structures; the latter utilizes the reaction of isocyanate with hydroxy acrylates, and the remaining -NCO reacts with polyether to obtain macromonomer dispersants containing unsaturated double bonds and polyols. These macromonomer dispersants are all products synthesized from petroleum raw materials, and have the following inherent defects: (1) Non-renewable raw materials: their synthesis heavily relies on petroleum-based chemicals, which contradicts the global trend of sustainable development and the industry's need to reduce carbon footprint. (2) Contradiction between molecular structure and viscosity: to ensure good dispersion stability, traditional macromonomers often have high molecular weights, which directly leads to their own high viscosity. When used for POP synthesis, it will significantly increase the initial viscosity of the entire system, which is not conducive to the preparation and subsequent processing of high-solids, low-viscosity products. (3) Reactivity and functional group limitations: The content and position of reactive double bonds in dispersant molecules are usually difficult to control, and they may interact with other functional groups such as hydroxyl groups in synthesis or application, which limits their applicability and reaction efficiency in different formulation systems.

[0004] Therefore, developing a novel dispersant based on renewable resources, possessing both low viscosity and high dispersion efficiency, and with flexibly controllable reactivity, is of urgent need and significant importance for promoting the greening and technological upgrading of polymer polyols (POPs), especially high-performance, high-solids-content, and low-viscosity POP products. There is a pressing need to synthesize a highly efficient, low-viscosity dispersant using a non-petroleum-derived, widely available, and inexpensive raw material, as an ideal replacement for existing macromolecular monomer dispersants, and for use in the preparation of high-solids, low-viscosity POPs. Summary of the Invention

[0005] To address the aforementioned problems, the inventors of this application, through extensive and in-depth research, have successfully developed a novel bio-based monomeric dispersant and its preparation method. Unexpectedly, it was discovered that this specially designed monomeric dispersant can meet the requirements of the field and effectively solve a long-standing problem that has been difficult to solve in the prior art.

[0006] The first aspect of this application provides a method for preparing a bio-based monomeric dispersant, the method comprising: Step 1: Compound A, as shown in Formula 1, undergoes an transesterification reaction with a polyhydroxy compound to generate compound B, as shown in Formula 2, wherein the molecular formula of the polyhydroxy compound is RO-(OH). n R0 represents a straight-chain or branched n-valent C3-C12 alkyl group, and n hydroxyl groups in the polyhydroxy compound are covalently connected to R0, where n is an integer from 3 to 12;

[0007] Formula 1 Formula 2

[0008] In Formulas 1 and 2, R1 represents a C6-C22 alkenyl group containing at least one hydroxyl group and at least one carbon-carbon double bond; m is an integer less than n, and m ≥ 1; Step 2: Compound B shown in Formula 2 undergoes an addition reaction with allyl glycidyl ether to generate the bio-based monomeric dispersant shown in Formula 3;

[0009] Formula 3

[0010] Where p is an integer less than n, p≥1, and n≥(m+p).

[0011] According to one embodiment of the first aspect of this application, the polyhydroxy compound used in step 1 is selected from one or more of the following: glycerol, pentaerythritol, erythritol (butanetetrol), xylitol (pentanetol), galactitol (hexanethyl alcohol), diglycerol, and bis(pentaerythritol).

[0012] According to another embodiment of the first aspect of this application, in the transesterification reaction of step 1, the molar ratio of compound A shown in Formula 1 to the polyhydroxy compound is 1:3.3 to 1:20.

[0013] According to another embodiment of the first aspect of this application, in the addition reaction of step 2, the molar ratio of compound B shown in Formula 2 to allyl glycidyl ether is 1:1 to 1:16.

[0014] According to another embodiment of the first aspect of this application, compound A represented by Formula 1 is derived from castor oil, and in Formula 1, R1 is 11-hydroxy-heptadec-8-enyl.

[0015] According to another embodiment of the first aspect of this application, the polyhydroxy compound used in step 1 is glycerol, pentaerythritol, or a combination of the two.

[0016] According to another embodiment of the first aspect of this application, in the transesterification reaction of step 1, the molar ratio of compound A shown in Formula 1 to the polyhydroxy compound is 1:3.3 to 1:9.3.

[0017] According to another embodiment of the first aspect of this application, in the addition reaction of step 2, the molar ratio of compound B shown in Formula 2 to allyl glycidyl ether is 1:1 to 1:4.

[0018] According to another embodiment of the first aspect of this application, the transesterification reaction in step 1 is carried out in the presence of an organic solvent.

[0019] According to another embodiment of the first aspect of this application, the organic solvent is selected from one or more of the following: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), formamide, dimethyl sulfoxide (DMSO), N-methylpyrrolidone, sulfolane, and acetonitrile.

[0020] According to another embodiment of the first aspect of this application, the mass ratio of the organic solvent to the polyhydroxy compound is 1:10 to 1:20.

[0021] According to another embodiment of the first aspect of this application, the transesterification reaction in step 1 is carried out in the presence of a basic catalyst.

[0022] According to another embodiment of the first aspect of this application, the alkaline catalyst includes one or more of the following: alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal alkoxide, and alkaline earth metal alkoxide.

[0023] According to another embodiment of the first aspect of this application, the amount of alkaline catalyst is 0.3-0.8 by mass, based on the total mass of all materials in the transesterification reaction.

[0024] According to another embodiment of the first aspect of this application, the addition reaction in step 2 is carried out in the presence of a bimetallic cyanide complex (DMC) catalyst.

[0025] According to another embodiment of the first aspect of this application, the amount of the bimetallic cyanide complex catalyst is 0.01-0.1 by mass, based on the total mass of all materials in the addition reaction.

[0026] According to another embodiment of the first aspect of this application, in step 1, a polyhydroxy compound is dissolved in an organic solvent to form an organic solution, and then the organic solution is added dropwise to a mixture of compound A shown in Formula 1 and an alkaline catalyst.

[0027] According to another embodiment of the first aspect of this application, in step 1, an organic solution is added dropwise to a mixture of compound A of formula 1 and an alkaline catalyst over a period of 0.5-1 hour.

[0028] According to another embodiment of the first aspect of this application, the reaction temperature of the transesterification reaction in step 1 is 120-180°C.

[0029] According to another embodiment of the first aspect of this application, the duration of the transesterification reaction in step 1 is 5-8 hours.

[0030] According to another embodiment of the first aspect of this application, in step 1, after the transesterification reaction is completed, the organic solvent is removed under vacuum conditions before the addition reaction in step 2 is carried out.

[0031] According to another embodiment of the first aspect of this application, the addition reaction in step 2 is carried out under an inert atmosphere.

[0032] According to another embodiment of the first aspect of this application, the reaction temperature of the addition reaction in step 2 is 80-120°C.

[0033] According to another embodiment of the first aspect of this application, the reaction time of the addition reaction in step 2 is 2-6 hours.

[0034] A second aspect of this application provides a bio-based monomeric dispersant having the structure shown in Formula 3:

[0035] Formula 3

[0036] Where R0 represents a straight-chain or branched n-valent C3-C12 alkyl group; n is an integer between 3 and 12, m is an integer less than n and m≥1, p is an integer less than n and p≥1, and n≥(m+p); R1 represents a C6-C22 alkenyl group containing at least one hydroxyl group and at least one carbon-carbon double bond.

[0037] According to one embodiment of the second aspect of this application, the bio-based monomeric dispersant is prepared by the method described in any embodiment of the first aspect of this invention.

[0038] The third aspect of this application provides a polymeric polyol (POP) prepared using a bio-based monomeric dispersant from the second aspect of this application.

[0039] The fourth aspect of this application provides a polyurethane material prepared by reacting a polymeric polyol from the third aspect of this invention with a polyisocyanate compound.

[0040] In the detailed description section below, the method and polymer product of this application will be further described with reference to the accompanying drawings. Attached Figure Description

[0041] Figure 1 This diagram illustrates the reaction mechanism of a method for preparing a bio-based monomeric dispersant according to an exemplary embodiment of this application. Figure 2 This application shows castor oil used in one embodiment.1 H NMR spectrum; Figure 3 This application shows the transesterification reaction product in one embodiment. 1 H NMR spectrum; Figure 4 This application shows a castor oil-based monomer dispersant prepared in one embodiment. 1 H NMR spectrum; Figure 5 The particle size distribution of a polymeric polyol (POP) prepared according to an embodiment of this application is shown. Figure 6 This image shows a scanning electron microscope (SEM) image of a polymeric polyol (POP) prepared according to one embodiment of this application. Detailed Implementation

[0042] The “range” disclosed in this document takes the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this way are inclusive and composable; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is also expected that ranges of 60-110 and 80-120 are also included. Furthermore, if the minimum range values ​​are listed as 1 and 2, and if the maximum range values ​​are listed as 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0043] In this application, unless otherwise stated, the numerical range "ab" is a shortened representation of any combination of real numbers from a to b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is simply a shortened representation of these numerical combinations.

[0044] Unless otherwise specified in this application, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0045] Unless otherwise specified, all technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0046] In this application, unless otherwise specified, the term "comprising" as used herein can be either open-ended or closed-ended. For example, "comprising" may mean that it may also include other components not listed, or it may only include the listed components.

[0047] One inventive aspect of this application lies in the development of a monomeric dispersant with a novel structure. This dispersant uses renewable resources as raw materials and has a specially designed molecular structure. The molecule contains double bonds and hydroxyl groups, both of which exhibit excellent activity. It possesses the low viscosity, high activity, and applicability urgently needed in the art. Compared to existing macromolecular monomeric dispersants, the dispersant prepared by this invention has a smaller molecular weight and viscosity. As can be seen from its molecular formula, it belongs to the category of "monomer" rather than "macromolecule" or "polymer," hence it is called a "monomeric dispersant."

[0048] The compound A represented by Formula 1, used as a raw material in this invention, is a glycerol ester of a C3-C23 alkenyl carboxylic acid containing at least one hydroxyl group and at least one carbon-carbon double bond. According to one embodiment of this application, the R1 group in Formula 1 may contain 1-6 hydroxyl groups, for example, 1-4 hydroxyl groups, or 1-3 hydroxyl groups, or 1-2 hydroxyl groups. According to another embodiment of this application, the R1 group in Formula 1 may contain 1-6 carbon-carbon double bonds, for example, 1-4 carbon-carbon double bonds, or 1-3 carbon-carbon double bonds, or 1-2 carbon-carbon double bonds. According to yet another embodiment of this application, the R1 group in Formula 1 contains 2-22 carbon atoms, or 4-20 carbon atoms, or 6-19 carbon atoms, or 8-18 carbon atoms, or 12-18 carbon atoms, or 16-18 carbon atoms.

[0049] According to a preferred embodiment, the compound of formula 1 used as a raw material in this invention is tris(ricinoleic acid) glyceride. For example, it may be derived from castor oil. The content of tris(ricinoleic acid) glyceride in the castor oil may be 80-90 wt%, for example 81-85 wt%, while the remaining components may include glycerides of the following long-chain aliphatic organic acids: oleic acid, linoleic acid, palmitic acid, stearic acid, etc. Castor oil can be used directly as a raw material for preparing the monomeric dispersant of this invention without separating components from the castor oil that are different from tris(ricinoleic acid) glyceride.

[0050] According to another embodiment of this application, the polyhydroxy compound used to react with compound A of formula 1 has the molecular formula RO-(OH). n This indicates that R0 represents a straight-chain or branched n-valent C3-C12 alkyl group, that is, the portion remaining after removing all n hydroxyl groups from the polyhydroxy compound. According to another embodiment of this application, R0 contains 3-10 carbon atoms, or 3-8 carbon atoms, or 3-6 carbon atoms, or 3-4 carbon atoms. According to another embodiment of this application, the value of n (i.e., the number of hydroxyl groups contained in the polyhydroxy compound) is an integer from 3 to 12, for example, an integer from 3 to 10, or an integer from 3 to 8, or an integer from 3 to 6, or an integer from 3 to 4.

[0051] According to an exemplary embodiment of this application, the polyhydroxy compound is selected from one or more of the following: glycerol, pentaerythritol, erythritol (butanetetrol), xylitol (pentanetol), galactitol (hexanethyl alcohol), diglycerol, and bis(pentaerythritol).

[0052] For example in Figure 1 The reaction mechanism diagram shown illustrates the preparation process of the monomeric dispersant of the present invention using triglyceride (ricinoleic acid) and pentaerythritol as examples.

[0053] According to an exemplary embodiment of this application, in step 1, compound A of formula 1 undergoes an transesterification reaction with a polyhydroxy compound to generate compound B of formula 2. That is, in step 1, m R1-C(=O)-O- groups that were originally esterified with glycerol are converted to esterification with a hydroxyl group of the polyhydroxy compound, where m is an integer less than n, and m ≥ 1, preferably m is 1 or 2. More preferably, nm ≥ 1, or nm ≥ 2, or nm ≥ 3.

[0054] For example in Figure 1 In the flowchart shown, after the transesterification reaction of tri(ricinoleic acid)glyceride and pentaerythritol in step 1, mono(ricinoleic acid)pentaerythritol ester is generated, but di(ricinoleic acid)pentaerythritol ester or tri(ricinoleic acid)pentaerythritol ester may also be generated. According to a preferred embodiment of this application, the formation of tetra(ricinoleic acid)pentaerythritol ester is minimized in the transesterification reaction in step 1.

[0055] According to one embodiment of this application, in step 1, the molar ratio of compound A shown in Formula 1 to the polyhydroxy compound is 1:3.3 to 1:20, or 1:3.3 to 1:15, or 1:3.3 to 1:12, or 1:3.3 to 1:10, or 1:3.3 to 1:9.3, or 1:4 to 6, or the molar ratio can be within the range of values ​​obtained by combining any two of the above endpoints.

[0056] According to another embodiment of this application, the transesterification reaction in step 1 is carried out in the presence of an organic solvent. The organic solvent is selected from one or more of the following: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), formamide, dimethyl sulfoxide (DMSO), N-methylpyrrolidone, sulfolane, acetonitrile; preferably DMF.

[0057] According to another embodiment of this application, in the transesterification reaction of step 1, the mass ratio of the organic solvent to the polyhydroxy compound is 1:10 to 1:20, or 1:12 to 1:18, or 1:14 to 1:16.

[0058] According to another embodiment of this application, the transesterification reaction in step 1 is carried out in the presence of an alkaline catalyst, which includes one or more of the following: alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, and alkaline earth metal alkoxides. The alkali metals include lithium, sodium, potassium, rubidium, and cesium, and the alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. The metal alkoxides include methoxides, ethoxides, propoxides, or butoxides. Preferably, the alkaline catalyst is sodium methoxide, calcium hydroxide, or a mixture thereof.

[0059] According to another embodiment of this application, the amount of alkaline catalyst is 0.3-0.8% by mass, for example 0.4-0.7% by mass, or 0.5-0.6% by mass, based on the total mass of all materials in the transesterification reaction.

[0060] According to another embodiment of this application, the reaction temperature of the transesterification reaction in step 1 is 120-180°C, preferably 120-160°C, and more preferably 120-130°C. According to another embodiment of this application, the reaction duration of the transesterification reaction in step 1 is 5-8 hours, preferably 6-7 hours.

[0061] According to another embodiment of this application, a polyhydroxy compound is dissolved in an organic solvent to form an organic solution, and then the organic solution is added dropwise to a mixture of compound A of Formula 1 and an alkaline catalyst, for example, over a period of 0.5 to 1 hour.

[0062] According to another embodiment of this application, the transesterification reaction in step 1 can be carried out under an inert atmosphere, such as under a nitrogen atmosphere.

[0063] According to another embodiment of this application, after the transesterification reaction in step 1 is completed, the organic solvent is removed under vacuum conditions, for example, by heating under vacuum conditions, the temperature of which depends on the saturated vapor pressure of the organic solvent used at the corresponding vacuum level. According to another embodiment of this application, after removing the organic solvent, the material is further neutralized, extracted, and purified. Neutralization can be performed using an organic acid (e.g., acetic acid) or an inorganic acid (e.g., hydrochloric acid), extraction can be performed using methanol, n-hexane, or a mixture thereof, and purification can be carried out using rotary evaporation.

[0064] According to one embodiment of the present invention, in step 2, compound B represented by formula 2 undergoes an addition reaction with allyl glycidyl ether to generate a bio-based monomeric dispersant represented by formula 3.

[0065] Formula 3

[0066] Where p is an integer less than n, p≥1, preferably p is an integer between 1 and 2, more preferably p=1. And n≥(m+p), preferably n-(m+p)≥1, more preferably n-(m+p)≥2.

[0067] According to another embodiment of this application, in the addition reaction of step 2, the molar ratio of compound B shown in Formula 2 to allyl glycidyl ether is 1:1 to 1:16, preferably 1:1 to 1:12, more preferably 1:1 to 1:8, or 1:1 to 1:6, and most preferably 1:1 to 1:4.

[0068] According to another embodiment of this application, the addition reaction in step 2 is carried out under an inert atmosphere, such as nitrogen.

[0069] According to another embodiment of this application, the addition reaction in step 2 is carried out at a temperature of 80-120°C, for example, the reaction temperature can be 90-110°C or 100-105°C. According to another embodiment of this application, the duration of the addition reaction in step 2 is 2-6 hours, preferably 2-4 hours.

[0070] According to another embodiment of this application, the catalyst used in the addition reaction of step 2 is a bimetallic cyanide complex (DMC) catalyst. The DMC catalyst contains one or more transition metals, a cyano group (CN) as a ligand, and one or more other ligands. The transition metal is selected from one or more of the following metallic elements: zinc, cobalt, nickel, iron, molybdenum, manganese, tungsten, copper, aluminum, vanadium, lead, strontium, chromium, rhodium, ruthenium, and iridium, and these transition metal elements are in cationic form in the catalyst. The other ligands are selected from one or more of the following: fluoride ions, chloride ions, bromide ions, iodide ions, hydroxyl groups, hydroxide ions, nitrate ions, nitrite ions, oxygen ions, carbonyl groups, CO, acetate ions, sulfate ions, thiocyanate ions, CNO-, NCO-, C1-C6 carboxylate ions, water molecules, organic ligands, etc. The organic ligands may include one or more of the following: alcohols, such as methanol, ethanol, n-butanol, isobutanol, sec-butanol, tert-butanol, isopropanol, tert-amyl alcohol, etc.; ethers, such as dioxane, dioxapentane, tetrahydrofuran, butyl ether, ethylpropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, etc.; ketones, such as acetone, methyl ethyl ketone, 3-pentanone, 2-hexanone, etc.; esters, such as methyl formate, ethyl acetate, ethyl formate, etc.; aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, benzaldehyde, etc.; and may also include urea, amides, thioethers, various nitriles, etc. The types, functions, and preparation processes of DMC catalysts are known in the art. The bimetallic cyanide complex (DMC) catalyst is a known catalyst in the art and is commercially available.

[0071] According to another embodiment of this application, the amount of the bimetallic cyanide complex catalyst is 0.01-0.1% by mass, for example 0.02-0.08% by mass, or 0.03-0.06% by mass, or 0.04-0.05% by mass, based on the total mass of all materials in the addition reaction.

[0072] According to another embodiment of this application, in step 2, allyl glycidyl ether is added dropwise to the compound shown in Formula 2, for example, over a period of 0.1-1 hour. According to another embodiment of this application, after the addition reaction is complete, the catalyst is removed by filtration, and then unreacted allyl glycidyl ether is removed by, for example, rotary evaporation. The temperature used for the rotary evaporation can be 100-120°C.

[0073] The monomer dispersant prepared by this invention can be used to prepare polymeric polyols (POPs). For example, in the presence of the monomer dispersant, a reaction can occur in a mixture containing a polyether polyol, an initiator, and an olefinically unsaturated monomer to generate POPs.

[0074] According to one embodiment of this application, the polyether polyol may be a polyether polyol obtained by addition polymerization or condensation polymerization of one or more C2-C16 epoxides and / or one or more C2-C16 polyols (e.g., diols, triols, tetraols, etc.), such as a polyether polyol obtained by condensation polymerization of ethylene oxide and / or propylene oxide.

[0075] According to one embodiment of this application, the hydroxyl functionality of the polyether polyol used to prepare POP is 2-10, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, or within the range of any combination of the above two end values; the number average molecular weight of the polyether polyol is 1500-50000, for example, 2000-40000, or 2500-30000, or 3000-20000, or 3500-18000, or 4000-16000, or 5000-15000, or 6000-14000, or 7000-13000, or 8000-12000, or within the range of any combination of the above two end values.

[0076] According to one embodiment of this application, in the method for preparing POP, the olefinically unsaturated monomer is selected from one or more of the following: C2-C12 aliphatic olefins, C6-C16 aliphatic olefins, C1-C12 alkyl vinyl carboxylate, C1-C12 alkyl allyl carboxylate, (meth)acrylic acid, (meth)acrylate, (meth)acrylonitrile, and (meth)acrylamide. For example, the unsaturated monomer containing a carbon-carbon double bond may be selected from one or more of the following: styrene, vinyl formate, vinyl acetate, vinyl propionate, allyl acetate, (meth)acrylic acid, (meth)acrylate C1-C8 alkyl ester, (meth)acrylonitrile, and (meth)acrylamide.

[0077] According to one embodiment of this application, in the method for preparing POP, the weight ratio of the polyether polyol to the olefinically unsaturated monomer can be 1:10 to 10:1, for example 1:8 to 8:1, or 1:7 to 7:1, or 1:6 to 6:1, or 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or 1:1 to 3:2, or within a range of values ​​obtained by combining any two of the above end values. According to one embodiment, the unsaturated monomer containing carbon-carbon double bonds can be a mixture of styrene and acrylonitrile.

[0078] According to one embodiment of this application, when preparing the POP, the weight ratio of the monomeric dispersant of the present invention to the unsaturated monomer containing carbon-carbon double bonds can be 1:100 to 1:1; for example, it can be 1:80 to 1:2; or 1:70 to 1:3; or 1:60 to 1:4; or 1:50 to 1:5; or 1:40 to 1:6; or 1:30 to 1:8; or 1:20 to 1:10; or 1:15 to 1:12; or within the numerical range obtained by combining any two of the above end values.

[0079] According to one embodiment of this application, various reagents may be used as needed in the method for preparing POP, such as initiators (e.g., azobisisobutyronitrile, di(C1-C6) alkyl azobisisobutyrate, etc.), chain transfer agents (e.g., isopropanol, xylene, etc.), catalysts, etc. The types and amounts of these reagents may be appropriately selected as needed.

[0080] According to a preferred embodiment of this application, the POP can maintain a relatively low viscosity while having a high solids content, for example, its solids content can be ≥35% by weight, more preferably ≥38% by weight, even more preferably ≥40% by weight, for example 40-49% by weight; and at this high solids content, its viscosity can be ≤5000 mPa. s -1 (25℃), for example, viscosity ≤4500mPa s -1 (25℃), or viscosity ≤4000 mPa s -1 (25℃). This is an exceptionally high performance, and it is something that cannot be achieved with POP synthesized using macromolecular monomer dispersants in existing technologies.

[0081] This application also provides a method for preparing polyurethane, the method comprising causing the polymeric polyol (POP) described above to undergo a polymerization reaction with a polyisocyanate to form polyurethane. According to an exemplary embodiment of this application, the polyisocyanate may be an aliphatic polyisocyanate, an aromatic polyisocyanate, an oligomeric polyisocyanate, or a combination thereof.

[0082] The advantages of this invention are: 1. The monomeric dispersant designed in this invention uses renewable castor oil as a starting material, replacing traditional petroleum-based raw materials, which is in line with the development trend of green chemistry in my country.

[0083] 2. The double bond content in the monomer dispersant designed in this invention is easy to control and is located at the chain end of the molecule, with low steric hindrance. In the subsequent reaction to prepare POP, it is easier to polymerize with small molecule monomers and anchor the dispersant molecules to the surface of polymer particles, thereby more effectively exerting the function of the dispersant.

[0084] 3. The monomer dispersant synthesized in this invention has a high hydroxyl value and does not lose hydroxyl groups during the double bond introduction reaction, thus ensuring its compatibility with polyether polyols.

[0085] 4. The monomeric dispersant synthesized in this invention has a small molecular weight and low viscosity, and has little impact on the viscosity of the POP system.

[0086] The following embodiments illustrate the methods of this application in detail, with the aim of providing a better understanding of the content of this application. It should be understood that these embodiments are merely illustrative and not restrictive. Unless otherwise stated, the reagents used in the embodiments are commercially available. Unless otherwise specified, the methods and conditions used in the embodiments are conventional methods and conditions.

[0087] Example

[0088] The castor oil used in the following examples was purchased from Aladdin Biochemical Technology Co., Ltd., and the triglyceride (ricinoleic acid) content in the castor oil was determined to be 87.5% using gas chromatography-mass spectrometry (GC-MS). The polyether 330 used in the following examples was purchased from Jiangsu Haian Petrochemical Plant, with a hydroxyl value of 56 mgKOH / g and a molecular weight of 3000 g / mol. The DMC used in the following examples was a zinc-cobalt type bimetallic cyanide complex catalyst, purchased from Jiangsu Bade Polyurethane Co., Ltd. All other reaction materials and reagents used in the examples were of analytical grade and were used directly without further processing.

[0089] The 1H NMR spectra of the raw material castor oil, the intermediate products and monomeric dispersants prepared in the examples were tested using a Bruker Avance III HD 400 NMR spectrometer; the particle size distribution of the POP prepared in the examples was determined using a Malvern Panaco Zetasizer Lab dynamic light scattering spectrometer; and the microstructure of the POP was observed using a Hitachi SU5000 scanning electron microscope.

[0090] Example 1

[0091] In this embodiment, according to Figure 1 The process flow shown uses castor oil and pentaerythritol as raw materials to prepare monomeric dispersants through the following steps: 15 g of castor oil and 0.15 g of sodium methoxide were added to a three-necked flask, and stirring was started. 8.5 g of pentaerythritol was dissolved in 120 mL of DMF, and the resulting solution was added to a constant-pressure dropping funnel mounted on the three-necked flask. The three-necked flask was sealed, and the air was purged with nitrogen to raise the temperature to 120°C. The pentaerythritol solution in DMF was then slowly added dropwise over 0.5 hours. After the addition was complete, stirring and the temperature of 120°C were maintained, and the reaction was allowed to proceed for 6 hours. After the reaction was complete, the reactants were rotary evaporated at 120°C and a vacuum of -0.09 MPa to remove the DMF solvent. 0.168 g of acetic acid was added and neutralized with stirring. Then, 15 mL of n-hexane, 30 mL of methanol, and 10 mL of saturated brine were added for extraction to separate the organic and inorganic phases. The obtained organic phase was subjected to rotary evaporation to obtain an intermediate product.

[0092] Figure 2 and Figure 3 The raw material castor oil and the intermediate product are shown separately. 1 H NMR spectrum. Figure 2 The chemical shift at 0.81 ppm corresponds to the hydrogen on the methyl group, at 1.23 ppm to the methylene hydrogen in the long chain, at 1.54 ppm to the hydrogen on the hydroxyl group in the castor oil chain, at 1.98 ppm to the methylene hydrogen connected to the double bond -CH=CH-, between 2.09 ppm and 2.25 ppm to the methylene hydrogen on the carbon chain connected to the ester group, at 3.53 ppm to the methylene hydrogen connected to the hydroxyl group in the castor oil carbon chain, at 4.20 ppm to the methylene hydrogen at the glycerol chain end in castor oil, and between 5.19 ppm and 5.45 ppm to the methylene hydrogen on the -CH=CH- carbon chain in castor oil. Figure 3 The chemical shift at 3.51 ppm represents the methylene hydrogen at the terminal of pentaerythritol, which is similar to the chemical shift of the methylene hydrogen attached to the hydroxyl group in the castor oil monoester chain, forming a single peak. The chemical shift at 3.99 ppm represents the methylene hydrogen located between the central carbon of pentaerythritol and the new ester group after transesterification between the primary alcohol of pentaerythritol and the glycerol terminal ester group in castor oil. This demonstrates that the intermediate product is... Figure 1 The pentaerythritol mono(ricinoleic acid) ester shown.

[0093] The average molecular weight of the intermediate was determined to be 605 g / mol using an Agilent 1260 Infinity gel permeation chromatography (GPC) system, and its viscosity at 25°C was determined to be 408 mPa using a Jingqi NDJ-8S viscometer. The hydroxyl value of the intermediate product was determined to be 358 mg KOH / g using the national standard GB / T 12008.3-2009 (Method A).

[0094] 10 g of the intermediate product synthesized in the above steps and 0.0026 g of DMC were added to a three-necked flask, and stirring was started. 3 g of allyl glycidyl ether was added to a constant-pressure dropping funnel mounted on the three-necked flask. The three-necked flask was sealed, and nitrogen gas was introduced to replace the air in the flask. The flask was then heated to 100°C. Allyl glycidyl ether was slowly added dropwise over 0.5 hours. After the addition was complete, the reaction continued for 2 hours. After the reaction was completed, the flask was cooled to room temperature, and the material was filtered to remove the catalyst. The resulting product was then subjected to rotary evaporation at 100°C to remove unreacted allyl glycidyl ether. The target monomeric dispersant was obtained. The average molecular weight and viscosity of the monomeric dispersant were measured to be 673 g / mol and 436 mPa, respectively, using the molecular weight, viscosity, and hydroxyl value detection techniques described above. The hydroxyl value of this monomeric dispersant is 301 mg KOH / g.

[0095] Figure 4 The prepared monomeric dispersant was shown. 1 H NMR spectrum, and Figure 3 of 1 Compared to H NMR spectra Figure 4 The value at 2.61 ppm corresponds to the chemical shift of the newly introduced epoxy group after ring opening, forming a new secondary hydroxyl hydrogen; simultaneously, Figure 4 A new peak with a chemical shift of 5.87 ppm appeared, corresponding to the chemical shift of the methylene hydrogen in the allyl group. These results prove that the desired synthesis was achieved. Figure 1 The target monomeric dispersant is shown.

[0096] Next, using the obtained monomeric dispersant, polymeric polyols (POPs) are prepared through the following steps: 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 57.2 g of acrylonitrile, 70.6 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 5% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7 MPa and a stirring speed of 300 rpm for 3.0 hours. The POP obtained in this way is denoted as POP1.

[0097] 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 28.6 g of acrylonitrile, 35.3 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 5% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7 MPa and a stirring speed of 300 rpm for 3.0 hours. The POP obtained in this way is denoted as POP2.

[0098] Figure 4 The particle size distribution curve of the POP1 prepared above is shown. From Figure 4 As can be seen, the particle size of POP1 is monodisperse, mainly concentrated in the range of 300nm to 1050nm, with an average particle size of 682nm.

[0099] Figure 5 Here is a scanning electron microscope image of POP1, from... Figure 5 As can be seen, there is no obvious aggregation between POP1 particles, and the particle size is mainly concentrated in the range of 500nm-600nm, which proves that the monomeric dispersant prepared in Example 1 of this invention has excellent dispersing effect.

[0100] The performance of the two POPs prepared in this embodiment was characterized, and the results are summarized in Table 1.

[0101] Table 1 Properties of Polymer Polyols (POPs)

[0102] As can be seen from Table 1, the polymer polyol synthesized using the monomeric dispersant of Example 1 achieved a viscosity of less than 4000 mPa when the solid content was greater than 40%. The results demonstrate that the dispersant synthesized in this embodiment possesses excellent viscosity and dispersion performance. The polymeric polyol synthesized in this way is highly suitable for use in polyurethane material synthesis processes.

[0103] Example 2

[0104] In this embodiment, castor oil and glycerol were used as raw materials to prepare a monomeric dispersant through the following steps: 15 g of castor oil and 0.12 g of sodium methoxide were added to a three-necked flask, and stirring was started. 5.8 g of glycerol was dissolved in 90 mL of DMF, and the resulting solution was added to a constant-pressure dropping funnel mounted on the three-necked flask. The flask was sealed, and the air was purged with nitrogen to raise the temperature to 120°C. The glycerol solution in DMF was then slowly added dropwise over 0.5 hours. After the addition was complete, stirring and the temperature of 120°C were maintained, and the reaction was allowed to proceed for 6 hours. After the reaction was complete, the reactants were rotary evaporated at 120°C and a vacuum of -0.09 MPa to remove the DMF solvent. 0.135 g of acetic acid was added and neutralized with stirring. Then, 15 mL of n-hexane, 30 mL of methanol, and 10 mL of saturated brine were added for extraction to separate the organic and inorganic phases. The obtained organic phase was rotary evaporated to obtain an intermediate product.

[0105] The average molecular weight of the intermediate product was determined to be 521 g / mol and the viscosity was 347 mPa using the detection technique described in Example 1. s, hydroxyl value is 358 mg KOH / g.

[0106] 10 g of the intermediate product synthesized in the above steps and 0.0026 g of DMC were added to a three-necked flask, and stirring was started. 3.4 g of allyl glycidyl ether was added to a constant-pressure dropping funnel mounted on the three-necked flask. The flask was sealed, and nitrogen gas was introduced to replace the air inside the flask. The flask was then heated to 100°C. Allyl glycidyl ether was slowly added dropwise over 0.5 hours. After the addition was complete, the reaction continued for 2 hours. After the reaction was complete, the flask was cooled to room temperature, and the material was filtered to remove the catalyst. The resulting product was then subjected to rotary evaporation at 100°C to remove unreacted allyl glycidyl ether. The target monomeric dispersant was obtained. The average molecular weight and viscosity of the monomeric dispersant were determined to be 584 g / mol and 421 mPa, respectively, using the molecular weight, viscosity, and hydroxyl value detection techniques described above. The hydroxyl value of this monomeric dispersant is 235 mg KOH / g.

[0107] Next, using the obtained monomeric dispersant, polymeric polyols (POPs) are prepared through the following steps: 150 g of polyether 330, 0.12 g of initiator azobisisobutyronitrile, 55.1 g of acrylonitrile, 78.2 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 7% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7MPa and a stirring speed of 300rpm for 3.0 hours. The POP obtained in this way is denoted as POP3.

[0108] 150 g of polyether 330, 0.12 g of initiator azobisisobutyronitrile, 25.8 g of acrylonitrile, 39.3 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 7% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7 MPa and a stirring speed of 300 rpm for 3.0 hours. The POP obtained in this way is denoted as POP4.

[0109] The performance of the two POPs prepared in this embodiment was characterized in the same manner as in Example 1, and the results are summarized in Table 2.

[0110] Table 2 Polymer Polyol POP Performance

[0111] As can be seen from the data in Table 2, compared with POP1 and POP2 prepared in Example 1, the viscosity of POP3 and POP4 prepared in Example 2 increased at a similar solid content.

[0112] Example 3

[0113] In this embodiment, castor oil and pentaerythritol were used as raw materials to prepare a monomeric dispersant through the following steps: 15 g of castor oil and 0.15 g of calcium hydroxide were added to a three-necked flask, and stirring was started. 8.5 g of pentaerythritol was dissolved in 120 mL of DMF, and the resulting solution was added to a constant-pressure dropping funnel mounted on the three-necked flask. The three-necked flask was sealed, and the air was purged with nitrogen to raise the temperature to 120°C. The pentaerythritol solution in DMF was then slowly added dropwise over 0.5 hours. After the addition was complete, stirring and the temperature of 120°C were maintained, and the reaction was allowed to proceed for 6 hours. After the reaction was complete, the reactants were rotary evaporated at 120°C and a vacuum of -0.09 MPa to remove the DMF solvent. 0.25 g of acetic acid was added for neutralization with stirring, followed by extraction with 15 mL of n-hexane, 30 mL of methanol, and 12 mL of saturated brine to separate the organic and inorganic phases. The obtained organic phase was subjected to rotary evaporation to obtain an intermediate product.

[0114] The average molecular weight of the intermediate product was determined to be 695 g / mol and the viscosity to be 527 mPa using the detection technique described in Example 1. s, hydroxyl value is 312 mg KOH / g.

[0115] 10g of the intermediate product synthesized in the above steps and 0.0026g of DMC were added to a three-necked flask, and stirring was started. 5g of allyl glycidyl ether was added to a constant-pressure dropping funnel mounted on the three-necked flask. The three-necked flask was sealed, and nitrogen gas was introduced to replace the air in the flask. The flask was then heated to 100°C. Allyl glycidyl ether was slowly added dropwise over 0.5 hours. After the addition was complete, the reaction continued for 2 hours. After the reaction was completed, the flask was cooled to room temperature, and the material was filtered to remove the catalyst. The resulting product was then subjected to rotary evaporation at 100°C to remove unreacted allyl glycidyl ether. The target monomeric dispersant was obtained. The average molecular weight and viscosity of the monomeric dispersant were measured to be 702g / mol and 558 mPa, respectively, using the molecular weight, viscosity, and hydroxyl value detection techniques described above. The hydroxyl value of this monomeric dispersant is 284 mg KOH / g.

[0116] Next, using the obtained monomeric dispersant, polymeric polyols (POPs) are prepared through the following steps: 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 57.2 g of acrylonitrile, 79.2 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 7.0% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7MPa and a stirring speed of 300rpm for 3.0 hours. The POP obtained in this way is denoted as POP5.

[0117] 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 28.6 g of acrylonitrile, 41.5 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 7.0% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7MPa and a stirring speed of 300rpm for 3.0 hours. The POP obtained in this way is denoted as POP6.

[0118] The properties of the two POPs prepared in this example were characterized in the same manner as in Example 1, and the results are summarized in Table 3. It can be seen that POP6 prepared in this example exhibits a Pareto osmosis of less than 4500 mPa when the solid content is higher than 45%. The viscosity of s.

[0119] Table 3. Polymer polyol POP properties

[0120] Example 4

[0121] In this embodiment, castor oil and pentaerythritol were used as raw materials to prepare a monomeric dispersant through the following steps: 15 g of castor oil and 0.15 g of sodium methoxide were added to a three-necked flask, and stirring was started. 6.0 g of pentaerythritol was dissolved in 120 mL of DMF, and the resulting solution was added to a constant-pressure dropping funnel mounted on the three-necked flask. The flask was sealed, and the air was purged with nitrogen to raise the temperature to 120°C. The pentaerythritol solution in DMF was then slowly added dropwise over 0.5 hours. After the addition was complete, stirring and the temperature of 120°C were maintained, and the reaction was allowed to continue for 6 hours. After the reaction was complete, the reactants were rotary evaporated at 120°C and a vacuum of -0.09 MPa to remove the DMF solvent. 0.168 g of acetic acid was added and neutralized with stirring. Then, 15 mL of n-hexane, 30 mL of methanol, and 10 mL of saturated brine were added for extraction to separate the organic and inorganic phases. The obtained organic phase was subjected to rotary evaporation to obtain an intermediate product.

[0122] The average molecular weight of the intermediate product was determined to be 555 g / mol and the viscosity to be 482 mPa using the detection technique described in Example 1. s, hydroxyl value is 311 mg KOH / g.

[0123] 10 g of the intermediate product synthesized in the above steps and 0.0031 g of DMC were added to a three-necked flask, and stirring was started. 5.5 g of allyl glycidyl ether was added to a constant-pressure dropping funnel mounted on the three-necked flask. The flask was sealed, and nitrogen gas was introduced to replace the air inside the flask. The flask was then heated to 100°C. Allyl glycidyl ether was slowly added dropwise over 0.5 hours. After the addition was complete, the reaction continued for 2 hours. After the reaction was complete, the flask was cooled to room temperature, and the mixture was filtered to remove the catalyst. The resulting product was then subjected to rotary evaporation at 100°C to remove unreacted allyl glycidyl ether. The target monomeric dispersant was obtained.

[0124] Next, using the obtained monomeric dispersant, polymeric polyols (POPs) are prepared through the following steps: 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 57.2 g of acrylonitrile, 79.6 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 7.0% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7MPa and a stirring speed of 300rpm for 3.0 hours. The POP obtained in this way is denoted as POP7.

[0125] 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 28.6 g of acrylonitrile, 39.3 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 7.0% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7MPa and a stirring speed of 300rpm for 3.0 hours. The POP obtained in this way is denoted as POP8.

[0126] The properties of the two POPs prepared in this example were characterized in the same manner as in Example 1, and the results are summarized in Table 4. It can be seen that the POP8 prepared in this example exhibits a Pareto osmosis of less than 4000 mPa when the solid content is higher than 49%. The viscosity of s.

[0127] Table 4. Polymer polyol POP properties

[0128] Example 5

[0129] In this embodiment, castor oil and pentaerythritol were used as raw materials to prepare a monomeric dispersant through the following steps: 15 g of castor oil and 0.15 g of sodium methoxide were added to a three-necked flask, and stirring was started. 9.6 g of pentaerythritol was dissolved in 120 mL of DMF, and the resulting solution was added to a constant-pressure dropping funnel mounted on the three-necked flask. The three-necked flask was sealed, and the air was purged with nitrogen to raise the temperature to 120°C. The pentaerythritol solution in DMF was then slowly added dropwise over 0.5 hours. After the addition was complete, stirring and the temperature of 120°C were maintained, and the reaction was allowed to proceed for 6 hours. After the reaction was complete, the reactants were rotary evaporated at 120°C and a vacuum of -0.09 MPa to remove the DMF solvent. 0.168 g of acetic acid was added and neutralized with stirring. Then, 15 mL of n-hexane, 30 mL of methanol, and 15 mL of saturated brine were added for extraction to separate the organic and inorganic phases. The obtained organic phase was subjected to rotary evaporation to obtain an intermediate product.

[0130] The average molecular weight of the intermediate product was determined to be 574 g / mol and the viscosity to be 436 mPa using the detection technique described in Example 1. The hydroxyl value is 342 mg KOH / g.

[0131] 10 g of the intermediate product synthesized in the above steps and 0.00371 g of DMC were added to a three-necked flask, and stirring was started. 7.2 g of allyl glycidyl ether was added to a constant-pressure dropping funnel mounted on the three-necked flask. The flask was sealed, and nitrogen gas was introduced to replace the air inside the flask. The flask was then heated to 100°C. Allyl glycidyl ether was slowly added dropwise over 0.5 hours. After the addition was complete, the reaction continued for 2 hours. After the reaction was complete, the flask was cooled to room temperature, and the material was filtered to remove the catalyst. The resulting product was then subjected to rotary evaporation at 100°C to remove unreacted allyl glycidyl ether. The target monomeric dispersant was obtained. Using the molecular weight, viscosity, and hydroxyl value detection techniques described above, the average molecular weight and viscosity of the monomeric dispersant were determined to be 601 g / mol and 501 mPa, respectively. The hydroxyl value of this monomeric dispersant is 315 mg KOH / g.

[0132] Next, using the obtained monomeric dispersant, polymeric polyols (POPs) are prepared through the following steps: 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 57.2 g of acrylonitrile, 79.2 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 5.0% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7MPa and a stirring speed of 300rpm for 3.0 hours. The POP obtained in this way is denoted as POP9.

[0133] 150 g of polyether 330, 0.1 g of initiator azobisisobutyronitrile, 28.6 g of acrylonitrile, 41.5 g of styrene and monomeric dispersant were added to a reactor. The amount of monomeric dispersant was 5.0% of the total mass of the materials. The reaction was carried out at a reaction temperature of 115℃, a reaction pressure of 0.7 MPa and a stirring speed of 300 rpm for 3.0 hours. The POP obtained in this way is denoted as POP10.

[0134] The properties of the two POPs prepared in this example were characterized in the same manner as in Example 1, and the results are summarized in Table 4. It can be seen that POP10 prepared in this example exhibits a Pareto osmosis of less than 4000 mPa when the solid content is higher than 48%. The viscosity of s.

[0135] The properties of the prepared POP are shown in Table 5. The prepared POP10 exhibits a solid content higher than 45% and a Pa0.05 below 3750 mPa. The viscosity of s.

[0136] Table 5. Polymer polyol POP properties

Claims

1. A method for preparing a bio-based monomeric dispersant, the method comprising: Step 1: Compound A, as shown in Formula 1, undergoes an transesterification reaction with a polyhydroxy compound to generate compound B, as shown in Formula 2, wherein the molecular formula of the polyhydroxy compound is RO-(OH). n R0 represents a straight-chain or branched n-valent C3-C12 alkyl group, and n hydroxyl groups in the polyhydroxy compound are covalently connected to R0, where n is an integer from 3 to 12; Formula 1 Formula 2 In Formulas 1 and 2, R1 represents a C6-C22 alkenyl group containing at least one hydroxyl group and at least one carbon-carbon double bond; m is an integer less than n, and m ≥ 1; Step 2: Compound B shown in Formula 2 undergoes an addition reaction with allyl glycidyl ether to generate the bio-based monomeric dispersant shown in Formula 3; Formula 3 Where p is an integer less than n, p≥1, and n≥(m+p).

2. The method according to claim 1, characterized in that, The polyhydroxy compound used in step 1 is selected from one or more of the following: glycerol, pentaerythritol, erythritol (butanetetrol), xylitol (pentanetol), galactitol (hexanethyl alcohol), diglycerol, and bis(pentaerythritol).

3. The method according to claim 1, characterized in that, In the transesterification reaction in step 1, the molar ratio of compound A shown in Formula 1 to the polyhydroxy compound is 1:3.3 to 1:20; In the addition reaction in step 2, the molar ratio of compound B shown in Formula 2 to allyl glycidyl ether is 1:1 to 1:

16.

4. The method according to claim 1, characterized in that, Compound A, represented by Formula 1, is derived from castor oil. In Formula 1, R1 is 11-hydroxy-heptadec-8-enyl. The polyhydroxy compound used in step 1 is glycerol, pentaerythritol, or a combination of the two; In the transesterification reaction in step 1, the molar ratio of compound A (represented by Formula 1) to the polyhydroxy compound is 1:3.3 to 1:9.3; In the addition reaction in step 2, the molar ratio of compound B shown in Formula 2 to allyl glycidyl ether is 1:1 to 1:

4.

5. The method according to claim 1, characterized in that, The transesterification reaction in step 1 is carried out in the presence of an organic solvent; The organic solvent is selected from one or more of the following: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), formamide, dimethyl sulfoxide (DMSO), N-methylpyrrolidone, sulfolane, and acetonitrile; The mass ratio of the organic solvent to the polyhydroxy compound is 1:10 to 1:

20.

6. The method according to claim 1, characterized in that, The transesterification reaction in step 1 is carried out in the presence of a basic catalyst; The alkaline catalyst includes one or more of the following: alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal alkoxide, and alkaline earth metal alkoxide. Based on the total mass of all materials involved in the transesterification reaction, the amount of the alkaline catalyst used is 0.3-0.8% by mass. The addition reaction in step 2 is carried out in the presence of a bimetallic cyanide complex (DMC) catalyst; Based on the total mass of all materials in the addition reaction, the amount of the bimetallic cyanide complex catalyst is 0.01-0.1 by mass.

7. The method according to claim 1, characterized in that, The method includes at least one of the following: In step 1, the polyhydroxy compound is dissolved in an organic solvent to form an organic solution, and then the organic solution is added dropwise to a mixture of compound A shown in Formula 1 and a basic catalyst; In step 1, the organic solution is added dropwise to the mixture of compound A (as shown in Formula 1) and the basic catalyst over a period of 0.5–1 hour; The reaction temperature for the transesterification reaction in step 1 is 120-180℃; The transesterification reaction in step 1 lasts for 5-8 hours; In step 1, after the transesterification reaction is completed, the organic solvent is removed under vacuum conditions before the addition reaction in step 2 is carried out. The addition reaction in step 2 is carried out under an inert atmosphere; The reaction temperature for the addition reaction in step 2 is 80-120℃; The reaction time for the addition reaction in step 2 is 2-6 hours.

8. A bio-based monomeric dispersant having the structure shown in Formula 3: Formula 3 Where R0 represents a straight-chain or branched n-valent C3-C12 alkyl group; n is an integer between 3 and 12, m is an integer less than n and m≥1, p is an integer less than n and p≥1, and n≥(m+p); R1 represents a C6-C22 alkenyl group containing at least one hydroxyl group and at least one carbon-carbon double bond; The bio-based monomeric dispersant is prepared by the method described in any one of claims 1-7.

9. A polymeric polyol prepared using the bio-based monomeric dispersant of claim 8.

10. A polyurethane material prepared by reacting the polymeric polyol of claim 9 with a polyisocyanate compound.

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