Polymer dispersion stabilizer as well as preparation method and application thereof

Abstract

The invention provides a macromolecular dispersion stabilizer as well as a preparation method and application thereof, RA is a residue of polyether polyol, the hydroxyl functionality of the polyether polyol is 4-10, and the number-average molecular weight of the polyether polyol is 1500-50000 g / mol. The polymer dispersion stabilizer provided by the invention can be very effectively used for synthesizing unprecedented polymer polyol with ultrahigh solid content, low viscosity and excellent storage performance, and can be further used for preparing a polyurethane material with greatly improved hardness, comprehensive foam performance, foam rebound resilience and other performances.

Description

Technical Field

[0001] This application relates to the field of polymer materials, and more specifically to a polymeric dispersion stabilizer and its preparation method, as well as a method for using the polymeric dispersion stabilizer to prepare polymer-grafted polyether polyols, and the use of the polymer-grafted polyether polyols 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. POPs are an indispensable upstream raw material for the preparation of high-performance polyurethane (PU) foams. They can effectively improve the hardness of polyurethane foams and enhance their overall performance, making them a key raw material for producing high-load-bearing and high-resilience foam materials. Polyurethane materials are widely used in various applications in production, daily life, and scientific research. The rapid development of these fields has placed higher demands on the comprehensive performance of polyurethane foam materials. To meet these requirements, polyurethane manufacturers and research institutions have invested significant funds and manpower in attempting to improve polyurethane production processes. As a crucial raw material for the production of high-performance PU foams, POPs have become a key focus of research.

[0003] For example, research has found that the solids content of polyurethane foam (POP) has a significant impact on various properties of polyurethane foam (such as load strength and resilience). There is a strong desire to develop POP with a solids content exceeding 40%, or even higher. Furthermore, existing POP technologies suffer from high viscosity and storage difficulties, issues that urgently need to be addressed.

[0004] To address the aforementioned problems, various improvements have been attempted to the POP synthesis process. One approach is to select different types and amounts of unsaturated monomers containing carbon-carbon double bonds (such as styrene and acrylonitrile). However, this method has a very limited effect on increasing the POP solids content, achieving only 20-30%, and the performance is also unsatisfactory. Another approach is to modify the dispersing stabilizers used in POP preparation, such as introducing unsaturated acid anhydrides (e.g., maleic anhydride) or polyisocyanates (e.g., toluene diisocyanate) into the dispersing stabilizer. However, the improvement achieved by this method is also extremely limited, and the resulting POP solids content and various properties are still unsatisfactory. Moreover, the newly introduced groups, such as polyisocyanates, can lead to waste and significantly increase costs due to coupling reactions.

[0005] Therefore, there is still an urgent need in the field to develop a novel polymeric dispersion stabilizer for POP synthesis in order to solve the aforementioned problems in the field.

[0006] To address the aforementioned problems, the inventors of this application, through extensive and in-depth research, have successfully developed a novel polymeric dispersion stabilizer and its preparation method. Unexpectedly, it was discovered that this specially designed polymeric dispersion stabilizer can be used to prepare high-quality POP with high solids content, low viscosity, and excellent storage performance, meeting people's needs. Furthermore, it can be used to prepare polyurethane foam materials with excellent performance, effectively solving a long-standing problem that has been difficult to solve in the prior art. Summary of the Invention

[0007] The first aspect of this application provides a polymeric dispersion stabilizer having the structure shown in Formula I:

[0008]

[0009] Where R A n is a residue of a polyether polyol, where n is an integer from 4 to 10, and the polyether polyol has a hydroxyl functionality of 4 to 10 and a number-average molecular weight of 1500 to 50000 g / mol.

[0010] R in Equation I B It has the structure shown in Formula II:

[0011]

[0012] Where * represents R B The site that connects to other parts in Formula I;

[0013] R1 represents a C1-C12 straight-chain alkylene group, and R1 is optionally substituted by one or more substituents selected from the following: C1-C6 alkyl, C1-C6 alkoxy, C2-C8 alkenyl, hydroxyl, halogen, amino, C1-C6 amino.

[0014] R2, R3, R4, and R5 each independently represent a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 hydroxyalkyl group, or a C2-C8 alkenyl group.

[0015] According to one embodiment of the first aspect of this application, n is an integer from 5 to 7, and the polyether polyol has a hydroxyl functionality of 5 to 7 and a number-average molecular weight of 5000-20000 g / mol.

[0016] According to another embodiment of the first aspect of this application, R1 represents a C1-C6 straight-chain alkylene group, and R1 is optionally substituted by one or more substituents selected from the following: C1-C4 alkyl, C1-C4 alkoxy, C2-C6 alkenyl, hydroxyl, halogen, amino, C1-C4 amino.

[0017] According to another embodiment of the first aspect of this application, R2, R3, R4 and R5 each independently represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 hydroxyalkyl group, and a C2-C6 alkenyl group.

[0018] According to another embodiment of the first aspect of this application, the polymeric dispersion stabilizer is selected from one or more of the structures shown in Formulas 1-10:

[0019]

[0020]

[0021] The second aspect of this application provides a method for preparing the polymeric dispersion stabilizer described in any embodiment of the first aspect above, the method comprising reacting a compound of formula A with a polyether polyol to form a polymeric dispersion stabilizer having the structure shown in formula I; wherein the polyether polyol has a hydroxyl functionality of 4-10 and a number-average molecular weight of 1500-50000 g / mol.

[0022]

[0023] In formula A, R1 represents a C1-C12 straight-chain alkylene group, and R1 is optionally substituted by one or more substituents selected from the following: C1-C6 alkyl, C1-C6 alkoxy, C2-C8 alkenyl, hydroxyl, halogen, amino, C1-C6 amino.

[0024] R2, R3, and R4 each independently represent a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 hydroxyalkyl group, and a C2-C8 alkenyl group.

[0025] According to an embodiment of the second aspect of this application, the compound of formula A is selected from one or more of the following: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate.

[0026] According to another embodiment of the second aspect of this application, in the reaction of the compound represented by Formula A with the polyether polyol, the reaction temperature is 25-90°C, the reaction time is 0.5-8 hours, and the molar ratio of the polyether polyol to the compound represented by Formula A is 1:0.3 to 1:3.

[0027] According to another embodiment of the second aspect of this application, the reaction of the compound represented by Formula A with the polyether polyol is carried out in the presence of a catalyst and a protective atmosphere. According to another embodiment of the second aspect of this application, the catalyst is a metal alkyl carboxylate, and the protective atmosphere is an inert atmosphere.

[0028] According to another embodiment of the second aspect of this application, the amount of catalyst used is 5-30 ppm, based on the total mass of all reactants.

[0029] A third aspect of this application provides a method for preparing polymer-grafted polyether polyols, the method comprising the following steps:

[0030] In the presence of a second polyether polyol, an initiator, a chain transfer agent, and a polymeric dispersion stabilizer, one or more unsaturated monomers containing carbon-carbon double bonds react to form the polymer-grafted polyether polyol; the polymeric dispersion stabilizer is the polymeric dispersion stabilizer described in any embodiment of the first aspect of this application, or a polymeric dispersion stabilizer prepared by the method of any embodiment of the second aspect of this application.

[0031] A fourth aspect of this application provides a method for preparing polyurethane, the method comprising causing a polymer-grafted polyether polyol to undergo a polymerization reaction with a polyisocyanate to form polyurethane, wherein the polymer-grafted polyether polyol is obtained by the method of a third aspect of this application.

[0032] 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

[0033] Figure 1 This demonstrates the polymeric dispersion stabilizers prepared in Examples 1-4 of this application. 1 H-NMR spectrum;

[0034] Figure 2 The electron micrographs show the morphological characteristics of the POP solid particles prepared in Example 5 of this application. Detailed Implementation

[0035] 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.

[0036] 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.

[0037] Unless otherwise specified in this application, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0038] Unless otherwise specified, all technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0039] 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.

[0040] One inventive aspect of this application is the development of a polymeric dispersion stabilizer with a novel structure that simultaneously possesses a composite structure of a polyol and an isocyanate-based alkyl ester of (meth)acrylate, and strictly limits this composite structure to containing only one isocyanate group. This not only avoids the defects of prior art such as coupling and waste, but also unexpectedly achieves a significant improvement in the performance of POP and PU foam materials prepared by this dispersion stabilizer.

[0041] In this application, the raw material used to prepare the polymeric dispersion stabilizer is polyether polyol (i.e., R). A -(OH) nThe first polyether polyol is called a polyether polyol or a first polyether polyol; while the second polyether polyol is called a second polyether polyol, in order to distinguish the two, the first polyether polyol is used to polymerize with unsaturated monomers containing carbon-carbon double bonds and polymeric dispersion stabilizers to form polymer grafted polyether polyols.

[0042] The first polyether polyol and the second polyether polyol may be the same or different. Specifically, the first polyether polyol and the second polyether polyol may have the same or different polymer monomers, molecular weights and hydroxyl functionalities.

[0043] According to one embodiment of this application, the polymeric dispersion stabilizer of this application has the structure shown in Formula I:

[0044]

[0045] Where R A It is a residue of the first polyether polyol, specifically having the structural formula R. A -(OH) n The residues remaining after removing all n OH groups from the first polyether polyol. According to one embodiment of this application, the residues are the main chain remaining after removing n free hydroxyl groups from the polyether polyol. For example, this main chain can be formed primarily by interconnected alkene groups as structural units, and the alkene groups can be derived from C2-C16 epoxides, C2-C16 polyols (e.g., diols, triols, tetraols, etc.). Based on the molecular weight range and hydroxyl functionality of the first polyether polyol, it can be determined that the number of carbon atoms contained in the first polyether polyol is greater than the number of hydroxyl groups it contains (i.e., the n value). According to one embodiment of this application, the free hydroxyl groups in the first polyether polyol are respectively connected to different carbon atoms, that is, no two free hydroxyl groups are connected to the same carbon atom. In other words, in the polymeric dispersion stabilizer shown in Formula I, written as R... A The "residues of the first polyether polyol" contain multiple carbon atoms, preferably having more than n carbon atoms, and more preferably having n-1 hydroxyl groups of formula I respectively with R A Different carbon atoms are connected together.

[0046] The synthesis method of this polymeric dispersion stabilizer shows that, during the synthesis of the polymeric dispersion stabilizer shown in Formula I, a structure with formula R is formed. A -(OH) n One hydroxyl hydrogen of the first polyether polyol is R B Replacement.

[0047] According to one embodiment of this application, the first polyether polyol may be a polyether polyol prepared 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 prepared by condensation polymerization of ethylene oxide and / or propylene oxide.

[0048] According to another embodiment of this application, the number average molecular weight of the first polyether polyol can be 1500-50000 g / mol, for example, 2000-40000 g / mol, or 2500-30000 g / mol, or 3000-20000 g / mol, or 4000-18000 g / mol, or 5000-17000 g / mol, or 6000-16000 g / mol, or 7000-15000 g / mol, or 8000-14000 g / mol, or 9000-13000 g / mol, or 10000-12000 g / mol, or within the range of values ​​obtained by combining any two of the above endpoints.

[0049] According to one embodiment of this application, n is an integer from 4 to 10, that is, the hydroxyl functionality of the first polyether polyol, which is used as a raw material for synthesizing polymer dispersion stabilizers, can be 4 to 10, for example, 4 to 8, or 5 to 7, or 5 to 6, or 6 to 8, or within the range of values ​​obtained by combining any two of the above end values.

[0050] According to one embodiment of this application, the compound represented by Formula I contains a total of 1 -OR B A group and n-1 hydroxyl groups. According to an exemplary embodiment of this application, R... B It has the structure shown in Formula II:

[0051] In Formula II, * denotes the linking site; that is, the substituent shown in Formula II binds to R via an ether bond. A The location of the connection.

[0052] According to one embodiment of this application, in Formula II, R2, R3, R4, and R5 each independently represent hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 hydroxyalkyl, or C2-C8 alkenyl; for example, each independently represents hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 hydroxyalkyl, or C2-C6 alkenyl; or each independently represents hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl, or C2-C4 alkenyl; or each independently represents hydrogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 hydroxyalkyl, or C2-C3 alkenyl. According to a preferred embodiment of this application, in Formula II, R2, R3, R4, and R5 each independently are selected from hydrogen atoms, methyl, methoxy, hydroxymethyl, or vinyl.

[0053] According to another embodiment of this application, in Formula II, R1 represents a C1-C12 straight-chain alkylene (e.g., a C1-C8 straight-chain alkylene, or a C1-C6 straight-chain alkylene, or a C1-C4 straight-chain alkylene, or an ethylene), wherein R1 may be unsubstituted or may be substituted by one or more substituents selected from the following: C1-C6 alkyl, C1-C6 alkoxy, C2-C8 alkenyl, hydroxyl, halogen, amino, C1-C6 amino. For example, the substituent may be selected from C1-C4 alkyl, C1-C4 alkoxy, C2-C6 alkenyl, hydroxyl, halogen, amino, or C1-C5 amino; or the substituent may be selected from C1-C3 alkyl, C1-C3 alkoxy, C2-C4 alkenyl, hydroxyl, halogen, amino, or C1-C4 amino; or the substituent may be selected from C1-C2 alkyl, C1-C2 alkoxy, C2-C3 alkenyl, hydroxyl, halogen, amino, or C1-C2 amino.

[0054] In this invention, halogens include one or more of the following: fluorine, chlorine, bromine, and iodine.

[0055] According to a specific embodiment of this application, the polymeric dispersion stabilizer has the structure shown in Formulas 1-10, where R... A The definition is as described above:

[0056]

[0057]

[0058] This application also provides a method for synthesizing the aforementioned polymeric dispersion stabilizer, the method comprising reacting a compound of formula A with a first polyether polyol to form a polymeric dispersion stabilizer having the structure of formula I; the first polyether polyol, as described above, has a hydroxyl functionality of 4-10 and a number-average molecular weight of 1500-50000 g / mol. The hydroxyl functionality, number-average molecular weight, molecular structure, and source of the first polyether polyol are preferably as described above.

[0059]

[0060] In Equation A, the definitions of R1, R2, R3, and R4 are the same as those in Equation II above.

[0061] According to a particularly specific embodiment of this application, the compound A is selected from at least one of the following: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate.

[0062] According to one embodiment of this application, the compound represented by Formula A reacts with a first polyether polyol (hereinafter referred to as "the first reaction") under conditions in the presence of a catalyst and a protective atmosphere.

[0063] According to one embodiment of this application, the catalyst is an organometallic compound, such as an alkyl metal carboxylate, for example, a (C1-C16)alkyl metal (C1-C16) carboxylate, wherein the metal is selected from tin, nickel, iron, titanium, zinc, etc., and an example of the catalyst may be dibutyltin dilaurate.

[0064] According to one embodiment of this application, the protective atmosphere may be an inert atmosphere, such as a nitrogen atmosphere.

[0065] According to one embodiment of this application, the reaction temperature of the first reaction is 25-90°C, for example 40-83°C, or 50-70°C, or 55-65°C, or within a numerical range obtained by combining any two of the above end values; the reaction time is 0.5-8 hours, for example 0.6-7 hours, or 1-5 hours, or 2-4 hours, or within a numerical range obtained by combining any two of the above end values; the molar ratio of the first polyether polyol to the compound of formula A is 1:0.3 to 1:3; for example 1:0.4 to 1:2.5, or 1:0.5 to 1:2.2, or 1:0.6 to 1:2, or 1:0.7 to 1:1.8, or 1:0.8 to 1:1.5, or 1:0.9 to 1:2, or 1:1 to 1:1.1, or within a numerical range obtained by combining any two of the above end values. According to one embodiment of this application, in the first reaction, based on the total weight of all materials in the first reaction, the amount of catalyst used is 5-30 ppm, for example, it can be 6 ppm, or 10 ppm, or 15.6 ppm, or 25 ppm, or within the range obtained by combining any two of the above values.

[0066] According to a preferred embodiment of this application, the method for preparing the polymeric dispersion stabilizer includes the following specific steps: adding a compound of formula A (e.g., any (meth)acrylate (isocyanate-alkyl) ester described above) and a first polyether polyol into a reaction vessel, stirring the material under an inert atmosphere (e.g., nitrogen), and then adding a catalyst (e.g., dibutyltin dilaurate) dropwise to it, allowing it to react at the reaction temperature described above, with a reaction time of 0.5-8 hours as described above. After the reaction is completed, a viscous target polymeric dispersion stabilizer is obtained.

[0067] During the reaction, the molar ratio of the polyether polyol to compound A is controlled within the range described above. According to one embodiment of this application, the content of isocyanate groups in the reaction system can be determined by di-n-butylamine titration during the reaction to monitor whether the reaction has reached its endpoint (whether the reaction has ended); if the isocyanate groups are completely consumed, the reaction is considered to have reached its endpoint; if the detection result shows that the isocyanate groups have not been completely consumed, the reaction is considered not to have reached its endpoint.

[0068] The dispersant stabilizer of the present invention can be used to synthesize polymer-grafted polyether polyols (POPs). Due to the special design of the simple and effective molecular structure of the polymeric dispersant stabilizer, which contains abundant polyether segments and simple reactive olefinic unsaturated end groups, and with special restrictions on isocyanate groups, it can unexpectedly achieve a significant increase in solids content and a reduction in viscosity when used to prepare polymeric polyols (POPs).

[0069] This application also provides a method for preparing a polymer-grafted polyether polyol, the method using the polymeric dispersion stabilizer of the present invention, specifically, in a reaction system in the presence of a second polyether polyol and the polymeric dispersion stabilizer, causing an unsaturated monomer containing a carbon-carbon double bond to undergo a polymerization reaction.

[0070] According to one embodiment of this application, the polymer grafted polyether polyol comprises the second polyether polyol mentioned above, a polymer and / or copolymer formed from one or more unsaturated monomers containing carbon-carbon double bonds, and a copolymer (e.g., a graft copolymer) formed from the one or more unsaturated monomers containing carbon-carbon double bonds and the polymeric dispersion stabilizer.

[0071] According to one embodiment of this application, the hydroxyl functionality of the second polyether polyol is 3-10, for example, 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 second 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.

[0072] According to one embodiment of this application, in the method for preparing POP, the unsaturated monomer containing a carbon-carbon double bond is selected from one or more of the following: C2-C12 aliphatic olefins, C6-C16 aromatic 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)acrylic acid C1-C8 alkyl ester, (meth)acrylonitrile, and (meth)acrylamide. According to one embodiment, the unsaturated monomer containing a carbon-carbon double bond may be a mixture of styrene and acrylonitrile.

[0073] According to one embodiment of this application, in the method for preparing POP, the weight ratio of the second polyether polyol to the unsaturated monomer containing carbon-carbon double bonds 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 numerical range obtained by combining any two of the above end values.

[0074] According to one embodiment of this application, when preparing the POP, the weight ratio of the polymeric dispersion stabilizer 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.

[0075] 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.

[0076] According to a preferred embodiment of this application, the polymeric polyether polyol 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, more preferably ≥40% by weight, and even more preferably ≥41% by weight, for example, 41-45% by weight; and at this high solids content, its viscosity can be ≤6000 mPa·s. -1(25℃), for example, viscosity ≤5800mPa·s -1 (25℃).

[0077] This application also provides a method for preparing polyurethane, the method comprising causing a polymer-grafted polyether polyol (POP) to undergo a polymerization reaction with a polyisocyanate to form polyurethane, wherein the POP is the polymer-grafted polyether polyol of the present invention prepared using a polymeric dispersion stabilizer as described above. According to an exemplary embodiment of this application, the polyisocyanate may be an aliphatic polyisocyanate, an aromatic polyisocyanate, an oligomeric polyisocyanate (isocyanurate), or a combination thereof.

[0078] The positive and progressive effects of this invention are as follows:

[0079] 1. This invention forms a high molecular weight dispersion stabilizer by reacting a simple alkyl ester of (meth)acrylate monoisocyanate with a first polyether polyol. This stabilizer enables the polyether polyol to be stably dispersed and is very suitable for preparing polymer-grafted polyether polyols. The resulting polymer-grafted polyether polyols have excellent properties of high solids content and low viscosity.

[0080] 2. Both the polymeric dispersion stabilizer and POP of the present invention can be synthesized through a very simple preparation process. In particular, the synthesis process of the polymeric dispersion stabilizer is significantly simplified compared to the process using polyfunctional isocyanates (e.g., diisocyanates).

[0081] 3. The dispersion stabilizer prepared by this invention can be used to prepare POP, which can participate in the preparation of polyurethane foam to produce PU foam materials with excellent performance.

[0082] 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.

[0083] Example

[0084] The polyether polyol with a functionality of 6 used in the following examples was purchased from Shanghai Dongda Chemical Co., Ltd., with a molecular weight of 12000 g / mol; the polyether polyol with a functionality of 3 was purchased from Shandong Longhua New Material Co., Ltd., with a molecular weight of 3000 g / mol. All other reaction materials and reagents used were of analytical grade and were used directly without further processing.

[0085] Example 1

[0086] In this embodiment, the polymeric dispersion stabilizer shown in Formula 3 was synthesized.

[0087]

[0088] 60 g (0.005 mol) of a polyether polyol with a functionality of 6 (used as the first polyether polyol) was weighed and thoroughly vacuum dried. Approximately 1 mg of dibutyltin dilaurate catalyst was added, followed by 0.705 g of acrylic acid (ethyl isocyanate). The mixture was heated to 75 °C in an oil bath under a nitrogen atmosphere and maintained at this temperature with continuous stirring. During the continuous reaction, samples of the reactants were intermittently taken, and the NCO content in the samples was determined by di-n-butylamine titration. The reaction was stopped when the NCO content was found to be 0. The reaction products were characterized by NMR. Figure 1 It showed its 1 The H-NMR spectrum confirmed that the polymeric dispersion stabilizer shown in Formula 3 was synthesized.

[0089] Example 2

[0090] In this embodiment, the polymeric dispersion stabilizer shown in Formula 4 was synthesized.

[0091]

[0092] 60 g (0.005 mol) of a polyether polyol with a functionality of 6 (used as the first polyether polyol) was weighed and thoroughly vacuum dried. Approximately 1 mg of dibutyltin dilaurate catalyst was added, followed by 0.75 g of methacrylic acid (ethyl isocyanate). The mixture was heated to 75 °C in an oil bath under a nitrogen atmosphere and maintained at this temperature with continuous stirring. During the continuous reaction, samples of the reactants were intermittently taken, and the NCO content in the samples was determined by di-n-butylamine titration. The reaction was stopped when the NCO content was found to be 0. The reaction products were characterized by NMR. Figure 1 It showed its 1 The H-NMR spectrum confirmed that the polymeric dispersion stabilizer shown in Formula 4 was synthesized.

[0093] Example 3 (Comparative Example)

[0094] In this embodiment, a polymeric dispersion stabilizer of formula a (which contains two NCO groups and therefore does not fall within the scope of protection of this invention) was synthesized.

[0095]

[0096] 60 g (0.005 mol) of a polyether polyol with a functionality of 6 (used as the first polyether polyol) was weighed and thoroughly vacuum dried. Approximately 1 mg of dibutyltin dilaurate catalyst was added, followed by 1.50 g of methacrylic acid (ethyl isocyanate). The mixture was heated to 75 °C in an oil bath under a nitrogen atmosphere and maintained at this temperature under continuous stirring. During the continuous reaction, samples of the reactants were intermittently taken, and the NCO content in the samples was determined by di-n-butylamine titration. The reaction was stopped when the NCO content was found to be 0. The reaction products were characterized by NMR. Figure 1 It showed its 1 The H-NMR spectrum confirmed the synthesis of the polymeric dispersion stabilizer shown in formula a.

[0097] Example 4 (Comparative Example)

[0098] In this embodiment, the polymeric dispersion stabilizer shown in formula b was synthesized (this embodiment uses a polyether polyol with a hydroxyl functionality of 3, and therefore does not fall within the scope of protection of this invention).

[0099]

[0100] 45 g (0.015 mol) of a polyether polyol with a functionality of 3 (used as the first polyether polyol) was weighed and thoroughly vacuum dried. Approximately 1 mg of dibutyltin dilaurate catalyst was added, followed by 2.30 g of methacrylic acid (ethyl isocyanate). The mixture was heated to 75 °C in an oil bath under a nitrogen atmosphere and maintained at this temperature with continuous stirring. During the continuous reaction, samples of the reactants were intermittently taken, and the NCO content in the samples was determined by di-n-butylamine titration. The reaction was stopped when the NCO content was found to be 0. The reaction products were characterized by NMR. Figure 1 It showed its 1 The H-NMR spectrum confirmed the synthesis of the polymeric dispersion stabilizer shown in formula a.

[0101] Example 5:

[0102] In this embodiment, the polymeric dispersion stabilizers prepared in Examples 1-4 above were used to prepare POPs, and their properties were characterized.

[0103] Specifically, 0.984g of AIBN (azobisisobutyronitrile), 31.80g of acrylonitrile, 7.20g of polymeric dispersion stabilizer (prepared from one of Examples 1-4), 16.80g of isopropanol, 79.75g of polyether 330 (purchased from Shanghai Dongda Chemical Co., Ltd.), and 63.60g of styrene were weighed out sequentially. The materials were stirred and mixed to form a monomer mixture, which was then stored in an ice-water bath for later use. 33.22g of polyether 330 was weighed and placed in a reactor. Nitrogen gas was introduced into the reactor, and the pressure was increased to 0.35MPa. After pressurization, the reactor was heated to 120°C. The monomer mixture was added to the reactor, and the polymerization reaction was started under continuous stirring. The addition rate of the monomer mixture was controlled to ensure that it was added completely in about 60 minutes. After the addition was complete, the reaction continued for another 60 minutes. After the temperature of the system began to drop, the reaction was stopped, and the material was discharged from the reactor. Then, low molecular weight substances in the material are removed under vacuum at 130°C. This impurity removal process is carried out for 4 hours to obtain the target POP product. Figure 2 An electron micrograph of POP synthesized using the polymeric dispersion stabilizer prepared in Example 1 through the above steps is shown, indicating that the synthesized POP product consists of uniformly sized spherical particles.

[0104] The solid content of the product was then determined using the following steps: Accurately weigh 0.8000-1.0000 g of POP into a 10 ml centrifuge tube, and record the mass as C; add 10 ml of ethanol to the centrifuge tube for dilution, and sonicate for 10 min; after sonication, place the centrifuge tube in a centrifuge and centrifuge at 7000 rpm for 40 min; after centrifugation, pour off the supernatant, disperse again with ethanol, and repeat the above operation four times; take a clean small beaker and weigh it, recording the weight as D; add 10 ml of ethanol to the precipitate obtained after the fourth repetition and sonicate for 20 min; after sonication, pour the liquid from the centrifuge tube into the small beaker; add 10 ml of ethanol to the centrifuge tube again and sonicate for 20 min; repeat the above operation until no sample remains on the centrifuge tube wall; after completion, place the small beaker in an oven at 115℃ for at least 8 hours, weigh the beaker, and record the mass as E. The solid content of the sample is calculated according to the following formula:

[0105]

[0106] The viscosity of the product was determined according to the national standard GB / T 12008.7-2010 and using an NDJ-1 rotational viscometer. The characterization results are summarized in Table 1 below.

[0107] Table 1: Performance of POP prepared using the polymeric dispersion stabilizers of Examples 1-4

[0108]

[0109] As can be seen from the experimental results shown in the table above, the polymeric dispersion stabilizers of Examples 1 and 2 of the present invention can be effectively used to synthesize POP with high solids content and low viscosity. Among them, Example 2 obtained the best results far superior to the other examples; while the viscosity of the POP synthesized in Example 3 increased to an unacceptable level, and the POP synthesized in Example 4 could not achieve the required high solids content and obvious solid-liquid phase separation occurred.

[0110] Furthermore, as shown in Examples 1 and 2, compared with some polymeric dispersion stabilizers described in the prior art, the polymeric dispersion stabilizer of the present invention can be prepared using cheaper raw materials and a simpler synthesis process, and can be used to prepare POPs with comparable or better performance.

[0111] Example 6

[0112] Polyurethane foam was prepared by condensation reaction of POP obtained with polymer dispersion stabilizers of Examples 1 and 2 in Example 5 with diphenylmethane diisocyanate (MDI) in an equimolar ratio. The results showed that the prepared polyurethane foam had extremely excellent high resilience properties.

Claims

1. A polymeric dispersion stabilizer having the structure shown in Formula I: Where R A n is a residue of a polyether polyol, where n is an integer from 4 to 10, and the polyether polyol has a hydroxyl functionality of 4 to 10 and a number-average molecular weight of 1500 to 50000 g / mol. R in Equation I B It has the structure shown in Formula II: Where * represents R B The site that connects to other parts in Formula I; R1 represents a C1-C12 straight-chain alkylene group, and R1 is optionally substituted by one or more substituents selected from the following: C1-C6 alkyl, C1-C6 alkoxy, C2-C8 alkenyl, hydroxyl, halogen, amino, C1-C6 amino. R2, R3, R4, and R5 each independently represent a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 hydroxyalkyl group, or a C2-C8 alkenyl group.

2. The polymeric dispersion stabilizer as described in claim 1, characterized in that, n is an integer from 5 to 7, and the hydroxyl functionality of the polyether polyol is 5 to 7 and the number average molecular weight is 5000-20000 g / mol. R1 represents a C1-C6 straight-chain alkylene group, and R1 is optionally substituted by one or more substituents selected from the following: C1-C4 alkyl, C1-C4 alkoxy, C2-C6 alkenyl, hydroxyl, halogen, amino, C1-C4 amino. R2, R3, R4, and R5 each independently represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 hydroxyalkyl group, or a C2-C6 alkenyl group.

3. The polymeric dispersion stabilizer as described in claim 1, characterized in that, It has the structure shown in Equation 1-10:

4. A method for preparing the polymeric dispersion stabilizer according to any one of claims 1-3, characterized in that, The method includes reacting a compound of formula A with a polyether polyol to form a polymeric dispersion stabilizer having the structure of formula I; wherein the polyether polyol has a hydroxyl functionality of 4-10 and a number-average molecular weight of 1500-50000 g / mol. In formula A, R1 represents a C1-C12 straight-chain alkylene group, and R1 is optionally substituted by one or more substituents selected from the following: C1-C6 alkyl, C1-C6 alkoxy, C2-C8 alkenyl, hydroxyl, halogen, amino, C1-C6 amino. R2, R3, and R4 each independently represent a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 hydroxyalkyl group, and a C2-C8 alkenyl group.

5. The method as described in claim 4, characterized in that, The compound of Formula A is selected from one or more of the following: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate.

6. The method as described in claim 4, characterized in that, In the reaction of the compound shown in Formula A with the polyether polyol, the reaction temperature is 25-90°C, the reaction time is 0.5-8 hours, and the molar ratio of the polyether polyol to the compound shown in Formula A is 1:0.3 to 1:

3.

7. The method as described in claim 4, characterized in that, The reaction of the compound shown in Formula A with the polyether polyol is carried out in the presence of a catalyst and a protective atmosphere; The catalyst is a metal alkyl carboxylate, and the protective atmosphere is an inert atmosphere.

8. The method as described in claim 7, characterized in that, Based on the total mass of all reactants, the amount of catalyst used is 5-30 ppm.

9. A method for preparing polymer-grafted polyether polyols, the method comprising the following steps: In the presence of a second polyether polyol, an initiator, a chain transfer agent, and a polymeric dispersion stabilizer, one or more unsaturated monomers containing carbon-carbon double bonds react to form the polymer-grafted polyether polyol; the polymeric dispersion stabilizer is the polymeric dispersion stabilizer according to any one of claims 1-3, or a polymeric dispersion stabilizer prepared by any one of claims 4-8.

10. A method for preparing polyurethane, the method comprising causing a polymer-grafted polyether polyol to undergo a polymerization reaction with a polyisocyanate to form polyurethane, wherein the polymer-grafted polyether polyol is obtained by the method of claim 9.

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