A modified polyether polyol, and a method of making and using the same

Abstract

The application discloses a modified polyether polyol and a preparation method and application thereof, the modified polyether polyol contains a polyether main chain, ester side groups, halogen atoms and customizable chemical active sites, and can be used for preparing novel functional structure polyurethane materials with rich ether bonds and ester bonds, and provides new raw material selection for preparation of the polyurethane materials. The preparation method of the modified polyether polyol is simple in process steps and easy to popularize and apply in industry. On one hand, the esterification degree can be adjusted and controlled through reaction temperature, time, catalyst and feeding ratio; on the other hand, the structure design of the modified polyether polyol can be realized through design of carboxylic acid salt structure, and the functional ester group modified polyether polyol is endowed with unique performance. The application not only provides a new upstream raw material for functional polyurethane and derivative products thereof, but also is expected to develop into a novel polymer material, and has good market potential.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of modified polymer resin, in particular to a halogen atom-containing polyether polyol resin modified by functional ester groups, and a preparation method and application thereof. BACKGROUND

[0002] Polyol resin is one of the important upstream raw materials of polymer materials, especially indispensable in widely used polyurethane materials. Among various polyol resin products, polyether polyol and polyester polyol are most commonly used, and are the main components for preparing polyurethane foam materials and elastomers with different performance characteristics. Although there are various polyol brands on the market, the structural composition is diverse but not deviating from the main theme. Polyether polyol is mainly obtained by ring-opening polymerization of ethylene oxide, propylene oxide and / or tetrahydrofuran; and polyester polyol is obtained by esterification of small molecule alcohols (such as ethylene glycol, butanediol, hexanediol, glycerol, pentaerythritol, etc.) with anhydride (phthalic anhydride) or carboxylic acid (such as adipic acid, terephthalic acid, etc.). Whether it is polyether or polyester polyol, the active site is in the terminal hydroxyl group, so there is a limitation of relatively single structure and insufficient modification site. In terms of performance, polyether polyol products have lower viscosity, are more convenient to use, and the prepared polyurethane materials have better flexibility, but the mechanical properties are inferior to those of polyester polyurethane materials; on the contrary, polyester polyol has the disadvantage of large viscosity and poor flowability due to the strong polar ester structure and more abundant hydrogen bonding, but the mechanical properties of its polyurethane products are more outstanding.

[0003] At present, the mixed use of polyether and polyester polyols is the main way to realize the complementary advantages of both, and there is still a lack of polyol products with abundant ether and ester bonds in the structure. Therefore, introducing more functional groups or active sites into polyether or polyester polyol products through structural design, and giving polyurethane materials more diverse performance characteristics, have good practical significance for the development and application of polyurethane new materials.

[0004] Polyepoxy chloro(bromo)propane is a special polyether polyol resin containing abundant halogen atoms, which has special properties such as flame retardance, oil resistance, ozone resistance, aging resistance, seawater resistance, and high damping coefficient, and can be widely used in special environments such as oil fields and oceans. Due to the strong electronegativity of halogen atoms, the chloro(bromo)methyl group (-CH2X, X=Cl and Br) in the structure of polyepoxy chloro(bromo)propane has high electrophilicity, so the halogen atom X can be replaced by a nucleophile to form a functional modified polyether polyol, for example, azido group (-N3) replacing X forms the significant energetic polyether polyol GAP, which is widely used in energetic polyurethane adhesives. At present, there is no report on more modified polyether products with specific functions for polyepoxy chloro(bromo)propane. SUMMARY

[0005] The purpose of this invention is to provide a modified polyether polyol with abundant ether and ester bonds, offering a new raw material option for the preparation, research, and development of polyurethane materials and novel polyether-derived polymeric materials. Furthermore, this invention also provides a method for preparing the modified polyether polyol and its application in the preparation of polyurethane and novel polyether-derived polymeric materials.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a modified polyether polyol possessing both abundant ether bonds and ester bonds, wherein the structure of the modified polyether polyol is shown in formula (I) or (II) below:

[0007]

[0008] In equation (Ⅰ), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. Numbers ranging from 1 to 120; R' and R are arbitrary groups;

[0009]

[0010] In formula (II), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. The number is 1 to 80, and R' and R are arbitrary groups.

[0011] The modified polyether polyol of the present invention is a polymer represented by formula (I) or formula (II), wherein a i b i c i Generally, it is an integer, and can be any integer. In equation (Ⅰ), a i b i They are generally integers between 1 and 120. This indicates that the a1+......a1+ of compounds with different molecular weights in the modified polyether polyol mixture are represented by the following formulas: i+ b1+......b i The average of the sums is any number between 1 and 120, and can be an integer or a decimal. For example, if i = 2... This represents the average sum of compounds a1+b1+a2+b2 with different degrees of polymerization in a mixture of modified polyether polyols with general structural formula (Ⅰ). In the modified polyether polyol represented by formula (Ⅱ) The meaning is similar to that of equation (Ⅰ).

[0012] a in formula (I) or formula (II) of the present invention i b i c iThe structure of the terminal hydroxyl group of the polyepoxy chloro(bromo)propane or the terminal hydroxyl group of the poly(3,3-bis chloro(bromo)methyl oxetane) in the following preparation method is closely related, specifically, a i , b i , c i determined by n i in the formula (III) and the formula (IV), a1+......a i+ b1+......b i =n1+......n i , or a1+......a i+ b1+......b i+ c 1...... +c i =n1+......n i .

[0013] The modified polyether polyol provided by the present application is a mixture of the compounds shown in the formula (I) or the formula (II) as described above, contains a polyether main chain, an ester side group, a halogen atom and a customizable chemical active site, the modified polyether polyol provided by the present application has a customizable functional ester side group modification and contains a chlorine or bromine atom from the perspective of chemical structure design, and can be used to prepare a new functional structure polyurethane or other high polymer material with rich ether bonds and ester bonds.

[0014] As a preferred embodiment of the modified polyether polyol provided by the present application, R' in the formula (I) and the formula (II) is independently selected from the following groups:

[0015]

[0016] More preferably, R' in the formula (I) and the formula (II) is independently selected from -CH2CH2-, -CH2CH2CH2CH2-.

[0017] As a preferred embodiment of the modified polyether polyol provided by the present application, R in the formula (I) and the formula (II) is independently selected from the following groups:

[0018]

[0019] wherein y is an integer of 0-10 and z is an integer of 2-8.

[0020] More preferably, R in the formula (I) and the formula (II) is independently selected from the following groups:

[0021]

[0022] wherein y is an integer of 0-10 and z is an integer of 2-8.

[0023] As a preferred embodiment of the modified polyether polyol according to the present application, the modified polyether polyol has a structural formula as shown below:

[0024]

[0025] wherein X is Cl or Br, is a number from 5 to 50, and R is selected from the following groups:

[0026]

[0027] wherein y is an integer from 0 to 10, and z is an integer from 2 to 8.

[0028] As a preferred embodiment of the modified polyether polyol according to the present application, the modified polyether polyol has a structural formula as shown below:

[0029]

[0030] wherein X is Cl, b1+a2=7.24, a1+b2=0.2, and R' is -CH2CH2CH2CH2-.

[0031] or, X is Cl, b1+a2=6.56, a1+b2=0.88, and R' is -CH2CH2CH2CH2-.

[0032] or, X is Cl, b1+a2=4.87, a1+b2=2.57, and R' is -CH2CH2CH2CH2-.

[0033] or, X is Cl, b1+a2=3.95, a1+b2=3.49, and R' is -CH2CH2CH2CH2-.

[0034] As a preferred embodiment of the modified polyether polyol according to the present application, the modified polyether polyol has a structural formula as shown below:

[0035]

[0036] wherein X is Cl, b1+a2=3.04, a1+b2=4.4, and R' is -CH2CH2CH2CH2-.

[0037] As a preferred embodiment of the modified polyether polyol according to the present application, the modified polyether polyol has a structural formula as shown below:

[0038]

[0039] wherein X is Cl, b1+a2=3.1, a1+b2=4.34, and R' is -CH2CH2CH2CH2-.

[0040] As a preferred embodiment of the modified polyether polyol of the present application, the structural formula of the modified polyether polyol is:

[0041]

[0042] wherein X is Cl, b1+a2=5.28, a1+b2=2.16, and R' is -CH2CH2CH2CH2-.

[0043] As a preferred embodiment of the modified polyether polyol of the present application, the structural formula of the modified polyether polyol is:

[0044]

[0045] wherein X is Cl, b1+a2=0, a1+b2=7.44, and R' is -CH2CH2CH2CH2-.

[0046] As a preferred embodiment of the modified polyether polyol of the present application, the structural formula of the modified polyether polyol is:

[0047]

[0048] wherein X is Cl, b1+a2=1.68, a1+b2=5.76, and R' is -CH2CH2CH2CH2-.

[0049] or X is Cl, b1+a2=2.09, a1+b2=5.35, and R' is -CH2CH2CH2CH2-.

[0050] or X is Cl, b1+a2=1.82, a1+b2=5.62, and R' is -CH2CH2CH2CH2-.

[0051] or X is Cl, b1+a2=9.5, a1+b2=6, and R' is -CH2CH2CH2CH2-.

[0052] or X is Cl, b1+a2=12.7, a1+b2=2.8, and R' is -CH2CH2CH2CH2-.

[0053] The b1+a2 and a1+b2 mentioned above are the average values of the sum of b1+a2 and a1+b2 in each compound in the mixture of the modified polyether polyol of the corresponding general formula.

[0054] In a second aspect, the present application also provides a method for preparing an ester side group modified polyether polyol containing chlorine or bromine atoms with customizable functions, to achieve the object, the technical scheme adopted by the present application is as follows: a method for preparing the modified polyether polyol described above, the method comprises the following steps:

[0055] (1) adding a hydroxyl-terminated polyepoxy chloro(bromo)propane or a hydroxyl-terminated poly(3,3-bis chloro(bromo)methyl oxetane), a carboxylate salt and a catalyst into a reaction container, then adding an organic solvent, and reacting at 70-130℃ for 6-48h, and then cooling to room temperature to obtain a reaction product;

[0056] (2) post-treatment of the reaction product:

[0057] pouring the reaction product into water, stirring thoroughly, and then standing until the water phase is clear, and then pouring off the water phase to obtain an organic phase; then dissolving the organic phase, and repeatedly washing with brine, drying, and removing the solvent to obtain the modified polyether polyol;

[0058] or adding the reaction product into a dialysis tube with a molecular weight cut-off of 200-1000Da, repeatedly dialyzing with deionized water for 3-5 days, and then collecting and drying the organic phase to obtain the modified polyether polyol.

[0059] As an embodiment of the method for preparing the modified polyether polyol described in the present application, the hydroxyl-terminated polyepoxy chloro(bromo)propane in step (1) has the following structural formula (III):

[0060]

[0061] In formula (III), X is Cl or Br, m is an integer of 1-6, i is an integer of 1-m, is a number of 1-120, and R' is any group.

[0062] The hydroxyl-terminated polyepoxy chloro(bromo)propane is a mixture of compounds with the general structural formula (III), wherein n i is generally an integer, is the average value of the sum of n1+...+n i of each compound in the mixture. Taking i=3 as an example, represents the average value of the sum of n1+n2+n3 of each compound in the polyepoxy chloro(bromo)propane mixture, and therefore it can be an integer or a decimal number.

[0063] As an embodiment of the method for preparing the modified polyether polyol described in the present application, the hydroxyl-terminated poly(3,3-bis chloro(bromo)methyl oxetane) in step (1) has the following structural formula (IV):

[0064]

[0065] In equation (Ⅳ), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. The number is 1 to 80, and R' is any group.

[0066] The hydroxyl-terminated poly(3,3-dichloro(bromo)methyloxetane) is also a mixture of compounds as shown in formula (Ⅳ) above. The meaning is similar to that in equation (Ⅲ).

[0067] As an embodiment of the preparation method of the modified polyether polyol of the present invention, R' in formula (III) and formula (IV) are each independently selected from the following groups:

[0068]

[0069] In the structural formula of the hydroxyl-terminated poly(3,3-dichloro(bromo)methyloxetane), X is Cl or Br, and m is an integer from 1 to 6, for example, m can be 1, 2, 3, 4, 5, or 6. The value is a number from 1 to 80, and R' is preferably -CH2CH2- or -CH2CH2CH2CH2-.

[0070] As an embodiment of the preparation method of the modified polyether polyol of the present invention, the organic solvent in step (1) is N,N-dimethylformamide (DMF). The organic solvent includes, but is not limited to, N,N-dimethylformamide (DMF), and those skilled in the art can choose it reasonably as needed. The reaction process in step (1) generally needs to be carried out under a nitrogen atmosphere and with thorough stirring. Under the conditions of the reaction, the raw materials undergo a substitution reaction to obtain the corresponding reactants for subsequent processing.

[0071] As an embodiment of the preparation method of the modified polyether polyol of the present invention, the carboxylate includes at least one of the following: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, their substituted derivatives, and potassium, sodium, and lithium salts of (substituted) isomers of carboxylic acids; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid; (substituted) phthalic acid, malic acid, tartaric acid, citric acid, their substituted derivatives, and monopotassium (sodium / lithium) salts of (substituted) isomers; and potassium, sodium, and lithium salts of acrylic acid and methacrylic acid.

[0072] The carboxylic acid salt can be at least one of potassium, sodium, lithium salts of acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, and the like and their substituted and (substituted) isomeric carboxylic acids, potassium, sodium, lithium salts of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, (substituted) phthalic acid, citric acid, and the like and their substituted and (substituted) isomeric monopotassium (sodium / lithium) salts, potassium, sodium, lithium salts of acrylic acid, methacrylic acid.

[0073] As an embodiment of the method for producing the modified polyether polyol according to the present application, the catalyst includes at least one of CsI, KI, and Nal.

[0074] As a preferred embodiment of the method for producing the modified polyether polyol according to the present application, the polyepoxy chloro(bromo)propane having a terminal hydroxyl group in the step (1) has a structure represented by the following formula (V):

[0075]

[0076] In the formula (V), X is Cl or Br, and n1+n2 is a number of 5 to 50, and R' is -CH2CH2- or -CH2CH2CH2CH2-. The n1+n2 is an average value of the sum of n1+n2 in each compound in the mixture of the hydroxyl group-containing polyepoxy chloro(bromo)propane of the formula (V).

[0077] As a preferred embodiment of the method for producing the modified polyether polyol according to the present application, the carboxylic acid salt includes at least one of potassium, sodium, lithium salts of acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, and the like and their substituted and (substituted) isomeric carboxylic acids, potassium, sodium, lithium salts of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, (substituted) phthalic acid, malic acid, tartaric acid, citric acid, and the like and their substituted and (substituted) isomeric monopotassium (sodium / lithium) salts, potassium, sodium, lithium salts of acrylic acid, methacrylic acid. Preferably, the carboxylic acid salt includes at least one of potassium, sodium salts of butyric acid, 3-hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, acrylic acid, methacrylic acid, potassium, sodium salts of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid.

[0078] As a preferred embodiment of the method for producing the modified polyether polyol according to the present application, the catalyst includes at least one of CsI, KI, and Nal. More preferably, the catalyst is CsI.

[0079] Preferably, in the post-treatment of the reactants in step (2), the first method is to pour the reactants into a large amount of water, stir well and stand until the aqueous phase is substantially clear, pour off the aqueous phase, dissolve the remaining organic phase with ethyl acetate, chloroform or dichloromethane, then repeatedly wash with brine, dry with anhydrous sulfate, and remove the solvent to obtain a yellow to brown-black viscous polyol resin product. The second method is to post-treat the reactants by dialysis, specifically: the reactants are added to a dialysis tube with a molecular weight cutoff of 200-1000 Da, and after repeated dialysis against deionized water for 3-5 days, the organic phase is collected and dried to obtain a yellow to brown-black viscous polyol resin product.

[0080] The preparation method of the modified polyether polyol is as follows: first, the hydroxyl-terminated polyepoxy chloro(bromo)propane or hydroxyl-terminated poly(3,3-bis chloro(bromo)methyl oxetane), carboxylate salt and catalyst are reacted under specific temperature conditions for a period of time, the reaction is completed, then cooled, and then the post-treatment of the reactants is performed. The post-treatment of the reactants has two methods, and different post-treatment methods can be selected according to needs, and both methods can obtain the modified polyether polyol.

[0081] Finally, the application also provides the use of the modified polyether polyol as described above in the preparation of polyurethane and polyether-derived novel high molecular materials. The modified polyether polyol contains a polyether main chain, ester side groups, halogen atoms and customizable chemical active sites, and can be used to prepare novel functional structure polyurethane materials with rich ether bonds and ester bonds, and can also develop novel high molecular products based on ether and ester structures, not only providing a new upstream raw material for functionalized polyurethane and its derived products, but also the resin itself is expected to develop into a new high molecular material, which has a wide range of applications.

[0082] The modified polyether polyol uses the substitution reaction of halogenated alkyl and carboxylate to link different structures of carboxylate to the side chain of the polyether polyol, and obtains functional ester group modified polyether polyol containing halogen atoms of different structures, and realizes the structural complementation of polyether and polyester polyol. The modified polyether polyol contains a polyether main chain, ester side groups, halogen atoms and customizable chemical active sites, and can be used to prepare novel functional structure polyurethane and polyether-derived novel high molecular materials with rich ether bonds and ester bonds, and provides a new raw material selection for the preparation and development of high molecular materials.

[0083] The preparation method of the modified polyether polyol has simple process steps and is easy to popularize and apply in industry. On the one hand, the esterification degree can be adjusted and controlled through reaction temperature, time, catalyst and feed ratio, and on the other hand, the structure of the modified polyether polyol can be designed by designing the structure of the carboxylate, and the functional ester group modified polyether polyol is given unique properties.

[0084] The modified polyether polyol can be used for preparing polyurethane materials, and the new functional structure polyurethane materials with rich ether bonds and ester bonds can be prepared, which not only provides new upstream raw materials for functional polyurethane and its derived products, but also is expected to develop into a new type of polymer material, and has good market potential. BRIEF DESCRIPTION OF DRAWINGS

[0085] Figure 1 The reaction process schematic diagram of the modified polyether polyol is shown.

[0086] Figure 2 The reaction process schematic diagram of the modified polyether polyol is shown.

[0087] Figure 3 The reaction process schematic diagram of the modified polyether polyol is shown.

[0088] Figure 4 The reaction process schematic diagram of the modified polyether polyol is shown.

[0089] Figure 5 The reaction process schematic diagram of the modified polyether polyol is shown.

[0090] Figure 6 The reaction process schematic diagram of the modified polyether polyol is shown.

[0091] Figure 7 The reaction process schematic diagram of the modified polyether polyol is shown.

[0092] Figure 8 The reaction process schematic diagram of the modified polyether polyol is shown. 1 H-NMR spectrum.

[0093] Figure 9 The FTIR spectrum of the modified polyether polyol and the raw material HTCH (molecular weight 800) thereof is shown.

[0094] Figure 10 The H-NMR spectrum of the modified polyether polyol and the raw material HTCH (molecular weight 800) thereof is shown. 1 H-NMR spectrum.

[0095] Figure 11 The FTIR spectrum of the modified polyether polyol and the raw material HTCH (molecular weight 800) thereof is shown.

[0096] Figure 12FTIR spectra of the modified polyether polyols described in Examples 9-11 and the raw material HTCH (molecular weight 800). 1 H-NMR spectra.

[0097] Figure 13 FTIR spectra of the modified polyether polyols described in Examples 9-11 and the raw material HTCH (molecular weight 800).

[0098] Figure 14 FTIR spectra of the modified polyether polyols described in Examples 12 and 13 and the raw material HTCH (molecular weight 1500). 1 H-NMR spectra.

[0099] Figure 15 FTIR spectra of the modified polyether polyols described in Examples 12 and 13 and the raw material HTCH (molecular weight 1500).

[0100] Figure 16 DSC and TGA curves of the foam prepared from the modified polyether polyols described in Example 3 and Example 6.

[0101] Figure 17 Contact angle test results of the polyurethane prepared from the modified polyether polyols described in Example 8 and Example 12.

[0102] Figure 18 Combustion photos of the foam and photocured resin prepared from the modified polyether polyols described in Example 3, Example 6 and Example 7 in air. DETAILED DESCRIPTION

[0103] For the purpose of better illustrating the object, technical scheme and advantages of the present application, the present application will be further described below in conjunction with the drawings and specific examples.

[0104] In the preparation method of the modified polyether polyols described in the present application, the reaction general formula is as shown in the accompanying Figure 1 First, the hydroxyl-terminated polyepoxy chloro(bromo)propane or hydroxyl-terminated poly(3,3-bis chloro(bromo)methyl oxetane), carboxylate salt and catalyst are reacted under specific temperature conditions for a period of time, after the reaction is completed, cooling is performed, and then the reactant post-treatment is performed. There are two methods for the reactant post-treatment, and different post-treatment methods can be selected according to the needs during use, and both methods can obtain the modified polyether polyols. The amount ratio of the hydroxyl-terminated polyepoxy chloro(bromo)propane or poly(3,3-bis chloro(bromo)methyl oxetane), carboxylate salt and catalyst in step (1) is related to the specific reaction conditions and the esterification degree of the desired product, and the person skilled in the art can reasonably select the amount ratio of the raw materials according to the reaction conditions and the esterification degree requirement of the target product, which is not specifically limited and exemplified here.

[0105] The technical solutions of the application are further described below with specific examples.

[0106] The chlorine content in the following examples was measured by a S8 Tiger II wavelength dispersive X-ray fluorescence spectrometer of Bruker Company. The raw materials used were directly purchased, and the molecular weight of the raw materials was provided by the supplier.

[0107] Example 1

[0108] An embodiment of the modified polyether polyol of the application, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

[0109] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 15 g of monosodium succinate, and 0.5 g of CsI were added into a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in an 80°C oil bath, and the reaction was stirred under a flowing nitrogen atmosphere for 24 h to become a yellow turbid system, which was cooled to room temperature to obtain a reaction product;

[0110] (2) The reaction product was poured into about 250 mL of water, stirred and then allowed to stand, and then the aqueous phase was removed, and the viscous organic phase was retained, and then the organic phase was washed with water for 2 times, and then dissolved in chloroform, and washed with saturated brine for 3 times, and then the organic phase was collected and the chloroform was removed, to obtain a yellow viscous monosuccinate-functionalized chlorine-containing polyether polyol, and the chlorine content was about 31.2 wt%, which was the modified polyether polyol described in this embodiment.

[0111] The reaction formula of the modified polyether polyol described in this embodiment is shown in the attached Figure 2 The obtained modified polyether polyol was a mixture of compounds with the following structural formula:

[0112]

[0113] In the reaction formula and the structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 7.24, a1+b2 = 0.2, and R' is -CH2CH2CH2CH2-. In the reaction formula and the structural formula, b1+a2+a1+b 2＝ n1+n2, and the n1+n2, b1+a2, and a1+b2 are average values of the sum of n1+n2, b1+a2, and a1+b2 of each compound in the mixture of the modified polyether polyol obtained in this embodiment.

[0114] Example 2

[0115] An embodiment of the modified polyether polyol of the application, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

[0116] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 15 g of monosodium succinate, and 0.5 g of CsI were added to a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in a 100°C oil bath, and the reaction was stirred under a flowing nitrogen atmosphere for 24 h to become a brownish yellow turbid system, which was cooled to room temperature to obtain a reaction product;

[0117] (2) The reaction product was poured into about 250 mL of water, stirred and then allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and then the organic phase was washed with water for 2 times, then dissolved in chloroform, washed with saturated brine for 3 times, and then the organic phase was collected and the chloroform was removed to obtain a brownish yellow viscous monosuccinate-functionalized chlorine-containing polyether polyol with a chlorine content of 27.6 wt%, which was the modified polyether polyol described in this example.

[0118] The reaction formula of the modified polyether polyol described in this example is shown in the accompanying Figure 2 The obtained modified polyether polyol is a mixture of compounds with the following structural formula:

[0119]

[0120] In the reaction formula and the structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 6.56, a1+b2 = 0.88, and R' is -CH2CH2CH2CH2-. In this example, the meanings of n1+n2, b1+a2, and a1+b2 are the same as those in Example 1.

[0121] Example 3

[0122] An embodiment of the modified polyether polyol of the present application, the preparation method of the modified polyether polyol described in this example comprises the following steps:

[0123] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 15 g of monosodium succinate, and 0.5 g of CsI were added to a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in a 120°C oil bath, and the reaction was stirred under a flowing nitrogen atmosphere for 24 h to become a brownish yellow turbid system, which was cooled to room temperature to obtain a reaction product;

[0124] (2) The reaction product was poured into about 250 mL of water, stirred and then allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and then the organic phase was washed with water for 2 times, then dissolved in chloroform, washed with saturated brine for 3 times, and then the organic phase was collected and the chloroform was removed to obtain a brownish yellow viscous monosuccinate-functionalized chlorine-containing polyether polyol with a chlorine content of 27.6 wt%, which was the modified polyether polyol described in this example.

[0125] The reaction formula of the modified polyether polyol in this embodiment is shown in the following formula (I) and the obtained modified polyether polyol is a mixture of compounds with the following structural formula (II): Figure 2

[0126]

[0127] In the reaction formula and the structural formula, X is Cl, n1+n2=7.44, b1+a2=4.87, a1+b2=2.57, and R' is -CH2CH2CH2CH2-. In this embodiment, the meanings of n1+n2, b1+a2, and a1+b2 are the same as those in Embodiment 1.

[0128] Embodiment 4

[0129] In one embodiment of the modified polyether polyol of the present application, the preparation method of the modified polyether polyol in this embodiment comprises the following steps:

[0130] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M=800, HTCH), 15 g of monosodium succinate, and 0.5 g of KI were added into a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in an oil bath at 120°C and stirred under a flowing nitrogen atmosphere for 24 h to become a brown-black turbid system, which was cooled to room temperature to obtain a reaction product;

[0131] (2) The reaction product was poured into about 250 mL of water, stirred and then allowed to stand, and then the water phase was removed and the viscous organic phase was retained, and then the organic phase was washed with water for 2 times, then dissolved in chloroform, washed with saturated brine for 3 times, and then the organic phase was collected and the chloroform was removed to obtain a brown-black chloro atom-containing monosuccinate-functionalized polyether polyol with a chlorine content of 14.4 wt%, which is the modified polyether polyol in this embodiment.

[0132] The reaction formula of the modified polyether polyol in this embodiment is shown in the following formula (I) and the obtained modified polyether polyol is a mixture of compounds with the following structural formula (II): Figure 2

[0133]

[0134] In the reaction formula and the structural formula, X is Cl, n1+n2=7.44, b1+a2=3.95, a1+b2=3.49, and R' is -CH2CH2CH2CH2-. In this embodiment, the meanings of n1+n2, b1+a2, and a1+b2 are the same as those in Embodiment 1.

[0135] Embodiment 5

[0136] ​​An embodiment of the modified polyether polyol of the present application, the method for preparing the modified polyether polyol of the present embodiment comprises the following steps:

[0137] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 13.5 g of sodium 3-hydroxybutyrate, and 0.5 g of CsI were added into a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in a 120°C oil bath, and the reaction was stirred under a flowing nitrogen atmosphere for 24 h to become a brownish yellow turbid system, which was cooled to room temperature to obtain a reactant;

[0138] (2) The reactant was dialyzed in water for 3-4 days using a dialysis bag with a molecular weight cut-off of 500 Da to obtain a deep viscous dark yellow 3-hydroxybutyrate functionalized polyether polyol, which is the modified polyether polyol of the present embodiment.

[0139] The reaction formula of the modified polyether polyol of the present embodiment is shown in the accompanying Figure 3 The obtained modified polyether polyol is a mixture of compounds with the following structural formula:

[0140]

[0141] In the reaction formula and the structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 3.04, a1+b2 = 4.4, and R' is -CH2CH2CH2CH2-. In the present embodiment, the meanings of n1+n2, b1+a2, and a1+b2 are the same as those in Embodiment 1.

[0142] Embodiment 6

[0143] An embodiment of the modified polyether polyol of the present application, the method for preparing the modified polyether polyol of the present embodiment comprises the following steps:

[0144] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 21.9 g of potassium hydrogen phthalate, and 0.5 g of CsI were added into a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in a 120°C oil bath, and the reaction was stirred under a flowing nitrogen atmosphere for 24 h to become a brownish yellow turbid system, which was cooled to room temperature to obtain a reactant;

[0145] (2) The reactant was poured into about 250 mL of water, stirred and then allowed to stand, and then the aqueous phase was removed and the viscous organic phase was retained, and then the organic phase was washed with water for 2 times, and then dissolved in ethyl acetate and washed with saturated brine for 3 times, and then the organic phase was collected and the ethyl acetate was removed to obtain a brownish viscous phthalic acid monoester functionalized polyether polyol containing chlorine atoms, which is the modified polyether polyol of the present embodiment.

[0146] The reaction formula for the modified polyether polyol described in this embodiment is attached. Figure 4 As shown, the obtained modified polyether polyol is a mixture of compounds with the following structural formulas:

[0147]

[0148] In the reaction formula and structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 3.1, a1+b2 = 4.34, and R' is -CH2CH2CH2CH2-. The meanings of n1+n2, b1+a2, and a1+b2 in this embodiment are the same as in Example 1.

[0149] Example 7

[0150] An embodiment of the modified polyether polyol of the present invention includes the following steps in the preparation method of the modified polyether polyol:

[0151] (1) 10g of hydroxyl-terminated polyepoxychloropropane (M=800, HTCH), 11.8g of potassium acrylate and 0.5g of CsI were added to a 150mL three-necked flask, and 30g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an 80℃ oil bath and stirred for 12h under a flowing nitrogen atmosphere to form a yellow turbid system. The system was cooled to room temperature to obtain the reactant.

[0152] (2) Pour the reactants into about 250 mL of water, stir and let stand, then remove the aqueous phase, retain the viscous organic phase, add water and stir and wash twice, then dissolve with ethyl acetate, wash three times with saturated saline, collect the organic phase and remove ethyl acetate, to obtain a yellow viscous acrylate-functionalized polyether polyol containing chlorine atoms, which is the modified polyether polyol described in this example.

[0153] The reaction formula for the modified polyether polyol described in this embodiment is attached. Figure 5 As shown, the obtained modified polyether polyol is a mixture of compounds with the following structural formulas:

[0154]

[0155] In the reaction formula and structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 5.28, a1+b2 = 2.16, and R' is -CH2CH2CH2CH2-. The meanings of n1+n2, b1+a2, and a1+b2 in this embodiment are the same as in Example 1.

[0156] Example 8

[0157] An embodiment of the modified polyether polyol of the present invention includes the following steps in the preparation method of the modified polyether polyol:

[0158] (1) Put 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 14.8 g of sodium hexanoate, and 0.5 g of CsI into a 150 mL three-necked flask, add 30 g of N,N-dimethylformamide (DMF) as a solvent, then put the three-necked flask into a 120°C oil bath, stir the reaction under a flowing nitrogen atmosphere for 24 h to become a brown turbid system, cool to room temperature to obtain a reaction product;

[0159] (2) Pour the reaction product into about 250 mL of water, stir and then stand, then remove the water phase, retain the viscous organic phase, add water to stir and wash 2 more times, then dissolve with ethyl acetate, wash 3 times with saturated brine, collect the organic phase and remove the ethyl acetate to obtain a brown viscous chloro atom-containing hexanoate functionalized polyether polyol, which is the modified polyether polyol described in this example.

[0160] The reaction formula of the modified polyether polyol described in this example is shown in the attached Figure 6 The obtained modified polyether polyol is a mixture of compounds as shown in the following structural formula:

[0161]

[0162] In the reaction formula and the structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 0, a1+b2 = 7.44, and R' is -CH2CH2CH2CH2-. In this example, the meanings of n1+n2, b1+a2, and a1+b2 are the same as in Example 1.

[0163] Example 9

[0164] An embodiment of the modified polyether polyol of the present application, the preparation method of the modified polyether polyol described in this example includes the following steps:

[0165] (1) Put 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 14.8 g of sodium hexanoate, and 0.5 g of CsI into a 150 mL three-necked flask, add 30 g of N,N-dimethylformamide (DMF) as a solvent, then put the three-necked flask into a 120°C oil bath, stir the reaction under a flowing nitrogen atmosphere for 24 h to become a brown turbid system, cool to room temperature to obtain a reaction product;

[0166] (2) Use a dialysis bag with a molecular weight cut-off of 500 Da to dialyze the reaction product in water for 3-4 days to obtain a deep viscous brown-black acetic ester functionalized polyether polyol, which is the modified polyether polyol described in this example.

[0167] The reaction formula of the modified polyether polyol described in this example is shown in the attached Figure 7As shown, the obtained modified polyether polyol is a mixture of compounds with the following structural formula:

[0168]

[0169] In the reaction formula and the structural formula, X is Cl, n1+n2=7.44, b1+a2=2.09, a1+b2=5.35, and R' is -CH2CH2CH2CH2-. In this embodiment, the meanings of n1+n2, b1+a2, and a1+b2 are the same as those in Embodiment 1.

[0170] Embodiment 10

[0171] In one embodiment of the modified polyether polyol of the present application, the preparation method of the modified polyether polyol in this embodiment includes the following steps:

[0172] (1) 10 g of hydroxyl-terminated polyepichlorohydrin (M=800, HTCH), 10.5 g of potassium acetate, and 0.5 g of CsI were added into a 150 mL three-necked flask, 30 g of N,N-dimethylformamide (DMF) was added as a solvent, and then the three-necked flask was placed in a 120°C oil bath, and the reaction was stirred under a flowing nitrogen atmosphere for 12 h to become a brown-black turbid system, which was cooled to room temperature to obtain a reactant;

[0173] (2) The reactant was dialyzed in water for 3-4 days using a dialysis bag with a molecular weight cut-off of 500 Da to obtain a deep viscous brown-black acetate-functionalized polyether polyol, which is the modified polyether polyol in this embodiment.

[0174] The reaction formula of the modified polyether polyol in this embodiment is shown in the accompanying Figure 7 As shown, the obtained modified polyether polyol is a mixture of compounds with the following structural formula:

[0175]

[0176] In the reaction formula and the structural formula, X is Cl, n1+n2=7.44, b1+a2=2.09, a1+b2=5.35, and R' is -CH2CH2CH2CH2-. In this embodiment, the meanings of n1+n2, b1+a2, and a1+b2 are the same as those in Embodiment 1.

[0177] Embodiment 11

[0178] In one embodiment of the modified polyether polyol of the present application, the preparation method of the modified polyether polyol in this embodiment includes the following steps:

[0179] (1) Put 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 10.5 g of potassium acetate, and 0.1 g of CsI into a 150 mL three-necked flask, add 30 g of N,N-dimethylformamide (DMF) as a solvent, then put the three-necked flask into a 120°C oil bath, and stir the reaction under a flowing nitrogen atmosphere for 24 h to become a brown-black turbid system, cool to room temperature, and obtain a reaction product;

[0180] (2) Dialyze the reaction product in water using a dialysis bag with a molecular weight cut-off of 500 Da for 3-4 days to obtain a deep viscous brown-black acetic ester functionalized polyether polyol, which is the modified polyether polyol described in this example.

[0181] The reaction formula of the modified polyether polyol described in this example is shown in the accompanying Figure 7 The obtained modified polyether polyol is a mixture of compounds with the following structural formula:

[0182]

[0183] In the reaction formula and the structural formula, X is Cl, n1+n2 = 7.44, b1+a2 = 1.82, a1+b2 = 5.62, and R' is -CH2CH2CH2CH2-. In this example, the meanings of n1+n2, b1+a2, and a1+b2 are the same as in Example 1.

[0184] Example 12

[0185] An embodiment of the modified polyether polyol of the present application, the preparation method of the modified polyether polyol described in this example includes the following steps:

[0186] (1) Put 10 g of hydroxyl-terminated polyepichlorohydrin (M = 800, HTCH), 10.5 g of potassium acetate, and 0.1 g of CsI into a 150 mL three-necked flask, add 30 g of N,N-dimethylformamide (DMF) as a solvent, then put the three-necked flask into a 120°C oil bath, and stir the reaction under a flowing nitrogen atmosphere for 24 h to become a brown-black turbid system, cool to room temperature, and obtain a reaction product;

[0187] (2) Dialyze the reaction product in water using a dialysis bag with a molecular weight cut-off of 500 Da for 3-4 days to obtain a deep viscous brown-black acetic ester functionalized polyether polyol, which is the modified polyether polyol described in this example.

[0188] The reaction formula of the modified polyether polyol described in this example is shown in the accompanying Figure 7 The obtained modified polyether polyol is a mixture of compounds with the following structural formula:

[0189]

[0190] In the reaction formula and structural formula, X is Cl, n1+n2 = 15.5, b1+a2 = 9.5, a1+b2 = 6, and R' is -CH2CH2CH2CH2-. The meanings of n1+n2, b1+a2, and a1+b2 in this embodiment are the same as in Example 1.

[0191] Example 13

[0192] An embodiment of the modified polyether polyol of the present invention includes the following steps in the preparation method of the modified polyether polyol:

[0193] (1) 14g of hydroxyl-terminated polyepoxychloropropane (M=1500, HTCH), 3.8g of potassium acetate and 0.5g of CsI were added to a 150mL three-necked flask, and 30g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120℃ and stirred for 12h under a flowing nitrogen atmosphere to form a brownish-black turbid system. The mixture was cooled to room temperature to obtain the reactant.

[0194] (2) The reactants were dialyzed in water for 3-4 days using a dialysis bag with a molecular weight cutoff of 500 Da to obtain a dark viscous brown-black acetate-functionalized polyether polyol, which is the modified polyether polyol described in this example.

[0195] The reaction formula for the modified polyether polyol described in this embodiment is attached. Figure 7 As shown, the obtained modified polyether polyol is a mixture of compounds with the following structural formulas:

[0196]

[0197] In the reaction formula and structural formula, X is Cl, n1+n2 = 15.5, b1+a2 = 12.7, a1+b2 = 2.8, and R' is -CH2CH2CH2CH2-. The meanings of n1+n2, b1+a2, and a1+b2 in this embodiment are the same as in Example 1.

[0198] Example 14

[0199] Structural identification of the modified polyether polyol described in this invention

[0200] The proton NMR and infrared spectra of the modified polyether polyols prepared in Examples 1-13 and the hydroxyl-terminated polyepoxychloropropane (HTCH) used as the raw material were tested respectively. The testing methods were as follows:

[0201] 1H NMR spectrum ( 1 H-NMR: Measured using a Bruker AVANCE HD 500 NMR spectrometer, with CDCl3 as the solvent;

[0202] Infrared spectrum (FT-IR): obtained using a PerkinElmer Spectrum 100 infrared spectrometer in total reflectance mode.

[0203] The test results are attached. Figures 8-15 As shown.

[0204] From the appendix Figure 8 It can be seen that the chemical shift δ = 1.64 ppm represents the proton signal of the two methylene groups (-OCH2CH2CH2CH2O-) in the middle of the initiator butanediol in HTCH. The range of δ = 3.4-4.4 ppm represents the proton signal of the epichlorohydrin repeating unit and the two methylene groups on both sides of the initiator (-OCH2CH2CH2CH2O-). In Example 1, the chemical shift δ = 2.64 ppm represents the proton signal of the succinic acid monoester structure (-OOCCH2CH2COOH) introduced by esterification. The degree of esterification substitution is calculated to be 2.7% based on the integral ratio at 1.64 and 2.64 ppm.

[0205] From the appendix Figure 9 It can be seen that in the raw material HTCH, 3500cm -1 The peak at 2960-2870 cm⁻¹ originates from the stretching vibration of the terminal OH group. -1 The peak at 1430 cm⁻¹ represents the stretching vibration of the saturated CH structure. -1 Nearby is the in-plane bending vibration of the CH bond in CH2Cl, 1100 cm⁻¹. -1 The position represents the antisymmetric stretching vibration of the ether bond COC, at 750 cm⁻¹. -1 The absorption peak at 1732 cm⁻¹ is C-Cl. Compared with HTCH, Example 1 shows an absorption peak at 1732 cm⁻¹. -1 There is a new absorption peak, which belongs to the C=O absorption peak of ester and carboxyl groups.

[0206] The modified polyether polyols described in Examples 2-4 1 The H-NMR and FTIR spectra were consistent with those of Example 1, but in Example 2, the proton signal at δ = 2.64 ppm and the signal at 1732 cm⁻¹ were different. -1 The C=O absorption peak at ppm is stronger, and the degree of esterification substitution is calculated to be 11.8% based on the integral ratio at 1.64 and 2.64 ppm. In Example 3, due to the introduction of more carboxyl structures, the absorption peak at 3500 cm⁻¹ is stronger. -1 The OH stretching vibration peak is broader. The degree of esterification substitution was calculated to be 34.6% based on the integral ratio at 1.64 and 2.64 ppm. In Example 4, the degree of esterification substitution was calculated to be 46.9% based on the integral ratio at 1.64 and 2.64 ppm.

[0207] From the appendix Figure 10 It can be seen that:

[0208] In Example 5, δ = 1.25 ppm corresponds to the methyl signal in 3-hydroxybutyrate, δ = 2.45 ppm and 4.25 ppm are methylene and methine, respectively, and the chemical shift of the pendant methylene on the epoxide chloropropane repeat unit also moves to 4-4.5 ppm due to esterification. The signals at 1.26, 2.05 and 4.12 ppm are unreacted ethyl acetate, and the degree of esterification is calculated to be 59.2% from the integral ratio at 1.64 and 2.45 ppm;

[0209] In Example 6, the signals at δ = 7.45-8 ppm are from the benzene ring structure introduced by esterification, and the signals at 1.26, 2.05 and 4.12 ppm are unreacted ethyl acetate, and the degree of esterification is calculated to be 58.4% from the integral ratio at 1.64 and 7.45-8 ppm;

[0210] In Example 7, the three signals at δ = 6-6.5 ppm are attributed to the double bond structure of the acrylate ester, and the degree of esterification is calculated to be 29.0% from the integral ratio at 1.64 and 6-6.5 ppm.

[0211] In Example 8, δ = 0.9 ppm is the methyl signal of the hexanoate ester, and δ = 1.31, 1.62 and 2.33 ppm are the methylene signals of the hexanoate ester, and δ = 1.62 ppm is superimposed with the methylene signal of the initiator butanediol in the raw material. Due to esterification, the methylene chemical shift of the pendant group of the polyether main chain moves to 3.96-4.38 ppm, while the methylene and methine chemical shifts on the main chain remain at 3.4-3.8 ppm, and the integral ratio is 1.99 / 3≈2 / 3 (theoretical maximum), so the degree of esterification is close to 100%.

[0212] From the above Figure 11 It can be seen that:

[0213] In Example 5, the product has a wide and strong OH stretching vibration peak near 3400 cm -1 , indicating that the product has more OH functional groups than the raw material HTCH, the ester group absorption at 1720 cm -1 , and the change in the saturated hydrocarbon structure absorption peak between 2980-2870 cm -1 indicates the substitution process as shown in the following reaction.

[0214] In Example 6, there is a wide and strong OH stretching vibration peak near 3400 cm -1 , which is derived from the end OH and the COOH brought by the benzene ring structure, 1720 cm -1 and 1260 cm -1The position represents the C=O and COC structure of the ester group, 750cm -1 This is the CH vibration peak of ortho-disubstituted benzene, approximately 1600 cm⁻¹. -1 and 3070cm -1 The weak peak at that point belongs to the benzene ring skeleton.

[0215] In Example 7, 1720cm -1 and 1272cm -1 The position represents the C=O and COC structure of the ester group, 980 cm. -1 and 910cm -1 =CH bending vibration from the acrylic structure. GPC indicates Mw = 701.

[0216] In Example 8, due to the introduction of hexanoate, the concentration was 2960–2860 cm⁻¹. -1 The ester structure shows distinct characteristic peaks of -CH3 and -CH2- at 1720 cm⁻¹. -1 This is reflected in the local context.

[0217] From the appendix Figure 12 It can be seen that in Example 9, the chemical shift at 2.1 ppm is the methyl signal of the acetate, and the remaining signals are all from the raw material HTCH. The degree of esterification substitution is calculated to be 77.3% based on the integral ratio at 1.64 and 2.1 ppm.

[0218] From the appendix Figure 13 It can be seen that in Example 9, 2950cm -1 Changes in absorption peak at 1720 cm⁻¹ and 1720 cm⁻¹ -1 and 1220cm -1 The C=O and COC structures at the location both indicate the presence of an acetate structure.

[0219] The modified polyether polyols described in Examples 10 and 11 1 The H-NMR and FTIR spectra were consistent with those of Example 9, but in Example 10, the degree of esterification substitution was calculated to be 71.9% based on the integral ratios at 1.64 and 2.1 ppm. GPC showed Mw = 1041.

[0220] In Example 11, the degree of esterification substitution was calculated to be 75.6% based on the integral ratios at 1.64 and 2.1 ppm.

[0221] From the appendix Figure 14 and 15 It can be seen that the modified polyether polyols described in Examples 12 and 13... 1The H-NMR and FTIR spectra were consistent with those of Example 9, but the degree of esterification was calculated to be 38.5% from the integral ratio at 1.64 and 2.1 ppm in Example 12. The degree of esterification was calculated to be 18.1% from the integral ratio at 1.64 and 2.1 ppm in Example 13.

[0222] Example 15

[0223] Performance test of the modified polyether polyol according to the present application

[0224] The glass transition temperature Tg, thermal decomposition temperature Td and combustion behavior in air of the high molecular foam materials prepared from the modified polyether polyols obtained in Example 3 and Example 6 were tested, respectively. g d The hardness and combustion behavior in air of the high molecular materials prepared from the modified polyether polyols obtained in Example 3, Example 6 and Example 7 and the common polyether polyol PPG after UV light curing were tested, respectively. The contact angle of the polyurethane prepared from the modified polyether polyol obtained in Example 8 and Example 12 and the common polyether polyol PPG was tested, and the test method was as follows:

[0225] T g : determined by using Perkinelmer DSC8500 differential scanning calorimeter, the scanning temperature range was -50°C-100°C, and the temperature increasing rate was 10°C / min.

[0226] T d : determined by using TA Instruments thermal gravimetric analyzer (TGA5500) in air atmosphere, the temperature range was 25°C-800°C, and the temperature increasing rate was 10°C / min.

[0227] Water contact angle: determined by using German Kruss contact angle measuring instrument DSA100 at room temperature.

[0228] Hardness: determined by using LX-A type Shore rubber hardness tester.

[0229] Combustion behavior: the test sample was ignited in air using a lighter, and whether it had self-extinguishing and molten droplet dropping phenomena during combustion was observed.

[0230] Method for preparing different high molecular material samples from the modified polyether polyol:

[0231] 1) Preparation of high molecular foam material

[0232] ​Take 5 g of dry modified polyether polyol obtained from Example 3 and 2 g of XDI in a plastic cup and mix them well at room temperature, then put them in a 50 °C oven to react and foam freely, and mark it as Foam A.

[0233] Take 5 g of dry modified polyether polyol obtained from Example 6 and 2 g of XDI in a plastic cup and mix them well at room temperature, then put them in a 50 °C oven to react and foam freely, and mark it as Foam B.

[0234] As a control, take 15 g of ordinary six-functional polyether polyol (Donol 6028E, provided by Shanghai Dongda Chemical Co., Ltd., molecular weight 12000), 1.1 g of XDI and 0.03 g of deionized water (as a foaming agent) in a plastic cup and mix them well at room temperature, then put them in a 50 °C oven to react and foam freely, and mark it as Foam Ref.

[0235] 2) Preparation of photocurable resin

[0236] Take 4 g of modified polyether polyol obtained from Example 7 and a little photoinitiator I2959 in a plastic culture and mix them well, then cure them under 365 nm UV light for 0.5 h after the mixture spontaneously levels, and mark it as UV-S.

[0237] As a control, take 4 g of commercially available polyethylene glycol diacrylate (PEGDA, M = 600, provided by Shanghai Aladdin Reagent Co., Ltd.) and a little photoinitiator I2959 in a plastic culture and mix them well, then cure them under 365 nm UV light for 0.5 h after the mixture spontaneously levels, and mark it as UV-Ref.

[0238] 3) Preparation of polyurethane material.

[0239] Take 5 g of dry modified polyether polyol obtained from Example 8 or Example 12, 0.89 g of 4,4'-diphenylmethane diisocyanate (MDI) and 0.32 g of butanediol (BDO) in a nitrogen atmosphere and stir them at 70 °C for 4 h to obtain samples, and mark them as PU-S1 or PU-S2, respectively.

[0240] As a control, use unmodified polyepoxy chloropropane (HTCH, M = 1500, provided by Yuyao Huihong Plastic Factory) instead of the above polyether polyol to prepare a reference sample, and mark it as PU-Ref.

[0241] The test results are shown in the following tables. Figures 16-18

[0242] As can be seen from the following tables: Figure 16 The T g ​The temperatures were 11℃ and 41℃ respectively, T d The temperatures were 216℃ and 276℃ respectively, both higher than the T of the foam Ref. g and T d (at 10°C and 211°C respectively), demonstrating that the modified polyether polyol can be used to prepare foam materials with higher heat resistance.

[0243] Hardness tests showed that the UV-S resin had a Shore A34 hardness, which was lower than the Shore A45 of the control sample UV-Ref, meaning that modified polyether polyols can be used to prepare photocurable resins with better flexibility.

[0244] From the appendix Figure 17 It can be seen that:

[0245] Contact angle tests showed that PU-S1 and PU-S2, prepared from the modified polyether polyols obtained in Examples 8 and 12, had contact angles of 100° and 88°, respectively, which were greater than the contact angle (82°) of the unmodified polyepoxychloropropane polyurethane PU-Ref, indicating better hydrophobicity. This demonstrates that the rigid polyether polyols and their preparation methods can be used to adjust the hydrophobicity of polyurethane materials.

[0246] From the appendix Figure 18 It can be seen that:

[0247] (1) Foam A exhibited almost no melting and dripping during combustion and was self-extinguishing, making it difficult to re-ignite due to the well-formed char layer on its surface. Foam B showed no melting and dripping throughout the combustion process and extinguished its flame after complete surface charring. Ordinary foam Ref exhibited severe melting and dripping throughout the combustion process, but the sample did not have char-forming properties and could burn completely. This demonstrates that the polymer foam prepared from modified polyether polyol has better flame-retardant properties.

[0248] (2) The UV-S photocurable resin prepared from the modified polyether polyol obtained in Example 7 showed no melting and dripping during the entire combustion process, and formed a rich char layer during combustion. In contrast, the UV-Ref photocurable resin prepared from polyethylene glycol diacrylate showed significant melting and dripping during combustion, with no residual char formed. This demonstrates that the photocurable resin prepared from the modified polyether polyol has better flame retardant properties.

[0249] The modified polyether polyols prepared in other embodiments of the present invention have similar effects, and will not be described in detail here.

[0250] Finally, it should be noted that the above examples are merely intended to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A modified polyether polyol characterized in that, The structure is shown in the following formula (I): （Ⅰ）； In formula (I), X is Cl or Br, m is an integer of 1 to 6, i is an integer of 1 to m, is a number of 1 to 120; R' is selected from the following groups: ； R is selected from the following groups: Wherein, y is an integer of 0~10, z is an integer of 2-10.

2. The modified polyether polyol of claim 1, wherein The structural formula of the modified polyether polyol is: ； wherein X is CI or Br, is a number from 5 to 50, R is selected from the following groups: ； Wherein, y is an integer of 0~10, z is an integer of 2-10.

3. The modified polyether polyol of claim 1, wherein The structural formula of the modified polyether polyol is: Wherein, X is Cl, b1+a2=7.24, a1+b2=0.2, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2=6.56, a1+b2=0.88, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2 =4.87, a1+b2=2.57, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2=3.95, a1+b2=3.49, R' is -CH2CH2CH2CH2-; Or, the structural formula of the modified polyether polyol is: Wherein, X is Cl, b1+a2=3.04, a1+b2=4.4, R' is -CH2CH2CH2CH2-; Or, the structural formula of the modified polyether polyol is: Wherein, X is Cl, b1+a2=3.1, a1+b2 =4.34, R' is -CH2CH2CH2CH2-; Or, the structural formula of the modified polyether polyol is: Wherein, X is Cl, b1+a2=5.28, a1+b2=2.16, R' is -CH2CH2CH2CH2-; Or, the structural formula of the modified polyether polyol is: Wherein, X is Cl, b1+a2=0, a1+b2=7.44, R' is -CH2CH2CH2CH2-; Or, the structural formula of the modified polyether polyol is: Wherein, X is Cl, b1+a2 =1.68, a1+b2=5.76, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2=2.09, a1+b2=5.35, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2=1.82, a1+b2=5.62, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2=9.5, a1+b2=6, R' is -CH2CH2CH2CH2-; Or, X is Cl, b1+a2=12.7, a1+b2=2.8, R' is -CH2CH2CH2CH2-.

4. A process for the preparation of a modified polyether polyol according to any one of claims 1 to 3, characterized in that The method comprises the following steps: (1) adding hydroxyl-terminated polyepoxy chloropropane or hydroxyl-terminated poly-3,3-bis-chloromethyl oxetane, carboxylate and catalyst into a reaction container, then adding organic solvent, and reacting at 70~130℃ for 6~48h, and cooling to room temperature after reaction to obtain a reaction product; (2) post-treatment of the reaction product: Pouring the reaction product into water, stirring thoroughly, and standing until the water phase is clear, then pouring off the water phase to obtain an organic phase; then dissolving the organic phase, repeatedly washing with brine, drying, and removing the solvent to obtain the modified polyether polyol; Or the reactants are added into dialysis tube with molecular weight cut-off of 200-1000 Da, and after repeated replacement of deionized water dialysis for 3-5 days, the organic phase is collected and dried, to obtain the modified polyether polyol; The structure of the polyepichlorohydrin with terminal hydroxyl group in the step (1) is shown in the following formula (III): （Ⅲ） In formula (III), X is Cl or Br, m is an integer of 1 to 6, i is an integer of 1 to m, is a number of 1 to 120; The structure of the poly-3,3-bis-chloromethyl oxetane with terminal hydroxyl group in the step (1) is shown in the following formula (IV): （Ⅳ） In formula (IV), X is Cl or Br, m is an integer of 1 to 6, i is an integer of 1 to m, n is an integer of 1 to 80, and R is a C1-6 alkyl group. is a number of 1 to 80; R' in the formula (III) and formula (IV) is independently selected from the following groups: 。 5. The method for preparing the modified polyether polyol as described in claim 4, characterized in that, The carboxylic acid salt includes potassium salt, sodium salt, lithium salt of at least one of acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, their substituted and substituted isomer carboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, substituted phthalic acid, malic acid, tartaric acid, citric acid, their substituted and substituted isomer monopotassium salt, monosodium salt or monolithium salt, potassium salt, sodium salt, lithium salt of propenoic acid, methacrylic acid; And / or, the catalyst includes at least one of CsI, KI, and NaI.

6. Use of the modified polyether polyol according to any one of claims 1-3 in the preparation of polyurethane material.

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