Modified polyether polyol as well as preparation method and application thereof

Abstract

The invention discloses modified polyether polyol as well as a preparation method and application thereof, the modified polyether polyol simultaneously contains a polyether main chain, ester side groups, halogen atoms and customizable chemical active sites, and can be used for preparing a novel functional structure polyurethane material with rich ether bonds and ester bonds. And a new raw material selection is provided for preparation of a polyurethane material. The preparation method of the modified polyether polyol, disclosed by the invention, is simple in process steps and easy to industrially popularize and apply. On one hand, the esterification degree can be adjusted and controlled through the reaction temperature, the reaction time, the catalyst, the feeding ratio and the like, on the other hand, the structural design of the modified polyether polyol can be achieved by designing the carboxylate structure, and the functional ester group modified polyether polyol is endowed with unique performance. According to the invention, a novel upstream raw material is provided for functionalized polyurethane and derivative products thereof, and the resin is expected to be developed into a novel high polymer material and has good market potential.

Description

Technical Field

[0001] The invention belongs to the technical field of modified polymer resins, in particular to a halogen-containing polyether polyol resin modified by a functionalized ester group, and a preparation method and application thereof. Background Art

[0002] Polyol resin is one of the important upstream raw materials for polymer materials, especially in the widely used polyurethane materials. Among the various polyol resin products, polyether polyols and polyester polyols are the most commonly used and are the main components for preparing polyurethane foam materials and elastomers with different performance characteristics. Although there are many types of polyol brands on the market, the structural composition remains the same. Polyether polyols are mainly formed by ring-opening polymerization of ethylene oxide, propylene oxide and (or) tetrahydrofuran; polyester polyols are formed by esterification of small molecule alcohols (such as ethylene glycol, butanediol, hexanediol, glycerol, pentaerythritol, etc.) with acid anhydrides (phthalic anhydride) or carboxylic acids (such as adipic acid, terephthalic acid, etc.). Whether it is polyether or polyester polyol, its active site is at the terminal hydroxyl group, so it has the limitation of relatively simple structure and insufficient modification sites. In terms of performance, polyether polyol products have lower viscosity, are more convenient to use, and the prepared polyurethane materials are more flexible, but their mechanical properties are inferior to polyester polyol polyurethane materials; on the contrary, polyester polyols have the disadvantages of high viscosity and poor fluidity due to their strong polar ester structure and more abundant hydrogen bonding, but their polyurethane products have more outstanding mechanical properties.

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

[0004] Poly(epoxychloro(bromo)propane) is a special polyether polyol resin rich in halogen atoms. It has special properties such as flame retardancy, oil resistance, ozone resistance, aging resistance, seawater resistance, and high damping coefficient. It 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 (-CH2X, X=Cl and Br) in the structure of poly(epoxychloro(bromo)propane) has high electrophilicity, so the halogen atom X can be replaced by a nucleophilic reagent to form a functionalized modified polyether polyol. For example, the substitution of X by an azide group (-N3) forms a significant energetic polyether polyol GAP, which is widely used in energetic polyurethane binders. At present, there are no reports on more modified polyether products with specific functions for poly(epoxychloro(bromo)propane). Summary of the invention

[0005] The purpose of the present invention is to provide a modified polyether polyol with abundant ether bonds and ester bonds, so as to provide a new raw material selection for the preparation research and development of polyurethane materials and novel polymer materials derived from polyethers. At the same time, the present invention also provides a preparation method of the modified polyether polyol and its application in the preparation of polyurethane and novel polymer materials derived from polyethers.

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

[0007]

[0008] In formula (I), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. is a number from 1 to 120; R' and R are any 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. is a number from 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 It is generally an integer and can be any integer. i 、b i Generally, it is an integer from 1 to 120. Indicates the a1+......a of compounds with different molecular weights in the modified polyether polyol mixture i+ b1+......b i The average value after summing is any number between 1 and 120, which can be an integer or a decimal. Taking i=2 as an example, It represents the average value of the sum of compounds a1+b1+a2+b2 with different polymerization degrees in the modified polyether polyol mixture of the general structural formula (I). The meaning is similar to that of formula (I).

[0012] a in the formula (I) or (II) of the present invention i 、b i 、c iIt is closely related to the structure of the terminal hydroxyl poly(epoxychloro(bromo)propane) or terminal hydroxyl poly(3,3-bis(chloro(bromo)methyloxetane) in the following preparation method. Specifically, a in the formula (I) or (II) i 、b i 、c i According to the formula (III) and formula (IV), n i OK, 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 described in the present invention is a mixture of compounds represented by formula (I) or (II) as described above, containing a polyether main chain, ester side groups, halogen atoms and customizable chemical active sites. From the perspective of chemical structure design, the modified polyether polyol provided by the present invention has customizable functional ester side groups and contains chlorine or bromine atoms, and can be used to prepare new functional structural polyurethanes or other polymer materials with rich ether bonds and ester bonds.

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

[0015]

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

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

[0018]

[0019] Here, y is an integer from 0 to 10, and z is an integer from 2 to 8.

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

[0021]

[0022] Here, 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 of the present invention, the structural formula of the modified polyether polyol is as follows:

[0024]

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

[0026]

[0027] Here, y is an integer of 0-10, and z is an integer of 2-8.

[0028] As a preferred embodiment of the modified polyether polyol of the present invention, the structural formula of the modified polyether polyol is:

[0029]

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

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

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

[0033] Alternatively, 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 of the present invention, the structural formula of the modified polyether polyol is:

[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 of the present invention, the structural formula of the modified polyether polyol is:

[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 invention, 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 invention, 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 invention, 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] Alternatively, X is Cl, b1+a2=2.09, a1+b2=5.35, and R' is -CH2CH2CH2CH2-;

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

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

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

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

[0054] In a second aspect, the present invention further provides a method for preparing a polyether polyol containing chlorine or bromine atoms and modified with ester side groups having customizable functions. To achieve this purpose, the technical solution adopted by the present invention is: a method for preparing the modified polyether polyol as described above, the method comprising the following steps:

[0055] (1) adding terminal hydroxyl group poly(epoxychloro(bromo)propane) or terminal hydroxyl group poly(3,3-bis(chloro(bromo)methyloxetane), carboxylate and a catalyst into a reaction vessel, then adding an organic solvent, reacting at 70 to 130° C. for 6 to 48 hours, cooling to room temperature after the reaction, and obtaining a reactant;

[0056] (2) Post-treatment of reactants:

[0057] The reactants are poured into water, stirred thoroughly, and allowed to stand until the aqueous phase is clear, and the aqueous phase is discarded to obtain an organic phase; the organic phase is then dissolved, and repeatedly washed with saline, dried, and the solvent is removed to obtain a modified polyether polyol;

[0058] Alternatively, the reactants are added to a dialysis tube with a molecular weight cutoff of 200 to 1000 Da, and the deionized water is repeatedly replaced for 3 to 5 days, and then the organic phase is collected and dried to obtain the modified polyether polyol.

[0059] As an embodiment of the method for preparing the modified polyether polyol of the present invention, the structural formula of the terminal hydroxyl polyepoxychloro(bromo)propane in step (1) is as shown in the following formula (III):

[0060]

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

[0062] The terminal hydroxyl polyepoxychloro(bromo)propane is a mixture of compounds of the general structural formula (III), wherein n i Usually an integer, is n1+......+n in each compound in the mixture i The average value of the sum. Taking i as 3 as an example, It represents the average value of the sum of n1+n2+n3 in each compound in the poly(epichlorohydrin)chloropropane mixture, and thus it can be an integer or a decimal.

[0063] As an embodiment of the method for preparing the modified polyether polyol of the present invention, the structural formula of the hydroxy-terminated poly(3,3-bis(chloro(bromo)methyloxetane)) in step (1) is as shown in the following formula (IV):

[0064]

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

[0066] The terminal hydroxyl group poly (3,3-bis(chloro(bromo)methyl)oxetane) is also a mixture of compounds as shown in the above formula (IV), The meanings are similar to those in formula (III).

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

[0068]

[0069] In the structural formula of the hydroxy-terminated poly(3,3-bis(chloro(bromo)methyl)oxetane), X is Cl or Br, and m is an integer of 1 to 6, for example, m can be 1, 2, 3, 4, 5, or 6. is a number of 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 reasonably select it as needed. The reaction process of step (1) generally needs to be carried out under a nitrogen atmosphere and with sufficient stirring, and the raw materials undergo a substitution reaction under the conditions to obtain the corresponding reactants for subsequent treatment.

[0071] As an embodiment of the preparation method of the modified polyether polyol of the present invention, the carboxylate includes acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, their substituents and (substituted) isomers of carboxylic acid potassium salt, sodium salt, lithium salt, 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 substituents and (substituted) isomers of monopotassium (sodium / lithium) salt, acrylic acid, methacrylic acid potassium salt, sodium salt, lithium salt.

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

[0073] As an implementation of the method for preparing the modified polyether polyol of the present invention, the catalyst includes at least one of CsI, KI, and NaI.

[0074] As a preferred embodiment of the method for preparing the modified polyether polyol of the present invention, the structural formula of the terminal hydroxyl polyepoxychloro(bromo)propane in step (1) is as shown in the following formula (V):

[0075]

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

[0077] As a preferred embodiment of the preparation method of the modified polyether polyol of the present invention, the carboxylate includes acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, their substituents and (substituted) isomers of carboxylic acid potassium salt, sodium salt, lithium salt, 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 substituents and (substituted) isomers of monopotassium (sodium / lithium) salt, acrylic acid, methacrylic acid potassium salt, sodium salt, lithium salt. Preferably, the carboxylate comprises at least one of the potassium salt and sodium salt of butyric acid, 3-hydroxybutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, acrylic acid and methacrylic acid, and the potassium salt and sodium salt of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and phthalic acid.

[0078] As a preferred embodiment of the method for preparing the modified polyether polyol of the present invention, the catalyst includes at least one of CsI, KI and NaI. 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 them thoroughly and let them stand until the water phase is basically clear, pour out the water phase, dissolve the remaining organic phase with ethyl acetate, chloroform or dichloromethane, and then repeatedly wash with saline, 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: add the reactants to a dialysis tube with a molecular weight cutoff of 200 to 1000Da, repeatedly replace deionized water and dialyze for 3-5 days, then collect and dry the organic phase to obtain a yellow to brown-black viscous polyol resin product.

[0080] The preparation method of the modified polyether polyol described above comprises the following steps: firstly reacting terminal hydroxyl group polyepoxychloro(bromo)propane or terminal hydroxyl group poly(3,3-bischloro(bromo)methyloxetane), carboxylate and catalyst under specific temperature conditions for a period of time, cooling after the reaction is completed, and then post-treating the reactants. There are two methods for post-treating the reactants, and different post-treating methods can be selected as needed during specific use. Both methods can obtain modified polyether polyols.

[0081] Finally, the present invention also provides the use of the modified polyether polyol as described above in the preparation of polyurethane and polyether-derived novel polymer materials. The modified polyether polyol of the present invention contains a polyether main chain, an ester side group, a halogen atom, and a customizable chemical active site, and can be used to prepare a novel functional structure polyurethane material with abundant ether bonds and ester bonds, and can also develop novel polymer products based on ether and ester structures, which not only provides a novel upstream raw material for functional polyurethane and its derivative products, but also the resin itself is expected to develop into a novel polymer material with a wide range of applications.

[0082] The modified polyether polyol of the present invention utilizes the substitution reaction of alkyl halide and carboxylate to bond carboxylate esters of different structures to the side chains of polyether polyols, thereby obtaining functionalized ester-modified polyether polyols containing halogen atoms of different structures, thereby achieving structural complementarity between polyether and polyester polyols. 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 new functional structural polyurethanes with rich ether bonds and ester bonds and new polymer materials derived from polyethers, thereby providing new raw material options for the preparation and development of polymer materials.

[0083] The preparation method of the modified polyether polyol of the present invention has simple process steps and is easy to be promoted and applied in industrialization. On the one hand, the esterification degree can be adjusted and controlled by reaction temperature, time, catalyst, feed ratio, etc., and on the other hand, the structure design of the modified polyether polyol can be realized by designing the carboxylate structure, thereby giving the functionalized ester group-modified polyether polyol unique properties.

[0084] When the modified polyether polyol of the present invention is used to prepare polyurethane materials, a new functional structural polyurethane material with abundant ether bonds and ester bonds can be prepared, which not only provides a new upstream raw material for functional polyurethane and its derivative products, but also the resin itself is expected to develop into a new polymer material with good market potential. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] Figure 1 The figure is a schematic diagram of the general reaction process of the modified polyether polyol of the present invention.

[0086] Figure 2 Schematic diagram of the reaction process of the modified polyether polyol described in Examples 1 to 4 of the present invention.

[0087] Figure 3 This is a schematic diagram of the reaction process of the modified polyether polyol described in Example 5 of the present invention.

[0088] Figure 4 This is a schematic diagram of the reaction process of the modified polyether polyol described in Example 6 of the present invention.

[0089] Figure 5 This is a schematic diagram of the reaction process of the modified polyether polyol described in Example 7 of the present invention.

[0090] Figure 6 This is a schematic diagram of the reaction process of the modified polyether polyol described in Example 8 of the present invention.

[0091] Figure 7 Schematic diagram of the reaction process of the modified polyether polyol described in Examples 9 to 13 of the present invention.

[0092] Figure 8 The modified polyether polyols and their raw materials HTCH (molecular weight 800) described in Examples 1 to 4 of the present invention are 1 H-NMR spectrum.

[0093] Fig. 9 FTIR spectra of the modified polyether polyols described in Examples 1 to 4 of the present invention and their raw material HTCH (molecular weight 800).

[0094] Fig.10 The modified polyether polyols and their raw materials HTCH (molecular weight 800) described in Examples 5 to 8 of the present invention are 1 H-NMR spectrum.

[0095] Fig.11 FTIR spectra of the modified polyether polyols described in Examples 5 to 8 of the present invention and their raw material HTCH (molecular weight 800).

[0096] Fig.12The modified polyether polyols and their raw materials HTCH (molecular weight 800) described in Examples 9 to 11 of the present invention are 1 H-NMR spectrum.

[0097] Fig.13 FTIR spectra of the modified polyether polyols described in Examples 9 to 11 of the present invention and their raw material HTCH (molecular weight 800).

[0098] Fig.14 The modified polyether polyol and its raw material HTCH (molecular weight 1500) described in Examples 12 and 13 of the present invention are 1 H-NMR spectrum.

[0099] Fig.15 FTIR spectra of the modified polyether polyol described in Examples 12 and 13 of the present invention and its raw material HTCH (molecular weight 1500).

[0100] Fig.16 These are the DSC and TGA curves of the foam materials prepared with the modified polyether polyols described in Examples 3 and 6.

[0101] Fig.17 These are the contact angle test results of the polyurethanes prepared from the modified polyether polyols described in Examples 8 and 12.

[0102] Fig.18 These are combustion photos of the foams and photocurable resins prepared with the modified polyether polyols described in Examples 3, 6 and 7 in the air. DETAILED DESCRIPTION

[0103] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0104] In the preparation method of the modified polyether polyol of the present invention, the general reaction formula is as shown in the attached figure: Figure 1 As shown. First, terminal hydroxyl polyepoxychloro(bromo)propane or terminal hydroxyl poly(3,3-bischloro(bromo)methyloxetane), carboxylate and catalyst are reacted under specific temperature conditions for a period of time, cooled after the reaction is completed, and then the reactants are post-treated. There are two methods for post-treatment of the reactants. Different post-treatment methods can be selected as needed during specific use. Both methods can obtain modified polyether polyols. The amount ratio of terminal hydroxyl polyepoxychloro(bromo)propane or poly(3,3-bischloro(bromo)methyloxetane), carboxylate and catalyst in step (1) is related to the specific reaction conditions and the degree of esterification of the desired product. Those skilled in the art can reasonably select the amount ratio of the raw materials according to the reaction conditions and the degree of esterification of the target product. No specific restrictions or examples are given here.

[0105] The technical solution of the invention is further described below with reference to specific embodiments.

[0106] The chlorine content described in the following examples was measured by a Bruker S8 Tiger II wavelength dispersive X-ray fluorescence spectrometer. The raw materials used were purchased directly, 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 present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

[0109] (1) 10 g of hydroxy-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, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an 80° C. oil bath and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a yellow turbid system, which was then cooled to room temperature to obtain a reactant;

[0110] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred to wash twice, and then dissolved with chloroform. After washing with saturated brine three times, the organic phase was collected and the chloroform was removed to obtain a yellow viscous succinic acid monoester functionalized chlorine-containing polyether polyol with a chlorine content of about 31.2 wt%, which is the modified polyether polyol described in this embodiment.

[0111] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 2 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0112]

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

[0114] Example 2

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

[0116] (1) 10 g of hydroxy-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, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 100° C. and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a brown-yellow turbid system. The mixture was cooled to room temperature to obtain a reactant.

[0117] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred to wash twice, and then dissolved with chloroform, washed three times with saturated brine, and the organic phase was collected and chloroform was removed to obtain a brown-yellow viscous succinic acid monoester functionalized chlorine-containing polyether polyol with a chlorine content of 27.6 wt%, which is the modified polyether polyol described in this embodiment.

[0118] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 2 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0119]

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

[0121] Example 3

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

[0123] (1) 10 g of hydroxy-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, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120° C. and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a brown-yellow turbid system. The mixture was cooled to room temperature to obtain a reactant.

[0124] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred to wash twice, and then dissolved with chloroform, washed three times with saturated brine, and the organic phase was collected and chloroform was removed to obtain a brown-yellow chlorine-containing succinic acid monoester functionalized polyether polyol with a chlorine content of 18.8 wt%, which is the modified polyether polyol described in this embodiment.

[0125] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 2 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0126]

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

[0128] Example 4

[0129] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

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

[0131] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred to wash twice, and then dissolved with chloroform, washed three times with saturated brine, and the organic phase was collected and chloroform was removed to obtain a brown-black chlorine-containing succinic acid monoester functionalized polyether polyol with a chlorine content of 14.4 wt%, which is the modified polyether polyol described in this embodiment.

[0132] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 2 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0133]

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

[0135] Example 5

[0136] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

[0137] (1) 10 g of hydroxy-terminated polyepichlorohydrin (M=800, HTCH), 13.5 g of sodium 3-hydroxybutyrate and 0.5 g of CsI were added to a 150 mL three-necked flask, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120° C. and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a brown-yellow turbid system. The reaction was then 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 cutoff of 500 Da to obtain a dark viscous dark yellow 3-hydroxybutyrate functionalized polyether polyol, which is the modified polyether polyol described in this example.

[0139] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 3 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0140]

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

[0142] Example 6

[0143] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

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

[0145] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred and washed twice, and then dissolved with ethyl acetate. After washing three times with saturated brine, the organic phase was collected and the ethyl acetate was removed to obtain a brown viscous chlorine-containing phthalic acid monoester functionalized polyether polyol, which is the modified polyether polyol described in this embodiment.

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

[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-. In this embodiment, n1+n2, b1+a2, and a1+b2 have the same meanings as those in Example 1.

[0149] Example 7

[0150] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

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

[0152] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred and washed twice, and then dissolved with ethyl acetate. After washing three times with saturated brine, the organic phase was collected and the ethyl acetate was removed to obtain a yellow viscous chlorine-containing acrylate functionalized polyether polyol, which is the modified polyether polyol described in this embodiment.

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

[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-. In this embodiment, n1+n2, b1+a2, and a1+b2 have the same meanings as in Example 1.

[0156] Example 8

[0157] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

[0158] (1) 10 g of hydroxy-terminated polyepichlorohydrin (M=800, HTCH), 14.8 g of sodium hexanoate and 0.5 g of CsI were added to a 150 mL three-necked flask, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120° C. and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a brown turbid system, which was then cooled to room temperature to obtain a reactant;

[0159] (2) The reactants were poured into about 250 mL of water, stirred and allowed to stand, and then the aqueous phase was removed, the viscous organic phase was retained, and water was added and stirred and washed twice, and then dissolved with ethyl acetate. After washing three times with saturated brine, the organic phase was collected and the ethyl acetate was removed to obtain a brown viscous chlorine-containing hexanoate functionalized polyether polyol, which is the modified polyether polyol described in this embodiment.

[0160] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 6 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0161]

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

[0163] Example 9

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

[0165] (1) 10 g of hydroxy-terminated polyepichlorohydrin (M=800, HTCH), 10.5 g of potassium acetate and 0.5 g of CsI were added to a 150 mL three-necked flask, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120° C. and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a brown-black turbid system. The reaction was then cooled to room temperature to obtain a reactant.

[0166] (2) The reactant was 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.

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

[0168]

[0169] In the reaction formula and structural formula, X is Cl, n1+n2=7.44, b1+a2=1.68, a1+b2=5.76, and R' is -CH2CH2CH2CH2-. In this embodiment, n1+n2, b1+a2, and a1+b2 have the same meanings as those in Example 1.

[0170] Example 10

[0171] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

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

[0173] (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.

[0174] The reaction formula of the modified polyether polyol described in this embodiment is as shown in the attached figure. Figure 7 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0175]

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

[0177] Embodiment 11

[0178] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

[0179] (1) 10 g of hydroxy-terminated polyepichlorohydrin (M=800, HTCH), 10.5 g of potassium acetate and 0.1 g of CsI were added to a 150 mL three-necked flask, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120° C. and stirred for reaction for 24 h under a flowing nitrogen atmosphere to form a brown-black turbid system. The reaction was then cooled to room temperature to obtain a reactant.

[0180] (2) The reactant was dialyzed in water for 3-4 days using a dialysis bag with a molecular weight cutoff of 500 Da to obtain a dark brown acetate 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 embodiment is as shown in the attached figure. Figure 7 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[0182]

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

[0184] Example 12

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

[0186] (1) 12 g of hydroxy-terminated polyepichlorohydrin (M=1500, HTCH), 6.5 g of potassium acetate and 0.5 g of CsI were added to a 150 mL three-necked flask, and 30 g of N,N-dimethylformamide (DMF) was added as a solvent. The three-necked flask was then placed in an oil bath at 120° C. and stirred for reaction for 12 h under a flowing nitrogen atmosphere to form a brown-black turbid system. The reaction was then cooled to room temperature to obtain a reactant.

[0187] (2) The reactant was dialyzed in water for 3-4 days using a dialysis bag with a molecular weight cutoff of 500 Da to obtain a dark brown acetate 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 embodiment is as shown in the attached figure. Figure 7 As shown, the obtained modified polyether polyol is a mixture of compounds with the structural formula shown below:

[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-. In this embodiment, n1+n2, b1+a2, and a1+b2 have the same meanings as in Example 1.

[0191] Example 13

[0192] An embodiment of the modified polyether polyol of the present invention, the preparation method of the modified polyether polyol described in this embodiment comprises the following steps:

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

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

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

[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-. In this embodiment, n1+n2, b1+a2, and a1+b2 have the same meanings as those in Example 1.

[0198] Embodiment 14

[0199] Structural identification of the modified polyether polyols described in the present invention

[0200] The nuclear magnetic resonance hydrogen spectra and infrared spectra of the modified polyether polyols prepared in Examples 1 to 13 and the raw material terminal hydroxyl polyepichlorohydrin (HTCH) used were tested respectively, and the testing method was:

[0201] H NMR ( 1 H-NMR): measured using a Bruker AVANCE HD 500 nuclear magnetic resonance spectrometer, the solvent used was CDCl3;

[0202] Infrared spectra (FT-IR): PerkinElmer Spectrum 100 infrared spectrometer was used to obtain the results in total reflection mode.

[0203] The test results are as follows: Figure 8-15 shown.

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

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

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

[0207] By the attached Fig.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. At the same time, due to esterification, the chemical shift of the side methylene on the epichlorohydrin repeating unit also shifts to between 4-4.5 ppm. The signals at the chemical shift positions of 1.26, 2.05 and 4.12 ppm are the signals of ethyl acetate that has not been completely removed. The degree of esterification substitution calculated from the integral ratio at 1.64 and 2.45 ppm is 59.2%;

[0209] In Example 6, the signal at δ=7.45-8 ppm originates from the benzene ring structure introduced by esterification, while the signals at the chemical shift positions of 1.26, 2.05 and 4.12 ppm are the ethyl acetate that has not been completely removed. The degree of esterification substitution is calculated to be 58.4% from the integral ratio at 1.64 and 7.45-8 ppm;

[0210] In Example 7, the three signal peaks with chemical shifts between 6-6.5 ppm were attributed to the double bond structure of acrylate, and the degree of esterification substitution was calculated to be 29.0% based on the integral ratio at 1.64 and 6-6.5 ppm.

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

[0212] By the attached Fig.11 It can be seen that:

[0213] In Example 5, the product is at 3400 cm -1 There is a broad and strong OH stretching vibration peak near 1720 cm -1 The ester group absorption at 2980-2870cm -1 The changes in the absorption peaks of the saturated hydrocarbon structures illustrate the substitution process shown in the following reaction.

[0214] In Example 6, 3400cm -1 There is a broad and strong OH stretching vibration peak nearby, which is derived from the terminal OH and COOH brought by the benzene ring structure, 1720cm -1 and 1260cm -1The C=O and COC structures of the ester group are at 750cm -1 It is the CH vibration peak of o-disubstituted benzene, about 1600cm -1 and 3070cm -1 The weak peak at is attributed to the benzene ring skeleton.

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

[0216] In Example 8, because of the introduction of caproate, 2960-2860 cm -1 There are obvious characteristic peaks of -CH3 and -CH2- between them, and the ester structure is at 1720cm -1 Be reflected everywhere.

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

[0218] By the attached Fig.13 It can be seen that in Example 9, 2950cm -1 The change of the absorption peak at 1720cm -1 and 1220cm -1 The C=O and COC structures at both indicate the presence of acetate structures.

[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 esterification substitution degree was calculated to be 71.9% from the integration ratio 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% from the integrated ratio at 1.64 and 2.1 ppm.

[0221] By the attached Fig.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 esterification substitution degree was calculated to be 38.5% from the integration ratio at 1.64 and 2.1 ppm in Example 12. The esterification substitution degree was calculated to be 18.1% from the integration ratio at 1.64 and 2.1 ppm in Example 13.

[0222] Embodiment 15

[0223] Performance test of the modified polyether polyol of the present invention

[0224] The glass transition temperatures T of the polymer foam material prepared by the modified polyether polyol obtained in Example 3 and Example 6 and the ordinary polyurethane foam material were tested respectively. g , thermal decomposition temperature T d and combustion behavior in air; respectively test the hardness and combustion behavior in air of the polymer materials after UV curing of the modified polyether polyols obtained in Example 3, Example 6, and Example 7 and ordinary polyethylene glycol diacrylate; respectively test the contact angles of the polyurethanes prepared from the modified polyether polyols obtained in Example 8 and Example 12 and the polyurethanes prepared from ordinary polyether polyol PPG, and the test method is:

[0225] T g :Perkinelmer DSC8500 differential scanning calorimeter was used for determination. The scanning temperature range was -50℃—100℃ and the heating rate was 10℃ / min.

[0226] T d : TA Instruments thermogravimetric analyzer (TGA5500) was used for measurement in air atmosphere, with a temperature range of 25°C-800°C and a heating rate of 10°C / min.

[0227] Water contact angle: measured using a German Kruss contact angle meter DSA100 at room temperature.

[0228] Hardness: measured by LX-A Shore rubber hardness tester.

[0229] Combustion behavior: Use a lighter to ignite the test sample in the air and observe whether there is self-extinguishing and dripping of molten material during the combustion process.

[0230] Methods for preparing different polymer material samples using modified polyether polyols:

[0231] 1) Preparation of polymer foam materials

[0232] 5 g of the dried modified polyether polyol obtained in Example 3 and 2 g of meta-xylylene diisocyanate (XDI) were vigorously stirred and mixed in a plastic cup at room temperature, and then placed in a 50° C. oven for free reaction and foaming, which was recorded as Foam A.

[0233] 5 g of the dried modified polyether polyol obtained in Example 6 and 2 g of XDI were mixed vigorously in a plastic cup at room temperature and then placed in a 50° C. oven for free reaction and foaming, which was recorded as Foam B.

[0234] As a control, 15 g of common hexafunctional polyether polyol (Donol 6028E, provided by Shanghai Dongda Chemical Co., Ltd., with a molecular weight of 12,000), 1.1 g of XDI and 0.03 g of deionized water (as a foaming agent) were vigorously stirred in a plastic cup at room temperature, and then placed in a 50°C oven for free reaction and foaming, which was recorded as foam Ref.

[0235] 2) Preparation of light-curing resin

[0236] 4 g of the modified polyether polyol obtained in Example 7 was mixed evenly with a small amount of photoinitiator I2959 in a plastic culture medium. After the mixture was spontaneously leveled, it was cured under 365 nm ultraviolet light for 0.5 h to obtain a sample, which was recorded as UV-S.

[0237] As a control, 4 g of commercially available polyethylene glycol diacrylate (PEGDA, M=600, provided by Shanghai Aladdin Reagent Co., Ltd.) was mixed evenly with a small amount of photoinitiator I2959 in a plastic culture medium. After the mixture spontaneously leveled, it was cured under 365 nm ultraviolet light for 0.5 h to obtain a sample, which was recorded as UV-Ref.

[0238] 3) Preparation of polyurethane materials.

[0239] 5 g of the dried modified polyether polyol obtained in Example 8 or Example 12, 0.89 g of 4,4'-diphenylmethane diisocyanate (MDI) and 0.32 g of butanediol (BDO) were stirred and reacted at 70° C. for 4 h in a nitrogen atmosphere to obtain a sample, which was recorded as PU-S1 or PU-S2.

[0240] As a control, unmodified polyepichlorohydrin (HTCH, M=1500, provided by Yuyao Huihong Plastic Factory) was used to replace the above polyether polyol to prepare a reference sample, which was recorded as PU-Ref.

[0241] The test results are as follows: Figures 16 to 18 shown.

[0242] By the attached Fig.16 It can be seen that the T values ​​of the polymer foams prepared by the modified polyether polyols obtained from foam A and foam B are g11℃ and 41℃ respectively, T d 216℃ and 276℃ respectively, both higher than the T of foam Ref g and T d (10°C and 211°C, respectively), demonstrating that the modified polyether polyol can be used to prepare foam materials with higher heat resistance.

[0243] The hardness test shows that the hardness of UV-S resin is Shore A34, which is lower than the Shore A45 of the control sample UV-Ref, which means that the modified polyether polyol can be used to prepare photocurable resin with better flexibility.

[0244] By the attached Fig.17 It can be seen that:

[0245] The contact angle test shows that the contact angles of PU-S1 and PU-S2 prepared from the modified polyether polyols obtained in Example 8 and Example 12 are 100° and 88°, respectively, which are greater than the contact angle (82°) of the unmodified polyepichlorohydrin type polyurethane PU-Ref, and have better hydrophobicity. This indicates that the rigid polyether polyol and its preparation method can be used to adjust the hydrophobicity of polyurethane materials.

[0246] By the attached Fig.18 It can be seen that:

[0247] (1) Foam A has almost no melt dripping during the combustion process and exhibits self-extinguishing. It is difficult to ignite again due to the good carbonization layer formed on the combustion surface. Foam B has no melt dripping during the entire combustion process and the flame is extinguished after the surface is completely carbonized. Ordinary foam Ref is accompanied by severe melt dripping during the entire combustion process. The sample has no carbonization and can burn completely. This proves that the polymer foam prepared by modified polyether polyol has better flame retardant effect.

[0248] (2) The photocurable resin UV-S prepared from the modified polyether polyol obtained in Example 7 had no melting dripping phenomenon during the entire combustion process, and a rich carbonized layer was formed during combustion. During the combustion of the photocurable resin UV-Ref prepared from polyethylene glycol diacrylate, the melting dripping phenomenon was obvious, and no residual carbon was formed. This proves that the photocurable resin prepared from the modified polyether polyol has a better flame retardant effect.

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

[0250] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A modified polyether polyol, characterized in that: Its structure is shown in the following formula (I) or (II): In formula (I), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. is a number from 1 to 120; R' and R are any groups; 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. is a number from 1 to 80, and R' and R are arbitrary groups.

2. The modified polyether polyol according to claim 1, characterized in that R' in the formula (I) and formula (II) is independently selected from the following groups:

3. The modified polyether polyol according to claim 1, characterized in that R in the formula (I) and formula (II) is independently selected from the following groups: Here, y is an integer from 0 to 10, and z is an integer from 2 to 10.

4. The modified polyether polyol according to claim 1, characterized in that The structural formula of the modified polyether polyol is: Wherein, X is Cl or Br, is a number from 5 to 50, and R is selected from the following groups: Here, y is an integer from 0 to 10, and z is an integer from 2 to 10.

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

6. A method for preparing the modified polyether polyol according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: (1) adding terminal hydroxyl group poly(epoxychloro(bromo)propane) or terminal hydroxyl group poly(3,3-bis(chloro(bromo)methyloxetane), carboxylate and a catalyst into a reaction vessel, then adding an organic solvent, reacting at 70 to 130° C. for 6 to 48 hours, cooling to room temperature after the reaction, and obtaining a reactant; (2) Post-treatment of reactants: The reactants are poured into water, stirred thoroughly, and allowed to stand until the aqueous phase is clear, and the aqueous phase is discarded to obtain an organic phase; the organic phase is then dissolved, and repeatedly washed with saline, dried, and the solvent is removed to obtain a modified polyether polyol; Alternatively, the reactants are added to a dialysis tube with a molecular weight cutoff of 200 to 1000 Da, and the deionized water is repeatedly replaced for 3 to 5 days, and then the organic phase is collected and dried to obtain the modified polyether polyol.

7. The method for preparing the modified polyether polyol according to claim 6, characterized in that: The structural formula of the hydroxy-terminated poly(epoxychloro(bromo)propane) in step (1) is as shown in the following formula (III): In formula (III), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. is a number from 1 to 120, and R' is any group; The structural formula of the hydroxy-terminated poly(3,3-bis(chloro(bromo)methyl)oxetane) in step (1) is as shown in the following formula (IV): In formula (IV), X is Cl or Br, m is an integer from 1 to 6, and i is an integer from 1 to m. is a number from 1 to 80, and R' is an arbitrary group.

8. The method for preparing the modified polyether polyol according to claim 7, characterized in that: R' in the formula (III) and formula (IV) is independently selected from the following groups:

9. The method for preparing the modified polyether polyol according to claim 6, characterized in that: The carboxylate comprises at least one of acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, their substitutes and (substituted) isomers of carboxylic acid potassium salt, sodium salt, lithium salt, 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 substitutes and (substituted) isomers of monopotassium (sodium / lithium) salt, acrylic acid, methacrylic acid potassium salt, sodium salt, lithium salt; And / or, the catalyst includes at least one of CsI, KI, and NaI.

10. Use of the modified polyether polyol according to any one of claims 1 to 5 in the preparation of polyurethane materials.

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