Emulsifier composition and method for preparing polytrifluorostyrene

Abstract

Provided in the present application is an emulsifier composition. The emulsifier composition comprises a non-perfluorinated fluorine-containing anionic surfactant, a non-fluorinated aliphatic or aromatic anionic surfactant, and at least one of a cationic surfactant and a non-ionic surfactant. Further provided in the present application are a method for preparing polytrifluorostyrene by means of the polymerization of trifluorostyrene by using the emulsifier composition, and a polytrifluorostyrene product obtained thereby. By using the emulsifier composition in the present application, the synthesis of polytrifluorostyrene can be carried out in a simple and convenient manner with a good yield, and effective control of the molecular weight and glass transition temperature of a polymerization product can be achieved.

Description

Emulsifier composition and method for preparing polytrifluorostyrene Technical Field

[0001] The present application relates to the field of polymers, and more specifically to a novel emulsifier composition, a method for preparing polytrifluorostyrene using the emulsifier composition, and a product obtained thereby. Background Art

[0002] α,β,β-trifluorostyrene (TFS), also known as trifluorostyrene, is a fluorinated monomer used to prepare fluorinated polymers and fluorinated intermediates. Fluorinated polymers (polytriflurostyrene, PTFS) with TFS as the key monomer exhibit excellent heat resistance, high transparency, good solubility, low dielectric loss, radiation resistance, and ion exchange activation. Consequently, they hold great potential for broad application in proton exchange membranes, ion exchange membranes, optoelectronic communications, filtration materials, and microelectronics.

[0003] However, there are many long-standing problems in the polymerization technology of trifluorostyrene, such as trifluorostyrene is easy to cyclodimerization or oligomerization, which easily causes the dimer and oligomer to be included in the product in a large proportion, has a strong impact on the ratio of the required high molecular weight polytrifluorostyrene product. In order to solve this problem, people attempt to develop various improved technologies, such as adopting emulsion polymerization process or adding various improved components in the system of polyreaction, but these attempts have not really obtained satisfactory results, and even unexpectedly bring new problems on the contrary. For example, although the above-mentioned attempt can slightly improve the ratio of the higher molecular weight polytrifluorostyrene in the product to a certain extent, it is often necessary to use a high emulsifier dosage, such as the emulsifier dosage used may be up to 20% of the total monomer weight, so high emulsifier dosage easily causes serious foaming in the polymerization system, brings great inconvenience to the subsequent treatment (such as demulsification, washing, product recovery etc.) after the polyreaction, and may cause adverse effects on the performance of the polytrifluorostyrene product, the cost, actual waste and environmental protection issues that high emulsifier dosage brings have also seriously restricted the promotion and application of these technologies. In addition, the yield of polytrifluorostyrene products prepared by existing technologies is often significantly low, and the molecular weight and glass transition temperature of the products cannot be effectively controlled.

[0004] Therefore, this field urgently hopes to develop a novel technology in order to overcome the technical problems existing in the above-mentioned prior art.

[0005] Summary of the Invention

[0006] In response to the above problems, the applicant has developed a novel emulsion polymer through long-term and in-depth research. This emulsion polymer can be used to synthesize polytrifluorostyrene with high yield through emulsion polymerization, significantly reducing the amount of emulsifier used, and can effectively control the molecular weight and glass transition temperature of the polymer product, thereby completing the present invention.

[0007] The first aspect of the present application provides an emulsifier composition, which comprises:

[0008] a first emulsifier, wherein the first emulsifier is a non-perfluorinated substituted fluorinated anionic surfactant;

[0009] a second emulsifier, wherein the second emulsifier is a non-fluorinated aliphatic or aromatic anionic surfactant;

[0010] The third emulsifier is a cationic surfactant, a nonionic surfactant, or a combination thereof.

[0011] According to one embodiment of the first aspect of the present application, the first emulsifier has a structure shown in Formula I: CF3-[(O) t -CFX] n (CX2) s [O-CX2] p (CH2) m (C6H4) o M Formula I

[0012] wherein t is 0 or 1, n is an integer from 1 to 6, s is an integer from 0 to 2, m is an integer from 1 to 4, o is an integer from 0 to 1, and p is an integer from 0 to 2;

[0013] Each X is independently selected from -F, C1-C 12 Perfluoroalkyl, C1-C 12 perfluoroalkoxy;

[0014] M is selected from a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof.

[0015] According to another embodiment of the first aspect of the present application, the first emulsifier is selected from at least one of the following: CF3CF2CF2CF2CH2COOH, CF3CF2CF2CF2CH2C6H4COOH, CF3CF2CF2CF2CH2CH2COOH, CF3CF2CF2CF2CH2CH2C6H4COOH, CF3CF2CF2CF2(CH2)3COOH, CF3CF2CF2CF2(CH2)4COOH, CF3(CF2)5CH2COOH, CF3(CF2)5CH2C6H4COOH, C F3(CF2)5CH2CH2COOH, CF3(CF2)5CH2CH2C6H4COOH, CF3(CF2)5(CH2)4COOH, CF3CF2CF2C(CF3)2CH2COOH, CF3CF2CF2C(CF3)2CH2C6 H4COOH, CF3CF2CF2C(CF3)2(CH2)2COOH, CF3CF2CF2C(CF3)2(CH2)3COOH, CF3CF2CF2C(CF3)2(CH2)4COOH, CF3(CF-CF3)2CH2COOH,CF3(CF-CF3)2CH2C6H4COOH, CF3(CF-CF3)2CH2CH2COOH, CF3(CF-CF3)2(CH2)4COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2COOH, CF3-O-CF(CF3)-CF2-O-CF2-(CH2)2COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4COOH, CF3CF2CF2CF2CH2SO3H, CF3CF2CF2CF2CH2C6H4SO3H, CF3CF2CF2CF2CH2CH2SO3H, CF3CF2CF2CF2CH2CH2C6H4SO3H, CF3CF2CF2CF2(CH2)3SO3H, CF3CF2CF2CF2(CH2)4SO3H, CF3(CF2)5CH2SO3H, CF3(CF2)5CH2C6H4SO3H, CF3(CF2)5CH2CH2SO3H, CF3(CF2)5CH2CH2C6H4SO3H, CF3(CF2)5(CH2)4SO3H, CF3CF2CF2C(CF3)2CH2SO3H, CF3CF2CF2C(CF3)2CH2C6H4SO3H, CF3CF2CF2C(CF3)2(CH2)2SO3H, CF3CF2CF2C(CF3)2(CH2)3SO3H, CF3CF2CF2C(CF3)2(CH2)4SO3H, CF3(CF-CF3)2CH2SO3H, CF3(CF-CF3)2CH2C6H4SO3H, CF3(CF-CF3)2CH2CH2SO3H, CF3(CF-CF3)2(CH2)4SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2SO3H, CF3-O-CF(CF3)-CF2-O-(CF2)2-CH2SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)2SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4SO3H, and their sodium, potassium, and ammonium salts.

[0016] According to another embodiment of the first aspect of the present application, the second emulsifier is selected from at least one of the following: C6-C22 alkyl sulfates, C6-C22 alkyl sulfonates, C2-C22 alkyl phosphates, C4-C22 carboxylates, C6-C22 aryl sulfonates, C6-C22 arylalkyl sulfonates, C2-C22 alkyl ether sulfates, C2-C22 alkyl ether sulfonates, and C2-C22 alkyl ether carboxylates.

[0017] According to another embodiment of the first aspect of the present application, the third emulsifier is selected from at least one of the following: R 1 R 2 R 3 N and its salts, nitrogen-containing heteroaryl compounds and their salts, polyoxygenated (C1-C12) alkylene, C1-C22 alkyl ether, C1-C22 alkyl C6-C22 aryl ether, polyoxygenated (C1-C12) alkylene C1-C22 alkyl ether, polyoxygenated (C1-C12) alkylene C6-C22 aryl ether, C1-C22 alkyl ether of a polyol containing three or more hydroxyl groups, C6-C22 aryl ether of a polyol containing three or more hydroxyl groups, polyoxygenated (C1-C12) alkylene C1-C22 carboxylate,

[0018] where R 1 、R 2 and R 3 Each group is independently selected from the following: H, C1-C16 alkyl, C2-C16 alkenyl, C3-C16 cycloalkyl, C6-C16 aryl, C6-C16 aralkyl, C6-C16 alkaryl.

[0019] According to another embodiment of the first aspect of the present application, based on the total weight of the emulsifier composition, the content of the first emulsifier is 10-35 weight%, the content of the second emulsifier is 40-75 weight%, and the content of the third emulsifier is 5-25 weight%.

[0020] The second aspect of the present application provides a method for preparing polytrifluorostyrene, the method comprising:

[0021] Step 1: using the emulsifier composition of the present application, trifluorostyrene monomer and water to form a pre-emulsion;

[0022] Step 2: adding an initiator to the pre-emulsion to polymerize the trifluorostyrene monomer; and

[0023] Step 3: Demulsify the reaction system after step 2.

[0024] According to one embodiment of the second aspect of the present application, in step 1, based on 100 parts by weight of the trifluorostyrene monomer, the content of the emulsifier composition is 0.5-10 parts by weight.

[0025] According to another embodiment of the second aspect of the present application, in step 1, based on the total weight of the pre-emulsion being 100 weight%, the content of the trifluorostyrene monomer is 10-60 weight%.

[0026] According to another embodiment of the second aspect of the present application, in the step 2, the trifluorostyrene monomer is polymerized at a temperature of 30-80°C. According to another embodiment of the second aspect of the present application, in the step 2, the duration of the polymerization of the trifluorostyrene monomer is 1-24 hours. According to another embodiment of the second aspect of the present application, in the step 2, the amount of the initiator is 0.1-1.5 parts by weight based on 100 parts by weight of the trifluorostyrene monomer. According to another embodiment of the second aspect of the present application, in the step 2, the initiator is selected from at least one of the following: ammonium persulfate, potassium persulfate, ammonium persulfate / sodium sulfite, potassium persulfate / sodium sulfite, azobisisobutyronitrile, dibenzoyl peroxide, and dodecanoyl peroxide.

[0027] The third aspect of the present application provides a polytrifluorostyrene prepared by the method described above in the present application. According to one embodiment of the third aspect of the present application, the glass transition temperature of the polytrifluorostyrene is 190-215°C. According to another embodiment of the third aspect of the present application, the weight average molecular weight of the polytrifluorostyrene is 5-150×10 4 According to another embodiment of the third aspect of the present application, the particle size of the polytrifluorostyrene is 30-70 nm. DETAILED DESCRIPTION

[0028] " Scope " disclosed herein is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0029] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0030] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0031] In this application, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0032] In this application, unless otherwise specified, the terms "include" and "comprising" used herein may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0033] In the description of this article, it should be noted that, unless otherwise specified, “above” and “below” are inclusive of the number themselves, and “several” in “one or several” means two or more.

[0034] In the description herein, unless otherwise indicated, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0035] Herein, unless otherwise specified, percentages (%) or parts refer to percentages or parts by weight relative to the composition.

[0036] Herein, unless otherwise stated, the sum of the contents of the various components in the composition is 100%.

[0037] Herein, unless otherwise stated, the sum of the parts of each component in the composition may be 100 parts by weight.

[0038] In this context, unless otherwise stated, "a combination thereof" means a multi-component mixture of the elements mentioned, for example a mixture of two, three, four and up to the maximum possible multi-component mixture.

[0039] If not specifically stated, the terms "a" and "an" used in this specification mean "at least one".

[0040] Herein, unless otherwise stated, all reactions were carried out under normal pressure.

[0041] One of the inventive points of the present application is the development of a novel three-component emulsifier composition, which may also be referred to as a ternary emulsifier system or a three-emulsifier combination in the present application. The three-component emulsifier composition comprises a first emulsifier, which is a non-perfluorinated fluorinated anionic surfactant; a second emulsifier, which is a non-fluorinated aliphatic or aromatic anionic surfactant; and a third emulsifier, which is a cationic surfactant, a nonionic surfactant, or a combination thereof. The three emulsifiers in the emulsifier composition can be uniformly mixed with each other, for example, by forming an aqueous solution or a solution in other suitable solvents to form an emulsifier system that can be used to prepare polytrifluorostyrene.

[0042] According to one embodiment of the present application, the first emulsifier has a structure shown in Formula I: CF3-[(O) t -CFX] n (CX2) s [O-CX2]p (CH2) m (C6H4) o M Formula I

[0043] In the above formula I, t is 0 or 1; n is an integer of 1-6, for example, 2-5, or 3-4, or within the numerical range obtained by combining any two of the above end values; s is an integer of 0-2, for example, 0-1, or 1-2, or within the numerical range obtained by combining any two of the above end values; m is an integer of 1-4, for example, 2-3, or an integer of 1, 2, 3 or 4, or within the numerical range obtained by combining any two of the above end values; o is an integer of 0-1, for example, an integer of 0 or 1, or within the numerical range obtained by combining any two of the above end values; p is an integer of 0-2, for example, 0-1, or 1-2, or an integer of 0, 1 or 2, or within the numerical range obtained by combining any two of the above end values.

[0044] In the above formula I, each X can be independently selected from -F, C1-C 12 Perfluoroalkyl, C1-C 12 Perfluoroalkoxy; for example, each X can be independently selected from -F, C1-C 10 Perfluoroalkyl, C1-C 10 perfluoroalkoxy; or each X can be independently selected from -F, C1-C8 perfluoroalkyl, C1-C8 perfluoroalkoxy; or each X can be independently selected from -F, C1-C6 perfluoroalkyl, C1-C6 perfluoroalkoxy; or each X can be independently selected from -F, C1-C3 perfluoroalkyl, C1-C3 perfluoroalkoxy. According to an exemplary embodiment of the present application, each X can be independently selected from one or more of the following: -F, -CF3, -OCF3, -CF2CF(CF3)2, -CF2C(CF3)3.

[0045] According to one embodiment of the present application, in the above formula I, M is selected from a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof. The salt may include a sodium salt, a potassium salt, or an ammonium salt. According to an exemplary embodiment of the present application, M is selected from one or more of the following: -COOH, -SO3H, -COOK, -COONa, -COONH4, -SO3K, -SO3Na.

[0046] According to one embodiment of the present application, the first emulsifier is selected from at least one of the following: CF3CF2CF2CF2CH2COOH, CF3CF2CF2CF2CH2C6H4COOH, CF3CF2CF2CF2CH2CH2COOH, CF3CF2CF2CF2CH2CH2C6H4COOH, CF3CF2CF2CF2(CH2)3COOH, CF3CF2CF2CF2(CH2)4COOH, CF3(CF2)5CH2COOH, CF3(CF2)5CH2C6H4COOH, CF3(CF2)5CH2CH2COOH, CF3(CF2)5CH2CH2C6H4 COOH, CF3(CF2)5(CH2)4COOH, CF3CF2CF2C(CF3)2CH2COOH, CF3CF2CF2C(CF3)2CH2C6H4COOH, CF3CF2CF2C(CF3)2(CH2)2COOH, CF3CF2CF2C(CF3)2(CH 2)3COOH, CF3CF2CF2C(CF3)2(CH2)4COOH, CF3(CF-CF3)2CH2COOH, CF3(CF-CF3)2CH2C6H4COOH, CF3(CF-CF3)2CH2CH2COOH, CF3(CF-CF3)2(CH2)4COOH , CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2COOH, CF3-O-CF(CF3)-CF2-O-CF2-(CH2)2COOH, CF3-O-CF(CF3)-C F2-O-CF(CF3)-(CH2)4COOH, CF3CF2CF2CF2CH2SO3H, CF3CF2CF2CF2CH2C6H4SO3H, CF3CF2CF2CF2CH2CH2SO3H, CF3CF2CF2CF2CH2CH2C6H4SO3H, CF3CF2 CF2CF2(CH2)3SO3H, CF3CF2CF2CF2(CH2)4SO3H, CF3(CF2)5CH2SO3H, CF3(CF2)5CH2C6H4SO3H, CF3(CF2)5CH2CH2SO3H, CF3(CF2)5CH2CH2C6H4SO3H, CF 3(CF2)5(CH2)4SO3H, CF3CF2CF2C(CF3)2CH2SO3H, CF3CF2CF2C(CF3)2CH2C6H4SO3H, CF3CF2CF2C(CF3)2(CH2)2SO3H, CF3CF2CF2C(CF3)2(CH2)3SO3H,CF3CF2CF2C(CF3)2(CH2)4SO3H, CF3(CF-CF3)2CH2SO3H, CF3(CF-CF3)2CH2C6H4SO3H, CF3(CF-CF3)2CH2CH2SO3H, CF3(CF-CF3)2(CH2)4SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2SO3H, CF3-O-CF(CF3)-CF2-O-(CF2)2-CH2SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)2SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4SO3H, and their sodium salts, potassium salts and ammonium salts. According to a preferred embodiment of the present application, the first emulsifier is selected from at least one of the following: CF3(CF2)5CH2CH2SO3H, CF3CF2CF2C(CF3)2CH2C6H4COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4SO3H, and their sodium salts, potassium salts and ammonium salts.

[0047] According to one embodiment of the present application, based on the total weight of the emulsifier composition (that is, the total weight of the first emulsifier, the second emulsifier and the third emulsifier), the content of the first emulsifier is 10-35 weight%, for example, it can be 12-32 weight%, or it can be 15-30 weight%, or it can be 18-28 weight%, or it can be 20-26 weight%, or it can be 22-25 weight%, or it can be within the numerical range obtained by combining any two of the above end values.

[0048] According to one embodiment of the present application, the second emulsifier can be various organic sulfates, organic sulfonates, organic phosphates, organic phosphonates, organic carboxylates, etc. that are not fluorinated (do not contain fluorine). For example, the second emulsifier can be obtained by connecting one or more sulfates, sulfonates, phosphates, phosphonates, or carboxylates at any position selected from the following organic compounds: C1-C22 alkanes, C1-C22 cycloalkanes, C6-C22 aromatics, C6-C22 aromatic hydrocarbons, polyethers, polyether-C1-C11 alkyl ethers, and the second emulsifier can be various suitable salts, such as sodium salts, potassium salts, ammonium salts, etc. According to one embodiment of the present application, the second oxidant can be selected from alkyl sulfates, alkylbenzene sulfonates, or alkyl ether sulfates. According to one embodiment of the present application, the second emulsifier is selected from at least one of the following: C6-C22 alkyl sulfates, C6-C22 alkyl sulfonates, C2-C22 alkyl phosphates, C4-C22 carboxylates, C6-C22 aryl sulfonates, C6-C22 arylalkyl sulfonates, C2-C22 alkyl ether sulfates, C2-C22 alkyl ether sulfonates, and C2-C22 alkyl ether carboxylates. According to one embodiment of the present application, the second emulsifier is selected from at least one of the following: C8-C12 alkyl sulfates, such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium decyl sulfate, sodium octyl sulfate, sodium 2-ethylhexyl sulfate; C8 to C18 alkyl ether sulfates, such as sodium lauryl ether sulfate, sodium myristyl alcohol polyether sulfate; sulfonates, such as dialkyl sodium sulfosuccinate, sodium dioctyl sulfosuccinate; C10 to C16 alkylbenzenesulfonates, such as sodium decylphenylsulfonate, sodium dodecylbenzenesulfonate; alkylbenzene ether sulfonates, such as potassium salt of poly(ethylene glycol) 4-nonylphenol 3-sulfopropyl ethyl ether; phosphates, such as C1-C16 alkyl C6-C16 aryl ether phosphates, C1-C16 alkyl ether phosphates; C2-C18 alkyl carboxylates, such as sodium stearate. According to a preferred embodiment of the present application, the second emulsifier is sodium lauryl sulfate.

[0049] According to one embodiment of the present application, based on the total weight of the emulsifier composition (that is, the total weight of the first emulsifier, the second emulsifier and the third emulsifier), the content of the second emulsifier is 40-75 weight%, for example, 45-70 weight%, or 48-68 weight%, or 50-65 weight%, or 52-62 weight%, or 55-60 weight%, or 56-58 weight%, or within the numerical range obtained by combining any two of the above end values.

[0050] According to another embodiment of the present application, the third emulsifier can be a primary amine, secondary amine or tertiary amine with a chain alkyl, cycloalkyl substituent, aryl substituent, aralkyl substituent or alkaryl substituent and an acid-neutralized ammonium salt thereof, so it can be written as R 1 R 2 R 3 N and its salt forms, wherein R 1 、R 2 and R 3 Each independently selected from the following groups: H, C1-C16 alkyl, C2-C16 alkenyl, C3-C16 cycloalkyl, C6-C16 aryl, C6-C16 aralkyl, C6-C16 alkaryl. The third emulsifier may also be a substituted or unsubstituted heterocyclic amine or its salt, such as a substituted or unsubstituted pyridine. The salt may be a salt formed by the aforementioned amines or nitrogen-containing compounds with a suitable acid, such as a hydrochloride, sulfate, nitrate, or phosphate. The third emulsifier may also be an ether or polyether.

[0051] According to an exemplary embodiment, the third emulsifier is selected from at least one of the following: 1 R 2 R 3 N and its salts, nitrogen-containing heteroaryl compounds and their salts, polyoxygenated (C1-C12) alkylene, C1-C22 alkyl ether, C1-C22 alkyl C6-C22 aryl ether, polyoxygenated (C1-C12) alkylene C1-C22 alkyl ether, polyoxygenated (C1-C12) alkylene C6-C22 aryl ether, C1-C22 alkyl ether of a polyol containing three or more hydroxyl groups, C6-C22 aryl ether of a polyol containing three or more hydroxyl groups, polyoxygenated (C1-C12) alkylene C1-C22 carboxylate, wherein R 1 、R 2 and R 3 Each is independently selected from the following groups: H, C1-C16 alkyl, C2-C16 alkenyl, C3-C16 cycloalkyl, C6-C16 aryl, C6-C16 aralkyl, C6-C16 alkaryl. According to another exemplary embodiment, the third emulsifier is selected from at least one of the following: C8-C12 alkylamine hydrochloride, such as dodecylamine hydrochloride, didodecylamine hydrochloride, cetyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, N-dodecylpyridinium chloride, etc.; octylphenyl ether, polyethylene glycol monoalkyl ether (such as octylethylene glycol mono-n-dodecyl ether or pentaethylene glycol mono-dodecyl ether) or polypropylene glycol monoalkyl ether; polyoxyethylene sorbitan monooleate, etc. According to a preferred embodiment, the third emulsifier is dodecylamine hydrochloride.

[0052] According to one embodiment of the present application, based on the total weight of the emulsifier composition (that is, the total weight of the first emulsifier, the second emulsifier and the third emulsifier), the content of the third emulsifier is 5-25 weight%, for example, 6-22 weight%, or 8-20 weight%, or 10-18 weight%, or 12-16 weight%, or 13-15 weight%, or within the numerical range obtained by combining any two of the above end values.

[0053] According to one embodiment of the present application, the emulsifier composition of the present application can be used to form the polytrifluorostyrene of the present invention by a method comprising the following steps:

[0054] Step 1: using the emulsifier composition of the present invention, trifluorostyrene monomer and water to form a pre-emulsion;

[0055] Step 2: adding an initiator to the pre-emulsion to polymerize the trifluorostyrene monomer; and

[0056] Step 3: Demulsify the reaction system after step 2.

[0057] According to one embodiment of the present application, in the step 1, based on the weight of the trifluorostyrene monomer as 100 parts by weight, the content of the emulsifier composition (i.e., the total amount of the first emulsifier, the second emulsifier, and the third emulsifier) ​​is 0.5-10 parts by weight, for example, 1-9% by weight, or 2-8% by weight, or 3-7% by weight, or 4-6% by weight, or 4.5-5% by weight, or within the numerical range obtained by combining any two of the above end values. According to one embodiment of the present application, the amount of the emulsifier composition used in the present application is less than the amount of conventional emulsifiers used in the existing synthesis of trifluorostyrene polymer emulsions.

[0058] According to one embodiment of the present application, in the step 1, based on the total weight of the pre-emulsion as 100 weight%, the content of the trifluorostyrene monomer is 10-60 weight%, for example, 15-55 weight%, or 20-50 weight%, or 25-45 weight%, or 30-40 weight%, or 32-45 weight%, or within the numerical range obtained by combining any two of the above end values. According to one embodiment of the present application, in addition to the above-mentioned emulsifier and trifluorostyrene monomer, the pre-emulsion may also contain a balance of water and (optionally) other required additives.

[0059] According to one embodiment of the present application, in the first step, the pre-emulsion is formed by the following method: according to the required amount, the ternary emulsifier is added to deionized water to dissolve, and then trifluorostyrene monomer is added to the emulsifier solution, and stirred for 30-60 minutes to obtain the pre-emulsion.

[0060] In one embodiment of the present invention, after the pre-emulsion is prepared, it is first heated to the reaction temperature, and then the initiator is added to start the reaction. For example, the reaction temperature can be 30-80°C, such as 35-75°C, or 40-70°C, or 45-65°C, or 50-60°C, or 52-55°C, or can be within a numerical range obtained by combining any two of the above end values.

[0061] According to one embodiment of the present application, in the second step, the polymerization reaction is continued for 1-24 hours, for example, 2-22 hours, or 4-20 hours, or 6-18 hours, or 8-16 hours, or 10-14 hours, or 12-13 hours, or within the numerical range obtained by combining any two of the above end values.

[0062] The initiator used in the second step can be an inorganic peroxide initiator, such as ammonium persulfate, potassium persulfate, ammonium persulfate / sodium sulfite (i.e., a mixture of ammonium persulfate / sodium sulfite, as an oxidation / reduction initiator), potassium persulfate / sodium sulfite (i.e., a mixture of potassium persulfate / sodium sulfite, as an oxidation / reduction initiator) or one or more thereof; or an organic initiator, such as azobisisobutyronitrile, dibenzoyl peroxide, or one or more thereof. According to a preferred embodiment, the initiator used in the second step of the method of the present application can be selected from at least one of the following: potassium persulfate, ammonium persulfate, potassium persulfate / sodium bisulfite. The initiator can be added to the pre-emulsion in the form of a solid, or it can be first dissolved or dispersed in water and added to the pre-emulsion in the form of a solution or dispersion.

[0063] According to one embodiment of the present application, based on 100 parts by weight of the trifluorostyrene monomer, the amount of the initiator is 0.1-1.5 parts by weight, for example, 0.2-1.4 parts by weight, or 0.3-1.3 parts by weight, or 0.4-1.2 parts by weight, or 0.5-1.1 parts by weight, or 0.6-1.0 parts by weight, or 0.7-0.9 parts by weight, or 0.7-0.8 parts by weight, or within the numerical range obtained by combining any two of the above end values.

[0064] After the polymerization is completed, in the third step, the material is cooled to room temperature and stirring is then stopped; a certain amount of coagulant is added to the reaction system, and the mixture is stirred at a high speed until the polytrifluorostyrene emulsion breaks and separates; the demulsified polymer is filtered, deionized water is added, and the mixture is washed until the conductivity meets the requirements; the washed polytrifluorostyrene is placed in a vacuum oven and dried to obtain the final polytrifluorostyrene.

[0065] According to one embodiment of the present application, the particle size of the prepared polytrifluorostyrene can be 30-70 nm, such as 40-60 nm, or 35-55 nm, or 45-50 nm, or can be within the numerical range obtained by combining any two of the above end values.

[0066] According to one embodiment of the present application, the water used in the method of the present application can be distilled water, deionized water, double distilled water, etc., preferably deionized water.

[0067] According to one embodiment of the present application, the polytrifluorostyrene synthesized by the method of the present application can have a well-controlled glass transition temperature, for example, 190-215°C, or 195-212°C, or 198-210°C, or 200-208°C, or 202-206°C, or 203-205°C, or can be within the numerical range obtained by combining any two of the above end values.

[0068] According to one embodiment of the present application, the polytrifluorostyrene synthesized by the method of the present application has a well-controlled molecular weight, such as a weight average molecular weight, for example, the weight average molecular weight can be 5-150×10 4 g / mol, or 8-120×10 4 g / mol, or 10-100×10 4 g / mol, or 12-90×10 4 g / mol, or 16-80×10 4 g / mol, or 18-70×10 4 g / mol, or 20-60×10 4 g / mol, or 25-50×10 4 g / mol, or 30-40×10 4 g / mol, or within the numerical range obtained by combining any two of the above end values.

[0069] By adopting the technology of the present application, a polytrifluorostyrene product can be prepared with a yield of up to 91-97% by weight, and it has the desired excellent glass transition temperature and well-controlled molecular weight. As an amorphous polymer, it has excellent optical transparency and birefringence properties, and is particularly suitable as an optical film for use in optics, electronic equipment and other fields.

[0070] The preferred embodiments of the present invention are described in detail below so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more precise definition of the protection scope of the present invention.

[0071] Example

[0072] In the following examples and comparative examples, the following testing techniques were used to test the various properties of the products:

[0073] (1) Determination of solid content of polytrifluorostyrene product microemulsion

[0074] Weigh approximately 5 g of the resulting polytrifluorostyrene microemulsion and heat it at 140°C for 2 hours to remove all moisture. Calculate the solids content by weighing it before and after heating, and take the average of three experiments.

[0075] (2) Determination of molecular weight of polytrifluorostyrene

[0076] Approximately 5 mg of polymer was dissolved in 2 mL of HPLC-grade DMF and its molecular weight was characterized by gel permeation chromatography. The specific testing conditions were as follows: 0.02 mol / L LiBr in DMF, flow rate: 1 mL / min, column temperature: 70°C, sample concentration: 2.5 mg / mL.

[0077] (3) Determination of glass transition temperature of polytrifluorostyrene

[0078] Approximately 10 mg of polymer was weighed and placed in a solid crucible. Its glass transition temperature was characterized using a differential scanning calorimeter. Specific test conditions were as follows: temperature range 50-300°C, nitrogen flow rate 50 mL / min, and heating rate: 10°C / min.

[0079] (4) Determination of particle size of polytrifluorostyrene microemulsion

[0080] 0.1 μL of polytrifluorostyrene microemulsion was diluted in 2 mL of deionized water, and its particle size was characterized by a laser particle size analyzer. The dispersed phase was water.

[0081] (5) Determination of polymer yield Polymer yield = (solid content of polymer emulsion × total weight of emulsion - weight of surfactant - weight of initiator) / weight of monomer × 100%.

[0082] Comparative Example 1

[0083] In this comparative example, CF3CF2CF2C(CF3)2CH2C6H4COONa was used as an emulsifier for trifluorostyrene microemulsion polymerization.

[0084] Weigh 1.2g of CF3CF2CF2C(CF3)2CH2C6H4COONa into a 500mL reaction vessel, add 182g of deionized water, and stir to dissolve. After complete dissolution, add 140g of trifluorostyrene monomer and continue stirring for 45 minutes to form a pre-emulsion. The temperature of the pre-emulsion is raised to 55°C, and 0.54g of potassium persulfate and 0.28g of sodium bisulfite are added in the form of an aqueous solution. Stir and maintain the temperature for 18 hours. After the polymerization is completed, the reaction system is cooled to room temperature, and a small amount of coagulant is added to the reaction system. The emulsion generated by the polymerization reaction is agglomerated and demulsified by stirring. The demulsified material is filtered, washed, and dried to obtain a white powdery polytrifluorostyrene resin.

[0085] The properties of the product obtained in Comparative Example 1 were characterized, and the results are summarized in Table 1 below.

[0086] Example 1

[0087] In this embodiment, a ternary emulsifier system of CF3(CF2)5CH2CH2SO3Na: sodium dodecylsulfonate: dodecylamine hydrochloride is used as an emulsifier for trifluorostyrene microemulsion polymerization, wherein the weight ratio of the three emulsifiers is 25:55:20.

[0088] A total of 5g of the above-mentioned ternary emulsifier was weighed and added to a 500mL reaction vessel. 182g of deionized water was added and stirred to dissolve. After complete dissolution, 140g of trifluorostyrene monomer was added and stirring was continued for 45 minutes to form a pre-emulsion. The temperature of the pre-emulsion was raised to 55°C, 0.54g of potassium persulfate and 0.28g of sodium bisulfite were added to the reactor, and stirring was continued to maintain a constant temperature for 18 hours. After the polymerization was completed, the reaction system was cooled to room temperature, and a small amount of coagulant was added to the reaction system. The emulsion generated by the polymerization reaction was agglomerated and demulsified by stirring. The demulsified material was filtered, washed, and dried to obtain a white powdery polytrifluorostyrene resin.

[0089] The properties of the product obtained in Example 1 were characterized, and the results are summarized in Table 1 below.

[0090] Example 2

[0091] In this embodiment, a ternary emulsifier system of CF3CF2CF2C(CF3)2CH2C6H4COONa: sodium lauryl sulfate: dodecylamine hydrochloride is used as an emulsifier for trifluorostyrene microemulsion polymerization, wherein the weight ratio of the three emulsifiers is 20:60:20.

[0092] Weigh 6g of ternary emulsifier into a 500mL reaction vessel, add 182g of deionized water, and stir to dissolve. After complete dissolution, add 140g of trifluorostyrene monomer and continue stirring for 45 minutes to form a pre-emulsion. Raise the temperature of the pre-emulsion to 55°C, add 0.54g of potassium persulfate and 0.28g of sodium bisulfite, and continue stirring at this constant temperature for 18 hours. After the polymerization is completed, cool the reaction system to room temperature, add a small amount of coagulant to the reaction system, and stir to demulsify the emulsion generated by the polymerization reaction. Filter, wash, and dry the demulsified material to obtain a white powdery polytrifluorostyrene resin.

[0093] The properties of the product obtained in Example 2 were characterized, and the results are summarized in Table 1 below.

[0094] Example 3

[0095] In this embodiment, a ternary emulsifier system of CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4SO3Na: sodium lauryl sulfate: dodecylamine hydrochloride is used as an emulsifier for trifluorostyrene microemulsion polymerization, wherein the weight ratio of the three emulsifiers is 30:60:10.

[0096] Weigh 4.5g of ternary emulsifier and add it to a 500mL reaction vessel. Add 182g of deionized water and stir to dissolve. After complete dissolution, add 140g of trifluorostyrene monomer and continue stirring for 45 minutes to form a pre-emulsion. Raise the temperature of the pre-emulsion to 55°C, add 0.54g of potassium persulfate and 0.28g of sodium bisulfite, and continue stirring at this constant temperature for 18 hours. After the polymerization is completed, cool the reaction system to room temperature and add a small amount of coagulant to the reaction system. Stir to demulsify the emulsion generated by the polymerization reaction. Filter, wash, and dry the demulsified material to obtain a white powdery polytrifluorostyrene resin.

[0097] The properties of the product obtained in Example 3 were characterized, and the results are summarized in Table 1 below.

[0098] Comparative Example 2

[0099] Comparative Example 2 was carried out using the same steps and process conditions as Example 1. The total weight of the emulsifier used was 9 grams, but the emulsifier only contained sodium lauryl sulfonate and dodecylamine hydrochloride in a weight ratio of 2:1.

[0100] Comparative Example 3

[0101] Comparative Example 3 was carried out using the same steps and process conditions as Example 1. The total weight of the emulsifier used was 6 grams, but the emulsifier only contained a 1:1 ratio of CF3CF2CF2C(CF3)2CH2C6H4COONa:dodecylamine hydrochloride.

[0102] Comparative Example 4

[0103] Comparative Example 3 was carried out using the same steps and process conditions as Example 1. The total weight of the emulsifier used was 4.5 grams, but the emulsifier only contained 1:2 CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4SO3Na: sodium lauryl sulfate.

[0104] Table 1 Experimental data of Examples and Comparative Examples

[0105] It can be seen from the above test results that all the embodiments of the invention can achieve higher yields, and the obtained polymers have controllable molecular weight and glass transition temperature.

Claims

1. An emulsifier composition, comprising: A first emulsifier, wherein the first emulsifier is a non-perfluorinated substituted fluorinated anionic surfactant; a second emulsifier, wherein the second emulsifier is a non-fluorinated aliphatic or aromatic anionic surfactant; The third emulsifier is a cationic surfactant, a nonionic surfactant, or a combination thereof.

2. The emulsifier composition according to claim 1, characterized in that The first emulsifier has a structure shown in Formula I: CF3-[(O) t -CFX] n (CX2) s [O-CX2] p (CH2) m (C6H4) o M Type I Wherein t is 0 or 1, n is an integer from 1 to 6, s is an integer from 0 to 2, m is an integer from 1 to 4, o is an integer from 0 to 1, and p is an integer from 0 to 2; Each X is independently selected from -F, C1-C 12 Perfluoroalkyl, C1-C 12 Perfluoroalkoxy; M is selected from a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof.

3. The emulsifier composition according to claim 2, characterized in that The first emulsifier is selected from at least one of the following: CF3CF2CF2CF2CH2COOH, CF3CF2CF2CF2CH2C6H4COOH, CF3CF2CF2CF2CH2CH2COOH, CF3CF2CF2CF2CH2CH2C6H4COOH, CF3CF2CF2CF2(CH2)3COOH, CF3CF2CF2CF2(CH2)4COOH, CF3(CF2)5CH2COOH, CF3(CF2)5CH2C6H4COOH, CF3(CF2)5CH2CH2COOH, CF3(CF2)5CH2CH2C6H4COOH, CF3(CF2)5(CH2)4COOH, CF3CF2CF2C(CF3)2CH2COOH, CF3CF2CF2C(CF3)2CH2C6H4COOH, CF3CF2CF2C(CF3)2CH2 3)2(CH2)2COOH, CF3CF2CF2C(CF3)2(CH2)3COOH, CF3CF2CF2C(CF3)2(CH2)4COOH, CF3(CF-CF3)2C H2COOH, CF3(CF-CF3)2CH2C6H4COOH, CF3(CF-CF3)2CH2CH2COOH, CF3(CF-CF3)2(CH2)4COOH, CF3- O-CF(CF3)-CF2-O-CF(CF3)-CH2COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2COOH, CF3-O-CF(CF3) -CF2-O-CF2-(CH2)2COOH, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4COOH, CF3CF2CF2CF2CH2SO3H,CF3CF2CF2CF2CH2C6H4SO3H, CF3CF2CF2CF2CH2CH2SO3H, CF3CF2CF2CF2CH2CH2C6H4SO3H, CF3CF2CF2CF2(CH2)3SO3H, CF3CF2CF2CF2(CH2)4SO3H, CF3(CF2)5CH2SO3H, CF3(CF2)5CH2C6H4SO3H, CF3(CF2)5CH2CH2SO3H, CF3(CF2)5CH2CH2C6H4SO3H, CF3(CF2)5(CH2)4SO3H, CF3CF2CF2C(CF3)2CH2SO3H, CF3CF2CF2C(CF3)2CH2C6H4SO3H, CF3CF2CF2C(CF3)2(CH2)2SO3H, CF3CF2CF2C(CF3)2(CH2)3SO3H, CF3CF2CF2C(CF3)2(CH2)4SO3H, CF3(CF-CF3)2CH2SO3H, CF3(CF-CF3)2CH2C6H4SO3H, CF3(CF-CF3)2CH2CH2SO3H, CF3(CF-CF3)2(CH2)4SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-CH2SO3H, CF3-O-CF(CF3)-CF2-O-(CF2)2-CH2SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)2SO3H, CF3-O-CF(CF3)-CF2-O-CF(CF3)-(CH2)4SO3H, and their sodium, potassium, and ammonium salts.

4. The emulsifier composition according to claim 1, characterized in that The second emulsifier is selected from at least one of the following: C6-C22 alkyl sulfates, C6-C22 alkyl sulfonates, C2-C22 alkyl phosphates, C4-C22 carboxylates, C6-C22 aryl sulfonates, C6-C22 arylalkyl sulfonates, C2-C22 alkyl ether sulfates, C2-C22 alkyl ether sulfonates, and C2-C22 alkyl ether carboxylates.

5. The emulsifier composition according to claim 1, characterized in that The third emulsifier is selected from at least one of the following: 1 R 2 R 3 N and its salts, nitrogen-containing heteroaryl compounds and their salts, polyoxygenated (C1-C12) alkylene, C1-C22 alkyl ether, C1-C22 alkyl C6-C22 aryl ether, polyoxygenated (C1-C12) alkylene C1-C22 alkyl ether, polyoxygenated (C1-C12) alkylene C6-C22 aryl ether, C1-C22 alkyl ether of a polyol containing three or more hydroxyl groups, C6-C22 aryl ether of a polyol containing three or more hydroxyl groups, polyoxygenated (C1-C12) alkylene C1-C22 carboxylates, Where R 1 , R 2 and R 3 Each is independently selected from the following groups: H, C1-C16 alkyl, C2-C16 alkenyl, C3-C16 cycloalkyl, C6-C16 aryl, C6-C16 aralkyl, C6-C16 alkaryl.

6. The emulsifier composition according to claim 1, characterized in that Based on the total weight of the emulsifier composition, the content of the first emulsifier is 10-35% by weight, the content of the second emulsifier is 40-75% by weight, and the content of the third emulsifier is 5-25% by weight.

7. A method for preparing polytrifluorostyrene, the method comprising: Step 1: using the emulsifier composition according to any one of claims 1 to 6, trifluorostyrene monomer and water to form a pre-emulsion; Step 2: adding an initiator to the pre-emulsion to polymerize the trifluorostyrene monomer; as well as Step 3: Demulsify the reaction system after step 2.

8. The method according to claim 7, characterized in that In step one, Based on 100 parts by weight of the trifluorostyrene monomer, the content of the emulsifier composition is 0.5-10 parts by weight; Based on the total weight of the pre-emulsion being 100 weight %, the content of the trifluorostyrene monomer is 10-60 weight %.

9. The method according to claim 7, characterized in that In the step 2, The trifluorostyrene monomer is polymerized at a temperature of 30-80°C for 1-24 hours; Based on 100 parts by weight of the trifluorostyrene monomer, the amount of the initiator is 0.1-1.5 parts by weight; The initiator is selected from at least one of the following: ammonium persulfate, potassium persulfate, ammonium persulfate / sodium sulfite, potassium persulfate / sodium sulfite, azobisisobutyronitrile, dibenzoyl peroxide, and dodecanoyl peroxide.

10. A polytrifluorostyrene prepared by the method according to any one of claims 7 to 9, wherein the polytrifluorostyrene has a glass transition temperature of 190-215°C and a weight average molecular weight of 5-150×10 4 g / mol, and its particle size is 30-70nm.

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