A polymerization catalyst and its preparation method and use

Abstract

The present application provides a polymerization catalyst and a preparation method and use thereof, wherein the catalyst comprises polymerization units derived from a first monomer and a second monomer, respectively, wherein the molar ratio of the polymerization units derived from the first monomer to the polymerization units derived from the second monomer is 20:1 to 1:20. The polymerization catalyst of the present application can be used for acyl chloride reaction, and has the advantages of high catalytic activity, high conversion rate, no residue, and easy recycling.

Description

Technical Field

[0001] The present application relates to the field of catalysis, and more specifically to a polymeric catalyst specially designed for acyl chlorination reaction, a method for synthesizing the polymeric catalyst, and a method for performing acyl chlorination reaction using the polymeric catalyst. Background Art

[0002] Acid chloride compounds refer to compounds containing "C(=O)-Cl group. This is an important class of carboxylic acid derivatives, which can be mainly used for hydrolysis, alcoholysis, ammonia (amine) hydrolysis, reaction with organometallic reagents, reduction reaction, α-hydrohalogenation and other reactions. Acid chloride is the most active acylating agent. In some reactions that carboxylic acids cannot proceed or proceed very slowly, the reaction activity and yield can be greatly improved after the carboxylic acid is converted into an acid chloride. There are many types of acyl chlorides, and their uses include the production of papermaking additives AKD, amino acid surfactants and other daily chemicals, pesticide and pharmaceutical intermediates, polymer initiators, etc.

[0003] The industrial production of acyl chlorides initially mainly included the phosphorus trichloride method, the thionyl chloride method and the phosgene method, but each of these three methods has its own defects and shortcomings. For example, the phosphorus trichloride method is only suitable for preparing low-boiling acyl chlorides, and its main disadvantage is that the product purity is low and a large amount of byproduct phosphorous acid waste liquid that is difficult to handle will be produced. The defect of the thionyl chloride method is that the product color is poor, the acyl chloride product often needs further distillation and purification, and the SO2 waste gas produced in the reaction is very difficult to handle. The main defect of the phosgene method is that the reaction activity of phosgene is low. Under the condition of no catalyst, it is difficult to react with carboxylic acid to form acyl chlorides, and the catalyst used in it often has potential toxicity and carcinogenic risks, which has great safety hazards.

[0004] In order to solve the above problems, the technical personnel of scientific research institutions and manufacturers have invested a lot of energy and cost to further improve the reaction process and catalyst system, but the results obtained so far are quite limited. The results of these studies can often only alleviate one or several of the above defects, but cannot achieve overall systematic improvement, and often bring some new troubles. For example, some newly developed catalysts are often easy to decompose and remain in the acyl chloride product, which is difficult to completely remove, resulting in many restrictions on the downstream application of the acyl chloride product. For example, the products obtained by these technologies often have odor and poor color. In addition, these reported technologies often have problems such as harsh reaction conditions, poor reaction activity, low conversion rate, poor yield, and catalyst residue.

[0005] Although some early studies have reported that relatively excellent results can be achieved, the applicant has analyzed these research results and found that after the reaction is completed, the chlorine content is directly tested by sampling without nitrogen expulsion. The phosgene and HCl present in the system will make the tested chlorine content higher, which will undoubtedly make the conversion rate calculated by the chlorine content significantly higher than the actual conversion rate. After removing the phosgene and HCl, the actual measured conversion rate is less than 90%, which has no real practical value.

[0006] Therefore, to date, the art is still eager to develop a novel technology to solve the above problems. Summary of the invention

[0007] In view of the above problems, the inventors of the present application conducted in-depth research and successfully developed a novel catalyst system, which effectively solved the problems that have long been urgently needed to be solved in the prior art.

[0008] The first aspect of the present application provides a polymerization catalyst, which comprises polymerization units derived from a first monomer and a second monomer, respectively, wherein the polymerization unit derived from the first monomer has the following structural formula:

[0009]

[0010] The polymerized unit derived from the second monomer has the structural formula shown below:

[0011]

[0012] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each of the following is independently selected from the group consisting of hydrogen, C1-C12 straight chain alkyl, C3-C12 branched chain alkyl, C3-C12 cycloalkyl, C6-C12 aryl, R 2 , R 3 and the nitrogen atom and carbon atom connected thereto form a nitrogen four-membered to six-membered ring, and R 6 , R 8 and the nitrogen atom and the carbon atom respectively connected thereto together form an aza four-membered to six-membered ring, wherein a is an integer from 1 to 12;

[0013] Wherein * represents the connecting bond between the polymer unit and the adjacent polymer unit;

[0014] The molar ratio of the first monomer to the second monomer is 20:1 to 1:20;

[0015] The polymerization degree of the catalyst is 10-9500.

[0016] According to one embodiment of the first aspect of the present invention, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each of the following is independently selected from the group consisting of hydrogen, C1-C4 straight chain alkyl, C3-C4 branched chain alkyl, C3-C6 cycloalkyl, C6-C9 aryl, R 2 , R 3 and the nitrogen atom and carbon atom connected thereto form a nitrogen five-membered to six-membered ring, and R 6 , R 8 The nitrogen atom and the carbon atom respectively connected thereto form a nitrogen five-membered to six-membered ring; and the number of polymerization units derived from the first monomer in the polymerization catalyst is 1-9000, and the number of polymerization units derived from the second monomer is 1-9000.

[0017] According to another embodiment of the first aspect of the present invention, the first monomer is selected from at least one of the following:

[0018]

[0019] According to another embodiment of the first aspect of the present invention, the second monomer is selected from at least one of the following:

[0020]

[0021] According to another embodiment of the first aspect of the present invention, the polymerization catalyst is supported on at least one carrier selected from the group consisting of activated carbon, molecular sieves, silicon dioxide, titanium dioxide, silica gel, pumice, diatomaceous earth, kaolin, glass fiber mesh, ceramic balls / particles / powders, hollow glass beads, quartz glass tubes, expanded perlite, and resin particles.

[0022] A second aspect of the present invention provides a method for synthesizing the polymerizable catalyst as described herein, the method comprising allowing the first monomer and the second monomer to undergo a polymerization reaction in the presence of a solvent and an initiator to form the polymerizable catalyst.

[0023] According to another embodiment of the second aspect of the present invention, the initiator includes a peroxide initiator, an azo initiator, or a combination thereof. According to another embodiment of the second aspect of the present invention, the solvent includes at least one of the following: aromatic hydrocarbons, esters, ketones, alcohols, ethers. According to another embodiment of the second aspect of the present invention, the total molar amount of the first monomer and the second monomer is 100 mol%, and the amount of the initiator is 0.05-20 mol%. According to another embodiment of the second aspect of the present invention, the total weight of the first monomer and the second monomer is 1 part by weight, and the amount of the solvent is 1-1000 parts by weight.

[0024] According to another embodiment of the second aspect of the present invention, the polymerization reaction is carried out at a temperature of 20-150° C. for 1-24 hours. According to another embodiment of the second aspect of the present invention, after the polymerization reaction, the product of the polymerization reaction is washed with a washing agent. According to another embodiment of the second aspect of the present invention, the washing agent is selected from at least one of the following: alkanes, aromatic hydrocarbons, chloroalkanes, esters, ketones, alcohols, and ethers. According to another embodiment of the second aspect of the present invention, based on the total weight of the first monomer and the second monomer as 100 parts by weight, the amount of the washing agent is 200-1000 parts by weight.

[0025] The third aspect of the present invention provides an acyl chlorination method, which comprises reacting at least one carboxylic acid compound with at least one chlorinating agent to generate an acyl chloride compound under the conditions of the polymerization catalyst of the present invention or the catalyst synthesized by the method of the present invention.

[0026] According to another embodiment of the third aspect of the present invention, the carboxylic acid compound is selected from at least one of the following: C4-C30 saturated straight-chain carboxylic acids containing at least one carboxyl group, C4-C30 unsaturated straight-chain carboxylic acids containing at least one carboxyl group, C4-C30 saturated branched carboxylic acids containing at least one carboxyl group, C4-C30 unsaturated branched carboxylic acids containing at least one carboxyl group, C4-C30 saturated cycloalkane carboxylic acids containing at least one carboxyl group, C4-C30 unsaturated cycloalkane carboxylic acids containing at least one carboxyl group, C6-C30 aromatic carboxylic acids containing at least one carboxyl group. According to another embodiment of the third aspect of the present invention, the chlorinating agent is selected from at least one of the following: phosgene, thionyl chloride, trichloromethyl chloroformate and bis(trichloromethyl)carbonate. DETAILED DESCRIPTION

[0027] "Range" disclosed herein is in the form of lower limit and upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundaries of a particular range. All ranges that can be defined in this way are inclusive and combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, a range of 60-120 and 80-110 is listed for a particular parameter, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0028] In this application, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[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, if there is no special explanation, the "including" mentioned herein means open or closed. For example, the "including" may mean that other components not listed may also be included, or only the listed components may be included.

[0032] The catalyst of the present application is a polymerization catalyst, which comprises a polymerization unit derived from a first monomer (hereinafter referred to as a first polymerization unit) and a polymerization unit derived from a second monomer (hereinafter referred to as a second polymerization unit). The first monomer comprises at least one carbon-carbon double bond and at least one amide group in the same molecule, and the second monomer comprises at least one carbon-carbon double bond and at least one aldehyde group connected to a nitrogen atom in the same molecule. The first monomer and the second monomer undergo a polymerization reaction (copolymerization reaction), and the carbon-carbon double bonds contained in the molecules of the two undergo an addition polymerization reaction to form a carbon chain main chain, while the other parts of the first monomer and the second monomer (such as the amide group and the aldehyde group connected to the nitrogen atom) are connected to the carbon chain main chain as side functional groups.

[0033] According to one embodiment of the present application, the molar ratio of the first polymerization unit and the second polymerization unit in the polymerization catalyst of the present application is 20:1 to 1:20, for example, it can be 18:1 to 1:18, or 15:1 to 1:15, or 12:1 to 1:12, or 10:1 to 1:10, or 9:1 to 1:9, or 8:1 to 1:8, or 7:1 to 1:7, or 6:1 to 1:6, or 5:1 to 1:5, or 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2, or 3:2 to 1:1, or 1:1 to 2:3, or the molar ratio of the two can be within the numerical range obtained by combining any two of the above end values.

[0034] According to one embodiment of the present application, the polymerization degree of the polymerization catalyst of the present application is 10-10000, for example, 20-9500, or 50-9000, or 80-8500, or 100-8000, or 200-7500, or 300-7000, or 400-6500, or 500-6000, or 600-5500, or 700-5000, or 800-4000, or 1000-3000, or 1500-2000, or within the numerical range obtained by combining any two of the above end values.

[0035] According to one embodiment of the present application, the polymerization catalyst of the present application comprises a first unit and a second unit at the same time. According to one embodiment of the present application, the first unit and the second unit can be connected to each other in the form of a random copolymer, a block copolymer, or an alternating copolymer in the polymerization catalyst. According to one embodiment of the present application, the polymerization units connected at both ends of the main chain of the polymerization catalyst can be two first units, two second units, or a first unit and a second unit connected at both ends of the main chain. All of the above situations are included in the scope of the present invention, and the polymerization catalyst of the present invention can be written as shown in the following formula I:

[0036]

[0037] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11Each of the following is independently selected from the group consisting of hydrogen, C1-C12 straight chain alkyl, C3-C12 branched chain alkyl, C3-C12 cycloalkyl, C6-C12 aryl, R 2 , R 3 and the nitrogen atom and carbon atom connected thereto form a nitrogen four-membered to six-membered ring, and R 6 , R 8 and the nitrogen atoms and carbon atoms connected thereto respectively form an aza four-membered to six-membered ring; for example, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each of the above is independently selected from the group consisting of hydrogen, C1-C10 straight chain alkyl (e.g., C1 straight chain alkyl, C2 straight chain alkyl, C3 straight chain alkyl, C4 straight chain alkyl, C5 straight chain alkyl, C6 straight chain alkyl, C7 straight chain alkyl, C8 straight chain alkyl, C9 straight chain alkyl, C10 straight chain alkyl), C3-C10 branched chain alkyl (e.g., C3 branched chain alkyl, C4 branched chain alkyl, C5 branched chain alkyl, C6 branched chain alkyl, C7 branched chain alkyl, C8 branched chain alkyl, C9 branched chain alkyl, C10 branched chain alkyl), C3-C10 cycloalkyl (e.g., C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl, C9 cycloalkyl, C10 cycloalkyl), C6-C10 aryl (e.g., C6 aryl, C7 aryl, C8 aryl, C9 aryl, C10 aryl), R 2 , R 3 and the nitrogen atom and the carbon atom connected thereto respectively form an aza four-membered to six-membered ring (eg, an aza four-membered ring, an aza five-membered ring or an aza six-membered ring), and R 6 , R 8 and the nitrogen atom and the carbon atom connected thereto respectively form an aza four-membered to six-membered ring (eg, an aza four-membered ring, an aza five-membered ring or an aza six-membered ring). 3 According to another embodiment of the present invention, R 3 It's hydrogen.

[0038] According to one embodiment of the present application, in Formula I, the value of m is 1-9000, or 2-8000, or 5-7000, or 10-6000, or 20-5000, or 50-3000, or 60-2000, or 80-1500, or 100-1000, or 200-800, or 400-600, or within the numerical range obtained by combining any two of the above end values; the value of n is 1-9000, or 2-8000, or 5-7000, or 10-6000, or 20-5000, or 50-3000, or 60-2000, or 80-1500, or 100-1000, or 200-800, or 400-600, or within the numerical range obtained by combining any two of the above end values. According to one embodiment of the present application, the ratio of m to n can be 20:1 to 1:20, for example, 18:1 to 1:18, or 15:1 to 1:15, or 12:1 to 1:12, or 10:1 to 1:10, or 9:1 to 1:9, or 8:1 to 1:8, or 7:1 to 1:7, or 6:1 to 1:6, or 5:1 to 1:5, or 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2, or 3:2 to 1:1, or 1:1 to 2:3, or the molar ratio of the two can be within the numerical range obtained by combining any two of the above end values. According to another embodiment of the present invention, a is an integer of 1-12, for example, 1-10, or 1-8, or 1-6, or 1-5, or 1-4, or 1-3, or 1-2, or can be within the numerical range obtained by combining any two of the above end values.

[0039] More specifically, the polymerization catalyst represented by Formula I comprises a first polymerization unit derived from a first monomer represented by the following Formula II, and a second polymerization unit derived from a second monomer represented by the following Formula III:

[0040]

[0041] Where R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 and R 11 The definition of each of is as described above.

[0042] According to a specific embodiment of the present application, the first monomer is selected from at least one of the following:

[0043]

[0044] According to another specific embodiment of the present application, the second monomer is selected from at least one of the following:

[0045]

[0046]

[0047] According to one embodiment of the present application, the catalyst of the present application may be a supported catalyst, that is, the above-mentioned polymerization catalyst is supported on a carrier, and the carrier may be a solid carrier that is inert to or has a promoting effect on the acyl chloride reaction of the present application, for example, the carrier may be selected from one or more of the following: activated carbon, molecular sieve, silicon dioxide, titanium dioxide, silica gel, pumice, diatomaceous earth, kaolin, glass fiber mesh, ceramic balls / particles / powders, hollow glass beads, quartz glass tubes / sheets, expanded perlite, resin particles. For example, the carrier may be activated carbon, such as activated carbon with a particle size of 100-4000 mesh.

[0048] For supported catalysts, the weight ratio of the polymerization catalyst component to the carrier can be from 1:20 to 20:1, for example, from 18:1 to 1:18, or from 15:1 to 1:15, or from 12:1 to 1:12, or from 10:1 to 1:10, or from 9:1 to 1:9, or from 8:1 to 1:8, or from 7:1 to 1:7, or from 6:1 to 1:6, or from 5:1 to 1:5, or from 4:1 to 1:4, or from 3:1 to 1:3, or from 2:1 to 1:2, or from 3:2 to 1:1, or from 1:1 to 2:3, or the weight ratio of the polymerization catalyst component to the carrier can be within the numerical range obtained by combining any two of the above end values.

[0049] The method for preparing the polymerization catalyst of the present invention may include allowing the first monomer and the second monomer to undergo a polymerization reaction in the presence of a solvent and an initiator to form the polymerization catalyst.

[0050] For example, the method for preparing a polymerization catalyst may include the following steps:

[0051] (1) mixing and dissolving the first monomer, the second monomer, the initiator and the solvent in a certain proportion;

[0052] (2) heating the above materials to a certain temperature for copolymerization reaction and maintaining the temperature for a suitable time to generate the polymerization catalyst;

[0053] (3) After the reaction is completed, the materials in the reaction system are evaporated (for example, at room temperature or under heating conditions, under normal pressure or under reduced pressure conditions) to remove most of the solvent (for example, 50%, 60%, 70%, 80%, 90%, 95%, or 99%), and the concentrated reaction solution is added to a certain amount of washing agent for washing, and filtered to obtain a white powder, which is the polymer catalyst.

[0054] In the case of supported catalysts, the required amount of the carrier can be added to the reaction system in the above step (1), or the required amount of the carrier can be added to the reaction system when the copolymerization reaction reaches a certain required stage in the above step (2).

[0055] According to one embodiment of the present application, the initiator can be a peroxide initiator or an azo initiator. Peroxide initiators include but are not limited to tert-butyl hydroperoxide, di-tert-butyl peroxide, benzoyl oxide, diisooctyl peroxydicarbonate, tert-butyl peroxytivalate, methyl ethyl ketone peroxide or cyclohexanone peroxide, etc.; azo initiators include but are not limited to perazobisisobutyronitrile or azobisisoheptanenitrile, etc. Preferably, azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide and di-tert-butyl peroxide, more preferably azobisisobutyronitrile and di-tert-butyl peroxide. The molar amount of the initiator is 0.05-20 mol% of the sum of the molar amounts of monomer II and monomer III, for example, 0.1-18 mol%, or 0.5-15 mol%, or 1-10 mol%, or 2-8 mol%, or 3-6 mol%, or 4-5 mol%, or can be within the numerical range obtained by combining any two of the above end values.

[0056] According to one embodiment of the present application, the solvent may be aromatic hydrocarbons, esters, ketones, alcohols, ethers or a mixture of two or more thereof. Aromatic hydrocarbon solvents include but are not limited to toluene, xylene and isomers, 1,2,4-trimethylbenzene, propylbenzene or isopropylbenzene, etc.; ester solvents include but are not limited to methyl acetate, ethyl acetate, butyl acetate, ethyl propionate or ethyl butyrate, etc.; ketone solvents include but are not limited to acetone, methyl ethyl ketone, cyclohexanone or methyl isobutyl ketone, etc.; alcohol solvents include but are not limited to methanol, ethanol, isopropanol, propanol, n-butanol, isobutanol, etc.; ether solvents include but are not limited to n-propyl ether, methyl butyl ether, ethyl butyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether or propylene glycol dimethyl ether, etc. According to an exemplary embodiment of the present application, based on 1 part by weight of the total weight of the first monomer and the second monomer, the amount of the solvent is 1-1000 parts by weight, for example, 10-800 parts by weight, or 50-700 parts by weight, or 100-600 parts by weight, or 200-500 parts by weight, or 300-400 parts by weight, or can be within the numerical range obtained by combining any two of the above end values.

[0057] According to one embodiment of the present application, the reaction temperature of the polymerization reaction (copolymerization reaction) for preparing the polymerization catalyst is 20-150°C, for example, 40-120°C, or 50-100°C, or 60-80°C, or can be within the numerical range obtained by combining any two of the above end values.

[0058] According to one embodiment of the present application, the polymerization reaction time of the polymerization reaction (copolymerization reaction) for preparing the polymerization catalyst is 1-24 hours, for example, 3-20 hours, or 4-16 hours, or 6-12 hours, or 8-10 hours, or can be within the numerical range obtained by combining any two of the above end values.

[0059] According to one embodiment of the present application, the washing agent is alkanes, aromatic hydrocarbons, chloroalkanes, esters, ketones, alcohols or ethers, etc. Alkanes include but are not limited to n-pentane, n-hexane, cyclohexane, n-heptane, petroleum ether, etc. Aromatic hydrocarbons include but are not limited to toluene, xylene and isomers, 1,2,4-trimethylbenzene, propylbenzene or isopropylbenzene, etc. Chloroalkanes include but are not limited to dichloromethane, chloroform, 1,2-dichloroethane, trichloroethylene or tetrachloroethylene, etc. Esters include but are not limited to methyl acetate, ethyl acetate, butyl acetate, ethyl propionate or ethyl butyrate, etc. Ketones include but are not limited to acetone, methyl ethyl ketone, cyclohexanone or methyl isobutyl ketone, etc. Alcohols include but are not limited to methanol, ethanol, isopropanol, propanol, n-butanol, isobutanol, etc. Ethers include but are not limited to n-propyl ether, methyl butyl ether, ethyl butyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether or propylene glycol dimethyl ether, etc. According to one embodiment, based on 100 parts by weight of the total weight of the first monomer and the second monomer, the amount of the detergent is 200-1000 parts by weight, for example, 150-900 parts by weight, or 200-800 parts by weight, or 300-600 parts by weight, or 400-500 parts by weight, or within the numerical range obtained by combining any two of the above end values. When the detergent is used, it can be added once for washing, or added multiple times for washing.

[0060] The acyl chlorination method of the present invention comprises allowing at least one carboxylic acid compound to undergo an acyl chlorination reaction with at least one chlorinating agent in the presence of the polymerization catalyst of the present invention as described above or the polymerization catalyst synthesized by the method of the present invention as described above to generate an acyl chloride compound. Preferably, the acyl chlorination reaction is a solvent-free system.

[0061] For example, the chlorination method of the present invention may comprise the following steps:

[0062] (1) heating and melting the carboxylic acid, mixing it with a polymerization catalyst or a supported polymerization catalyst in a certain ratio, and heating it to a temperature required for the reaction;

[0063] (2) maintaining the reaction temperature and continuously adding the chlorination reagent until the reaction is completed;

[0064] (3) introducing nitrogen to remove the remaining chlorination reagent and the generated acidic gas in the reaction system;

[0065] (4) Filter and separate the acyl chloride product and recover the catalyst.

[0066] According to one embodiment of the present application, the carboxylic acid compound is selected from at least one of the following: a C4-C30 (e.g., C6-C22, or C8-C18) saturated straight-chain carboxylic acid containing at least one carboxyl group, a C4-C30 (e.g., C6-C22, or C8-C18) unsaturated straight-chain carboxylic acid containing at least one carboxyl group, a C4-C30 (e.g., C6-C22, or C8-C18) saturated branched carboxylic acid containing at least one carboxyl group, a C4-C30 (e.g., C6-C22, or C8-C18) saturated branched carboxylic acid containing at least one carboxyl group, C4-C30 (e.g. C6-C22, or C8-C18) unsaturated branched carboxylic acids containing at least one carboxyl group, C4-C30 (e.g. C6-C22, or C8-C18) saturated cycloalkane carboxylic acids containing at least one carboxyl group, C4-C30 (e.g. C6-C22, or C8-C18) unsaturated cycloalkane carboxylic acids containing at least one carboxyl group, C6-C30 (e.g. C6-C22, or C8-C18) aromatic carboxylic acids containing at least one carboxyl group. According to a more specific embodiment, the carboxylic acid compound is selected from one or more of the following: n-octanoic acid, n-decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid.

[0067] The chlorinating agent is selected from at least one of the following: phosgene, thionyl chloride, trichloromethyl chloroformate and bis(trichloromethyl)carbonate.

[0068] According to one embodiment of the present application, the reaction temperature of the acyl chlorination reaction may generally be 40-120°C, preferably 60-100°C, and more preferably 70-90°C.

[0069] The amount of the chlorinating agent added satisfies the following relationship: when the chlorinating agent is a chlorinating agent other than trichloromethyl chloroformate and bis(trichloromethyl)carbonate, the amount of the chlorinating agent added is at least equivalent to the number of moles of the carboxylic acid functional group, preferably 1.05-1.5 equivalents; when the chlorinating agent is trichloromethyl chloroformate, the amount added is at least 1 / 2 of the number of moles of the carboxylic acid, preferably 0.55-0.8, more preferably 0.6-0.75; when the chlorinating agent is bis(trichloromethyl)carbonate, the amount added is at least 1 / 3 of the number of moles of the carboxylic acid, preferably 0.35-0.7, more preferably 0.4-0.6.

[0070] According to one embodiment of the present application, based on 100 wt % of the weight of the carboxylic acid compound added in the reaction, the amount of the catalyst may be 0.05-10 wt %, such as 0.1-8 wt %, or 0.15-6 wt %, or 0.2-1 wt %.

[0071] The acyl chloride reaction is carried out under heat preservation conditions, and the reaction temperature can be 60-120°C, or 70-110°C, or 75-100°C, or 80-90°C, or 80-85°C. The end time of the reaction is determined by detecting the conversion rate of the carboxylic acid, and the conversion rate is calculated by testing the content of the carboxylic acid in the reaction system. Depending on the reactor or the size of the reaction vessel, the reaction time of the kettle reactor is generally 1-20h, preferably 4-15h; the reaction time of the loop reactor is generally 1-15h, preferably 2-12h.

[0072] The catalyst can be recovered by solid-liquid separation methods such as filtration pressing, suction filtration, centrifugation, and sedimentation, preferably by solid-liquid separation methods such as filtration pressing, suction filtration, and centrifugation under anhydrous conditions.

[0073] After the reaction is completed, the catalyst can be easily recovered by filtration and reused, for example, the catalyst can be reused 2-50 times, such as 3-40 times, or 4-30 times, or 5-20 times, or 3-8 times, or 4-5 times, or 6-10 times.

[0074] Without wishing to be limited to any particular theory, the catalyst system and method of the present application can achieve at least the following advantages:

[0075] (1) The catalyst monomer is cheap and readily available, and its synthesis is simple.

[0076] (2) The polymerization catalyst of the present invention has strong catalytic activity and can achieve a conversion rate of more than 99%;

[0077] (3) There is no catalyst residue, the color of the acyl chloride product is less than 20APHA, and no further purification methods such as distillation are required;

[0078] (4) The acyl chloride product has good stability;

[0079] (5) The polymer catalyst is easy to separate and can be recycled;

[0080] (6) The polymerization catalyst of the present invention can avoid the problem of residual nitrogen-containing small molecules caused by decomposition.

[0081] (7) The first monomer can induce copolymerization of the second monomer, and the copolymer has higher catalytic activity in the acyl chloride catalytic reaction than the homopolymer of the first monomer or the copolymer of the first monomer and other monomers.

[0082] The present application is described below in the form of specific examples, and its purpose is to better understand the content of the present application. It should be understood that these examples are merely illustrative and non-restrictive. The reagents used in the examples are conventionally purchased from the market unless otherwise specified. The methods and conditions used in the examples are conventional methods and conditions unless otherwise specified.

[0083] Example

[0084] All chemical reagents used in the following examples were commercially available of analytical grade and used directly without further purification. In the following examples, the following techniques were used for performance testing:

[0085] High performance liquid chromatography: Agilent Technologies (China) Co., Ltd. Agilent 1260;

[0086] Chroma measurement method: HACH LICO 620 colorimeter, add 3 / 4 of the liquid to be tested into the colorimetric tube, and read the value in the "Chroma Value-Hazen" mode.

[0087] Molecular weight test method of polymerization catalyst: The molecular weight and molecular weight distribution of the copolymer are determined by gel permeation chromatography (GPC). The test instrument is Waters 1525 gel permeation chromatograph, the chromatographic columns are Waters HR1 and HR4, the detector is 2414, and the test conditions are: the test temperature is 30°C, ultrapure water is used as the eluent, the elution rate is set to 1.0mL / min, the mobile phase is 0.2mol / L NaNO3, 0.01mol / L NaH2PO4, pH=7.

[0088] Embodiment 1:

[0089] Polymer Catalyst Synthesis:

[0090] Preparation of polymer catalyst: Pre-dry the 250mL four-necked flask, three-way stopper, magnet, condenser, beaker glassware, etc. used in the experiment. Add 19.83g (0.20mol) of monomer N-vinyl-N-methylacetamide (Ⅱa), 2.51g (0.02mol) of (2-vinyl-tetrahydropyrrole) formamide (Ⅲa), 89.36g of anhydrous ethanol, and 0.72g (0.0044mol) of azobisisobutyronitrile (AIBN) to the four-necked flask. Nitrogen is passed through the system for 30 minutes to replace the reaction system, and the temperature is quickly raised to 75°C and reacted for 8 hours. After the reaction is completed, most of the ethanol in the reaction solution is evaporated, and the concentrated reaction solution is added to 4 times the weight of ether to precipitate the polymer. After suction filtration, a white powder solid is obtained. Dissolve it in anhydrous ethanol again, precipitate it in ether again, and suction filter it to obtain a white solid polymer, which is the catalyst active substance. The high performance liquid chromatography showed that the residual amount of monomer IIa was 0.06%, and the residual amount of monomer IIIa was 0.09%.

[0091] Acyl chloride synthesis:

[0092] In a 250mL four-necked bottle equipped with a thermometer, a stirrer, a reflux condenser, a ventilation device and a tail gas absorption device, add 60g (0.30mol) of lauric acid, heat to 80-85°C, add 0.18g of the catalyst prepared as described above after all the lauric acid is melted, keep constant temperature and continuously pass 44.51g (0.45mol) of phosgene, which lasts for 4h, and keep this temperature reaction for 1h after the ventilation is completed. Nitrogen is driven out, cooled, filtered, and weighed to obtain 65.02g of acyl chloride, with a yield of 99.23%, and the filter residue is recycled. The product tested fatty acid content 0.42%, acyl chloride content 99.27%, chromaticity 15APHA, and appearance is light yellow transparent liquid. After the product is sealed and placed for 30 days, the appearance is light yellow transparent liquid, and the test chromaticity is 14APHA.

[0093] Embodiment 2-8

[0094] In Examples 2-8, the steps are the same as in Example 1, except that the catalyst formulation shown in Table 1 below is used.

[0095] Example 9

[0096] In this Example 9, the acyl chloride synthesis reaction was carried out according to the same steps as in Example 1, but the only difference was that the catalyst in Example 1 that had undergone one acyl chloride synthesis reaction was used.

[0097] Example 10

[0098] Example 10 The steps of Example 1 were completely repeated, except that the catalyst formula shown in Table 1 below was used when synthesizing the polymerization catalyst, and 800 mesh activated carbon was added to the four-necked flask at the beginning, and the amount of activated carbon added was selected so that the content of the polymerization catalyst in the supported catalyst was 45% by weight. In addition, when performing the acyl chloride reaction, the amount of the supported catalyst was 0.40 g.

[0099] Embodiment 11

[0100] Example 11 The steps of Example 1 were completely repeated, except that the catalyst formula shown in Table 1 below was used when synthesizing the polymerization catalyst, and 800 mesh activated carbon was added to the four-necked flask at the beginning, and the amount of activated carbon added was selected so that the content of the polymerization catalyst in the supported catalyst was 45% by weight. In addition, when performing the acyl chloride reaction, the amount of the supported catalyst was 0.40 g.

[0101] Example 12

[0102] Example 12 The steps of Example 1 were completely repeated, except that the catalyst formula shown in Table 1 below was used when synthesizing the polymerization catalyst, and 800 mesh activated carbon was added to the four-necked flask at the beginning, and the amount of activated carbon added was selected so that the content of the polymerization catalyst in the supported catalyst was 45% by weight. In addition, when performing the acyl chloride reaction, the amount of the supported catalyst was 0.40 g.

[0103] Comparative Example 1

[0104] In this comparative example 1, only the monomer (N-ethyl-N-(3-isobutylenyl)formamide) shown in IIIj was used to attempt to prepare a polymerization catalyst.

[0105] Pre-dry the 250mL four-necked flask, three-way stopper, magnet, condenser, beaker glassware, etc. used in the experiment. Add 25.43g (0.20mol) of monomer N-ethyl-N-(3-isobutylenyl)formamide (IIIj), 101.76g of anhydrous ethanol, and 0.65g (0.0040mol) of azobisisobutyronitrile (AIBN). Nitrogen was passed through the system for 30 minutes to replace the reaction system, and the temperature was quickly raised to 75°C and reacted for 8 hours. After the reaction was completed, most of the ethanol in the reaction solution was evaporated, and the concentrated reaction solution was added to ether, and no polymer was precipitated. The ether was removed by vacuum distillation first, and then 24.15g of N-ethyl-N-(3-isobutylenyl)formamide was obtained, with a recovery rate of 95%, and polymerization did not occur.

[0106] Comparative Example 2

[0107] In this comparative example 2, the acyl chloride reaction steps in example 1 were repeated, but the only difference was that poly (N-vinyl-2-pyrrolidone) (PVP) was used as a catalyst. PVP K30 was purchased from Topbike New Materials Technology (Shanghai) Co., Ltd., with a weight average molecular weight of 37,900.

[0108] Comparative Example 3

[0109] In this comparative example 3, the acyl chlorination reaction steps in example 1 were repeated, but the only difference was that poly N-vinylacetamide (PNVA) was used as a catalyst.

[0110] PNVA is synthesized by the following steps: pre-dry the 250mL four-necked flask, three-way stopper, magnet, condenser, beaker glassware, etc. used in the experiment. Add 17.02g (0.20mol) of monomer N-vinyl acetamide, 68.08g of anhydrous ethanol, and 0.17g (0.0010mol) of azobisisobutyronitrile (AIBN) to the four-necked flask. Nitrogen is passed through the system for 30min to replace the reaction system, and the temperature is quickly raised to 75°C and reacted for 3h. After the reaction is completed, most of the ethanol in the reaction solution is evaporated, and the concentrated reaction solution is added to 4 times the weight of ether to precipitate the polymer, and a white powder solid is obtained after suction filtration. Dissolve it in anhydrous ethanol again, precipitate it in ether again, and filter it to obtain a white solid polymer, which is the catalyst active substance. The residual monomer content is 0.05% and the weight-average molecular weight is 14000 as detected by high-performance liquid chromatography.

[0111] Comparative Example 4

[0112] In this comparative example 4, the acyl chloride reaction steps in example 1 were repeated, but the only difference was that poly N,N-dimethylacrylamide (PDMA) was used as a catalyst. PDMA was purchased from Shenzhen Lijing Biochemical Technology Co., Ltd., with a weight average molecular weight of 150,000.

[0113] Comparative Example 5

[0114] In this comparative example 4, the acyl chloride reaction steps in example 1 were repeated, but the only difference was that 0.15 g of N,N-dimethylformamide (DMF) was used as a catalyst. DMF was purchased from Aladdin Reagent (Shanghai) Co., Ltd.

[0115] Comparative Example 6

[0116] The lauroyl chloride obtained in Comparative Example 5 was subjected to reduced pressure distillation with a yield of 97.23%.

[0117] Table 1 Experimental results

[0118]

[0119]

[0120] Through experimental verification, compared with the comparative example, the copolymer catalyst of the present invention exhibits more excellent catalytic activity when synthesizing acyl chloride by the solvent-free method. The acyl chloride synthesized by the copolymer catalyst of the present invention can obtain a product with lower chromaticity without additional distillation. And the applicant also noticed that the color performance of the acyl chloride product obtained after the copolymer catalyst is loaded is more excellent, and after long-term storage, the color remains basically unchanged, and the color stability is extremely high.

[0121] The above examples are only specific examples listed in this application, but the technical features of this application are not limited to them. Any simple changes, equivalent replacements or other modifications made based on this application to solve basically the same technical problems and achieve basically the same technical effects are all covered within the protection scope of this application.

Claims

1. A polymerization catalyst comprising polymerization units derived from a first monomer and a second monomer, The polymerized unit derived from the first monomer has the following structural formula: The polymerized unit derived from the second monomer has the structural formula shown below: Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each of R is independently: hydrogen, C1-C12 straight chain alkyl, C3-C12 branched chain alkyl, C3-C12 cycloalkyl, C6-C12 aryl, or 2 , R 3 and the nitrogen atom and carbon atom connected thereto form a nitrogen four-membered to six-membered ring, or R 6 , R 8 and the nitrogen atom and the carbon atom respectively connected thereto together form an aza four-membered to six-membered ring, wherein a is an integer from 1 to 12; Wherein * represents the connecting bond between the polymerized unit and the adjacent polymerized unit; the molar ratio of the polymerized unit derived from the first monomer to the polymerized unit derived from the second monomer is 20:1 to 1:20; The polymerization degree of the catalyst is 10-9500.

2. The polymerization catalyst according to claim 1, characterized in that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each of R is independently: hydrogen, C1-C4 straight chain alkyl, C3-C4 branched chain alkyl, C3-C6 cycloalkyl, C6-C9 aryl, or 2 , R 3 and the nitrogen atom and carbon atom connected thereto form a nitrogen five-membered to six-membered ring, or R 6 , R 8 and the nitrogen atom and the carbon atom respectively connected thereto together form an aza five-membered to six-membered ring; In addition, the number of polymerization units derived from the first monomer in the polymerization catalyst is 1-9000, and the number of polymerization units derived from the second monomer is 1-9000.

3. The polymerization catalyst according to claim 1, characterized in that The first monomer is selected from at least one of the following:

4. The polymerization catalyst according to claim 1, characterized in that The second monomer is selected from at least one of the following:

5. The polymerization catalyst according to any one of claims 1 to 4, wherein the polymerization catalyst is supported on at least one carrier selected from the group consisting of activated carbon, molecular sieves, silicon dioxide, titanium dioxide, silica gel, pumice, diatomaceous earth, kaolin, glass fiber mesh, ceramic balls / particles / powders, hollow glass beads, quartz glass tubes, expanded perlite, and resin particles.

6. A method for synthesizing the polymerization catalyst according to any one of claims 1 to 5, the method comprising allowing the first monomer and the second monomer to undergo a polymerization reaction in the presence of a solvent and an initiator to form the polymerization catalyst.

7. The method according to claim 6, characterized in that The initiator includes a peroxide initiator, an azo initiator, or a combination thereof; The solvent includes at least one of the following: aromatic hydrocarbons, esters, ketones, alcohols, and ethers; Based on the total molar amount of the first monomer and the second monomer as 100 mol %, the amount of the initiator is 0.05-20 mol %; Based on 1 part by weight of the total weight of the first monomer and the second monomer, the amount of the solvent is 1-1000 parts by weight.

8. The method according to claim 6, characterized in that The polymerization reaction is carried out at a temperature of 20-150° C. for 1-24 hours; After the polymerization reaction, washing the product of the polymerization reaction using a washing agent; The washing agent is selected from at least one of the following: alkanes, aromatic hydrocarbons, chloroalkanes, esters, ketones, alcohols, and ethers; Based on 100 parts by weight of the total weight of the first monomer and the second monomer, the amount of the washing agent used is 200-1000 parts by weight.

9. A method for acyl chlorination, comprising subjecting at least one carboxylic acid compound to an acyl chlorination reaction with at least one chlorinating agent in the presence of a polymeric catalyst as described in any one of claims 1 to 5 or a catalyst synthesized by the method as described in any one of claims 6 to 8 to generate an acyl chloride compound.

10. The chlorination method according to claim 9, wherein The acyl chlorination reaction is a solvent-free system.

11. The method for acylating as claimed in claim 9, wherein: The carboxylic acid compound is selected from at least one of the following: a C4-C30 saturated straight-chain carboxylic acid containing at least one carboxyl group, a C4-C30 unsaturated straight-chain carboxylic acid containing at least one carboxyl group, a C4-C30 saturated branched carboxylic acid containing at least one carboxyl group, a C4-C30 unsaturated branched carboxylic acid containing at least one carboxyl group, a C4-C30 saturated cycloalkane carboxylic acid containing at least one carboxyl group, a C4-C30 unsaturated cycloalkane carboxylic acid containing at least one carboxyl group, and a C6-C30 aromatic carboxylic acid containing at least one carboxyl group; and / or The chlorinating agent is selected from at least one of the following: phosgene, thionyl chloride, trichloromethyl chloroformate and bis(trichloromethyl)carbonate.

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