CN111499783A - Preparation method of polyacrylate with extremely narrow molecular weight distribution - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
The invention discloses a preparation method of polyacrylate with extremely narrow molecular weight distribution, which comprises the following steps: mixing a catalyst, an initiator, a solvent and acrylic ester for reaction; adding ethanol to terminate the reaction to obtain polyacrylate; the catalyst is organic Lewis acid, the initiator is silyl enol acetal, and the solvent is an aprotic solvent. Compared with the active free radical preparation method, the method can avoid monomer residue and use metal catalyst, thereby avoiding the coloring of the product and the aging of the product caused by the metal residue. Compared with the anion polymerization method, the method can avoid the use of dangerous anion initiator and the harsh conditions of ultralow temperature, strict anhydrous oxygen-free and the like required by anion polymerization. Compared with the traditional group transfer polymerization catalyzed by transition metal compounds, the method can greatly reduce the use of catalysts, and can also prepare polyacrylate with the molecular weight of 1000-1000000 g/mol and narrow distribution.
Description
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a preparation method of polyacrylate with extremely narrow molecular weight distribution.
Background
Polyacrylates are a class of synthetic resins produced by the polymerization of the corresponding acrylates. Because of their high transparency and flexibility, are widely used in paints and other surface coatings, adhesives and textiles. Among the known polymerization methods of acrylic ester, the traditional free radical polymerization has been dominant in the industrial application of acrylic ester synthesis for a long time due to the advantages of low requirements on reaction conditions, easy production operation, simple requirements on equipment and the like. The specific implementation methods in the polymerization can be suspension polymerization, emulsion polymerization and solution polymerization. Different types of industrial products can be obtained by selecting the way of carrying out the polymerization. For example, emulsion polymerization can yield high molecular weight, aqueous polyacrylate emulsions for direct use in architectural coatings. The solution polymerization can obtain polyacrylate solution with high solid content, and the polyacrylate solution can be directly applied to warp sizing solution of fabrics such as adhesive, polyester/cotton, polyester/viscose, polyester/nitrile and the like. Although free-radical polymerization has the above-noted advantages in the preparation of polyacrylates, its disadvantages are likewise evident. The defects are mainly reflected in that the polymerization process is non-active polymerization, and the molecular weight is difficult to control; the obtained polyacrylate has wide molecular weight distribution and nonuniform polymer chain length, so that the performance of the polyacrylate is not uniform; the polymerization process is rapid in reaction, and can cause short-time large-amount heat release and implosion; this method does not allow the preparation of block type polyacrylate copolymers. Therefore, conventional free radical polymerization cannot be adapted to the preparation of polyacrylates of uniform properties with a very narrow molecular weight distribution.
Molecular weight and molecular weight distribution are two of the main parameters that determine polymer properties, and are no exception to polyacrylates. Taking polyacrylate pressure-sensitive adhesive materials as an example, when the molecular weight of polyacrylate is low, the polymer shows insufficient adhesive force; when the molecular weight is more than 1000000g/mol, the melt state shows an extremely high flow viscosity, resulting in difficulty in application. Patent US5073611A reports an increase in the viscous flow and adhesion achieved by first synthesizing a low molecular weight polyacrylate and then crosslinking it with uv light. However, the shear strength of the pressure-sensitive adhesive synthesized by the method is still unsatisfactory. To achieve the synthesis of narrow distribution polyacrylates, reactive/controlled polymerization of the acrylates is required. The currently available methods include three methods, living radical polymerization, anionic polymerization and conventional group transfer polymerization. Each method has its own advantages and its own fatal disadvantages, which are separately described below. Although the living radical polymerization developed in the last 90 years can realize better control of polyacrylate in terms of molecular weight and molecular weight distribution, the molecular weight distribution can be controlled within the range of 1.2-2.0, but the living radical polymerization also has fatal defects. On the one hand, most living radical polymerization requires the use of transition metal catalysts, which makes the polymer product undergo a complicated post-treatment procedure and cannot be completely removed. The residue of the transition metal catalyst makes the polymer product colored and toxic, which greatly impairs the range of use of the polymer product. In addition, the residual transition metal catalyst also accelerates the aging of the polymer product. On the other hand, the radical polymerization is further characterized by the termination of the diradical, which makes the polymerization proceed to termination at a certain conversion of the monomer, which is difficult to convert completely. Most acrylates have an extremely unpleasant and harsh odor, and therefore, the residual monomers require additional steps to remove the monomers at the end of the polymerization, increasing the complexity of the production process. Therefore, living radical polymerization has not been reported to be used for large-scale polymer production in actual industry or production. In addition to transition metal catalyzed living radical polymerization, living radical polymerization may also be used without metal catalysts. For example, patent US6765078B2 reports that a polymer product having a molecular weight in the range of 250000 to 1000000g/mol can be obtained by synthesizing polyacrylate by reversible addition fragmentation chain transfer (RAFT) polymerization, but the molecular weight distribution is still too broad in the range of 2.5 to 5.0, and the residue of thioester chain transfer agent in the polymer, on the one hand, colors the polymer and, on the other hand, has a certain toxicity.
In addition to the known polymerization processes, which lead to polyacrylates with a very narrow molecular weight distribution, living radical polymerization is also a preferred process for preparing polymers or copolymers with a narrow molecular weight distribution. However, in industrial applications, such methods are greatly limited in the synthesis of polyacrylates due to: (1) the polymerization process needs extremely low temperature of-80 to-100 ℃, which greatly increases energy consumption, (2) an anionic initiator is needed in the polymerization process, and the initiator is generally high in reactivity, easy to catch fire and dangerous to use, (3) the polymerization process is extremely fast and easy to generate implosion danger, (4) extremely severe conditions of no water, no oxygen and no oxidant are required, monomers, solvents and equipment need to be subjected to impurity removal treatment, the process requirement is extremely high and the cost is high, and (5) the anionic polymerization of acrylic ester is easy to generate crosslinking side reaction, and the product is possibly deviated from the expectation. Therefore, anionic polymerization is also difficult to achieve in large-scale production of polyacrylate polymers. Patent US5494983A reports a method for the synthesis of polyacrylates using stable anionic initiators, but the polymers obtained have molecular weights not exceeding 20000g/mol and the molecular weight dispersion increases significantly with increasing molecular weight.
Based on the limitation of anionic polymerization method in preparing acrylate polymer, DuPont developed traditional group transfer polymerization method in 1983 for producing acrylate binder, pigment dispersant, and other industrial additives. The group transfer polymerization method is referred to as a suppressed type anionic polymerization method. The method adopts silyl enol acetal as an initiator, main group metal or transition metal compound as a catalyst, and acrylate can realize active polymerization in an aprotic solvent. Compared with the living radical polymerization, the reaction condition is slightly harsh, but the catalyst can adopt non-toxic and colorless halides or organic compounds of metal Al, Zn and the like, the polymer cannot be dyed, the monomers can be completely converted in the polymerization, and the residual smelly monomers are removed without post-treatment. The advantages are very clear compared to anionic polymerization processes. For example, the process can be carried out at ambient temperature; according to the dosage of the initiator, the catalyst and the monomer, the reaction process is easy to control; the selection range of the solvent is wide; the polymerization process does not generate cross-linking side reaction and the like. In the reports up to now, the amount of the catalyst is large, 10-30 mol% of the monomer is required to be used, and the molecular weight of the polymer product is low, generally not higher than 10000g/mol, which is the biggest defect of the traditional group transfer polymerization method.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a process for producing a polyacrylate having an extremely narrow molecular weight distribution.
The technical scheme of the invention is as follows:
a method for preparing polyacrylate with extremely narrow molecular weight distribution comprises the following steps:
mixing a catalyst, an initiator, a solvent and acrylic ester for reaction;
adding ethanol to terminate the reaction to obtain polyacrylate;
wherein the catalyst is an organic Lewis acid, the initiator is a silyl vinyl acetal, and the solvent is an aprotic solvent.
Optionally, the step of mixing a catalyst, an initiator, a solvent and an acrylate to perform a reaction specifically includes:
mixing a catalyst, an initiator and a solvent, and stirring to obtain a first mixed solution;
and mixing the solvent and the acrylic ester, and dropwise adding the mixture into the first mixed solution for reaction.
Optionally, the organic lewis acid comprises one or more of a boron-containing organic lewis acid and a silicon-containing organic lewis acid;
the boron-containing organic Lewis acid comprises one or more of triphenylborane, tri (pentafluorophenyl) borane, tri (pentachlorophenyl) borane, tri [3, 5-bis (trifluoromethyl) phenyl ] borane and tri (4-trifluoromethylphenyl) borane;
the silicon-containing organic Lewis acid comprises one or more of N-trialkyl silicon base-di (trifluoromethanesulfonic acid) imide, trialkyl [ (perfluorophenyl) bis ((trifluoromethyl) sulfonyl) methyl ] silane, trialkylsilyl trifluoromethanesulfonate, trialkylsilyl nitrate and trialkylsilyl perchlorate.
Alternatively, the acrylate is an alkyl acrylate or a functional acrylate;
the alkyl acrylate comprises one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isopropyl acrylate, sec-butyl acrylate, 2-phenyl ethyl acrylate, 3-phenyl propyl acrylate, 1-cyclohexyl methyl acrylate, 2-cyclohexyl ethyl acrylate, 3-cyclohexyl propyl acrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate and dicyclopentyl acrylate;
the functional acrylate comprises one or more of silicon acrylate, alkoxy alkyl acrylate, phenoxy alkyl acrylate, benzyloxy alkyl acrylate, siloxy alkyl acrylate, alkylene oxide alkyl acrylate, alkylene alkyl acrylate and alkynyl alkyl acrylate.
Alternatively, the silyl enol acetal has the formula R3R4C＝C(OR5)(OSiR6R7R8)，R3、R4、R5、R6、R7、R8Alkyl or aryl, optionally R3、R4Is methyl, R5Is alkyl or aryl, R6、R7、R8Independently a sterically bulky isopropyl, phenyl, benzyl or trisilyl silicon group.
Optionally, the aprotic solvent is an aprotic low polar solvent or an aprotic polar solvent;
the aprotic low-polarity solvent is selected from one or more of dichloromethane, trichloromethane, tetrachloromethane, 1, 2-dichloromethane, benzene, chlorobenzene, nitrobenzene, toluene, xylene and cyclohexane;
the aprotic polar solvent is selected from aliphatic ketones, alkyl esters, alkyl carbonates, particularly preferably one or more of acetone, diethyl ketone, ethyl acetone, ethyl methyl ethyl ketone, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, dimethyl carbonate, diethyl carbonate.
Optionally, when the molar ratio of the acrylate to the initiator is in the range of 10 to 1000, the molar ratio of the catalyst to the initiator is 0.005 to 0.02, and the polymerization time is 1 to 30 minutes.
Optionally, when the molar ratio of the acrylate to the initiator is in the range of 1000 to 10000, the molar ratio of the catalyst to the initiator is 0.02 to 0.10, and the polymerization time is 30 minutes to 2 hours.
Optionally, the polyacrylate has a molecular weight in the range of 1000-500000 g/mol and a molecular weight distribution in the range of 1.02-1.20;
or the molecular weight of the polyacrylate is in the range of 500000-1000000 g/mol, and the molecular weight distribution is in the range of 1.20-1.50.
Optionally, the solvent is dried to remove water, and the acrylate is dried to remove water.
Has the advantages that: the invention provides a novel organic catalytic group transfer polymerization preparation method of polyacrylate with extremely narrow molecular weight distribution. The invention adopts silyl enol acetal as an initiator, organic Lewis acid as a catalyst and an aprotic solvent as a polymerization solvent, adopts a solution polymerization mode to carry out polymerization reaction, and can realize batch or continuous preparation under the condition of normal temperature. Through the polymerization reaction, the molecular weight of the polymer (polyacrylate) can be controlled between 1000 and 1000000g/mol according to the proportion of the monomer (acrylate) and the initiator. When the molecular weight of the polymer product is within the range of 1000-500000 g/mol, the molecular weight distribution can be controlled within the range of 1.02-1.20; the molecular weight distribution can be controlled within the range of 1.20-1.50 within the range of 500000-1000000 g/mol. The polymerization process adopts an organic catalyst, no metal is participated in the whole process, and no metal residue exists in a polymer product. The polymerization can adopt environment-friendly solvents such as ethyl acetate, butyl butyrate, dimethyl carbonate and the like as reaction solvents of polymerization, and can realize green preparation of polyacrylate. In terms of all aspects such as molecular weight, molecular weight distribution, monomer conversion efficiency, product quality, green synthesis and the like, no matter the method is living radical polymerization, anion polymerization or traditional group transfer polymerization method can not be compared with the method of the invention. Therefore, the invention provides a simple and feasible new method for preparing polyacrylate with extremely narrow molecular weight distribution while solving the technical problems.
Detailed Description
The present invention provides a method for preparing polyacrylate with a very narrow molecular weight distribution, and the present invention is further described in detail below in order to make the objects, technical schemes, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of polyacrylate with extremely narrow molecular weight distribution, which comprises the following steps:
mixing a catalyst, an initiator, a solvent and acrylic ester for reaction;
adding ethanol to terminate the reaction to obtain polyacrylate;
wherein the catalyst is an organic Lewis acid, the initiator is a silyl vinyl acetal, and the solvent is an aprotic solvent. The general polymerization reaction formula is shown as the following formula:
in one embodiment, the step of mixing the catalyst, the initiator, the solvent and the acrylate to perform the reaction specifically comprises:
mixing a catalyst, an initiator and a solvent, and stirring to obtain a first mixed solution;
and mixing the solvent and the acrylic ester, and dropwise adding the mixture into the first mixed solution for reaction.
In other words, in the polymerization reaction, the polymerization reaction may be carried out by adding the components to the reactor together at the beginning of the polymerization, or may be carried out by adding the solvent, the catalyst and the initiator first and then adding the monomer step by step. The latter is preferred for controlling the release of the heat of reaction. The addition of the monomers can be continuous or intermittent. In addition, the rate of addition of the monomer may be constant or may vary.
In a specific embodiment, the preparation method comprises the steps of:
adding half of the calculated amount of a drying solvent, an initiator and a catalyst into a pre-dried glass reactor with a stirrer at room temperature, and stirring to obtain a first mixed solution. And mixing the other half of the solvent with the dried monomer, and slowly dropwise adding the mixture into the first mixed solution. After the dropwise addition, the mixture is continuously stirred for a set time, and a proper amount of ethanol is added to terminate the reaction. Monomer conversion, molecular weight, and molecular weight distribution were determined. The polymerization solvent is recycled by rotary evaporation or other reduced pressure distillation modes.
The organic catalytic group transfer polymerization reaction in the embodiment of the invention is implemented in a solution polymerization mode, and relates to four components of a catalyst, an initiator, a solvent and a monomer (acrylate). In the embodiment of the invention, organic Lewis acid is used as a catalyst, silyl enol acetal is used as an initiator, an aprotic solvent is used as a polymerization solvent, a solution polymerization mode is adopted for polymerization reaction, and batch or continuous preparation can be realized at normal temperature. Through the polymerization reaction, the molecular weight of the polymer product (polyacrylate) can be controlled to be 1000-1000000 g/mol according to the proportion of the monomer and the initiator. When the molecular weight of the polymer product is within the range of 1000-500000 g/mol, the molecular weight distribution can be controlled within the range of 1.02-1.20, and when the molecular weight is within the range of 500000-1000000 g/mol, the molecular weight distribution can be controlled within the range of 1.20-1.50.
Compared with the prior art, the embodiment of the invention has the following advantages:
1. the polymerization process adopts an organic catalyst, no metal participates in the whole process, and no metal residue exists in a polymer product;
2. compared with the catalyst dosage of 10-30 mol% of the monomer dosage required by the traditional group transfer polymerization catalyzed by the transition metal compound, the method only needs the dosage of 0.5-10 mol% of the initiator dosage, and the dosage of the catalyst is greatly reduced;
3. the polymerization can adopt environment-friendly solvents such as ethyl acetate, butyl butyrate, dimethyl carbonate and the like as reaction solvents for polymerization, and the green preparation of polyacrylate can be realized;
4. in terms of the aspects of comprehensive molecular weight, molecular weight distribution, monomer conversion efficiency, product quality, green synthesis and the like, no matter the method is living radical polymerization, anion polymerization or traditional group transfer polymerization method, the method can not be compared with the method of the embodiment of the invention. Therefore, the embodiment of the invention provides a simple, convenient and feasible new method for preparing polyacrylate with extremely narrow molecular weight distribution while solving the technical problems.
In the embodiment of the invention, organic lewis acid is used as the catalyst, and the organic lewis acid comprises one or more of boron-containing organic lewis acid, silicon-containing organic lewis acid and the like. In one embodiment, the boron-containing organic lewis acid comprises triphenylborane (B (C)6H5)3) Or a derivative (B (C) wherein the benzene ring thereof contains an electron-withdrawing group6Xn)3N-1-5, X-F, -Cl and-CF3Etc.), such as tris (pentafluorophenyl) borane, tris (pentachlorophenyl) borane, tris [3, 5-bis (trifluoromethyl) phenyl ] borane]Borane, tris (4-trifluoromethylphenyl) borane. In one embodiment, the silicon-containing organic lewis acid comprises N-trialkylsilyl-bis (trifluoromethanesulfonic) imide (R)1R2R3SiNTf2) Trialkyl [ (perfluorophenyl) bis ((trifluoromethyl) sulfonyl) methyl group)]Silane (R)1R2R3SiC(C6F5)Tf2) Trialkylsilyltriflate (R)1R2R3SiOTf) Trialkyl silicon nitrate (R)1R2R3SiNO3) Trialkylsilyl perchlorate (R)1R2R3SiClO4) And the like. Wherein R is1、R2、R3Independently an alkyl or cycloalkyl group having 1 to 20 carbon atoms, particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. In particular, part of the silicon-containing organic Lewis acid can be obtained by an in-situ preparation method, which is based on the principle that trialkylsilyl halide is used for reaction with soluble silver salt in a dry solution. The chemical structure of the commonly used boron-and silicon-containing organic Lewis acid and the in-situ preparation reaction formula of the silicon-containing organic Lewis acid are shown as follows.
In the examples of the present invention, the acrylate is an acrylate (R' OCOCH ═ CH) containing no active proton2) May be an alkyl acrylate (R)1OCOCH＝CH2，R1Alkyl) or acrylates with functional groups (R)2OCOCH＝CH2，R2Alkyl with functional groups), and the like. Wherein, the alkyl acrylate can be a primary n-alkyl acrylate containing 1-30 carbons, and particularly preferably common methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, etc., and can also be a primary non-n-alkyl acrylate, particularly preferably common isobutyl acrylate, 2-ethylhexyl acrylate, etc.; secondary alkyl esters having 1 to 30 carbons, particularly preferred are the common isopropyl acrylates, sec-butyl acrylates; primary or secondary aralkyl esters having 8 to 20 carbons, and particularly preferably the usual (2-phenyl) ethyl acrylate, (3-phenyl) propyl acrylate, etc.; primary or secondary cyclic alkyl esters having 8 to 20 carbons, and particularly preferably the usual (1-cyclohexyl) methyl acrylate, 2-cyclohexyl) ethyl acrylate, 3-cyclohexyl propyl acrylate and the like; and secondary cycloalkyl esters having 3 to 20 carbons, and particularly preferred are the common cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, dicyclopentyl acrylate and the like. What is needed isExemplary alkyl or aryl acrylates are shown below.
Wherein the functional acrylate comprises one or more of silicon acrylate, alkoxy alkyl acrylate, phenoxy alkyl acrylate, benzyloxy alkyl acrylate, siloxy alkyl acrylate, alkylene oxide alkyl acrylate, alkylene alkyl acrylate, alkynylalkyl acrylate, etc. Some of the functionalized acrylates listed have the formula below.
In the examples of the invention, the initiator is a silyl enol acetal having the general formula R3R4C＝C(OR5)(OSiR6R7R8)，R3、R4、R5、R6、R7、R8Alkyl or aryl, wherein R3、R4Particular preference is given to methyl, R5Optionally alkyl or aryl, R6、R7、R8Independently, a sterically hindered isopropyl group, phenyl group, benzyl group, trisilylsilyl group, or the like is particularly preferred. The initiator preferably contains sterically bulky silane groups such as triisopropylsilane groups, triphenylsilane groups, tribenzylsilane groups, trisilyl silicon groups, etc., to ensure complete polymerization and narrow polymer dispersion.
In the embodiment of the invention, the adopted solvent is an aprotic solvent, and the aprotic solvent is an aprotic low-polarity solvent or an aprotic polar solvent. In one embodiment, the aprotic low polarity solvent may preferably be one or more of dichloromethane, trichloromethane, tetrachloromethane, 1, 2-dichloromethane, benzene, chlorobenzene, nitrobenzene, toluene, xylene, cyclohexane, and the like. In one embodiment, the aprotic polar solvent may preferably be an aliphatic ketone, an alkyl ester, an alkyl carbonate, and particularly preferably one or more of acetone, diethyl ketone, ethyl acetone, ethyl butanone, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, dimethyl carbonate, diethyl carbonate, and the like. The polymerization adopts an environment-friendly solvent, and the green preparation of the polyacrylate can be realized.
In the embodiment of the invention, the polymerization method is living polymerization, and monomers in the polymerization reaction can be quantitatively converted into polymers. According to the molar ratio of the monomer and the initiator, namely the polymerization degree n value in the reaction general formula, the n value of the polymer can be controlled to be 10-10000, and the molecular weight is controlled to be 1000-1000000 g/mol. When the polymerization degree n value of the polymer product is 10-1000 and the molecular weight is 1000-500000 g/mol, the molecular weight distribution can be controlled between 1.02-1.20. When the polymerization degree n of the polymer product is 1000-10000 and the molecular weight is 500000-1000000 g/mol, the molecular weight distribution can be controlled between 1.20-1.50. Because the monomer conversion rate and the initiation efficiency are quantitative, the feeding molar ratio n of the monomer and the initiator required in the polymerization reaction can be simply and quantitatively calculated by the following formula:
n＝Mn/M.W.；
wherein M isnIs the theoretical number average molecular weight (g/mol) of the polyacrylate, and m.w. is the molecular weight (g/mol) of the acrylate monomer; and n is the molar charge ratio of the monomer to the initiator, namely the theoretical polymerization degree.
In the embodiment of the invention, in the process of acrylate polymerization, the concentration of acrylate is preferably 0.5-3.0 mol/L, when the molar ratio n of acrylate to initiator is within the range of 10-1000, the preferred molar ratio of catalyst to initiator is 0.005-0.02, and the polymerization time is 1-30 minutes, when the molar ratio n of acrylate to initiator is within the range of 1000-10000, the preferred molar ratio of catalyst to initiator is 0.02-0.10, and the polymerization time is 30 minutes-2 hours.
In one embodiment, the solvent is dried to remove water, and the acrylate is dried to remove water. Namely, the related monomers and solvents are dehydrated and dried before the polymerization reaction. The polymerization is preferably carried out by continuous addition of the monomer solution under an inert gas such as nitrogen or argon, usually under nitrogen. The reaction temperature is not particularly limited, and may be suitably selected depending on the degree of control of living polymerization, polymerization reactivity and balance thereof, and may be selected, for example, from-100 to 100 ℃ and room temperature (for example, from 20 to 30 ℃) is preferable for the convenience of operation.
The method of measuring the monomer conversion rate, molecular weight and molecular weight distribution in the examples of the present invention will be described below.
The conversion of the monomers was determined by means of a nuclear magnetic resonance spectrometer (BRUKER ASCEND TM 600, Bruker Biospin GmbHRheinstetten, Germany). Before polymerization, the monomer double bond-CH ═ CH2The hydrogen spectrum absorption peak of (A) appears at 5.0-7.0 ppm, the hydrogen spectrum absorption peak of the double bond in the unreacted monomer still appears at 5.0-7.0 ppm after polymerization, and-CH ═ CH in the reacted monomer2Conversion to-CH in polymerized units2A structure having a hydrogen absorption spectrum peak at 1.5 to 2.5 ppm. Therefore, on the hydrogen nuclear magnetic spectrum of the polymerization reaction liquid, the monomer conversion rate of the polymerization reaction is obtained by dividing the hydrogen spectrum area appearing at 1.5 to 2.5ppm by the sum of the hydrogen spectrum area appearing at 5.0 to 7.0 ppm. Number average molecular weight (M)n) The molecular weight distribution was measured by gel permeation chromatography (Tosoh H L C-8320GPC) equipped with two TSKgel Super Multipore HZ-M columns and a parallax and UV detector under the conditions of measurement temperature of 40 ℃ and flow rate of 0.35M L/min, mobile phase, THF, sample concentration of 0.2 wt%, internal standard, polystyrene standard.
The present invention is described in detail below with reference to specific examples.
Example 1
Adding catalyst B (C) into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)39.2mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of toluene, 246m L were dried and the stirring was switched onThe remaining 300M L of toluene was mixed with 51.7g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was terminated in about 20 minutes, the mixed solution was further stirred for 60 minutes, the reaction was terminated by adding 2M L of ethanol, and a sample was taken to determine that the monomer conversion was 100% and the molecular weight (M)n) And molecular weight distribution (M)w/Mn) 92100g/mol and 1.05 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 2
Adding catalyst B (C) into a pre-dried 500m L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)39.2mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of toluene 46M L were dried and stirring was started, the remaining 200M L of toluene was mixed with 51.7g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, about 15 minutes was added to the end of the dropwise addition, the mixed solution was further stirred for 60 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion was determined by sampling to be 100%, M was addednAnd Mw/Mn89500g/mol and 1.08 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 3
Adding catalyst B (C) into a pre-dried 300m L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)39.2mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of toluene 46M L were dried and stirring was started, the remaining 100M L of toluene was mixed with 51.7g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, about 15 minutes was added to the end of the dropwise addition, the mixed solution was further stirred for 60 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion was 100% by taking a sample and the M was determinednAnd Mw/Mn96200g/mol and 1.12 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 4
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiOTf 13.3mg, initiator Me2C＝C(OMe)(OSiiPr3)1.55g of toluene 191M L were dried and stirring was started, the remaining 300M L of toluene was mixed with 103.4g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, approximately 25 minutes was added to the end of the dropwise addition, the mixed solution was further stirred for 10 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion was 100% by taking a sample, M was determined to be MnAnd Mw/Mn18600g/mol and 1.04 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 5
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiNTf221.1mg, initiator Me2C＝C(OMe)(OSiiPr3)1.55g of ethyl acetate 191M L was dried and stirring was started, the remaining 300M L of ethyl acetate was mixed with 103.4g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed in about 25 minutes, the mixed solution was stirred for 15 minutes, 2M L of ethanol was added to terminate the reaction, and sampling was carried out to determine that the monomer conversion was 100%, M was MnAnd Mw/Mn17900g/mol and 1.09 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 6
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiNTf221.1mg, initiator Me2C＝C(OMe)(OSiiPr3)1.55g of dried dimethyl carbonate 191M L, stirring was started, the remaining 300M L of dimethyl carbonate was mixed with 103.4g of methyl acrylate, slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed within about 25 minutes, the mixed solution was stirred for 15 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion rate was 100% by sampling and M was determinednAnd Mw/Mn169900 g/mol and 1.11. The solvent is recovered from the reaction solution by rotary evaporation.
Example 7
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiNTf221.1mg, initiator Me2C＝C(OMe)(OSiPh3)2.16g of ethyl acetate 191M L were dried and stirring was turned on, the remaining 300M L of ethyl acetate was mixed with 103.4g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was terminated after about 20 minutes, the mixed solution was further stirred for 18 minutes, 2M L of ethanol was added to terminate the reaction, and sampling was carried out to determine that the monomer conversion was 100%, M was MnAnd Mw/Mn18600g/mol and 1.05 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 8
Adding catalyst B (C) into a pre-dried 2L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)33.9mg, initiator Me2C＝C(OMe)(OSiPh3)27mg of toluene 1.3L was dried and stirring was turned on, the remaining 132M L of toluene was mixed with 64.6g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed in about 20 minutes, the mixed solution was further stirred for 100 minutes, 2M L of ethanol was added to terminate the reaction, and the conversion of monomer was determined to be 98% by sampling, M was addednAnd Mw/Mn953000g/mol and 1.38 g/mol, respectively. The unreacted monomer and the solvent are recovered from the reaction solution by rotary evaporation.
Example 9
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiNTf26.4mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of ethyl acetate 236M L were dried and stirring was started, the remaining 300M L of ethyl acetate was mixed with 60.1g of ethyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed in about 20 minutes, the mixed solution was further stirred for 50 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion rate was determined to be 100% by sampling, M was added to the mixture, and M was stirrednAnd Mw/Mn112000g/mol and 1.13, respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 10
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiNTf26.4mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of ethyl acetate 213M L was dried and stirring was started, the remaining 300M L of ethyl acetate was mixed with 76.9g of ethyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed in about 20 minutes, the mixed solution was further stirred for 60 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion rate was 100% by sampling and M was measurednAnd Mw/Mn146200g/mol and 1.16, respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 11
Adding catalyst Me into a pre-dried 1L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature3SiNTf26.4mg, initiator Me2C＝C(OMe)(OSiPh3)216mg of ethyl acetate 175M L was dried and stirring was turned on, the remaining 300M L of ethyl acetate was mixed with 111g of 2-ethylhexyl acrylate and slowly added dropwise to the above solution through a dropping funnel, approximately 20 minutes was added to the end of the dropwise addition, the mixed solution was further stirred for 60 minutes, 2M L of ethanol was added to terminate the reaction, and a sample was taken to determine that the monomer conversion was 100%, and M wasnAnd Mw/Mn201800g/mol and 1.15 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 12
Adding catalyst B (C) into a pre-dried 2L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)33.9mg, initiator Me2C＝C(OMe)(OSiPh3)27mg of toluene 1.2L was dried and stirring was started, the remaining 144M L of toluene was mixed with 138g of methyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed in about 20 minutes, the mixed solution was further stirred for 180 minutes, 2M L of ethanol was added to terminate the reaction, and the monomer conversion was 86% by taking a sample and measuring MnAnd Mw/Mn1692300g/mol and 1.46 g/mol, respectively. The unreacted monomer and the solvent are recovered from the reaction solution by rotary evaporation.
Example 13
Adding into a pre-dried 1L three-neck round-bottom flask with stirrer under the protection of nitrogen at room temperatureIntroduction of catalyst Me3SiNTf26.4mg, initiator Me2C＝C(OMe)(OSiPh3)216mg of ethyl acetate 205M L was dried and stirring was turned on, the remaining 300M L of ethyl acetate was mixed with 92.5g of cyclohexyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was terminated after about 20 minutes, the mixed solution was further stirred for 60 minutes, 2M L of ethanol was added to terminate the reaction, and sampling was carried out to determine the monomer conversion rate to 100%, M was added to the solution, and M was then added to the solutionnAnd Mw/Mn186500g/mol and 1.12 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 14
Adding catalyst B (C) into a pre-dried 300m L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)36.1mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg, drying the dimethyl carbonate 13M L and starting stirring, mixing the remaining 100M L of dimethyl carbonate with 33.6g of cyclohexyl acrylate, slowly adding dropwise the mixture into the solution through a dropping funnel, ending the dropwise addition for about 20 minutes, continuing stirring the mixed solution for 30 minutes, adding 2M L of ethanol to terminate the reaction, sampling and determining that the monomer conversion rate is 100%, and M is equal tonAnd Mw/Mn65200g/mol and 1.03 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 15
Adding catalyst B (C) into a pre-dried 300m L three-neck round-bottom flask with a stirrer under the protection of nitrogen at room temperature6F5)36.1mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of ethyl acetate 15M L was dried and stirring was started, the remaining 100M L of ethyl acetate was mixed with 33.0g of cyclohexyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed within about 20 minutes, the mixed solution was further stirred for 30 minutes, 2M L of ethanol was added to terminate the reaction, and sampling was carried out to determine that the monomer conversion was 100%, M was an amount of MnAnd Mw/Mn61200g/mol and 1.04 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
Example 16
Introducing nitrogen at room temperatureUnder the protection of gas, the catalyst Me is added into a previously dried 300m L three-neck round-bottom flask with a stirrer3SiNTf24.3mg, initiator Me2C＝C(OMe)(OSiiPr3)155mg of ethyl acetate 11M L was dried and stirring was started, the remaining 100M L of ethyl acetate was mixed with 39.0g of cyclohexyl acrylate and slowly added dropwise to the above solution through a dropping funnel, the dropwise addition was completed within about 20 minutes, the mixed solution was further stirred for 35 minutes, 2M L of ethanol was added to terminate the reaction, and sampling was carried out to determine that the monomer conversion was 100%, M was addednAnd Mw/Mn71300g/mol and 1.08 respectively. The solvent is recovered from the reaction solution by rotary evaporation.
The synthesis results of the above examples are shown in table 1 below.
Table 1, synthetic results of examples
In summary, the present invention provides a novel method for the efficient polymerization of non-active proton-type acrylates using organic lewis acid catalysts. Compared with the active free radical preparation method, the method can avoid monomer residue and use metal catalyst, thereby avoiding the coloring of the product and the aging of the product caused by the metal residue. Compared with the anion polymerization method, the method can avoid the use of dangerous anion initiator and the use of harsh conditions of ultralow temperature, strict anhydrous oxygen-free and the like required by anion polymerization. Compared with the traditional group transfer polymerization catalyzed by transition metal compounds, the method can greatly reduce the use of catalysts on one hand, and can prepare the polyacrylate with the molecular weight of 1000-1000000 g/mol and narrow distribution on the other hand.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing polyacrylate with extremely narrow molecular weight distribution is characterized by comprising the following steps:
mixing a catalyst, an initiator, a solvent and acrylic ester for reaction;
adding ethanol to terminate the reaction to obtain polyacrylate;
wherein the catalyst is an organic Lewis acid, the initiator is a silyl vinyl acetal, and the solvent is an aprotic solvent.
2. The method for preparing polyacrylate with extremely narrow molecular weight distribution according to claim 1, wherein the step of mixing the catalyst, the initiator, the solvent and the acrylate for reaction specifically comprises:
mixing a catalyst, an initiator and a solvent, and stirring to obtain a first mixed solution;
and mixing the solvent and the acrylic ester, and dropwise adding the mixture into the first mixed solution for reaction.
3. The method for producing a polyacrylate having a very narrow molecular weight distribution according to claim 1, wherein the organic Lewis acid comprises one or more of a boron-containing organic Lewis acid and a silicon-containing organic Lewis acid;
the boron-containing organic Lewis acid comprises one or more of triphenylborane, tri (pentafluorophenyl) borane, tri (pentachlorophenyl) borane, tri [3, 5-bis (trifluoromethyl) phenyl ] borane and tri (4-trifluoromethylphenyl) borane;
the silicon-containing organic Lewis acid comprises one or more of N-trialkyl silicon base-di (trifluoromethanesulfonic acid) imide, trialkyl [ (perfluorophenyl) bis ((trifluoromethyl) sulfonyl) methyl ] silane, trialkylsilyl trifluoromethanesulfonate, trialkylsilyl nitrate and trialkylsilyl perchlorate.
4. The method for producing a polyacrylate having a very narrow molecular weight distribution according to claim 1, wherein the acrylate is an alkyl acrylate or a functional acrylate;
the alkyl acrylate comprises one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isopropyl acrylate, sec-butyl acrylate, 2-phenyl ethyl acrylate, 3-phenyl propyl acrylate, 1-cyclohexyl methyl acrylate, 2-cyclohexyl ethyl acrylate, 3-cyclohexyl propyl acrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate and dicyclopentyl acrylate;
the functional acrylate comprises one or more of silicon acrylate, alkoxy alkyl acrylate, phenoxy alkyl acrylate, benzyloxy alkyl acrylate, siloxy alkyl acrylate, alkylene oxide alkyl acrylate, alkylene alkyl acrylate and alkynyl alkyl acrylate.
5. The method for producing a polyacrylate having a very narrow molecular weight distribution according to claim 1, wherein said silyl enol acetal has the formula R3R4C＝C(OR5)(OSiR6R7R8)，R3、R4、R5、R6、R7、R8Alkyl or aryl.
6. The method for producing a polyacrylate having a very narrow molecular weight distribution according to claim 5, wherein R is3、R4Is methyl, R5Is alkyl or aryl, R6、R7、R8Independently in a stereotactic positionBlocked isopropyl, phenyl, benzyl or trisilyl silicon groups.
7. The method for producing a polyacrylate having a very narrow molecular weight distribution according to claim 1, wherein the aprotic solvent is an aprotic low-polarity solvent or an aprotic polar solvent;
the aprotic low-polarity solvent is selected from one or more of dichloromethane, trichloromethane, tetrachloromethane, 1, 2-dichloromethane, benzene, chlorobenzene, nitrobenzene, toluene, xylene and cyclohexane;
the aprotic polar solvent is selected from one or more of acetone, diethyl ketone, ethyl acetone, ethyl butanone, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, dimethyl carbonate and diethyl carbonate.
8. The method for preparing polyacrylate with extremely narrow molecular weight distribution according to claim 1, wherein when the molar ratio of acrylate to initiator is in the range of 10 to 1000, the molar ratio of catalyst to initiator is 0.005 to 0.02, and the polymerization time is 1 to 30 minutes;
or when the molar ratio of the acrylate to the initiator is within the range of 1000-10000, the molar ratio of the catalyst to the initiator is 0.02-0.10, and the polymerization time is 30 minutes-2 hours.
9. The method for preparing polyacrylate with very narrow molecular weight distribution according to claim 1, wherein the polyacrylate has a molecular weight in the range of 1000 to 500000g/mol and a molecular weight distribution in the range of 1.02 to 1.20;
or the molecular weight of the polyacrylate is in the range of 500000-1000000 g/mol, and the molecular weight distribution is in the range of 1.20-1.50.
10. The method for preparing polyacrylate with extremely narrow molecular weight distribution according to claim 1, wherein the solvent is dried to remove water, and the acrylate is dried to remove water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791181A (en) * | 1987-02-13 | 1988-12-13 | Imperial Chemical Industries Plc | Rate-moderated group transfer polymerization |
| CN101643412A (en) * | 2009-03-17 | 2010-02-10 | 江苏工业学院 | Hydroxyl-terminated polyacrylate oligomer as well as preparation method and application thereof |
| CN101993512A (en) * | 2009-08-12 | 2011-03-30 | 德莎欧洲公司 | Process for preparing polyacrylates |
| CN108148187A (en) * | 2018-01-08 | 2018-06-12 | 吉林大学 | The method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone |
| CN110628034A (en) * | 2019-08-28 | 2019-12-31 | 昆山博益鑫成高分子材料有限公司 | Polyacrylate polymer and preparation method thereof |
-
2020
- 2020-05-29 CN CN202010478792.9A patent/CN111499783B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791181A (en) * | 1987-02-13 | 1988-12-13 | Imperial Chemical Industries Plc | Rate-moderated group transfer polymerization |
| CN101643412A (en) * | 2009-03-17 | 2010-02-10 | 江苏工业学院 | Hydroxyl-terminated polyacrylate oligomer as well as preparation method and application thereof |
| CN101993512A (en) * | 2009-08-12 | 2011-03-30 | 德莎欧洲公司 | Process for preparing polyacrylates |
| CN108148187A (en) * | 2018-01-08 | 2018-06-12 | 吉林大学 | The method of living control polymerization (γ-methyl)-ɑ-methylene-y-butyrolactone |
| CN110628034A (en) * | 2019-08-28 | 2019-12-31 | 昆山博益鑫成高分子材料有限公司 | Polyacrylate polymer and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| KEITA FUCHISE，等: "Recent progress in organocatalytic group transfer polymerization", 《POLYMER CHEMISTRY》 * |
| KENJI TAKADA，等: "Controlled Polymerization of Methyl Acrylate for High-Molecular-Weight Polymers by Pentafluorophenylbis(triflyl)methane-Promoted Group Transfer Polymerization Using Triisopropylsilyl Ketene Acetal", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
| KENJI TAKADA，等: "Synthesis of Homopolymers, Diblock Copolymers, and Multiblock Polymers by Organocatalyzed Group Transfer Polymerization of Various Acrylate Monomers", 《MACROMOLECULES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079950A (en) * | 2020-08-28 | 2020-12-15 | 长春理工大学 | Thermal activation delayed fluorescence temperature-sensitive polymer and preparation method thereof |
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