CN110540610B - (methyl) acrylate polymer and preparation method thereof - Google Patents

(methyl) acrylate polymer and preparation method thereof Download PDF

Info

Publication number
CN110540610B
CN110540610B CN201810520849.XA CN201810520849A CN110540610B CN 110540610 B CN110540610 B CN 110540610B CN 201810520849 A CN201810520849 A CN 201810520849A CN 110540610 B CN110540610 B CN 110540610B
Authority
CN
China
Prior art keywords
potassium
meth
molecular weight
polymer
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810520849.XA
Other languages
Chinese (zh)
Other versions
CN110540610A (en
Inventor
郭寅天
徐文前
郑昀红
陈清
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Original Assignee
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Chemical Industry Research Institute Co Ltd, Sinochem Lantian Co Ltd filed Critical Zhejiang Chemical Industry Research Institute Co Ltd
Priority to CN201810520849.XA priority Critical patent/CN110540610B/en
Publication of CN110540610A publication Critical patent/CN110540610A/en
Application granted granted Critical
Publication of CN110540610B publication Critical patent/CN110540610B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/02—Alkylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a (methyl) acrylate polymer with a structural formula (I), wherein each substituent group is shown in the specification,
Figure DDA0001674759720000011
the invention also discloses a preparation method of the (methyl) acrylate polymer. The polymer disclosed by the invention has a novel structure and a wide application range.

Description

(methyl) acrylate polymer and preparation method thereof
Technical Field
The invention belongs to the field of organic high molecular compounds, and relates to a (methyl) acrylate polymer and a preparation method thereof.
Background
The acrylate materials have wide application range, such as: polymethyl methacrylate is used as a medical bone cement raw material for a long time; the polyacrylate/montmorillonite composite system can be used as a flame retardant material; water-soluble polyacrylates are often used as adhesives and paints; the polycyanoacrylate is a main raw material of the instant adhesive; the fluorine-containing polyacrylate can be used in the fields of textile finishing agents, paper product treating agents, electronic device protection and the like. The acrylate polymer with the novel structure is also expected to be applied to the fields of biomedicine, coating paint, macromolecular modification, polymer grafting and the like.
The synthesis method of the acrylate polymer mainly comprises three methods of free radical polymerization, coordination polymerization and anion polymerization. The free radical polymerization method has already realized the commercial process at present, and the controlled/"living" free radical polymerization that evolves on the basis of traditional free radical polymerization can prepare the polymer with controllable microstructure, polymer, polydispersity, but this method preparation route is longer, often cause heavy metal initiator or sulphur-containing initiator residue, post treatment (purification) are complicated.
Coordination polymerization processes are usually carried out in systems with a low degree of solvation, and in such cases polymers with stereoregularity are often prepared by utilizing the strong coordination capacity of polar monomers such as acrylates in combination with homogeneous initiators. In recent years, more and more polar monomers are introduced into a coordination polymerization system using a novel coordination polymerization catalyst to produce a variety of novel acrylic polymers. However, it is often difficult to incorporate more polar monomer and less polar monomer species are used.
The anion polymerization method mainly utilizes the characteristic that the electron cloud density of vinyl double bonds on acrylate which has electron-withdrawing groups and conjugated by pi-pi is low, so that anion active centers generated after anion attack can stably exist to initiate polymerization reaction, and the polymerization system of the method can keep activity all the time theoretically due to the fact that no double-group termination exists, so that the method is also called active anion polymerization. In recent years, oxyanion polymerization, which has evolved based on anion polymerization, has become a focus of research, for example:
(1) tomoi et al, Tomoi M., Sekiya K., Kakiuchi H.Polymer Journal, 1974,6(5),438-444, 1974, disclose a process for preparing methyl methacrylate polymers after initiating the polymerization of methyl methacrylate using sodium n-butoxide and methoxy oxyethyl salts as initiators. The method can obtain high monomer conversion rate under certain experimental conditions, but the applicable alkali metal alkoxy compound and (methyl) acrylate monomer are too single, and the polymerization time is too long;
(2) the publications Nagasaki Y., Sato Y., Kato M.macromolecular Rapid Communications,1997, 18(9), 827-835; iijima M., Nagasaki Y., Kato M., Kataoka K.Polymer,1997,38(5), 1197-. The method can prepare polymers with narrow molecular weight distribution, but the types of the applicable alkali metal alkoxy compounds are few, and the types of the (methyl) acrylic ester monomers are too single.
The structure of the (meth) acrylate polymer represented by the structural formula (I) described in the present application is not reported in the prior art.
Therefore, it is necessary to develop a structure of a novel (meth) acrylate polymer and to study a method for producing the same.
Disclosure of Invention
The invention aims to provide a (methyl) acrylate polymer, which has the following structural formula (I):
Figure BDA0001674759700000021
wherein:
n is selected from 3-300;
r1 is selected from
Figure BDA0001674759700000022
Figure BDA0001674759700000023
R2 is selected from-H or-CH3；
R3 is selected from-CH3、-CH2CH3、
Figure BDA0001674759700000031
-CH2CH2CH2CH3、
Figure BDA0001674759700000032
-(CH2)5CH3、 -(CH2)7CH3、-(CH2)11CH3、-(CH2)17CH3、-(CH2CH2O)PCH3、
Figure BDA0001674759700000033
Figure BDA0001674759700000034
Figure BDA0001674759700000035
CH2CF3、-CH2CHFCF3、-CH2CF2CF3、-CH2CH2CF2CF3、-CH2CF2CHFCF3、 -CH2CF2CF2CF3、-CH2CH2(CF2)3CF3、
Figure BDA0001674759700000036
CH2CH2(CF2)5CF3or-CH2CH2(CF2)7CF3Wherein p is an integer of 8-20;
the number average molecular weight of the (meth) acrylate polymer is 1200 to 75000, and the molecular weight distribution is 1 to 4.
The invention provides a (methyl) acrylic ester polymer with a structural formula (I), wherein a substituent R1 is selected from
Figure BDA0001674759700000037
Figure BDA0001674759700000038
Figure BDA0001674759700000039
Or CH2CH2CH2CH2OCH＝CH2。
Preferably, R1 is selected from
Figure BDA00016747597000000310
Figure BDA0001674759700000041
Figure BDA0001674759700000042
or-CH2CH2CH2CH2OCH＝CH2。
Further preferably, R1 is selected from
Figure BDA0001674759700000043
Figure BDA0001674759700000044
or-CH2CH2CH2CH2OCH＝CH2。
More preferably, R1 is selected from
Figure BDA0001674759700000045
or-CH2CH2CH2CH2OCH＝CH2。
The substituent R2 of the (methyl) acrylate polymer with the structural formula (I) provided by the invention is selected from-H or-CH3。
Preferably, the substituent R2 is selected from-CH3。
The invention provides a (methyl) acrylic ester polymer with a structural formula (I), wherein a substituent R3 is selected from-CH3、 -CH2CH3、
Figure BDA0001674759700000046
-CH2CH2CH2CH3、
Figure BDA0001674759700000047
-(CH2)5CH3、-(CH2)7CH3、-(CH2)11CH3、 -(CH2)17CH3、-(CH2CH2O)PCH3、
Figure BDA0001674759700000048
Figure BDA0001674759700000049
-CH2CH2OH、
Figure BDA00016747597000000410
-CH2CF3、 -CH2CHFCF3、-CH2CF2CF3、-CH2CH2CF2CF3、-CH2CF2CHFCF3、-CH2CF2CF2CF3、-CH2CH2(CF2)3CF3、
Figure BDA0001674759700000051
-CH2CH2(CF2)5CF3or-CH2CH2(CF2)7CF3Wherein p is an integer of 8 to 20.
Preferably, R3 is selected from-CH3、-CH2CH3、
Figure BDA0001674759700000052
-CH2CH2CH2CH3、
Figure BDA0001674759700000053
-(CH2)5CH3、-(CH2)7CH3、-(CH2)11CH3、-(CH2)17CH3、-(CH2CH2O)PCH3、
Figure BDA0001674759700000054
Figure BDA0001674759700000055
-CH2CH2OH、
Figure BDA0001674759700000056
-CH2CF3、-CH2CHFCF3、 -CH2CF2CF3、-CH2CH2CF2CF3、-CH2CF2CHFCF3、-CH2CF2CF2CF3、-CH2CH2(CF2)3CF3、
Figure BDA0001674759700000057
-CH2CH2(CF2)5CF3or-CH2CH2(CF2)7CF3Wherein p is an integer of 8 to 20.
Further preferably, R3 is selected from-CH3、-CH2CH3、
Figure BDA0001674759700000058
-CH2CH2CH2CH3、 -(CH2CH2O)PCH3、
Figure BDA0001674759700000059
-CH2CF3、-CH2CHFCF3、
Figure BDA00016747597000000510
or-CH2CH2(CF2)7CF3Wherein p is an integer of 8 to 20.
Most preferably, R3 is selected from-CH3、-CH2CH2CH2CH3Or
Figure BDA00016747597000000511
The number average molecular weight of the (methyl) acrylate polymer with the structural formula (I) is 1200-75000, and the molecular weight distribution is 1-4.
Preferably, the number average molecular weight of the (meth) acrylate polymer is 1200 to 30000, and the molecular weight distribution is 1 to 4.
The present invention also provides a method for preparing the (meth) acrylate polymer having the structural formula (I), using an initiator including an alkali metal alkoxide.
For the acrylate monomer, the ester group connected with the vinyl has the charge absorption property, so that the density of vinyl electron cloud of the acrylate is reduced, thereby facilitating the attack of a nucleophilic reagent to the double bond and initiating the polymerization. The use of alkali metal alkoxide compounds with high nucleophilicity can effectively initiate the polymerization of acrylate monomers.
The alkali metal alkoxide is preferably selected from the group consisting of potassium trimethylsilanolate, sodium trimethylsilanolate, potassium 3-cyclohexene-1-methanolate, sodium 3-cyclohexene-1-methanolate, potassium diphenylmethanolate, sodium diphenylmethanolate, potassium 2-phenoxyethanolate, sodium 2-phenoxyethanolate, potassium 3-piperidinemethanolate, sodium 3-piperidinemethanolate, potassium tridecafluorooctanoate, sodium tridecafluorooctanoate, potassium 4- (difluoromethoxy) benzylalkoxide, sodium 4- (difluoromethoxy) benzylalkoxide, potassium 2, 3-difluorophenylmethanolate, sodium 2, 3-difluorophenylmethanolate, potassium 4-fluoro-3- (trifluoromethyl) phenylmethanolate, sodium methoxide, sodium 3-piperidinemethanolate, potassium tridecafluorooctanoate, potassium 4-fluoro-3- (trifluoromethyl) phenylmethanolate, sodium 2, 3-piperidinemethanolate, potassium tridecafluoromethanoate, 2-methyl-1-phenyl-2-propanol potassium, 2-methyl-1-phenyl-2-propanol sodium, 3-benzene propanol potassium, 3-benzene propanol sodium, p-aminobenzene methanol potassium, p-aminobenzene sodium methoxide, 4-chlorine-2-formic acid phenol potassium, 4-chlorine-2-formic acid phenol sodium, 4-bromine-2-formic acid phenol potassium, 4-bromine-2-formic acid phenol sodium, 4-vinyl oxygen-1-butanol potassium and 4-vinyl oxygen-1-butanol sodium at least one kind.
It is further preferred that the alkali metal alkoxide is selected from the group consisting of potassium trimethylsilanolate, potassium 3-cyclohexene-1-methoxide, sodium 3-cyclohexene-1-methoxide, potassium diphenylmethoxide, sodium diphenylmethoxide, potassium 2-phenoxyethoxide, sodium 2-phenoxyethoxide, potassium 3-piperidinecarboxylate, sodium 3-piperidinecarboxylate, potassium tridecafluorooctanoate, sodium tridecafluorooctanoate, potassium 4- (difluoromethoxy) benzylate, potassium 2, 3-difluorophenoxymethoxide, potassium 4-fluoro-3- (trifluoromethyl) benzylate, potassium 2-methyl-1-phenyl-2-propoxide, sodium 2-methyl-1-phenyl-2-propoxide, potassium 3-phenylpropanoate, potassium 2-methyl-1-phenyl-2-propoxide, potassium phenoxide, and the like, At least one of sodium 3-phenylpropionate, potassium p-aminobenzoate, sodium p-aminobenzoate, potassium 4-vinyloxy-1-butoxide, and sodium 4-vinyloxy-1-butoxide.
Still more preferably, the alkali metal alkoxide is at least one selected from the group consisting of potassium trimethylsilanolate, potassium 3-cyclohexene-1-methoxide, sodium 3-cyclohexene-1-methoxide, potassium diphenylmethoxide, sodium diphenylmethoxide, potassium 2-phenoxyethoxide, sodium 2-phenoxyethoxide, potassium 3-piperidinemethanolate, sodium 3-piperidinemethanolate, potassium 2-methyl-1-phenyl-2-propoxide, potassium 3-phenylpropionate, potassium p-aminobenzoate, potassium 4-vinyloxy-1-butoxide and sodium 4-vinyloxy-1-butoxide.
Most preferably, the alkali metal alkoxide is at least one selected from the group consisting of potassium trimethylsilanolate, potassium 3-cyclohexene-1-methoxide, potassium diphenylmethoxide, potassium 2-phenoxyethoxide, potassium 3-piperidinemethanolate, potassium 4-vinyloxy-1-butoxide, and sodium 4-vinyloxy-1-butoxide.
The invention also provides a preparation method of the (methyl) acrylate polymer with the structural formula (I), which is preferably carried out in the presence of an aprotic organic solvent.
The amount of the initiator may be such that the polymerization reaction proceeds smoothly.
Preferably, the molar ratio of the initiator to the polymerization monomer is 3-300: 1.
More preferably, the molar ratio of the initiator to the polymerization monomer is 25-75: 1.
The aprotic organic solvent is preferably at least one selected from the group consisting of tetrahydrofuran, toluene, benzene, dimethyl sulfoxide, N-dimethylformamide, diethyl ether, isopropyl ether, carbon tetrachloride, cyclohexane, N-hexane, petroleum ether, dioxane, triethylamine, 1,1,1,3, 3-pentafluorobutane, methyl perfluoropropyl ether, methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether.
Further preferably, the aprotic organic solvent is at least one selected from the group consisting of tetrahydrofuran, toluene, dimethyl sulfoxide and N, N-dimethylformamide.
The amount of the aprotic organic solvent used is sufficient to allow the polymerization reaction to proceed smoothly.
Preferably, the volume ratio of the aprotic organic solvent to the polymerized monomer is 1:8 to 100: 3.
More preferably, the volume ratio of the aprotic organic solvent to the polymerizable monomer is 2:1 to 6: 1.
The invention also provides a preparation method of the (methyl) acrylate polymer with the structural formula (I), and the reaction temperature is satisfied to ensure that the polymerization reaction is smoothly carried out.
Preferably, the reaction temperature is-20 to 80 ℃.
Further preferably, the reaction temperature is 20-65 ℃.
Part of index testing methods of the (methyl) acrylate polymer prepared by the invention are as follows:
(1) number average molecular weight, molecular weight distribution: characterized by Gel Permeation Chromatography (GPC) using a PL-220 type gel permeation chromatograph (Polymer Laboratories) using 2 PL-gel 5 μm MIXED-C columns with a separation range of 500 to 6X 106And processing data by a universal correction method based on narrow-distribution polystyrene standard samples. Preparing a sample of the polymer at normal temperature, taking Tetrahydrofuran (THF) as a solvent, and obtaining the following sample concentration: 2 to 3 wt%. The test temperature was 40 ℃ and THF was used as the mobile phase at a flow rate of 1.0mL/min；
(2) A hydrogen spectrum; measured by NMR spectroscopy using a Bruker model 600MHz NMR spectrometer. The frequency of the test is 600MHz by adopting a 5mm nuclear magnetic tube. When the sample is tested, the sample is dissolved in deuterated chloroform containing tetramethylsilane, the concentration is 3 wt%, the testing temperature is 25 ℃, scanning is carried out for 16 times, and tetramethylsilane is used as an internal standard.
Drawings
FIG. 1 GPC curves of polymers prepared in example 1.
FIG. 2 preparation of polymer from example 11H nuclear magnetic map.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
A100 ml Schlenk reaction flask with a mouth was evacuated, the flask was baked with an electric heating gun under vacuum for 3 minutes, cooled to room temperature (about 25 ℃ C.) and then replaced with nitrogen gas 3 times, and finally the flask was filled with 0.1MPa of nitrogen gas. The reaction was placed in a constant temperature magnetic water bath at a set polymerization temperature (65 ℃). To the flask were added in this order 25 ml (volume ratio 1: 4) of a tetrahydrofuran/dimethylene sulfoxide mixed solution as a solvent and sodium 4-vinyloxy-1-butoxide (1.96 mmol) as an alkali metal alkoxide to dissolve potassium 4-vinyloxy-1-butoxide in dimethyl sulfoxide, and then methyl methacrylate (5 ml) was added to the flask to start the polymerization reaction. The pressure in the bottle was kept at 0.1MPa during the polymerization. After 2 hours of polymerization, the reaction flask was charged with anhydrous methanol to quench the polymerization. After quenching, the contents were treated with cation exchange resin in the hydrogen form, collected by spin drying, and finally dried under vacuum at 50 ℃ to constant weight and weighed. 2.55 g of polymer are obtained with a conversion of 49%.
The polymer obtained by the test is
Figure BDA0001674759700000081
The polymerization degree n was 28, the number average molecular weight was 3000g/mol as determined by GPC (see FIG. 1), and the molecular weight distribution was 1.19.
Of the polymers prepared1The H nuclear magnetic diagram is shown in figure 2.
Example 2
Polymerization conditions were the same as in example 1 except that the polymerization temperature was changed from 65 ℃ to 22 ℃, the reaction solvent was changed from the tetrahydrofuran/dimethylene sulfoxide mixed solution to 16 ml of tetrahydrofuran, and the alkali metal alkoxide sodium 4-vinyloxy-1-butoxide (1.96 mmol) was changed to potassium 4-vinyloxy-1-butoxide (1.65 mmol). 4.36 g of polymer are obtained, conversion 85%.
The polymer obtained by the test is
Figure BDA0001674759700000091
The polymerization degree n value is 30, the number average molecular weight is 3200g/mol, and the molecular weight distribution is 1.61. The hydrogen spectrum confirmed that the above polymer was obtained.
Example 3
Polymerization conditions As in example 1, the polymerization temperature was changed from 65 ℃ to 20 ℃ only, the reaction solvent was changed from the tetrahydrofuran/dimethylene sulfoxide mixed solution to 10 ml of tetrahydrofuran, the sodium alkali metal alkoxide 4-vinyloxy-1-butoxide (1.96 mmol) to potassium trimethylsilanolate (0.40 mmol), the monomer methyl methacrylate (5 ml) was changed to benzyl methacrylate (2 ml), and the polymerization time was changed from 2 hours to 8 hours. 1.96 g of polymer are obtained, the conversion being 92%.
The polymer obtained by the test is
Figure BDA0001674759700000092
The polymerization degree n was 17, the number average molecular weight was 3100g/mol, and the molecular weight distribution was 1.32. The hydrogen spectrum confirmed that the above polymer was obtained.
Example 4
Polymerization conditions As in example 1, the polymerization temperature was changed from 65 ℃ to 30 ℃ only, the reaction solvent was changed from the tetrahydrofuran/dimethylene sulfoxide mixed solution to 10 ml (volume ratio 4: 1) of the tetrahydrofuran/N, N-dimethylformamide mixed solution, the sodium alkali metal alkoxide 4-vinyloxy-1-butoxide (1.96 mmol) was changed to potassium 3-piperidinemethanolate (0.91 mmol), and the amount of the monomeric methyl methacrylate was changed from 5 ml to 3 ml. 2.43 g of polymer are obtained with a conversion of 79%.
The polymer obtained by the test is
Figure BDA0001674759700000101
The polymerization degree n was 23, the number average molecular weight was 2500g/mol, and the molecular weight distribution was 1.21. The hydrogen spectrum confirmed that the above polymer was obtained.
Example 5
Polymerization conditions were the same as in example 1 except that the polymerization temperature was changed from 65 ℃ to 20 ℃, the reaction solvent was changed from the tetrahydrofuran/dimethylene sulfoxide mixed solution to 10 ml of tetrahydrofuran, the sodium alkali metal alkoxide 4-vinyloxy-1-butoxide (1.96 mmol) was changed to potassium 2-phenoxyethoxide (0.90 mmol), and the monomer methyl methacrylate was changed to n-butyl methacrylate. 3.58 g of polymer are obtained with a conversion of 78%.
The polymer obtained by the test is
Figure BDA0001674759700000102
The polymerization degree n was 38, the number average molecular weight was 5600g/mol, and the molecular weight distribution was 1.65. The hydrogen spectrum confirmed that the above polymer was obtained.
Example 6
Polymerization conditions were the same as in example 1 except that the polymerization temperature was changed from 65 ℃ to 60 ℃, 25 ml (volume ratio 1: 4) of the tetrahydrofuran/dimethylene sulfoxide mixed solution as the reaction solvent was changed to 12 ml (volume ratio 7: 5) of the tetrahydrofuran/dimethylene sulfoxide mixed solution, sodium 4-vinyloxy-1-butoxide (1.96 mmol) as the alkali metal alkoxide was changed to potassium 3-cyclohexene-1-methoxide (0.32 mmol), methyl methacrylate (5 ml) as the monomer was changed to n-butyl methacrylate (2 ml), and the polymerization time was changed from 2 hours to 0.5 hours. 1.47 g of polymer were obtained with a conversion of 81%.
The polymer obtained by the test is
Figure BDA0001674759700000111
) The polymerization degree n value was 36, the number average molecular weight was 5200g/mol, and the molecular weight distribution was 1.30. The hydrogen spectrum confirmed that the above polymer was obtained.
Example 7
Polymerization conditions were the same as in example 1, except that the polymerization temperature was changed from 65 ℃ to 25 ℃, the reaction solvent was changed from the tetrahydrofuran/dimethylene sulfoxide mixed solution to the tetrahydrofuran/toluene mixed solution of 10 ml (volume ratio: 9: 1), the alkali metal alkoxide sodium 4-vinyloxy-1-butoxide (1.96 mmol) was changed to potassium diphenylmethoxide (0.27 mmol), the amount of the monomeric methyl methacrylate was changed from 5 ml to 2 ml, and the polymerization time was changed from 2 hours to 1 hour. 1.97 g of polymer are obtained with a conversion of 97%.
The polymer obtained by the test is
Figure BDA0001674759700000112
The polymerization degree n value is 63, the number average molecular weight is 6500g/mol, and the molecular weight distribution is 2.20. The hydrogen spectrum confirmed that the above polymer was obtained.

Claims (8)

1. A (meth) acrylate polymer having the following structural formula (I):
Figure DEST_PATH_IMAGE002
（I）
wherein:
n is selected from 3-300;
r1 is selected from
Figure DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE006
、
Figure DEST_PATH_IMAGE008
、
Figure DEST_PATH_IMAGE010
、
Figure DEST_PATH_IMAGE012
Or
Figure DEST_PATH_IMAGE014
；
R2 is selected from
Figure DEST_PATH_IMAGE016
Or
Figure DEST_PATH_IMAGE018
；
R3 is selected from
Figure DEST_PATH_IMAGE018A
、
Figure DEST_PATH_IMAGE021
、
Figure DEST_PATH_IMAGE023
、
Figure DEST_PATH_IMAGE025
、
Figure DEST_PATH_IMAGE027
、
Figure DEST_PATH_IMAGE029
、
Figure DEST_PATH_IMAGE031
、
Figure DEST_PATH_IMAGE033
、
Figure DEST_PATH_IMAGE035
、
Figure DEST_PATH_IMAGE037
、
Figure DEST_PATH_IMAGE039
、
Figure DEST_PATH_IMAGE041
、
Figure DEST_PATH_IMAGE043
、
Figure DEST_PATH_IMAGE045
、
Figure DEST_PATH_IMAGE047
、
Figure DEST_PATH_IMAGE049
、
Figure DEST_PATH_IMAGE051
、
Figure DEST_PATH_IMAGE053
、
Figure DEST_PATH_IMAGE055
、
Figure DEST_PATH_IMAGE057
、
Figure DEST_PATH_IMAGE059
、
Figure DEST_PATH_IMAGE061
、
Figure DEST_PATH_IMAGE063
、
Figure DEST_PATH_IMAGE065
、
Figure DEST_PATH_IMAGE067
Or
Figure DEST_PATH_IMAGE069
Wherein p is an integer of 8-20;
the number average molecular weight of the (meth) acrylate polymer is 1200 to 75000, and the molecular weight distribution is 1 to 4.
2. The (meth) acrylic acid ester-based polymer according to claim 1, wherein:
r3 is selected from
Figure DEST_PATH_IMAGE018AA
、
Figure DEST_PATH_IMAGE021A
、
Figure DEST_PATH_IMAGE023A
、
Figure DEST_PATH_IMAGE025A
、
Figure DEST_PATH_IMAGE027A
、
Figure DEST_PATH_IMAGE029A
、
Figure DEST_PATH_IMAGE031A
、
Figure DEST_PATH_IMAGE033A
、
Figure DEST_PATH_IMAGE035A
、
Figure DEST_PATH_IMAGE037A
、
Figure DEST_PATH_IMAGE039A
、
Figure DEST_PATH_IMAGE043A
、
Figure DEST_PATH_IMAGE045A
、
Figure DEST_PATH_IMAGE051A
、
Figure DEST_PATH_IMAGE053A
、
Figure DEST_PATH_IMAGE055A
、
Figure DEST_PATH_IMAGE057A
、
Figure DEST_PATH_IMAGE059A
、
Figure DEST_PATH_IMAGE061A
、
Figure DEST_PATH_IMAGE063A
、
Figure DEST_PATH_IMAGE065A
、
Figure DEST_PATH_IMAGE067A
Or
Figure DEST_PATH_IMAGE069A
Wherein p is an integer of 8-20;
the number average molecular weight of the (meth) acrylate polymer is 1200 to 30000, and the molecular weight distribution is 1 to 4.
3. The (meth) acrylic acid ester-based polymer according to claim 2, wherein:
r3 is selected from
Figure DEST_PATH_IMAGE018AAA
、
Figure DEST_PATH_IMAGE021AA
、
Figure DEST_PATH_IMAGE023AA
、
Figure DEST_PATH_IMAGE025AA
、
Figure DEST_PATH_IMAGE037AA
、
Figure DEST_PATH_IMAGE039AA
、
Figure DEST_PATH_IMAGE043AA
、
Figure DEST_PATH_IMAGE045AA
、
Figure DEST_PATH_IMAGE051AA
、
Figure DEST_PATH_IMAGE053AA
、
Figure DEST_PATH_IMAGE065AA
Or
Figure DEST_PATH_IMAGE069AA
Wherein p is an integer of 8-20;
the number average molecular weight of the (methyl) acrylate polymer is 2500-6500, and the molecular weight distribution is 1-3.
4. The (meth) acrylic ester polymer according to claim 3, wherein:
r3 is selected from
Figure DEST_PATH_IMAGE018AAAA
、
Figure DEST_PATH_IMAGE025AAA
Or
Figure DEST_PATH_IMAGE043AAA
。
5. The (meth) acrylic ester polymer according to claim 1, wherein the (meth) acrylic ester polymer is prepared by a method comprising:
the initiator used comprises an alkali metal alkoxide selected from at least one of potassium trimethylsilanolate, potassium 3-cyclohexene-1-methanolate, potassium diphenylmethanolate, potassium 2-phenoxyethanolate, potassium 3-piperidinemethanollate, potassium 4-vinyloxy-1-butanolate, and sodium 4-vinyloxy-1-butanolate.
6. The (meth) acrylate polymer according to claim 5, wherein the preparation of the (meth) acrylate polymer is carried out in the presence of an aprotic organic solvent selected from at least one of tetrahydrofuran, toluene, dimethyl sulfoxide and N, N-dimethylformamide.
7. The (meth) acrylic ester polymer according to claim 6, wherein the (meth) acrylic ester polymer is prepared by a method comprising:
the molar ratio of the initiator to the polymerized monomer is 1: 3-1: 300;
the volume ratio of the aprotic organic solvent to the polymerization monomer is 1: 8-100: 3;
the reaction temperature is-20 to 80 ℃.
8. The (meth) acrylic ester polymer according to claim 7, wherein the (meth) acrylic ester polymer is prepared by a method comprising:
the molar ratio of the initiator to the polymerized monomer is 1: 25-1: 75;
the volume ratio of the aprotic organic solvent to the polymerization monomer is 2: 1-6: 1;
the reaction temperature is 20-65 ℃.
CN201810520849.XA 2018-05-28 2018-05-28 (methyl) acrylate polymer and preparation method thereof Active CN110540610B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810520849.XA CN110540610B (en) 2018-05-28 2018-05-28 (methyl) acrylate polymer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810520849.XA CN110540610B (en) 2018-05-28 2018-05-28 (methyl) acrylate polymer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110540610A CN110540610A (en) 2019-12-06
CN110540610B true CN110540610B (en) 2021-08-20

Family

ID=68700914

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810520849.XA Active CN110540610B (en) 2018-05-28 2018-05-28 (methyl) acrylate polymer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110540610B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617779A (en) * 1949-05-28 1952-11-11 Gen Electric Plasticized vinyl halide resins and electrical conductors insulated therewith
CN1089957A (en) * 1992-11-27 1994-07-27 埃勒夫阿托化学有限公司 Prepare the method for high heat resistance thermoplastic elastomeric block copolymers and the product of gained with conjugated diolefine and methyl methacrylate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617779A (en) * 1949-05-28 1952-11-11 Gen Electric Plasticized vinyl halide resins and electrical conductors insulated therewith
CN1089957A (en) * 1992-11-27 1994-07-27 埃勒夫阿托化学有限公司 Prepare the method for high heat resistance thermoplastic elastomeric block copolymers and the product of gained with conjugated diolefine and methyl methacrylate

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Climbing Back up the Nucleophilic Reactivity Scale. Use of Cyclosila Derivatives as Reactivity Boosters in Anionic Polymerization;Zundel, T等;《MACROMOLECULES》;19980505;第31卷(第9期);2724-2730 *
Effects of Different Reactive Oxyanionic Initiators on the Anionic Polymerizaition of n-Hexyl Isocyanate;Joonkeun Min等;《Macromolecules》;20110414;第44卷;3211-3216 *
MMA-DMAEMA两亲嵌段共聚物的合成;刘琼琼;《科技进展》;20031231;第17卷(第8期);29-32 *
甲基丙烯酸酯类单体的氧阴离子聚合;刘琼琼;《苏州大学硕士毕业论文》;20031231;第1.2.3节 *
醇钾及酚钾在甲基丙烯酸甲酯阴离子聚合中的应用;邹斌等;《功能高分子学报》;20160930;第29卷(第3期);258-266 *

Also Published As

Publication number Publication date
CN110540610A (en) 2019-12-06

Similar Documents

Publication Publication Date Title
Bohnert et al. Liquid‐Crystalline side‐chain AB block copolymers by direct anionic polymerization of a mesogenic methacrylate
JP4848735B2 (en) Polymers for electrochemical devices of polymerizable imidazole salts
JPS61215622A (en) Production of unsaturated group-terminated polyalkylene oxide
JP2008138219A (en) Method for producing fluorinated allyl ether polymer
CN105198916A (en) Functionalized double tower-type polyhedron oligomeric silsesquioxane and preparation method thereof
Iijima et al. A potassium alcoholate-initiated polymerization of 2-(trialkylsiloxyethyl) methacrylate
JPH04108808A (en) Production of macromonomer
Sweat et al. Synthesis of poly (4‐hydroxystyrene)‐based block copolymers containing acid‐sensitive blocks by living anionic polymerization
Kavaklı et al. Synthesis, characterization and amidoximation of a novel polymer: poly (N, N′-dipropionitrile acrylamide)
CN110540610B (en) (methyl) acrylate polymer and preparation method thereof
Vijayaraghavan et al. Anionic polymerization of styrene in ionic liquids
Zhang et al. Synthesis, characterization and properties of a novel fluorinated methacrylate polymer
CN110804137B (en) Block polymer containing perfluoropolyether structure
CN108948349B (en) Spiro-ring polymer material and preparation method thereof
CN110092849A (en) Cationic chain transfer agent and application thereof
Li et al. Characterization of poly (butyl acrylate) diols prepared via atom transfer radical polymerization and subsequent modification
Zhang et al. Facile functionalization of isotactic polypropylene by azide and alkyne groups for click chemistry application
Zheng et al. Controlled/living free‐radical copolymerization of 4‐(azidocarbonyl) phenyl methacrylate with methyl acrylate under 60Co γ‐ray irradiation
KR100222453B1 (en) Living statistic (meth)acrylate copolymers, copolymers prepared from these living copolymers, and process for preparing these copolymers by anionic copolymerization
JPH07258310A (en) Method and catalyst for controlling polymerization of acrylates
CN114846033A (en) Cyclic carbonate group-containing (methyl) acrylate monomer and polymer
JPH03200811A (en) Production of hydroxylated polymer
HAMAUDI et al. Anionic polymerization of methyl methacrylate as promoted by a n-butyl lithium-pyridazine-polyether alkoxide based complex initiator system
Mahy et al. Synthesis of novel photosensitive polymers and copolymers containing cinnamic groups as pendant photoreactive functions
WO2020150970A1 (en) Polymerization method for preparing block copolymer by inserting alkylthioether into bis(tri)thiocarbonate-terminated polymer by alkali-assisted catalysis

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A (meth) acrylate polymer and its preparation method

Effective date of registration: 20220628

Granted publication date: 20210820

Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch

Pledgor: SINOCHEM LANTIAN Co.,Ltd.

Registration number: Y2022330001143

PE01 Entry into force of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20230308

Granted publication date: 20210820

Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch

Pledgor: SINOCHEM LANTIAN Co.,Ltd.

Registration number: Y2022330001143

PC01 Cancellation of the registration of the contract for pledge of patent right