CN114276517A - Preparation method of epoxy-terminated polybutadiene series liquid rubber - Google Patents
Preparation method of epoxy-terminated polybutadiene series liquid rubber Download PDFInfo
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- CN114276517A CN114276517A CN202111520866.1A CN202111520866A CN114276517A CN 114276517 A CN114276517 A CN 114276517A CN 202111520866 A CN202111520866 A CN 202111520866A CN 114276517 A CN114276517 A CN 114276517A
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- 238000005406 washing Methods 0.000 claims abstract description 13
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- 238000002390 rotary evaporation Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
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- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 22
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010025 steaming Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 29
- 239000012300 argon atmosphere Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 239000002174 Styrene-butadiene Substances 0.000 description 12
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- 239000011115 styrene butadiene Substances 0.000 description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 11
- 239000005457 ice water Substances 0.000 description 10
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- -1 methyl epoxy propanol Chemical compound 0.000 description 5
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 4
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004449 solid propellant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The application discloses a preparation method of epoxy-terminated polybutadiene series liquid rubber, which comprises the following steps: the method comprises the following steps: under an inert environment, mixing an organic solvent and hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber according to the mass ratio of (0-5):1, adding diisocyanate according to the molar ratio of isocyanate group to hydroxyl group of 2-5, and reacting to obtain an isocyanate-terminated polybutadiene homopolymer or copolymer liquid rubber solution; step two: under inert environment, adding the epoxy reagent into the liquid rubber solution of the terminal isocyanate polybutadiene homopolymer or copolymer according to the molar ratio of hydroxyl to isocyanate group in the epoxy reagent of 1-3 for reaction. And washing and rotary steaming the reaction liquid to obtain the epoxy-terminated polybutadiene series liquid rubber. The invention has simple process and adjustable end-ring oxidation efficiency, and the obtained end-epoxy polybutadiene series liquid rubber has the characteristics of excellent water resistance, fluidity, adhesiveness, toughness, better compatibility with other high polymers and the like.
Description
Technical Field
The application relates to the field of preparation of end group functionalized polymers, in particular to a preparation method of epoxy-terminated polybutadiene series liquid rubber.
Background
The polybutadiene series liquid rubber containing reactive terminal hydroxyl is a polymer with the number average molecular weight less than 10000 and fluidity at room temperature, and is also called telechelic polymer because the molecular chain terminal of the polymer has reactive hydroxyl. The liquid rubber can be crosslinked and cured through chemical reaction to form an elastomer with a three-dimensional network structure and certain mechanical property. The currently synthesized liquid rubber products of hydroxyl-terminated polybutadiene series at home and abroad mainly include hydroxyl-terminated polybutadiene (HTPB), hydroxyl-terminated polybutadiene-acrylonitrile (HTBN), hydroxyl-terminated polybutadiene-styrene (HTBS), and the like. Because the hydroxyl-terminated polybutadiene series liquid rubber has the advantages of low viscosity, easy compounding with other polymers and fillers, excellent mechanical property after curing and forming and the like, the hydroxyl-terminated polybutadiene series liquid rubber is widely used in the fields of composite solid propellants, polyurethane matching materials and the like, and has wide application in the industries of aerospace, electronic and electric products, ships, automobiles, chemical engineering and the like. In order to meet the higher and higher engineering application requirements, the method for improving the comprehensive performance of the traditional hydroxyl-terminated polybutadiene liquid rubber by chemically modifying is a convenient and important method.
Epoxy groups are introduced by carrying out epoxidation modification on hydroxyl-terminated polybutadiene series liquid rubber, so that intermolecular force of the liquid rubber can be increased, the liquid rubber has good adhesion and good compatibility with materials in a wider polarity range, and a new thought is provided for preparing a composite material with excellent performance. However, the method is limited by the problems of unstable preparation process, undefined chemical structure of a synthetic product and the like, so that the epoxidized modified polybutadiene series liquid rubber is not applied on a large scale. Polybutadiene hydrocarbon molecular chain is rich in unsaturated double bond and active terminal hydroxyl, and the epoxidation modification of the polybutadiene series liquid rubber with the terminal hydroxyl at present mainly adopts a double bond oxidation method and a terminal group conversion method in the molecular chain. The controllability of the double bond oxidation method is poor, the yield is low, the product is easy to be branched and gelated, and the molecular structure and the composition are difficult to be clearly characterized. Therefore, the preparation of the epoxy-terminated polybutadiene liquid rubber with definite chemical structure, strong designability, stable and controllable reaction and excellent comprehensive performance is still a challenge to be solved.
Disclosure of Invention
In view of this, the embodiment of the present invention provides a method for preparing liquid rubber of epoxy-terminated polybutadiene series, so as to solve the above-mentioned disadvantages.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing liquid rubber of epoxy-terminated polybutadiene series, including:
the method comprises the following steps: under an inert environment, mixing an organic solvent and hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber according to a mass ratio of (0-5):1, adding diisocyanate according to a r value of 2-5, and reacting to obtain an isocyanate-terminated polybutadiene homopolymer or copolymer liquid rubber solution, wherein the r value is the molar ratio of-NCO groups in the diisocyanate to-OH groups in the hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber;
step two: under an inert environment, adding an epoxidizing reagent into a liquid rubber solution of the terminated isocyanate polybutadiene homopolymer or copolymer according to the r 'value of 1-3 for reaction, washing and carrying out rotary evaporation on reaction liquid to obtain the terminated epoxy polybutadiene series liquid rubber, wherein the r' value is the molar ratio of-OH groups in the epoxidizing reagent to-NCO groups in the liquid rubber solution of the terminated isocyanate polybutadiene homopolymer or copolymer.
The preparation method has the advantages of simple process, mild reaction conditions and the like.
Preferably, in the step one, the hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber is selected from butadiene homopolymer or copolymer liquid rubbers containing hydroxyl groups at two ends, the number average molecular weight is 200 to 10000, the hydroxyl value is 0.1 to 5.0mmol/g, and the general formula is as follows: HO-R1-OH; in the formula, R1Is a hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber backbone selected from the group consisting of polybutadiene, butadiene acrylonitrile copolymers, butadiene styrene copolymers, butadiene acrylic acrylonitrile copolymers, butadiene acrylate copolymers, butadiene-isoprene copolymers, and combinations thereofAny one of products after saturation hydrogenation of synthetic rubber.
Preferably, in the first step, the organic solvent is any one of tetrahydrofuran, dimethyl sulfoxide, toluene, xylene, chlorobenzene, dichloromethane and 1, 4-dioxane.
Preferably, in the first step, the diisocyanate has the general formula: OCN-R2-NCO; in the formula, R2Is alkyl, aryl, alicyclic group or benzyl, and is selected from any one of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI).
Preferably, in the second step, the structural general formula of the epoxidizing agent is as follows:
in the formula, R3Is alkyl, aryl, alicyclic group or benzyl, and n is 0 or 1.
Preferably, in the step one, in the reaction with the diisocyanate, a catalyst may be further added, and the feeding ratio of the catalyst to the total mass of the hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber solution is (0-0.5): 100.
preferably, in the second step, in the step of adding the epoxidizing agent into the liquid rubber solution of the isocyanate-terminated polybutadiene homopolymer or copolymer according to the r' value of 1-3, a catalyst can be added, and the feeding ratio of the catalyst to the total mass of the liquid rubber solution of the isocyanate-terminated polybutadiene homopolymer or copolymer is (0-0.5): 100.
preferably, the catalyst is selected from any one of an organometallic catalyst, an organic base catalyst and an organic acid catalyst.
Preferably, the reaction vessel is replaced with an inert gas/vacuum multiple times, allowing the reaction mass to be added under an inert environment.
Preferably, the reaction temperature in the reaction kettle is 45-90 ℃, the reaction time of the first step is 1-8 hours, and the reaction time of the second step is 2-12 hours.
The inventor conducts mechanism analysis on the preparation process based on the liquid rubber and product characterization data of the epoxy-terminated polybutadiene series, and the possibility is that: in the first step, high-activity hydroxyl in the added hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber is easy to react with isocyanate groups, so that the hydroxyl at two ends of a molecule of the hydroxyl-terminated butadiene copolymer liquid rubber is converted into the isocyanate groups, and the subsequent introduction of epoxy groups is facilitated; in the second step, the added epoxidizing agent reacts with isocyanate group to introduce epoxy group, so that the purpose of converting the hydroxyl at two ends of the molecular chain of hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber into epoxy group is achieved, and finally the epoxy-terminated polybutadiene liquid rubber is obtained. Through the terminal group conversion technology, hydroxyl groups at two ends of a liquid rubber molecular chain of hydroxyl-terminated polybutadiene homopolymer or copolymer are converted into epoxy groups, and the specific chemical reaction general formula is as follows:
in the above chemical reaction formula, R1The main chain of the liquid rubber is hydroxyl-terminated polybutadiene homopolymer or copolymer, and is any one of polybutadiene, butadiene acrylonitrile copolymer, butadiene styrene copolymer, butadiene acrylic acid acrylonitrile copolymer, butadiene acrylate copolymer, butadiene-isoprene copolymer and products obtained by saturated hydrogenation of the synthetic rubber.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
according to the embodiment of the application, the preparation method provided by the invention can be used for modifying hydroxyl-terminated polybutadiene series liquid rubber, and introducing epoxy groups into two ends of a molecular chain of the hydroxyl-terminated polybutadiene series liquid rubber to prepare the epoxy-terminated polybutadiene series liquid rubber with lower viscosity.
The product of the invention carries out chemical modification with definite structure on the end group of the liquid rubber, the product has good fluidity at room temperature or under the condition of slight heating, the processing technology is stable, and the prepared final composite material has excellent mechanical property. The product is mainly used in the fields of adhesives, solid rubber reactive plasticizers, thermosetting resin toughening modifiers and the like, and particularly can be widely used in scenes such as composite solid propellants, gas generating agents, two-stage roll-control system adhesives, solid rubber reactive plasticizers, epoxy thermosetting resin toughening modifiers and the like.
The preparation method of the epoxy-terminated polybutadiene series liquid rubber provided by the embodiment of the invention has the advantages of simple process, adjustable end-terminating oxidation efficiency and better commercial application value. The prepared epoxy-terminated polybutadiene series liquid rubber has the characteristics of excellent water resistance, better fluidity, adhesiveness, toughness, better compatibility with other high polymers and the like.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application.
FIG. 1 is an infrared spectrum of an isocyanate-terminated polybutadiene shown in accordance with an exemplary embodiment, and as can be seen in FIG. 1, 3500cm-1the-OH absorption peak disappears at 3300cm-1a-NH-characteristic absorption peak appears; at 1730cm-1Form C-O absorption peak; 2270cm-1The vicinity is an-NCO absorption peak, which shows that-OH in hydroxyl-terminated polybutadiene and-NCO in diisocyanate have relatively complete chemical reaction to generate isocyanate-terminated polybutadiene containing urethane bonds on the main chain and isocyanate groups at two ends.
FIG. 2 is an infrared spectrum of an epoxy-terminated polybutadiene shown in accordance with an exemplary embodiment. From FIG. 2, it can be seen that，2270cm-1The absorption peak of the terminal epoxy polybutadiene is disappeared at 846cm-1Characteristic absorption peaks of epoxy groups appear around the terminal, which shows that the terminal group of the isocyanate-terminated polybutadiene and the epoxidizing agent completely react to generate the epoxy-terminated polybutadiene.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present application. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present application, as detailed in the appended claims.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items
Example 1:
the method comprises the following steps: adding 60.0g of end hydroxyl polybutadiene liquid rubber and 180.0g of xylene into a 500ml three-neck flask under argon atmosphere, stirring to dissolve, heating to 90 ℃, adding 26.79g of hexamethylene diisocyanate under stirring, and carrying out heat preservation reaction for 4 hours to obtain an end isocyanate group polybutadiene liquid rubber solution;
step two: and (2) cooling the prepared isocyanate-terminated polybutadiene liquid rubber solution to 80 ℃ under the argon atmosphere, adding 19.04g of 4- (ethylene oxide-2-methoxyl) -1-butanol and 0.1429g of triphenylphosphine under the stirring state, keeping the temperature for reaction for 6 hours, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated polybutadiene liquid rubber.
Example 2:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated polybutadiene liquid rubber and 120.0g of tetrahydrofuran into a 500ml three-neck flask under the argon atmosphere, stirring to dissolve, heating to 60 ℃, adding 8.45g of hexamethylene diisocyanate under the stirring state, and carrying out heat preservation reaction for 3 hours to obtain an isocyanate-terminated polybutadiene liquid rubber solution;
step two: heating the prepared isocyanate-terminated polybutadiene liquid rubber solution to 90 ℃ under the argon atmosphere, adding 7.26g of methyl epoxy propanol and 0.9786g of dibutyltin diacetate under a stirring state, carrying out heat preservation reaction for 4 hours, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and carrying out rotary evaporation to obtain the epoxy-terminated polybutadiene liquid rubber.
Example 3:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated poly (styrene-butadiene) liquid rubber and 60.0g of toluene into a 500ml three-neck flask under argon atmosphere, stirring for dissolving, heating to 80 ℃, adding 66.16g of isophorone diisocyanate and 0.1862g of dibutyltin dilaurate under stirring, and carrying out heat preservation reaction for 2h to obtain an isocyanate-terminated poly (styrene-butadiene) liquid rubber solution;
step two: and cooling the prepared isocyanate-terminated poly (styrene-butadiene) liquid rubber solution to 50 ℃ in argon atmosphere, adding 23.15g of epoxy propanol under a stirring state, preserving heat for reaction for 5 hours, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated poly (styrene-butadiene) liquid rubber.
Example 4:
the method comprises the following steps: adding 60.0g of end hydroxyl poly-butyronitrile liquid rubber and 300.0g of xylene into a 500ml three-neck flask under argon atmosphere, stirring for dissolving, heating to 45 ℃, adding 37.36g of toluene diisocyanate and 0.5960g of triphenyl bismuth under stirring, and reacting for 4 hours under heat preservation to obtain an end isocyanate group poly-butyronitrile liquid rubber solution;
step two: heating the prepared isocyanate-terminated butyronitrile liquid rubber to 80 ℃ under argon atmosphere, adding 39.70g of 4- (ethylene oxide-2-methoxyl) -1-butanol under a stirring state, keeping the temperature for reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated butyronitrile liquid rubber.
Example 5:
the method comprises the following steps: adding 60.0g of end hydroxyl poly (styrene-butadiene) liquid rubber into a 500ml three-neck flask under argon atmosphere, reacting at 90 ℃, adding 4.01g of isophorone diisocyanate under a stirring state, and reacting for 8 hours under heat preservation to prepare an end isocyanate group poly (styrene-butadiene) liquid rubber solution, wherein an organic solvent can be absent, and no organic solvent is added in the embodiment;
step two: and (2) cooling the prepared isocyanate-terminated poly (styrene-butadiene) liquid rubber solution to 45 ℃ under the argon atmosphere, adding 0.55g of epoxy propanol and 0.1614g of dibutyltin dilaurate in a stirring state, keeping the temperature for reaction for 12 hours, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated poly (styrene-butadiene) liquid rubber.
Example 6:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated polyacrylonitrile-butadiene-acrylate liquid rubber and 150.0g of 1, 4-dioxane into a 500ml three-neck flask under the argon atmosphere, stirring for dissolving, heating to 65 ℃, adding 41.07g of toluene diisocyanate and 0.6277g of dibutyltin dilaurate under the stirring state, and carrying out heat preservation reaction for 4 hours to obtain an isocyanate-terminated polyacrylonitrile-butadiene-acrylate liquid rubber solution;
step two: and cooling the prepared isocyanate-terminated polyacrylonitrile-butadiene-acrylate liquid rubber solution to 60 ℃ under the argon atmosphere, adding 31.16g of methyl epoxy propanol under a stirring state, keeping the temperature for reaction for 8 hours, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated polyacrylonitrile-butadiene-acrylate liquid rubber.
Example 7:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated polybutadiene-isoprene liquid rubber and 90.0g of tetrahydrofuran into a 500ml three-neck flask under the argon atmosphere, stirring to dissolve, heating to 70 ℃, adding 41.31g of diphenylmethane diisocyanate and 0.9566g of triphenylphosphine under the stirring state, and reacting for 5 hours under the heat preservation condition to obtain an isocyanate-terminated polybutadiene-isoprene liquid rubber solution;
step two: heating the prepared isocyanate-terminated hydroxyl polybutadiene-isoprene liquid rubber to 80 ℃ under argon atmosphere, adding 16.29g of epoxy propanol under a stirring state, keeping the temperature for reaction for 4h, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated polybutadiene-isoprene liquid rubber.
Example 8:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated polybutadiene liquid rubber and 120.0g of tetrahydrofuran into a 500ml three-neck flask under the argon atmosphere, stirring to dissolve, heating to 60 ℃, adding 8.45g of hexamethylene diisocyanate under the stirring state, and carrying out heat preservation reaction for 3 hours to obtain an isocyanate-terminated polybutadiene liquid rubber solution;
step two: and cooling the prepared isocyanate-terminated polybutadiene liquid rubber solution to 30 ℃ under the argon atmosphere, adding 7.26g of methyl epoxy propanol and 0.9786g of dibutyltin diacetate under a stirring state, carrying out heat preservation reaction for 12h, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and carrying out rotary evaporation to obtain the epoxy-terminated polybutadiene liquid rubber.
Example 9:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated polybutadiene liquid rubber and 180.0g of xylene into a 500ml three-neck flask under argon atmosphere, stirring to dissolve, heating to 90 ℃, adding 10.14g of hexamethylene diisocyanate under stirring, and carrying out heat preservation reaction for 4 hours to obtain an isocyanate-terminated polybutadiene liquid rubber solution;
step two: and cooling the prepared isocyanate-terminated polybutadiene liquid rubber solution to 80 ℃ under the argon atmosphere, adding 30.87g of 4- (ethylene oxide-2-methoxyl) -1-butanol and 0.1405g of triphenylphosphine under the stirring state, keeping the temperature for reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid with ice water, and performing rotary evaporation to obtain the epoxy-terminated polybutadiene liquid rubber.
Example 10:
the method comprises the following steps: adding 60.0g of hydroxyl-terminated poly (styrene-butadiene) liquid rubber and 60.0g of toluene into a 500ml three-neck flask under argon atmosphere, stirring for dissolving, heating to 80 ℃, adding 66.16g of isophorone diisocyanate and 0.1862g of dibutyltin dilaurate under stirring, and carrying out heat preservation reaction for 2h to obtain an isocyanate-terminated poly (styrene-butadiene) liquid rubber solution;
step two: and cooling the prepared isocyanate-terminated poly (styrene-butadiene) liquid rubber solution to 50 ℃ under the argon atmosphere, adding 23.15g of epoxy propanol and 1.2565g of dibutyltin dilaurate under the stirring state, keeping the temperature for reaction for 2 hours, cooling the reaction liquid to room temperature after the reaction is finished, washing the reaction liquid by ice water, and performing rotary evaporation to obtain the epoxy-terminated poly (styrene-butadiene) liquid rubber.
Table 1: examples 1-examples 10 formulations and Processes
Table 2: examples 1-10 liquid rubber physical and chemical Properties of epoxy-terminated polybutadiene series
| Examples | Viscosity (40 ℃) is Pa.s | Epoxy value/mmol/g | Number average molecular weight |
| 1 | 7.35 | 1.694 | 4300 |
| 2 | 30.95 | 0.578 | 8200 |
| 3 | 3.78 | 4.983 | 428 |
| 4 | 14.89 | 2.607 | 5800 |
| 5 | 39.23 | 0.113 | 9800 |
| 6 | 4.52 | 3.854 | 1300 |
| 7 | 10.75 | 1.224 | 4800 |
| 8 | 18.34 | 0.228 | 6000 |
| 9 | Too high viscosity to measure | 1.624 | 11000 |
| 10 | Too high viscosity to measure | 4.502 | 2600 |
FIGS. 1 and 2 are comparative infrared images of isocyanate-terminated polybutadiene and epoxy-terminated polybutadiene obtained in example 1. As can be seen from FIG. 2, the wave number is 2270cm-1And the-NCO characteristic peak disappears before and after epoxy modification, so that the NCO group at the molecular chain end of the prepolymer at the molecular chain end of the isocyanate-terminated polybutadiene is judged to be completely converted into an epoxy group.
According to the embodiments 1, 2, 3, 4, 5, 6 and 7, the epoxy-terminated polybutadiene liquid rubber with a relatively low viscosity can be prepared by modifying the hydroxyl-terminated polybutadiene liquid rubber and introducing epoxy groups to both ends of the molecular chain of the hydroxyl-terminated polybutadiene liquid rubber by the preparation method provided by the invention, and the obtained epoxy-terminated polybutadiene liquid rubber has a number average molecular weight of 400-10000, an epoxy value of 0.1-5.0 mmol/g and a viscosity (40 ℃) of 3-40 Pa.s.
As can be seen from comparison of examples 1 and 9, if the amount of the epoxidizing agent added is too large, the post-treatment becomes difficult, and the excessive epoxidizing agent remaining in the system undergoes a side reaction to solidify the product, thereby losing fluidity; comparing example 2 with example 8, it can be seen that if the reaction temperature in step two is too low, the conversion efficiency of epoxy groups is affected, resulting in a lower epoxy group content; it can be seen from the comparison between examples 3 and 10 that, although the addition of the catalyst can accelerate the reaction rate, if the addition amount is too large, the reaction system will be crosslinked, and gelation will occur, and after post-treatment, the product viscosity is too high to be measured, which will greatly affect the application performance of the product.
The invention carries out chemical modification with definite structure on the terminal hydroxyl of the hydroxyl-terminated polybutadiene series liquid rubber, the prepared epoxy-terminated polybutadiene series liquid rubber product has good fluidity at room temperature or under slightly heating condition, the processing technology is stable, and the prepared final composite material has excellent mechanical property. The product is mainly used in the fields of adhesives, solid rubber reactive plasticizers, thermosetting resin toughening modifiers and the like, and particularly can be widely used in scenes such as composite solid propellants, gas generating agents, two-stage roll-control system adhesives, solid rubber reactive plasticizers, epoxy thermosetting resin toughening modifiers and the like.
The preparation method of the epoxy-terminated polybutadiene series liquid rubber provided by the embodiment of the invention has the advantages of simple process, adjustable end-terminating oxidation efficiency and better commercial application value. The prepared epoxy-terminated polybutadiene series liquid rubber has the characteristics of excellent water resistance, better fluidity, adhesiveness, toughness, better compatibility with other high polymers and the like.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It will be understood that the present application is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (10)
1. A method for preparing liquid rubber of epoxy-terminated polybutadiene series is characterized by comprising the following steps:
the method comprises the following steps: under an inert environment, mixing an organic solvent and hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber according to a mass ratio of (0-5):1, adding diisocyanate according to a r value of 2-5, and reacting to obtain an isocyanate-terminated polybutadiene homopolymer or copolymer liquid rubber solution, wherein the r value is the molar ratio of-NCO groups in the diisocyanate to-OH groups in the hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber;
step two: under an inert environment, adding an epoxidizing reagent into a liquid rubber solution of the terminated isocyanate polybutadiene homopolymer or copolymer according to the r 'value of 1-3 for reaction, washing and carrying out rotary evaporation on the reaction solution to obtain the terminated epoxy polybutadiene series liquid rubber, wherein the r' value is the molar ratio of-OH groups in the epoxidizing reagent to-NCO groups in the terminated isocyanate polybutadiene homopolymer or copolymer liquid rubber.
2. The method for preparing liquid rubber of polybutadiene series with terminal epoxy group according to claim 1, wherein in step one, the liquid rubber of polybutadiene homopolymer or copolymer with terminal hydroxyl group is selected from liquid rubber of butadiene homopolymer or copolymer containing hydroxyl group at both ends, the number average molecular weight is 200 to 10000, the hydroxyl value is 0.1 to 5.0mmol/g, and the general formula is: HO-R1-OH; in the formula, R1Is a hydroxyl-terminated polybutadiene homopolymer or copolymer liquid rubber main chain, and is selected from any one of polybutadiene, butadiene acrylonitrile copolymer, butadiene styrene copolymer, butadiene acrylic acid acrylonitrile copolymer, butadiene acrylate copolymer, butadiene-isoprene copolymer and products obtained by saturated hydrogenation of the synthetic rubber.
3. The method for preparing liquid rubber of the epoxy-terminated polybutadiene series according to claim 1, wherein in the first step, the organic solvent is any one of tetrahydrofuran, dimethyl sulfoxide, toluene, xylene, chlorobenzene, dichloromethane and 1, 4-dioxane.
4. A liquid rubber of the epoxy-terminated polybutadiene series according to claim 1The preparation method is characterized in that in the first step, the general formula of the diisocyanate is as follows: OCN-R2-NCO, wherein R2Is alkyl, aryl or alicyclic group, and is selected from any one of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI).
5. The method for preparing liquid rubber based on epoxy-terminated polybutadiene of claim 1, wherein in step two, the general structural formula of the epoxidizing agent is as follows:
in the formula, R3Is alkyl, aryl, alicyclic group or benzyl, and n is 0 or 1.
6. The method for preparing liquid rubber of polybutadiene series with terminal epoxy group as claimed in claim 1, wherein in the first step, in the reaction of adding diisocyanate, catalyst is added, and the ratio of the catalyst to the total mass of the liquid rubber solution of polybutadiene homopolymer or copolymer with terminal epoxy group is (0-0.5): 100.
7. the method for preparing liquid rubber of polybutadiene series with terminal epoxy group according to claim 1, wherein in step two, in the reaction of adding the epoxidizing agent to the liquid rubber solution of polybutadiene homopolymer or copolymer with terminal isocyanate group according to the r' value of 1-3, a catalyst is also added, and the ratio of the catalyst to the total mass of the liquid rubber solution of polybutadiene homopolymer or copolymer with terminal isocyanate group is (0-0.5): 100.
8. the method for preparing liquid rubber of the epoxy-terminated polybutadiene series according to claim 1, wherein said catalyst is selected from any one of organometallic catalysts, organic bases and organic acid catalysts.
9. The process for preparing liquid rubbers of the type based on epoxy-terminated polybutadiene according to claim 1, wherein the reaction vessel is replaced several times with inert gas/vacuum and the reaction mixture is introduced under inert conditions.
10. The method for preparing liquid rubber of terminal-epoxy polybutadiene series according to claim 1, wherein the reaction temperature in said reactor is 45-90 ℃, the reaction time in step one is 1-8 hours, and the reaction time in step two is 2-12 hours.
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| CN1978493A (en) * | 2005-12-05 | 2007-06-13 | 中国石油天然气集团公司 | Method for synthesizing liquid rubber-epoxy resin polymer |
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| CN110330625A (en) * | 2019-05-28 | 2019-10-15 | 西北矿冶研究院 | Hydroxyl-terminated liquid rubber-polyurethane modified epoxy resin polymer and preparation method thereof |
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| CN1978493A (en) * | 2005-12-05 | 2007-06-13 | 中国石油天然气集团公司 | Method for synthesizing liquid rubber-epoxy resin polymer |
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