CN112480295A - Preparation method of carboxyl-terminated telechelic liquid rubber - Google Patents

Preparation method of carboxyl-terminated telechelic liquid rubber Download PDF

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CN112480295A
CN112480295A CN202011438256.2A CN202011438256A CN112480295A CN 112480295 A CN112480295 A CN 112480295A CN 202011438256 A CN202011438256 A CN 202011438256A CN 112480295 A CN112480295 A CN 112480295A
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peroxide
isoprene
carboxyl
acrylonitrile
liquid rubber
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齐永新
吕徳斌
胡盼
张芬铭
朱月
朵生亮
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Tianyuan Hangzhou New Material Technology Co ltd
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Tianyuan Hangzhou New Material Technology Co ltd
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    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08—Isoprene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical

Abstract

The application discloses a preparation method of carboxyl-terminated telechelic liquid rubber, which comprises the following steps: adding a polar hydrocarbon solvent and diacid peroxide into a preparation tank according to the mass ratio of (5-10) to 1 to prepare an initiator solution, adding the initiator solution, and stirring until the diacid peroxide is completely dissolved in the polar hydrocarbon solvent to obtain a diacid peroxide initiator solution; adding a polymerization monomer and the diacid peroxide initiator solution into a pressure-resistant reactor for reaction, removing an upper layer solvent of reactants through sedimentation and layering, and then washing and drying to obtain the carboxyl-terminated telechelic liquid rubber, wherein the polymerization monomer is isoprene, or the polymerization monomer is isoprene and acrylonitrile mixed copolymerization, or the polymerization monomer is isoprene, acrylonitrile and butadiene mixed copolymerization. The carboxyl-terminated telechelic polymer has the characteristics of single functional group type, regular molecular chain structure and average functionality close to 2, and has good industrial application prospect.

Description

Preparation method of carboxyl-terminated telechelic liquid rubber
Technical Field
The application relates to the field of preparation of terminal functional group polymers, in particular to a preparation method of carboxyl-terminated telechelic liquid rubber.
Background
The carboxyl-terminated telechelic liquid rubber is a liquid polymer with active carboxyl at the tail end of a molecular main chain. Carboxyl-terminated polyisoprene homopolymer, carboxyl-terminated polyisoprene-acrylonitrile copolymer and hydroxyl-terminated polyisoprene-acrylonitrile-butadiene copolymer are all liquid rubbers, and flowability and molecular main chain tail ends and functional groups in molecules thereof under room temperature or heating conditions endow the liquid rubbers with excellent mechanical properties and processing technological properties. The product is mainly used as an adhesive of a two-stage roll control system of a solid composite propellant and a gas generating agent, a solid rubber reaction type plasticizer, a toughening modifier of thermosetting resin such as epoxy and the like, and the like.
The synthesis method of the carboxyl-terminated telechelic polymer mainly comprises anionic polymerization and free radical polymerization.
The anionic polymerization is a polymerization reaction initiated by an alkali metal or an alkyl alkali metal catalyst with a carboxyl protecting group, and the prepared polymer has C carried at the chain end-·M+The counter particle pair is reactive and reacts with different monomers to form telechelic polymers of different end groups, and british patent GB1029451A and GB972246A disclose the addition of carbon dioxide or a dianhydride to the active end of the polymer to form a carboxyl-terminated telechelic polymer. The carboxyl-terminated polymer synthesized by the anionic polymerization method has very strict requirements on the purity of raw materials and process precision, and the average functionality of the polymer is reduced by the compatibility of an initiator and a solvent and the 'pseudo gel' formed in the end-capping process of the carboxyl-terminated polymer, so the method is less in industrial use.
The free radical polymerization method of the carboxyl-terminated telechelic liquid rubber reported at present mainly comprises emulsion polymerization and solution polymerization, wherein free radical emulsion polymerization such as U.S. Pat. No. 4, 3292289A and U.S. Pat. No. 3, 3440292A disclose that cyclohexanone peroxide is used as an initiator, ferrous sulfate is used as a reducing agent, a nonionic emulsifier is used, the source of carboxyl is rearranged with 1-hydroxycyclohexyloxy to generate a free radical of caproic acid, the method has troublesome post-treatment emulsification system, and high-purity polymers are difficult to obtain. Free radical solution polymerization such as German patent DE1150205B and US patent US3285949A disclose a method for synthesizing carboxyl-terminated polymers using symmetric 4,4 '-azo-bis- (4-nitrilo acid) as an initiator and methanol or tert-butanol as a solvent, wherein dithiodiglycolic acid is added as a carboxyl regulator in addition to the 4, 4' -azo-bis- (4-nitrilo acid) initiator to obtain polymers with high carboxyl content, and the type of carboxyl is relatively complex, which affects the processing technology and mechanical properties.
Disclosure of Invention
The method is used for preparing carboxyl-terminated telechelic liquid rubber by using diacid peroxides with symmetrical structures as initiators to initiate monomers, so as to solve the problems of low glass transition temperature (Tg), poor temperature resistance, poor compatibility with SIS, poor adhesion between rubber and metal and poor adhesion between metal and fiber of the existing carboxyl-terminated telechelic liquid rubber products.
According to the embodiment of the application, the preparation method of the carboxyl-terminated telechelic liquid rubber comprises the following steps: polar hydrocarbon solvent and diacid peroxide are mixed according to the mass ratio of (5-10): 1, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the diacid peroxide is completely dissolved in the polar hydrocarbon solvent to obtain a diacid peroxide initiator solution; adding a polymerization monomer and the diacid peroxide initiator solution into a pressure-resistant reactor for reaction, removing an upper layer solvent of reactants through sedimentation and layering, and then washing and drying to obtain the carboxyl-terminated telechelic liquid rubber, wherein the polymerization monomer is isoprene, or the polymerization monomer is isoprene and acrylonitrile mixed copolymerization, or the polymerization monomer is isoprene, acrylonitrile and butadiene mixed copolymerization.
Preferably, the polar hydrocarbon solvent is selected from one or more of methanol, absolute ethanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene and toluene.
Preferably, the diacid peroxide is selected from the group consisting of n-glutaric peroxide, n-butyl peroxide, n-hexyl peroxide, iso-butyl peroxide, and iso-pentyl peroxide.
Preferably, when the polymerization monomer is mixed copolymerization of isoprene and acrylonitrile, the mass ratio of isoprene to acrylonitrile is (99-60) to (1-40).
Preferably, when the monomer is isoprene, acrylonitrile and butadiene, the mass ratio of isoprene, acrylonitrile and butadiene is any ratio.
Preferably, when the monomer is isoprene, acrylonitrile and butadiene, the mass ratio of the isoprene, the acrylonitrile and the butadiene is (1-59): (1-40): (98-1).
Preferably, the pressure-resistant reactor is replaced several times with nitrogen/vacuum, and the reaction mass is added after the reactor is brought to a negative pressure.
Preferably, the reaction temperature of the pressure-resistant reactor is 90 to 120 ℃.
Preferably, the reaction time of the pressure-resistant reactor is 2 to 10 hours.
It should be noted that the polymerization monomers isoprene, acrylonitrile, and butadiene may be added at one time, added multiple times, or added continuously. The continuous addition of the acrylonitrile can be constant-speed continuous addition or continuous descending addition.
The diacid peroxide initiator solution can be added at one time, can be added for multiple times, and can be continuously added. The continuous addition of the diacid peroxide initiator solution can be constant-speed continuous addition or continuous descending addition.
The carboxyl-terminated telechelic liquid rubber obtained by the preparation method has the following structural general formula:
Figure BDA0002821398990000031
wherein R is1、R2Is straight-chain alkane with 2-6 carbon atoms, R1、R2May be the same or different; m is a polymerization monomer, and M can be a monomer or 2-3 monomers; n is the polymerization degree of the monomer, and n is 10-200.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
from the above examples, it can be seen that the carboxyl-terminated telechelic polymer of the present application has the characteristics of polar functional groups, regular molecular chain structure, and high carboxyl value. The carboxyl-terminated polyisoprene liquid rubber, the carboxyl-terminated polyisoprene-acrylonitrile liquid rubber and the carboxyl-terminated polyisoprene-acrylonitrile-butadiene liquid rubber have the molecular chain segment mainly comprising isoprene, so that the glass transition temperature (Tg) of the liquid rubber is increased, the liquid rubber is favorable for use at higher temperature and the temperature resistance is improved; meanwhile, the structure of isoprene in the molecular chain is similar to that in the SIS molecular chain, and the isoprene is easily compatible with the SIS; and finally, as the terminal of the molecular chain has the telechelic carboxyl, the adhesion between rubber and metal and between metal and fiber is enhanced, and the polarity is stronger and the adhesion is better under the condition of introducing acrylonitrile into the molecular chain. Has good industrial application prospect in the aspects of solid rubber reaction type plasticization, SIS modification, adhesion of metal, rubber and fiber, toughening modification of thermosetting resin such as epoxy resin 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.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present application.
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:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and 13Kg of glutaric acid peroxide absolute ethyl alcohol solution into a pressure-resistant reactor for reaction, wherein the glutaric acid peroxide absolute ethyl alcohol solution is continuously added at a constant speed, the reaction temperature is 115 ℃, the reaction time is 6 hours, reactants are settled and layered to remove an upper layer solvent, and then the carboxyl-terminated telechelic liquid rubber is obtained by washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 2:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and acrylonitrile (the ratio IS/AN IS 9.9/0.1) and 13Kg of glutaric acid peroxide absolute ethanol solution into a pressure-resistant reactor for reaction, wherein the acrylonitrile IS added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 115 ℃, the reaction time IS 6 hours, reactants are settled and layered to remove AN upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 3:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and acrylonitrile (the ratio IS/AN IS 9.15/0.85) and 13Kg of glutaric acid peroxide absolute ethanol solution into a pressure-resistant reactor for reaction, wherein the acrylonitrile IS added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 115 ℃, the reaction time IS 6 hours, reactants are settled and layered to remove AN upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 4:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and acrylonitrile (the ratio IS/AN IS 8.65/1.35) and 13Kg of glutaric acid peroxide absolute ethanol solution into a pressure-resistant reactor for reaction, wherein the acrylonitrile IS added at one time, the glutaric acid peroxide absolute ethanol solution IS added at a constant speed and gradually decreased (the later hour IS 85% of the former hour), the reaction temperature IS 115 ℃, the reaction time IS 6 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by water washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 5:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and acrylonitrile (the ratio IS/AN IS 8.0/2.0) and 13Kg of glutaric acid peroxide absolute ethanol solution into a pressure-resistant reactor for reaction, wherein the acrylonitrile IS continuously added at a constant speed, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 115 ℃, the reaction time IS 6 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 6:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and acrylonitrile (the ratio IS/AN IS 7.5/2.5) and 13Kg of glutaric acid peroxide absolute ethanol solution into a pressure-resistant reactor for reaction, wherein the acrylonitrile IS added at a constant speed in a descending manner (the latter hour IS 80% of the former hour), the glutaric acid peroxide absolute ethanol solution IS added at a constant speed in a descending manner (the latter hour IS 85% of the former hour), the reaction temperature IS 115 ℃, the reaction time IS 6 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by water washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 7:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1:7, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene and acrylonitrile (the ratio IS/AN IS 6.0/4.0) and 13Kg of glutaric acid peroxide absolute ethanol solution into a pressure-resistant reactor for reaction, wherein the acrylonitrile IS added at a constant speed in a descending manner (the latter hour IS 80% of the former hour), the glutaric acid peroxide absolute ethanol solution IS added at a constant speed in a descending manner (the latter hour IS 85% of the former hour), the reaction temperature IS 115 ℃, the reaction time IS 6 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by water washing and drying.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Examples 1-7 polymerization monomer ratios, glutaric acid peroxide absolute ethanol solution addition mode, acrylonitrile addition mode and polymer physicochemical properties are shown in Table 1.
TABLE 1 monomer ratio, raw material addition mode and polymer physicochemical properties
Figure BDA0002821398990000071
Figure BDA0002821398990000081
Figure BDA0002821398990000091
As can be seen from Table 1, the carboxyl-terminated telechelic liquid rubber finally synthesized in examples 1-7 has a number average molecular weight of 1206-2880; the carboxyl value is 0.70-0.96 mmol/g; the viscosity (40 ℃) is 6.3 to 62.1 Pa.s; bound acrylonitrile can be between 0-31%; the Tg is between-32 ℃ and-66 ℃. The liquid rubber with the above performance is obtained, and the monomer can be isoprene or isoprene and acrylonitrile; the initiator solution can be continuously added at a constant speed or gradually added at a constant speed; the acrylonitrile can be added in a one-time, constant-speed, continuous and constant-speed descending manner.
Example 8:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 1/1/98) and 11Kg of glutaric acid peroxide absolute ethyl alcohol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added in a one-step mode, the glutaric acid peroxide absolute ethyl alcohol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled, layered and removed of AN upper layer solvent, and then water washing and drying are carried out to obtain the carboxyl-terminated telechelic liquid rubber. The resulting polymer had a molecular weight of 4200, a carboxyl value of 0.67mmol/g, a viscosity (40 ℃ C.) of 14.6 pas, a bound acrylonitrile content of 1.1%, a bound isoprene content of 0.97%, and a Tg of-75 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 9:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 2.5/1.0/6.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The molecular weight of the obtained polymer is 3500, the carboxyl value is 0.73mmol/g, the viscosity (40 ℃) is 11.2 Pa.s, the bound acrylonitrile content is 10.1 percent, the bound isoprene content is 22.3 percent, and the Tg is-62 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 10:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 2.5/2.0/5.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The obtained polymer had a molecular weight of 3200, a carboxyl value of 0.70mmol/g, a viscosity (40 ℃ C.) of 21.3 pas, a bound acrylonitrile content of 20.5%, a bound isoprene content of 23.2%, and a Tg of-49 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 11:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 4.5/1.0/4.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The obtained polymer had a molecular weight of 2500, a carboxyl value of 0.80mmol/g, a viscosity (40 ℃ C.) of 25.3 pas, a bound acrylonitrile content of 9.8%, a bound isoprene content of 42.0%, and a Tg of-56 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 12:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 4.5/1.0/4.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 90 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The resulting polymer had a molecular weight of 3100, a carboxyl group value of 0.75mmol/g, a viscosity (40 ℃ C.) of 21 pas, a bound acrylonitrile content of 9.9%, a bound isoprene content of 43.0%, and a Tg of-56 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 13:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 4.5/1.0/4.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 120 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The obtained polymer had a molecular weight of 2300, a carboxyl value of 0.82mmol/g, a viscosity (40 ℃ C.) of 30.0 pas, a bound acrylonitrile content of 10.1%, a bound isoprene content of 44.0%, and a Tg of-55 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 14:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 4.5/1.0/4.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 2 hours, reactants are settled and layered to remove AN upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The resulting polymer had a molecular weight of 2200, a carboxyl value of 0.81mmol/g, a viscosity (40 ℃ C.) of 17 pas, a bound acrylonitrile content of 11.0%, a bound isoprene content of 42.0%, and a Tg of-54 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 15:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 4.5/1.0/4.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 10 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The obtained polymer had a molecular weight of 2600, a carboxyl value of 0.85mmol/g, a viscosity (40 ℃ C.) of 46 Pa.s, a bound acrylonitrile content of 9.5%, a bound isoprene content of 41.0%, and a Tg of-55 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 16:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 4.5/2.0/3.5) and 11Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The resulting polymer had a molecular weight of 2416, a carboxyl value of 0.78mmol/g, a viscosity (40 ℃ C.) of 29.6 pas, a bound acrylonitrile content of 19.9%, a bound isoprene content of 43.5%, and a Tg of-47 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 17:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 5, adding the initiator solution into a preparation tank to prepare an initiator solution, and stirring the initiator solution after adding until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 5.8/1.0/3.2) and 7Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The resulting polymer had a molecular weight of 1836, a carboxyl value of 0.86mmol/g, a viscosity (40 ℃ C.) of 25.4 pas, a bound acrylonitrile content of 8.9%, a bound isoprene content of 56.2%, and a Tg of-59 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 18:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 10, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 5.8/2.0/2.2) and 16Kg of glutaric acid peroxide absolute ethanol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added at one time, the glutaric acid peroxide absolute ethanol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled and layered to remove the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by washing and drying. The obtained polymer had a molecular weight of 1750, a carboxyl value of 0.92mmol/g, a viscosity (40 ℃) of 33.5 pas, a bound acrylonitrile content of 18.8%, a bound isoprene content of 55.7% and a Tg of-40 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Example 19:
mixing glutaric acid peroxide and absolute ethyl alcohol according to a mass ratio of 1: 6, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the peroxyglutaric acid is completely dissolved in the solvent to obtain a peroxyglutaric acid absolute ethyl alcohol solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio IS/AN/Bd IS 59/40/1) and 11Kg of glutaric acid peroxide absolute ethyl alcohol solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene, the acrylonitrile and the butadiene are added in a one-step mode, the glutaric acid peroxide absolute ethyl alcohol solution IS continuously added at a constant speed, the reaction temperature IS 110 ℃, the reaction time IS 4 hours, the reactant IS settled, layered and removed of AN upper layer solvent, and then water washing and drying are carried out to obtain the carboxyl-terminated telechelic liquid rubber. The resulting polymer had a molecular weight of 1506, a carboxyl value of 0.69mmol/g, a viscosity (40 ℃ C.) of 62 pas, a bound acrylonitrile content of 32%, a bound isoprene content of 67%, and a Tg of-35 ℃.
In this embodiment, the absolute ethanol may be replaced by any one or a mixture of any two or more of methanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene, and toluene. The glutaric acid peroxide in this embodiment may be replaced with any one of n-butyl diacid peroxide, n-hexyl diacid peroxide, ethylsuccinic acid peroxide, or isopentyl diacid peroxide.
Comparative example 1:
adding an absolute ethyl alcohol solution (4,4 '-azo-bis- (4-nitrile valeric acid)) of 4, 4' -azo-bis- (4-nitrile valeric acid and absolute ethyl alcohol into a preparation tank according to the mass ratio of 1:7.5 to prepare an initiator solution, and stirring after adding until the absolute ethyl alcohol solution (4,4 '-azo-bis- (4-nitrile valeric acid)) of 4, 4' -azo-bis- (4-nitrile valeric acid) is completely dissolved in the absolute ethyl alcohol to obtain an initiator solution;
adding 10Kg of isoprene and 8.0Kg of the initiator solution into a 50L pressure-resistant reactor for reaction, wherein 10Kg of isoprene is added in a one-time manner, the initiator solution is added uniformly and continuously, the reaction temperature is 110 ℃, the reaction time is 6 hours, the upper layer solvent of reactants is removed by settling and layering, and the carboxyl-terminated telechelic liquid rubber is obtained by washing and drying. The molecular weight of the obtained polymer was 4000, the carboxyl group value was 0.41mmol/g, and the viscosity (40 ℃ C.) was 14.0 pas.
Comparative example 2:
adding a methanol solution (4,4 '-azo-bis- (4-nitrilo valeric acid) of 4, 4' -azo-bis- (4-nitrilo valeric acid) and methanol into a preparation tank according to the mass ratio of 1:7.5 to prepare an initiator solution, and stirring after adding until the methanol solution (4,4 '-azo-bis- (4-nitrilo valeric acid) of 4, 4' -azo-bis- (4-nitrilo valeric acid) is completely dissolved in the methanol to obtain an initiator solution;
adding 10Kg (IS/AN IS 8.5:1.5) of isoprene and acrylonitrile and 13.0Kg of the initiator solution into a 50L pressure-resistant reactor for reaction, wherein the isoprene and the acrylonitrile are added in a one-step mode, the initiator solution IS added uniformly and continuously, the reaction temperature IS 110 ℃, the total reaction time IS 4 hours, 2.0Kg of methanol solution of dithiodiglycolic acid (the mass ratio of dithiodiglycolic acid to methanol IS 1:7.5) IS added in one step after 3.5 hours of reaction, the reactants are settled and layered to remove the upper solvent, and then the carboxyl-terminated claw liquid rubber IS obtained by remote washing and drying. The resulting polymer had a molecular weight of 2000, a carboxyl group value of 0.53mmol/g, a viscosity (40 ℃ C.) of 21.3 pas and a bound acrylonitrile content of 15.8%.
Comparative example 3:
adding a methanol solution of 4,4 '-azo-bis- (4-nitrilo valeric acid) (4, 4' -azo-bis- (4-nitrilo valeric acid) and methanol into a preparation tank according to the mass ratio of 1:7.5 to prepare an initiator solution, and stirring after adding until the methanol solution of 4,4 '-azo-bis- (4-nitrilo valeric acid) (4, 4' -azo-bis- (4-nitrilo valeric acid) is completely dissolved in the methanol to obtain an initiator solution;
adding 10Kg of isoprene, acrylonitrile and butadiene (the ratio Bd/IS/AN IS 6.2/2.5/1.0) and 13.0Kg of the initiator solution into a 50L pressure-resistant reactor for reaction, wherein the 10Kg of isoprene, acrylonitrile and butadiene are added in a one-step mode, the initiator solution IS added uniformly and continuously, the reaction temperature IS 110 ℃, the total reaction time IS 6 hours, the reactants are settled, layered and removed of the upper layer solvent, and the carboxyl-terminated telechelic liquid rubber IS obtained by water washing and drying. The molecular weight of the obtained polymer was 2400, the carboxyl value was 0.55mmol/g, the viscosity (40 ℃ C.) was 24.0 pas, the bound acrylonitrile content was 10.2%, and the isoprene content was 23.6%.
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 disclosed herein. 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 that have been described above 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 preparation method of carboxyl-terminated telechelic liquid rubber is characterized by comprising the following steps:
polar hydrocarbon solvent and diacid peroxide are mixed according to the mass ratio of (5-10): 1, adding the mixture into a preparation tank to prepare an initiator solution, and stirring the mixture after adding the initiator solution until the diacid peroxide is completely dissolved in the polar hydrocarbon solvent to obtain a diacid peroxide initiator solution;
adding a polymerization monomer and the diacid peroxide initiator solution into a pressure-resistant reactor for reaction, removing an upper layer solvent of reactants through sedimentation and layering, and then washing and drying to obtain the carboxyl-terminated telechelic liquid rubber, wherein the polymerization monomer is isoprene, or the polymerization monomer is isoprene and acrylonitrile mixed copolymerization, or the polymerization monomer is isoprene, acrylonitrile and butadiene mixed copolymerization.
2. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein the polar hydrocarbon solvent is selected from one or more of methanol, absolute ethanol, n-propanol, isopropanol, tert-butanol, tetrahydrofuran, acetone, benzene and toluene.
3. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein the diacid peroxide is selected from n-glutaric peroxide, n-butyl diacid peroxide, n-hexyl diacid peroxide, iso-butyl diacid peroxide and isoprene peroxide.
4. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein when the polymerized monomers are isoprene and acrylonitrile, the mass ratio of isoprene to acrylonitrile is (99-60) to (1-40).
5. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein when the monomer is isoprene, acrylonitrile and butadiene, the mass ratio of isoprene, acrylonitrile and butadiene is any ratio.
6. The method of claim 5, wherein when the monomer is isoprene, acrylonitrile, and butadiene, the mass ratio of isoprene, acrylonitrile, and butadiene is (1-59): (1-40): (98-1).
7. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein the pressure-resistant reactor is replaced with nitrogen gas/vacuum for a plurality of times, and the reaction materials are added after the reactor is in a negative pressure state.
8. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein the reaction temperature of the pressure-resistant reactor is 90-120 ℃.
9. The method for preparing carboxyl-terminated telechelic liquid rubber according to claim 1, wherein the reaction time of the pressure-resistant reactor is 2-10 hours.
10. The preparation method of the carboxyl-terminated telechelic liquid rubber according to claim 1, wherein the feeding mass ratio of the polymerization monomer to the diacid peroxide initiator solution is 10: (7-16).
CN202011438256.2A 2020-12-07 2020-12-07 Preparation method of carboxyl-terminated telechelic liquid rubber Pending CN112480295A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276479A (en) * 2021-12-22 2022-04-05 天元(杭州)新材料科技有限公司 Preparation method of carboxyl-terminated liquid rubber

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB945713A (en) * 1959-11-13 1964-01-08 Thiokol Chemical Corp Polymer and method of making the same
US3285949A (en) * 1964-04-17 1966-11-15 Goodrich Co B F Carboxyl-terminated butadiene polymers prepared in tertiary butanol with bis-azocyano acid initiation
US3969326A (en) * 1973-09-28 1976-07-13 Bp Chemicals International Limited Carboxyl terminated polychloroprenes and compositions containing them
JPS53133253A (en) * 1977-04-27 1978-11-20 Denki Kagaku Kogyo Kk Curable liquid polymer composition
US20020103320A1 (en) * 1998-03-26 2002-08-01 Martin Melchiors Process for the production of telechelic substances, telechelic substances produced in this manner and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB945713A (en) * 1959-11-13 1964-01-08 Thiokol Chemical Corp Polymer and method of making the same
US3285949A (en) * 1964-04-17 1966-11-15 Goodrich Co B F Carboxyl-terminated butadiene polymers prepared in tertiary butanol with bis-azocyano acid initiation
US3969326A (en) * 1973-09-28 1976-07-13 Bp Chemicals International Limited Carboxyl terminated polychloroprenes and compositions containing them
JPS53133253A (en) * 1977-04-27 1978-11-20 Denki Kagaku Kogyo Kk Curable liquid polymer composition
US20020103320A1 (en) * 1998-03-26 2002-08-01 Martin Melchiors Process for the production of telechelic substances, telechelic substances produced in this manner and use thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOHNR.EBDON: "SYNTHESISOF NEW TELECHELIC OLIGOMERSAND MACRO MONOMERS BY "CONSTRUCTIVE DEGRADATION"", 《MACROMOL. SYMP.》 *
TAKAYUKIOTSU等: "SYNTHESIS OF TELECHELIC POLYMERS THROUGH RADICAL POLYMERIZATION WITH A TWO-COMPONENT INIFERTER SYSTEM", 《EUR. POLYM. J.》 *
卞新声: "端羧基聚丙烯酸正丁酯改性环氧树脂的结构与性能 ", 《中国胶粘剂》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276479A (en) * 2021-12-22 2022-04-05 天元(杭州)新材料科技有限公司 Preparation method of carboxyl-terminated liquid rubber

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