CN115505054A - Modified epoxidized rubber and preparation method and application thereof - Google Patents
Modified epoxidized rubber and preparation method and application thereof Download PDFInfo
- Publication number
- CN115505054A CN115505054A CN202211149119.6A CN202211149119A CN115505054A CN 115505054 A CN115505054 A CN 115505054A CN 202211149119 A CN202211149119 A CN 202211149119A CN 115505054 A CN115505054 A CN 115505054A
- Authority
- CN
- China
- Prior art keywords
- epoxidized
- ether
- rubber
- modified
- polyether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/40—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with epoxy radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Abstract
The invention provides a modified epoxidized rubber, and a preparation method and application thereof. The modified epoxidized rubber comprises the following components in parts by weight: epoxidized rubbers or epoxidized elastomers and polyether compounds; the polyether compound is one or more of polyether alcohols, polyether amines, polyether carboxylic acids, polyether sulfydryl and polyether epoxy. According to the invention, epoxy bond open-loop graft modification is carried out on the epoxidized rubber or the epoxidized elastomer through the polyether compound, so that the polarity of the epoxidized rubber or the epoxidized elastomer is reduced, the molecular chain flexibility is improved, particularly the glass transition temperature Tg of the modified epoxidized rubber or the epoxidized elastomer can be reduced, a stable bond is formed through epoxy bond open-loop, a stable structure is introduced into a side chain, and the temperature resistance of the epoxidized rubber is improved.
Description
Technical Field
The invention relates to the field of rubber modification, and particularly relates to modified epoxidized rubber, and a preparation method and application thereof.
Background
Rubber has been used in various fields including products, tires, adhesives, vibration damping, and conveyor belts. Sources of rubber products include natural rubber from plants (cis and trans) and synthetic rubber from petroleum. In recent years, petrochemical resources are used excessively, so that the petrochemical resources are in danger of being exhausted, and the petrochemical resources also cause emission of a large amount of carbon dioxide when being used, thereby causing global warming. Researchers engaged in the rubber industry are constantly searching for alternative products for preparing synthetic rubber from petrochemical resources.
The natural plant resources can be recycled, and the natural rubber produced from the plant resources has good strength, wear resistance and resilience, which causes continuous attention of researchers. However, compared with synthetic rubber prepared from petrochemical resources, natural rubber has no advantages in the aspects of weather resistance, ozone resistance, flame retardance, damping property, polarity and the like, and in order to reduce rolling resistance and improve wet skid resistance, special functional auxiliary oil and resin are used in the semi-steel tread at present, white carbon black is selected as a filler, and the materials have polarity and are poor in compatibility with the natural rubber.
The double bond epoxidation of natural rubber is explored by researchers in the rubber industry aiming at compatibility and polarity. The epoxidized natural rubber has excellent oil resistance, air tightness resistance, damping characteristic, good adhesiveness and good wet skid resistance due to polar epoxy bonds, and the epoxy bonds can perform chemical reaction with hydroxyl on the surface of the white carbon black to form physical hydrogen bonds, so that the dispersion of the white carbon black is improved. The epoxidized natural rubber can effectively solve the problems of polarity and compatibility of the natural rubber for replacing synthetic rubber of petrochemical resources.
The epoxidation of natural rubber can be carried out in a solution or latex system, the solution method is to dissolve dry rubber in an organic solvent to prepare a solution with a certain concentration and then carry out epoxidation, but the solvent method has low yield, high energy consumption and environmental pollution, and is not suitable for industrial production. The latex method is simple to operate, easy to obtain products, free of environmental pollution and stable in reaction, and therefore is an accepted mode generally adopted at present. However, the existing technology for producing epoxidized natural rubber by a latex method has the problems of excessive acid addition, unstable epoxy bonds and more ring-opening byproducts, and molecular chains of natural rubber can be broken under the condition of a large amount of acid, so that the molecular weight and the glass transition temperature are influenced, excessive acid needs to be treated by alkali, a large amount of waste water is inevitably generated, and the environment is polluted.
The product prepared by the prior patent technology has the problems of large amount of acid used in the process and inaccurate temperature control, more ring-opening byproducts and poor stability and thermal aging resistance of the final product. In the preparation process of the epoxidized natural rubber, the unsaturated carbon-carbon double bond can be epoxidized by adopting peroxy acid under the acidic condition or adopting peroxide under the alkaline condition theoretically, but for adopting a water-based latex system, the reaction system (1) is suitable for a water medium and has certain stability; (2) The reaction rate and the reaction intensity are moderate, and the reaction temperature is easy to control; (3) The reaction system has fewer byproducts and does not influence the application performance; (4) The reaction is easy to terminate, the main product is separated, the post-treatment is convenient, the residue has no influence on the performance of the product, and the method is difficult, and no method can simultaneously meet the four conditions at present.
The epoxidized natural rubber can improve the defects of natural rubber replacing synthetic rubber of petrochemical resources, but the epoxidized products of natural rubber provided by the prior art have the problems of unstable epoxy bonds, and the defects of poor thermal aging resistance and the glass transition temperature Tg of the epoxidized natural rubber which is far higher than that of the natural rubber are also existed, which is caused by the change of the thermal stability of molecular chain structure and epoxy bonds after the natural rubber is epoxidized. However, with the current research and investigation, researchers do not study on the reduction of the glass transition temperature and the thermal aging resistance of the epoxidized natural rubber, and the glass transition temperature Tg is higher than that of the natural rubber, so that the application range of the epoxidized natural rubber is still limited, and the epoxidized natural rubber can only be used in special products with relaxed temperature requirements, and the application of the epoxidized natural rubber is greatly limited.
Therefore, it is a problem to be solved if the increase in glass transition temperature and the decrease in heat aging resistance of epoxidized natural rubber are improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a modified epoxidized rubber and a preparation method and application thereof. According to the invention, an epoxy bond and flexible side chain ring-opening grafting reaction is designed based on the polarity of an epoxy bond of the epoxidized rubber/epoxidized elastomer, so that the polarity of the epoxidized rubber/epoxidized elastomer is reduced, and a certain amount of flexible side chain is introduced to reduce the glass transition temperature Tg of the epoxidized rubber/epoxidized elastomer, thereby improving the heat-resistant aging performance, improving the compatibility with non-polar materials and widening the application range of the epoxidized natural rubber.
The method is realized by the following technical scheme:
the modified epoxidized rubber comprises the following components in parts by weight:
epoxidized rubber or epoxidized elastomer;
a polyether compound.
Further, the polyether compound is one or more of polyether alcohols, polyether amines, polyether carboxylic acids, polyether sulfydryl and polyether epoxy. The polyether compound and epoxy bonds in the epoxidized rubber or the epoxidized elastomer are subjected to ring-opening grafting reaction, so that the epoxidized rubber or the epoxidized elastomer is grafted with flexible side chains with polarity, certain epoxy bonds and polarity are reserved, and meanwhile, the flexible side chains can play a role in improving flexibility of molecular chains of the rubber or the epoxidized elastomer, so that the glass transition temperature of the epoxidized rubber or the epoxidized elastomer is reduced.
<xnotran> , , , , , (1- -2- ) , , ,2- , , ,1,4- ,1,3- , , (2- ) , , , , , , , , -1,4- , , , , , , , , , , ,4- , , , , , , , alpha- -omega- - ,1,2,3- , , (2- ) , , , alpha- (2- -1- -2- -1- ) -omega- - , , </xnotran> <xnotran> , alpha- -omega- - , (2- ) , , , , (3- ) ,1,2- -1- , , , , , , , , , , 300 -, ,1,3- -2- , (2- ) , , , , , , , , , ( ) , , -3, -5, , , , , (2- ) , , , , , -10 , , , </xnotran> 2, 2-bis (allyloxymethyl) -1-butanol, propanetrimetanol monoallyl ether, C16-18 alcohol polyoxyethylene ether, C12-C14 fatty alcohol polyoxyethylene polyoxypropylene ether, C12-C15 fatty alcohol polyoxyethylene polyoxypropylene ether, C11-C15 secondary alcohol polyoxyethylene polyoxypropylene ether, C8-C10 fatty alcohol polyoxyethylene polyoxypropylene ether, 1-glycerol octyl ether, 2-hydroxyethyl 2-chloroethyl sulfide, polyoxyethylene-20 isohexadecyl ether, glycerol monoisooctyl ether, ethylene glycol mono (1, 1-dipropylbutyl) ether, branched octylphenol polyethylene glycol polypropylene glycol monoether, polyglycerol-2 oil ether, C8-10 fatty alcohol polyoxyethylene ether, C12-C15 fatty alcohol polyoxypropylene ether, vinyl glycol ether, lauryl alcohol polyoxyethylene ether, copolymers of propylene oxide and ethylene oxide; one or more of polyoxyethylene polyoxypropylene, polypropylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, cetyl alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, stearyl alcohol polyoxyethylene ether, polyethylene glycol monobutyl ether, polyoxypropylene monocetyl ether, polyethylene glycol polypropylene glycol monobutyl ether, isotridecyl alcohol polyoxyethylene ether, polyoxyethylene polyoxypropylene glycerol ether, diethylene glycol monovinyl ether, di (propylene glycol) propyl ether and fatty alcohol polyoxyethylene ether.
Specifically, the polyetheramines are one or more of polyetheramine, polyethylene glycol mono (2-laurylaminoethyl) ether, ethylene glycol di (3-aminopropyl) ether, polyethylene glycol mono (2-hexadecanoylaminoethyl) ether and diethylene glycol di (3-aminopropyl) ether.
Specifically, the polyether carboxylic acid is one or more of 4,4' -dithiodibutanoic acid, 3-carboxypropyl disulfide, cysteinyl homocysteine mixture disulfide, polyethylene glycol bis (2-carboxyethyl) ether, cystathionine, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, 2-carboxymethyl-3-aminopropyl selenide, branched C11-C14 fatty alcohol polyoxyethylene polyoxypropylene ether and polyoxyethylene lauryl ether carboxylic acid.
Specifically, the polythioether group is one or more of bis (dimethylthiocarbamoyl) trisulfide, 2' -thiobis (ethanethiol), dimercaptoethyl sulfide, 2-mercaptoethyl sulfide and dithiocarbamyl disulfide.
Specifically, the polyether epoxy is one or more of allyl epoxy terminated polyether.
Further, the modified epoxidized rubber or modified epoxidized elastomer has a modified epoxy bond content of not less than 5mol% and not more than 60mol%, preferably not less than 10mol% and not more than 55mol%, based on the total molar amount of epoxy bonds in the unmodified epoxidized rubber or epoxidized elastomer. When the modified epoxy bond content in the epoxidized rubber or epoxidized elastomer is less than 5mol%, sufficient anti-slip properties cannot be obtained; when the content is more than 60mol%, the tensile strength and abrasion resistance of the rubber start to decrease, and crosslinking between molecular chains occurs, which affects the effect of ring-opening modification, particularly, is disadvantageous in lowering the glass transition temperature.
The epoxy bond content may be measured by chemical titration, infrared spectroscopy (FTIR) analysis or Nuclear Magnetic Resonance (NMR) analysis.
Chemical titration method: the epoxy group is a three-membered ring structure and has certain tension, so that the epoxy group has greater chemical activity and can react with a plurality of reagents to cause the breakage of the ring and form an addition product. The determination of the epoxy group content by chemical titration is based on this property. Titration with HCl, HBr, tetraethylammonium bromide or perchloric acid provides a simple and rapid method for determining a compound having a low degree of epoxidation. However, for rubbers with a high degree of epoxidation, it was found that the results obtained by chemical titration were low, due to the furan reaction of the adjacent epoxide groups, according to the following reaction principle
The formula (a) is a HCl titration reaction when the epoxidation degree is low, and the formula (b) is a HCl titration reaction when the epoxidation degree is low.
Infrared spectroscopy (FTIR) analysis:
FTIR analysis can qualitatively analyze epoxy groups and side reactions, and the peak of antisymmetric stretching vibration of the epoxy groups is known to be 870 cm < -1 >, and the absorption intensity of the peak is correspondingly increased along with the increase of the epoxidation degree. The degree of epoxidation and the content of ring-opened product of natural rubber can be determined according to Lambert-Beer's law, where the degree of light absorption by a substance is proportional to the product of the thickness of the absorbing layer and the concentration of the substance, as shown in the following expression
Wherein, C e 、C d And C 0 Respectively representing the mole percentage contents of epoxy groups, double bonds and ring-opened substances. A835, A870, A1375 and A3460 correspond to the absorbances at 835 cm-1, 870 cm-1, 1375 cm-1 and 3460 cm-1, respectively. The values of k1 and k2, 0.77 and 0.34 respectively, were calculated by measuring Ce, cd, C0, A835, A870, A1375 and A3460 respectively by NMR and IR methods.
Nuclear Magnetic Resonance (NMR) analysis:
and (3) taking deuterated chloroform as a solvent (CDCl 3), and scanning by using a Bruker Fourier transform nuclear magnetic resonance spectrometer to obtain 1H NMR and 13C NMR spectrums of the rubber or the elastomer. The lower epoxidation level was completely soluble in CDCl3, but the epoxidation level was over 50% and a small portion of the sample was not dissolved by CDCl3 due to the presence of the gel. Thus, when analyzing ENR by NMR, it is also necessary to ensure that no ring-opened product is present. The 1H NMR spectrum of the rubber or elastomer showed chemical shifts of the olefin protons at 5.14 ppm and the methine protons at 2.70 ppm. Thus, the degree of epoxidation can be calculated by the integrated area of the proton chemical shifts of the olefin and epoxide groups.
The 13C NMR spectrum of natural rubber showed chemical shifts of the epoxy group at 64.5ppm and chemical shifts of the olefin at 124.4ppm, 125.0ppm and 125.6ppm.
Further, the latex of the epoxidized rubber is one or more selected from epoxidized natural rubber latex, epoxidized styrene-butadiene rubber latex, epoxidized nitrile-butadiene rubber latex, epoxidized chloroprene rubber latex, epoxidized cis-butadiene rubber latex, epoxidized eucommia rubber latex, epoxidized synthetic isoprene rubber latex or epoxidized synthetic trans-polyisoprene rubber latex, and preferably epoxidized natural rubber. The epoxidized elastomer can be a styrenic thermoplastic elastomer with an epoxy bond, such as ESBS/ESIS/ESEBS, and can also be an epoxidized bio-based polyester, and the like, such as bio-based polyitaconate with an epoxy bond, and the like.
Further, the epoxidized rubber or epoxidized elastomer has an epoxy degree of 5% to 75%, preferably 20% to 55%. The "epoxy degree" is a percentage of the epoxy bond content in the epoxidized rubber or epoxidized elastomer to the total chemical bond content thereof.
More specifically, the method for preparing the epoxidized rubber or the epoxidized elastomer comprises the following steps:
s1: adding a surfactant to an aqueous emulsion system of a rubber or elastomer;
s2: and adding molybdenum polyoxometallate and hydrogen peroxide in the step S1, reacting, and drying to obtain the epoxidized rubber or the epoxidized elastomer, wherein the hydrogen peroxide provides epoxy bonds.
Further, the molybdenum polyoxometallate is one or more of alkylammonium molybdate, imidazole molybdate and pyridine molybdate, preferably alkylammonium molybdate such as tetramethylammonium molybdate, tetraethylammonium molybdate, tetrabutylammonium molybdate, hexadecyltrimethylammonium molybdate, (1-butyl) triethylammonium molybdate, tetrapropylammonium molybdate and tetrapentylammonium molybdate, and more preferably tetraethylammonium molybdate.
Further, the reaction temperature of the step S2 is 30-80 ℃, preferably 40-60 ℃.
Further, the surfactant is one or more of an ionic surfactant, a nonionic surfactant or an amphoteric surfactant, preferably a nonionic surfactant, such as fatty alcohol polyoxyethylene ether, dodecylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether-10, octylphenol polyoxyethylene ether-10, polyoxyethylene castor oil, sorbitol ester, polyoxyethylene sorbitol ester, and the like, more preferably fatty alcohol polyoxyethylene ether. The surfactants are used for stabilizing the aqueous emulsion system of rubber or elastomers, wherein the fatty alcohol polyoxyethylene ethers have an optimum stabilizing effect.
Further, in step S2, the drying is flocculation drying, which may be conventional thermal steam flocculation, addition of calcium or magnesium chloride salt, or microwave ultra-frequency thermal flocculation. Preferably, through microwave high frequency thermal flocculation, can realize that the flocculation drying is fast, the product is batched homogeneous, and the product does not produce extra high salt waste water, can carry out the liquefaction of waste gas and retrieve, can not cause atmospheric pollution.
Further, the rubber or elastomer has a solid content of 15 to 60%, preferably 20 to 30%, in an aqueous emulsion system of the rubber or elastomer.
Further, the addition amount of the surfactant is 0.1-5% by mass of the rubber or elastomer.
Further, the concentration of hydrogen peroxide is 5% to 75%, preferably 15% to 30%. The amount of hydrogen peroxide added is 1.5-27%, preferably 6-15% of the solid mass of the rubber or elastomer.
Further, in step S1, natural rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butadiene rubber, eucommia rubber, synthetic isoprene rubber, synthetic trans-polyisoprene rubber, or the like can be used as the rubber, and natural rubber and styrene-butadiene rubber are preferred, and natural rubber is more preferred.
Further, in step S2, the amount of the molybdenum polyoxometallate is 0.1 to 10%, preferably 0.5 to 3% of the mole number of the unsaturated double bonds in the rubber or elastomer. The molybdenum polyoxometallate can be alkyl molybdate which is prepared by reacting alkyl ammonium bromide with potassium hydroxide to prepare alkyl quaternary ammonium base and then reacting with ammonium molybdate. The synthesis of the molybdenum polyoxometallate adopted by the invention belongs to a widely known and easily prepared method.
Further, in step S2, the reaction time is 3h-24h, preferably 12h-18h, and more preferably 16-18h.
Specifically, in step S2, the reaction stirring speed is 50-600 rpm, preferably 50-150 rpm.
Compared with the prior art, the preparation method of the epoxidized rubber or the epoxidized elastomer has the following advantages:
(1) The preparation process is carried out in a water emulsion system, so that the use of an organic solvent is avoided, and environmental pollution and human harm are avoided; and the synthesis temperature is controlled to be lower, the production wastewater is less, controllable recovery treatment can be realized, and the environment is protected.
(2) Different from the traditional method of heating or adding metal salt for flocculation, the invention adopts special customized equipment for microwave high-frequency thermal flocculation, can liquefy and recover waste gas, and can not cause air pollution.
(3) The molybdenum polyoxometallate used in the method has the advantages of easy preparation, stable chemical property and environmental friendliness, and can be used for catalyzing reactions such as epoxidation, double hydroxylation and the like of olefin.
(4) The problems of excessive acid addition and more ring-opening byproducts of products in the prior art are solved, and more remarkably, the stability and distribution of epoxy bonds of the epoxidized rubber and the epoxidized elastomer can be adjusted to a certain extent, so that the epoxy groups are uniformly distributed on the molecular main chain, and the problems of poor ring-opening and aging resistance of the epoxy bonds formed by the aggregation of the epoxy bonds are solved.
Of course, the epoxidized rubber or the epoxidized elastomer in the modified epoxidized rubber provided by the invention can be prepared by the above preparation method, or can be prepared by the existing process proposed by scientific researchers, or can be directly prepared by the existing commercial products.
Further, the modified epoxidized rubber further comprises a catalyst. The catalyst may be selected from Lewis acids, or basic catalysts, preferably p-toluenesulfonic acid or 4-dimethylaminopyridine, more preferably 4-dimethylaminopyridine.
The invention also provides a preparation method of the modified epoxidized rubber, which comprises the following steps:
s1: adding a polyether compound to the epoxidized rubber or the epoxidized elastomer;
s2: and controlling the reaction temperature and the reaction time to obtain the modified epoxidized rubber.
The method for producing the modified epoxidized rubber is not particularly limited with respect to the state of the reaction system, and can be carried out in any state of emulsion, rubber solution or solid rubber. When the modification is carried out in an emulsion, the emulsion of the epoxidized rubber or epoxidized elastomer used is also not particularly limited, but may be a commercially available ammonia-treated or self-prepared virgin epoxidized rubber/epoxidized elastomer emulsion. When the modification is carried out in solution, the organic solvent used is also not limited as long as it does not react with the epoxidized rubber/epoxidized elastomer and the polyether compound by itself, for example: aromatic hydrocarbons such as benzene, chlorobenzene, toluene, xylene; aliphatic hydrocarbons such as n-hexane, n-pentane and n-octane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, naphthalene tetrachloride and decalin may be used as the solvent, and methylene chloride may be used. When the modification is carried out in the solid rubber, the rubber may be directly mixed and modified by a roll or an extrusion mixer. From the viewpoint of cost and ease of handling, the present invention is preferably carried out in an emulsion system.
Further, a catalyst is also included in the step S1.
Further, in step S2, the reaction temperature is 40-160 ℃. When the reaction temperature is lower than 40 ℃, the reaction rate is low and the reactivity is reduced; whereas if the temperature is higher than 160 ℃, the polymer tends to gel during the reaction, and the heat-resistant stability of the product after a high temperature for a long time is lowered.
Further, in step S2, the reaction time is 1.5-10h, preferably 4-8h. If the reaction time is less than 1.5 hours, the modification reaction proceeds insufficiently, making it difficult to obtain the desired modified epoxidized rubber; if the reaction time exceeds 10 hours, the polymer tends to gel, and side reactions may occur.
The invention also provides application of the modified epoxidized rubber in preparing rubber products, wherein the rubber products can be tires, hand-drawn tires, rubber belts and the like.
In conclusion, compared with the prior art, the invention achieves the following technical effects:
epoxy bond open-loop grafting modification is carried out on the epoxidized rubber or the epoxidized elastomer through the polyether compound, so that a polyether long-chain structure is grafted on the side chain of the epoxidized rubber or the epoxidized elastomer, a corresponding flexible side chain is introduced, the polarity can be reduced, the molecular chain flexibility is provided, the dispersion of the filler is improved, particularly, the glass transition temperature Tg of the modified epoxidized rubber or the modified epoxidized elastomer can be reduced, a stable bond is formed through the open loop of the epoxy bond, and a stable structure is introduced into the side chain, so that the temperature resistance of the epoxidized rubber is improved, and the low-temperature resistance is particularly embodied.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic flow chart of a process for preparing a modified epoxy rubber according to the present invention;
FIG. 2 is an infrared spectrum of example 1;
FIG. 3 shows the results of the glass transition temperature test of example 1;
FIG. 4 shows the results of the glass transition temperature test of example 2;
FIG. 5 is an infrared spectrum of example 2;
FIG. 6 shows the results of the glass transition temperature test of example 3;
FIG. 7 is an infrared spectrum of example 3;
FIG. 8 shows the results of the glass transition temperature test of example 4;
FIG. 9 shows the results of the glass transition temperature test of example 5;
FIG. 10 shows the results of glass transition temperature tests on the first set of products of example 6;
FIG. 11 is the glass transition temperature test results for the second set of products from example 6;
FIG. 12 shows the results of the glass transition temperature test of the third group in example 6;
FIG. 13 shows the results of the glass transition temperature test of the fourth group in example 6;
FIG. 14 shows the results of a glass transition temperature test of a comparative example;
FIG. 15 is an infrared spectrum of a comparative example.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.
The synthesis mode of the molybdenum polyoxometallate is as follows:
under nitrogen (N) 2 ) Under the protection of atmosphere, adding alkyl ammonium bromide and potassium hydroxide into a reaction bottle according to the mass ratio of 1.2, adding a proper amount of absolute ethyl alcohol to fully dissolve the alkyl ammonium bromide and the potassium hydroxide, and placing the reaction bottle on a magnetic stirrer to stir at room temperature. And (3) continuously precipitating potassium bromide insoluble in ethanol in the reaction process, removing the potassium bromide after the reaction is finished, distilling the obtained ethanol solution of the alkyl quaternary ammonium base under reduced pressure to remove most of ethanol, transferring the ethanol solution into a small beaker, and adding a proper amount of water for dilution. Weighing ammonium molybdate according to the proportion of 1.1 to 1.1, adding the ammonium molybdate into a reaction bottle, adding water to dissolve the ammonium molybdate, placing the ammonium molybdate on a magnetic stirrer, and dropwise adding alkyl quaternary ammonium hydroxide into the ammonium molybdate by using a constant-pressure funnelThe reaction solution was stirred at room temperature for 24 hours, and the white solid precipitated in the reaction was washed, dehydrated and dried to obtain a catalyst alkylammonium molybdate.
Epoxidized Natural rubber A
Adding 100 parts by weight of natural rubber latex (with solid content of 60%) into a reaction flask, taking 0.5 part by weight of surfactant fatty alcohol-polyoxyethylene ether (peregal O), adding the surfactant fatty alcohol-polyoxyethylene ether into the natural rubber latex, stirring at a rotating speed of 50 rpm for 20min to stabilize the emulsion of the natural rubber latex, then adding the self-made catalyst tetraethylammonium molybdate, stirring for 10min to make the emulsion uniform, and adding 0.7% ammonia water to maintain the concentration of the total system of the emulsion at 30%, namely the solid content of the natural rubber latex at 30%. Then 42 parts by weight of 30% hydrogen peroxide aqueous solution is weighed and added dropwise into the diluted natural rubber latex, and the reaction temperature is controlled to be 50-55 ℃. And (3) after the dropwise addition is finished, controlling the reaction time to be 18h, after the reaction is finished, performing super-frequency heating flocculation and drying to obtain the epoxidized natural rubber A.
The product is extracted and purified, and then is characterized by nuclear magnetism and infrared tests, and the analysis result shows that the epoxy degree is 35 percent and the by-product is 0.9 percent.
Epoxidized natural rubber B
Adding 100 parts by weight of natural rubber latex (with solid content of 60%) into a reaction flask, taking 0.5 part by weight of surfactant fatty alcohol-polyoxyethylene ether (peregal O), adding the surfactant fatty alcohol-polyoxyethylene ether into the natural rubber latex, stirring at the rotating speed of 50 r/min for 20min to stabilize the emulsion of the natural rubber latex, then adding catalyst tetrabutylammonium molybdate, stirring for 10min to make the emulsion uniform, and adding 0.7% ammonia water to maintain the concentration of the total system of the emulsion at 30%, namely the solid content of the natural rubber latex at 30%. Then 42 parts by weight of an aqueous solution of hydrogen peroxide having a concentration of 30% was weighed and added dropwise to the diluted natural rubber latex, and the reaction temperature was controlled to 50 ℃ to 55 ℃. And (3) after the dropwise addition is finished, controlling the reaction time to be 18h, after the reaction is finished, performing super-frequency heating flocculation and drying to obtain the epoxidized natural rubber B.
The product is extracted and purified, and then is characterized by nuclear magnetism and infrared tests, and the analysis result shows that the epoxy degree is 29 percent and the by-product is 0.7 percent.
Epoxidized natural rubber C
Adding 100 parts by weight of natural rubber latex (with solid content of 60%) into a reaction flask, taking 0.5 part by weight of fatty alcohol polyoxyethylene ether (peregal O) as a surfactant, adding the surfactant into the natural rubber latex, stirring at the rotating speed of 50 r/min for 20min to stabilize the emulsion of the natural rubber latex, then adding the self-made catalyst tetraethylammonium molybdate, stirring for 10min to make the emulsion uniform, adding 0.7% ammonia water to maintain the concentration of the total system of the emulsion at 30%, namely the solid content of the latex at 30%. Then, 42 parts by weight of an aqueous solution of hydrogen peroxide having a concentration of 30% was weighed and added dropwise to the diluted natural rubber latex, and the reaction temperature was controlled at 75 ℃. And (4) after the dropwise addition is finished, controlling the reaction time to be 18h, after the reaction is finished, performing super-frequency heating flocculation and drying to obtain the epoxidized natural rubber C.
The product is extracted and purified, and then is characterized by nuclear magnetism and infrared tests, and the analysis result shows that the epoxy degree is 31 percent and the by-product is 4.1 percent.
Epoxidized natural rubber D
Adding 100 parts by weight of natural rubber latex (with solid content of 60%) into a reaction flask, taking 0.1 part by weight of surfactant fatty alcohol-polyoxyethylene ether (peregal O), adding the surfactant fatty alcohol-polyoxyethylene ether into the natural rubber latex, stirring at a rotating speed of 50 rpm for 20min to stabilize the emulsion of the natural rubber latex, then adding the self-made catalyst tetraethylammonium molybdate, stirring for 10min to make the emulsion uniform, and adding 0.7% ammonia water to maintain the concentration of the total system of the emulsion at 30%, namely the solid content of the latex at 30%. Then 42 parts by weight of 30% hydrogen peroxide aqueous solution is weighed and added dropwise into the diluted natural rubber latex, and the reaction temperature is controlled to be 50-55 ℃. And (4) after the dropwise addition is finished, controlling the reaction time to be 18h, after the reaction is finished, performing super-frequency heating flocculation and drying to obtain the epoxidized natural rubber D.
The product is extracted and purified, and then is characterized by nuclear magnetism and infrared tests, and the analysis result shows that the epoxy degree is 23 percent and the by-product is 1.2 percent.
Example 1
(polyetheramine D230) and a modification ratio of epoxy bond of 15%
Table 1.
According to the formula in the table 1, ENR25 containing 0.05mol of epoxy bonds and polyether amine are added into a 1L flask, the temperature is raised to 140 ℃, the reaction is carried out for 8 hours, and the product is obtained after the temperature is reduced and the microwave ultra-frequency flocculation drying is carried out.
The product is characterized to obtain figures 2 and 3, the success of ring-opening grafting can be seen from a hydroxyl peak on an infrared spectrum of figure 2, an epoxy bond is also remained, and the Tg is reduced as can be seen from figure 3.
Example 2
(Polyetheramine D230) and 30% modification ratio of epoxy bond
Table 2.
According to the formula in Table 2, ENR25 containing 0.05mol of epoxy bonds, polyetheramine and a certain amount of catalyst in mol number are added into a 1L flask, the temperature is raised to 140 ℃, the reaction is carried out for 8 hours, and the product is obtained by cooling and then microwave super-frequency flocculation drying.
The product is characterized to obtain figures 4 and 5, from figure 4, it can be seen that Tg is reduced, and compared with 15% mole number modification (i.e. example 1), glass transition temperature is reduced more, which indicates that in 30% modified ENR25, it is beneficial to overall flexibility and polarity of molecular chain, from figure 5, it can be seen that ring-opening grafting is successful, and epoxy bond is retained.
Example 3
(Polyetheramine D230) and a modification ratio of epoxy bond of 45%
Table 3.
According to the formula in the table 3, ENR25 containing 0.05mol of epoxy bond, polyether amine and a certain amount of catalyst in mol number are added into a 1L flask, the temperature is raised to 140 ℃, the reaction is carried out for 8h, and the product is obtained by microwave ultra-frequency flocculation drying after the temperature is lowered.
The product is characterized to obtain fig. 6, and it can be seen from fig. 6 that Tg of example 3 is a phenomenon that Tg is increased relative to 30% modified ENR25 (i.e., example 2) at the glass transition temperature Tg, and the reason for this is analyzed to be that the bifunctional amino group causes crosslinking of the internal molecular chain, so that the glass transition temperature is increased. This was also confirmed by subsequent analysis from insoluble gel tests. The insoluble substance gel test is to wrap the modified rubber by a filter screen, place the rubber in a good solvent, dissolve the rubber for more than 48 hours and finally leave insoluble substance residues.
Example 4
(polyetheraminocarboxylic acid) and modification ratio of epoxy bond of 15%
Table 4.
According to the formula in the table 4, ENR25 containing 0.05mol of epoxy bond, polyoxyethylene lauryl ether carboxylic acid and a certain amount of catalyst with a certain number of moles are added into a 1L flask, the temperature is raised to 140 ℃, the reaction is carried out for 8 hours, and the product is obtained by microwave ultra-frequency flocculation drying after the temperature is lowered.
The product was characterized to give FIG. 7, from which FIG. 7 it can be seen that the Tg was reduced by 3 ℃ above the glass transition temperature Tg relative to that of unmodified ENR25 (the glass transition temperature of unmodified ENR25 is between-40 ℃ and-41 ℃).
Example 5
(Polyetheraminocarboxylic acid) and epoxy bond modification ratio of 45%
Table 5.
According to the formula in the table 5, ENR25 containing 0.05mol of epoxy bond, polyoxyethylene lauryl ether carboxylic acid and a certain amount of catalyst with a certain number of moles are added into a 1L flask, the temperature is raised to 140 ℃, the reaction is carried out for 8 hours, and the product is obtained by microwave ultra-frequency flocculation drying after the temperature is lowered.
The product is characterized to obtain a figure 8, and as can be seen from figure 8, compared with the unmodified ENR25, the Tg of example 5 is reduced by about 8 ℃ above the glass transition temperature Tg, and because the product is monofunctional, no crosslinking phenomenon exists in the modified product, so the glass transition temperature Tg of the modified ENR25 can be continuously reduced in the modification, but after the modification of 60% mole number, the Tg of the modified product is not greatly influenced.
Example 6 Effect of temperature on modification results
(polyetheraminocarboxylic acid) and epoxy bond modification ratio of 45%
Table 6.
Four parallel control runs were carried out below, each following the recipe in table 6, differing only in the reaction temperature.
A first group: adding ENR25, polyoxyethylene lauryl ether carboxylic acid and a certain amount of catalyst in mol ratio into a 1L flask, heating to 50 ℃, reacting for 8h, cooling, and then performing microwave ultra-frequency flocculation drying to obtain the product.
Second group: adding ENR25, polyoxyethylene lauryl ether carboxylic acid and a certain amount of catalyst in mol number into a 1L flask according to the proportion, heating to 80 ℃, reacting for 8h, cooling, and then performing microwave ultra-frequency flocculation drying to obtain the product.
Third group: adding ENR25, polyoxyethylene lauryl ether carboxylic acid and a certain amount of catalyst in mol number into a 1L flask according to the proportion, heating to 110 ℃, reacting for 8 hours, cooling, and then performing microwave ultra-frequency flocculation drying to obtain the product.
And a fourth group: adding ENR25, polyoxyethylene lauryl ether carboxylic acid and a certain amount of catalyst in mol ratio into a 1L flask, heating to 160 ℃, reacting for 8h, cooling, and then performing microwave ultra-frequency flocculation drying to obtain the product.
The glass transition temperatures Tg of the four sets of products correspond to figures 9-11,
comparative example
Table 7.
According to the formula shown in Table 1, ENR25 containing 0.05mol of epoxy bonds and polyether amine with a certain mole number are added into a 1L flask, the temperature is raised to 140 ℃, the reaction is carried out for 8h, the temperature is reduced, and then the product is obtained by microwave ultra-frequency flocculation drying.
The product is characterized to obtain figures 12 and 13, the Tg is not reduced as can be seen from figure 12, the ring-opening reaction is generated as can be seen from a hydroxyl peak on an infrared spectrum of figure 13, and an epoxy bond is also reserved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (19)
1. The modified epoxidized rubber is characterized by comprising the following components in parts by weight:
epoxidized rubber or epoxidized elastomer;
a polyether compound;
the polyether compound is one or more of polyether alcohols, polyether amines, polyether carboxylic acids, polyether sulfydryl and polyether epoxy.
2. <xnotran> 1 , , , , , , (1- -2- ) , , ,2- , , ,1,4- ,1,3- , , (2- ) , , , , , , , , -1,4- , , , , , , , , , , ,4- , , , , , , , alpha- -omega- - ,1,2,3- , , (2- ) , , , alpha- (2- -1- -2- -1- ) -omega- - , </xnotran> <xnotran> , , alpha- -omega- - , (2- ) , , , , (3- ) ,1,2- -1- , , , , , , , , , , 300 , ,1,3- -2- , (2- ) , , , , , , , , , ( ) , , -3, -5, , , , , (2- ) , , , , , -10 , , , </xnotran> 2, 2-bis (allyloxymethyl) -1-butanol, propanetriol monoallyl ether, C16-18 alcohol polyoxyethylene ether, C12-C14 fatty alcohol polyoxyethylene polyoxypropylene ether, C12-C15 fatty alcohol polyoxyethylene polyoxypropylene ether, C11-C15 secondary alcohol polyoxyethylene polyoxypropylene ether, C8-C10 fatty alcohol polyoxyethylene polyoxypropylene ether, 1-glycerol octyl ether, 2-hydroxyethyl 2-chloroethyl sulfide, polyoxyethylene-20 isohexadecyl ether, glycerol monoisooctyl ether, ethylene glycol mono (1, 1-dipropylbutyl) ether, branched octyl phenol polyethylene glycol polypropylene glycol monoether, polyglycerol-2 oil ether, C8-10 fatty alcohol polyoxyethylene ether, glycerine mono-isooctyl ether C12-C15 fatty alcohol polyoxypropylene ether, vinyl glycol ether, lauryl alcohol polyoxyethylene ether, a copolymer of propylene oxide and ethylene oxide, polypropylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, cetyl alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, stearyl alcohol polyoxyethylene ether, polyethylene glycol monobutyl ether, polyoxypropylene monocetyl ether, polyethylene glycol polypropylene glycol monobutyl ether, isotridecyl alcohol polyoxyethylene ether, polyoxyethylene polyoxypropylene glycerol ether, diethylene glycol monovinyl ether, di (propylene glycol) propyl ether and fatty alcohol polyoxyethylene ether.
3. The modified epoxidized rubber of claim 1, wherein the polyetheramines are one or more of polyetheramine, polyethylene glycol mono (2-laurylaminoethyl) ether, ethylene glycol di (3-aminopropyl) ether, polyethylene glycol mono (2-hexadecanoylaminoethyl) ether and diethylene glycol di (3-aminopropyl) ether.
4. The modified epoxidized rubber of claim 1, wherein the polyether carboxylic acid is one or more of 4,4' -dithiodibutanoic acid, 3-carboxypropyl disulfide, cysteinyl homocysteine mixture disulfide, polyethylene glycol bis (2-carboxyethyl) ether, cystathionine, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, 2-carboxymethyl-3-aminopropyl seleno-ether, branched C11-C14 fatty alcohol polyoxyethylene polyoxypropylene ether, and polyoxyethylene lauryl ether carboxylic acid.
5. The modified epoxidized rubber of claim 1, wherein the polyether sulfydryl group is one or more of bis (dimethylthiocarbamoyl) trisulfide, 2' -thiobis (ethanethiol), dimercaptoethyl sulfide, 2-mercaptoethyl sulfide, and dithiocarbamyl disulfide.
6. The modified epoxidized rubber according to claim 1, wherein the polyether epoxy is one or more of acryl epoxy terminated polyethers.
7. The modified epoxidized rubber according to claim 1, wherein the modified epoxidized rubber has a modified epoxy bond content of not less than 5mol% and not more than 60mol%, preferably not less than 10mol% and not more than 55mol%, based on the total molar amount of epoxy bonds in the unmodified epoxidized rubber or epoxidized elastomer.
8. The modified epoxidized rubber according to claim 1, wherein the epoxidized rubber is one or more of epoxidized natural rubber latex, epoxidized styrene-butadiene latex, epoxidized nitrile-butadiene latex, epoxidized chloroprene latex, epoxidized cis-butadiene latex, epoxidized eucommia latex, epoxidized synthetic isoprene rubber latex or epoxidized synthetic trans-polyisoprene latex, preferably epoxidized natural rubber.
9. The modified epoxidized rubber according to claim 1, wherein the epoxidized rubber or epoxidized elastomer is prepared by a process comprising:
s1: adding a surfactant to an aqueous emulsion system of a rubber or elastomer;
s2: and adding molybdenum polyoxometallate and hydrogen peroxide into the step S1, reacting, and drying to obtain the epoxidized rubber or the epoxidized elastomer.
10. The modified epoxidized rubber according to claim 9, wherein the molybdenum polyoxometalate is one or more of alkylammonium molybdate, imidazole molybdate and pyridine molybdate, preferably alkylammonium molybdate, more preferably tetraethylammonium molybdate.
11. The modified epoxidized rubber according to claim 9, characterised in that the reaction temperature in step S2 is 50 to 80 ℃.
12. The modified epoxidized rubber according to claim 9, wherein the surfactant is one or more of an ionic surfactant, a nonionic surfactant or an amphoteric surfactant, preferably a nonionic surfactant, and more preferably a fatty alcohol-polyoxyethylene ether.
13. The modified epoxidized rubber of claim 1, wherein the modified epoxidized rubber further comprises a catalyst.
14. A process for producing the modified epoxidized rubber according to any one of claims 1 to 13, which comprises the steps of:
s1: adding a polyether compound to the epoxidized rubber or the epoxidized elastomer;
s2: and controlling the reaction temperature and the reaction time to obtain the modified epoxidized rubber.
15. The method for producing a modified epoxidized rubber according to claim 14, wherein a catalyst is further contained in step S1.
16. The method for producing a modified epoxidized rubber according to claim 14, wherein the reaction temperature in step S2 is 40 ℃ to 160 ℃.
17. The process for producing a modified epoxidized rubber according to claim 14, wherein the reaction time in step S2 is 1.5 to 10 hours, preferably 4 to 8 hours.
18. Use of the modified epoxidized rubber of any of claims 1 to 13 in rubber articles.
19. Use of the modified epoxidized rubber of any of claims 1 to 10 to prepare rubber articles.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211149119.6A CN115505054A (en) | 2022-09-21 | 2022-09-21 | Modified epoxidized rubber and preparation method and application thereof |
| PCT/CN2023/093417 WO2024060640A1 (en) | 2022-09-21 | 2023-05-11 | Modified epoxidized rubber, preparation method therefor, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211149119.6A CN115505054A (en) | 2022-09-21 | 2022-09-21 | Modified epoxidized rubber and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115505054A true CN115505054A (en) | 2022-12-23 |
Family
ID=84504771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211149119.6A Pending CN115505054A (en) | 2022-09-21 | 2022-09-21 | Modified epoxidized rubber and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115505054A (en) |
| WO (1) | WO2024060640A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024060640A1 (en) * | 2022-09-21 | 2024-03-28 | 江苏麒祥高新材料有限公司 | Modified epoxidized rubber, preparation method therefor, and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310819A (en) * | 1992-01-23 | 1994-05-10 | The United States Of America As Represented By The Secretary Of The Navy | Surface epoxidation of elastomers |
| CN105859917A (en) * | 2015-01-23 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of epoxidized emulsion polymerization rubber |
| CN114085538A (en) * | 2021-12-01 | 2022-02-25 | 宁国市瑞普密封件有限公司 | High-temperature-resistant natural rubber material and preparation method thereof |
| CN114729103A (en) * | 2019-11-28 | 2022-07-08 | 赢创运营有限公司 | Polyether modified polybutadiene and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS582321A (en) * | 1981-06-29 | 1983-01-07 | Nippon Zeon Co Ltd | Cis-1,4-polyisoprene rubber composition giving improved strength by vulcanization |
| DE602004001807T2 (en) * | 2003-06-03 | 2007-08-02 | Sumitomo Rubber Industries Ltd., Kobe | Rubber composition for tire treads and peneumatic tires based thereon |
| US9212239B2 (en) * | 2013-05-30 | 2015-12-15 | The Goodyear Tire & Rubber Company | Method of making functionalized elastomer |
| KR20170108083A (en) * | 2015-01-28 | 2017-09-26 | 사빅 글로벌 테크놀러지스 비.브이. | Functionalized elastomer, method of making same, and uses thereof |
| JP2019019221A (en) * | 2017-07-18 | 2019-02-07 | 宇部興産株式会社 | Method for producing epoxidated diene polymer |
| CN115505054A (en) * | 2022-09-21 | 2022-12-23 | 江苏麒祥高新材料有限公司 | Modified epoxidized rubber and preparation method and application thereof |
-
2022
- 2022-09-21 CN CN202211149119.6A patent/CN115505054A/en active Pending
-
2023
- 2023-05-11 WO PCT/CN2023/093417 patent/WO2024060640A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310819A (en) * | 1992-01-23 | 1994-05-10 | The United States Of America As Represented By The Secretary Of The Navy | Surface epoxidation of elastomers |
| CN105859917A (en) * | 2015-01-23 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of epoxidized emulsion polymerization rubber |
| CN114729103A (en) * | 2019-11-28 | 2022-07-08 | 赢创运营有限公司 | Polyether modified polybutadiene and preparation method thereof |
| CN114085538A (en) * | 2021-12-01 | 2022-02-25 | 宁国市瑞普密封件有限公司 | High-temperature-resistant natural rubber material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黎志平，蓝峻: "天然橡胶分子链双键中引入环氧基对其性能的影响" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024060640A1 (en) * | 2022-09-21 | 2024-03-28 | 江苏麒祥高新材料有限公司 | Modified epoxidized rubber, preparation method therefor, and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024060640A1 (en) | 2024-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gan et al. | Partial conversion of epoxide groups to diols in epoxidized natural rubber | |
| CN115505054A (en) | Modified epoxidized rubber and preparation method and application thereof | |
| CN110387004B (en) | Epoxidized ethylene propylene diene monomer, preparation method and elastomer | |
| CN105985472B (en) | A kind of preparation method of rare earth catalyst and preparation method thereof and polyisoprene | |
| US4465809A (en) | Conversion of polymer lithium to polymer carboxylate | |
| JPS61215622A (en) | Production of unsaturated group-terminated polyalkylene oxide | |
| JPS61215623A (en) | Production of unsaturated group-terminated polyalkylene oxide | |
| JPH0613605B2 (en) | Polyalkylene oxides containing unsaturated groups at the ends of the molecule and having a narrow molecular weight distribution | |
| GB1526297A (en) | Silylated organic polymers and organic-organopolysiloxane block copolymers | |
| US2979488A (en) | Modification of linear rubbery polymers | |
| CN103665217B (en) | A kind of continuous polymerization method | |
| US20220056209A1 (en) | Method for preparing reactive sealant resin | |
| Rasid et al. | Physicochemical properties of liquid natural rubber bearing fluoro groups for hydrophobic surfaces | |
| JPS63179908A (en) | Myrcene polymer and production thereof | |
| Greco et al. | Bulk functionalization of ethylene–propylene copolymers. II. Influence of the initiator concentration and of the copolymer composition and chain microstructure on the reaction kinetics | |
| Wang et al. | In situ epoxidation of ethylene propylene diene rubber by performic acid | |
| CN107915797B (en) | Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof | |
| CN104877131A (en) | Preparation method of blending-type non-isocyanate polyurethane rubber | |
| CN113292711B (en) | Method for synthesizing fluorescent functional polyester-based amphiphilic polymer | |
| GB934742A (en) | Improvements in or relating to hydrocarbon copolymers | |
| Soga et al. | Copolymerization of ethylene sulfide and carbon disulfide | |
| US3385800A (en) | Polymerization of alkylene oxides by a catalyst system comprising organometallic compounds in combination with an oxygen-containing cocatalyst | |
| CN109999716B (en) | Nonionic fluorine-containing surfactant and preparation method and application thereof | |
| JP3971481B2 (en) | Mercaptopolybutenyl derivative for rubber vulcanization, composition for rubber vulcanization and vulcanized rubber composition containing the same | |
| CN117248378B (en) | Deepened silicone oil emulsion, preparation method thereof and application of deepened silicone oil emulsion in vulcanized black and dark fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |