CN112745460B - Saturated polar polymer and preparation method thereof - Google Patents

Saturated polar polymer and preparation method thereof Download PDF

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CN112745460B
CN112745460B CN202011606814.1A CN202011606814A CN112745460B CN 112745460 B CN112745460 B CN 112745460B CN 202011606814 A CN202011606814 A CN 202011606814A CN 112745460 B CN112745460 B CN 112745460B
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unsaturated polymer
metal ion
polar
polymer
styrene
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CN112745460A (en
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宗迎夏
郎秀瑞
韩立静
王小蕾
王春芙
宗成中
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Qingdao University of Science and Technology
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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
    • C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
    • 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
    • C08C19/02—Hydrogenation
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

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Abstract

The invention provides a saturated polar polymer and a preparation method thereof, belonging to the technical field of modification. Mixing an anionic surfactant, a metal ion salt and water to obtain a metal ion mixed solution; mixing the metal ion mixed solution, the nonpolar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and carrying out hydrogenation reduction modification to obtain a hydrogenation reduction modified product; and directly mixing the hydrogenation reduction modified product, an acrylonitrile monomer and a redox initiation system, and carrying out graft polymerization reaction to obtain the saturated polar polymer. The invention takes hydrazine hydrate/hydrogen peroxide/metal ion salt as a catalytic system to carry out hydrogenation reduction modification on the nonpolar unsaturated polymer; then, acrylonitrile is grafted and polymerized to a polymer molecular chain in the presence of a redox initiation system, the emulsion polymerization has low viscosity, high heat transfer rate and high polymerization rate, the grafting efficiency can be effectively improved, and the continuous adjustment of the polar group content and the saturation degree is realized.

Description

Saturated polar polymer and preparation method thereof
Technical Field
The invention relates to the technical field of modification, and particularly relates to a saturated polar polymer and a preparation method thereof.
Background
At present, hydrogenated nitrile rubber (HNBR) is generally used as a high-saturation polar polymer material, and HNBR has both aging resistance and oil resistance, but the high price greatly limits the wide application of HNBR in rubber products. The conjugated diene polymer material is used as one of main raw materials in the rubber industry, has excellent comprehensive performance and wide application, but unsaturated carbon-carbon double bonds (C ═ C) with active chemical properties contained in a framework are easily attacked by heat, oxygen, ozone and the like, so that the molecular chain of the polymer is aged to degrade or crosslink, and the aging resistance is poor; and the non-polar property of the conjugated diene polymer material causes the oil resistance of the conjugated diene polymer material to have inherent defects. Through chemical modification, such as hydrogenation, graft copolymerization and the like, of a molecular chain of a nonpolar unsaturated conjugated diene polymer, an unsaturated carbon-carbon double bond (C ═ C) with active chemical properties in a main chain of the polymer is converted into a saturated structure with a polar group, so that the aging resistance and the oil resistance of the material can be further improved on the basis of keeping the original advantages of excellent performance, low cost and the like of the conjugated diene polymer material.
Chinese patent CN110527004A discloses a thiol-ene click chemistry method to graft and modify natural rubber latex, and introduces polar groups on its main chain to improve the oil resistance of natural rubber; meanwhile, the functionalized natural rubber is subjected to solution hydrogenation, so that residual unsaturated double bonds of a main chain are eliminated, the saturation degree of the functionalized natural rubber is further improved, the functionalized natural rubber with better oil resistance and excellent mechanical property is prepared, the application field and the application range of the natural rubber are enlarged, and the problem of poor polymer saturation degree still exists.
Disclosure of Invention
In view of the above, the present invention provides a saturated polar polymer and a preparation method thereof. The polymer prepared by the invention has high saturation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a saturated polar polymer, which comprises the following steps:
mixing an anionic surfactant, a metal ion salt and water to obtain a metal ion mixed solution;
mixing the mixed solution, the nonpolar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and carrying out hydrogenation reduction modification to obtain a hydrogenation reduction modified product;
and directly mixing the hydrogenation reduction modified product with an acrylonitrile monomer and a redox initiation system to carry out graft polymerization reaction to obtain the polar polymer.
Preferably, the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion includes one or more of natural rubber, isoprene rubber, a styrene-isoprene random copolymer, a styrene-isoprene block copolymer, a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a styrene-isoprene-butadiene random copolymer, and a styrene-isoprene-butadiene block copolymer.
Preferably, the metal ion salt comprises one or more of copper sulphate, copper chloride, copper nitrate, iron sulphate, iron chloride, zinc sulphate, zinc chloride, aluminium sulphate, aluminium chloride, neodymium chloride, cobalt sulphate, cadmium sulphate and magnesium sulphate.
Preferably, the mass ratio of the amount of the metal ion salt to the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion is 0.0001 to 0.01 mmol: 1g of the total weight of the composition.
Preferably, the mass of the anionic surfactant is 0.001-10% of the mass of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion.
Preferably, the molar ratio of the hydrazine hydrate to the carbon-carbon double bonds in the non-polar unsaturated polymer emulsion is 1-10: 1.
preferably, the molar ratio of the hydrogen peroxide to the hydrazine hydrate is 1-5: 1.
preferably, the acrylonitrile monomer is used in an amount of 0.1 to 100phr, based on the weight of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion.
Preferably, the temperature of the graft polymerization reaction is 10-30 ℃, and the time is 20-40 h.
The invention also provides a saturated polar polymer prepared by the preparation method of the technical scheme, and the saturation degree of the saturated polar polymer is 17-91%.
The invention provides a preparation method of a saturated polar polymer, which comprises the following steps: mixing an anionic surfactant, a metal ion salt and water to obtain a metal ion mixed solution; mixing the metal ion mixed solution, the nonpolar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and carrying out hydrogenation reduction modification to obtain a hydrogenation reduction modified product; and directly mixing the hydrogenation reduction modified product with an acrylonitrile monomer and a redox initiation system to carry out graft polymerization reaction to obtain the saturated polar polymer. The invention takes hydrazine hydrate/metal ion salt as a catalytic system to carry out hydrogenation reduction modification on the nonpolar unsaturated polymer; and then, acrylonitrile is grafted and polymerized to a polymer molecular chain in the presence of a redox initiation system, and hydrogenation reduction modification and graft polymerization are continuously carried out, so that the production process is simple, the viscosity of emulsion polymerization is low, the heat transfer is high, the polymerization rate is high, the graft polymerization is carried out in emulsion, the system viscosity is low, the heat transfer is high, the polymerization rate is high, the grafting efficiency is high, the saturation of the polar polymer can be effectively improved, the continuous adjustment of the content and the saturation of the polar group is realized, and the prepared polar polymer has the excellent performances of oil resistance and ageing resistance.
In addition, the hydrogen source in the invention is the reaction product diimine of hydrazine hydrate and hydrogen peroxide, hydrogen is not used, the reaction operation is simple, the safety is improved, and the method is green and environment-friendly.
Further, the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion of the invention comprises one or more of natural rubber, isoprene rubber, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-isoprene-butadiene random copolymer and styrene-isoprene-butadiene block copolymer, and the raw materials are easy to obtain and the cost is low.
Furthermore, the method does not use organic solvent and rare metal, and the reaction is carried out under normal pressure;
furthermore, the method realizes the controllable grafting rate of the acrylonitrile by regulating and controlling the temperature and time of the graft polymerization reaction and the dosage of the acrylonitrile monomer.
Detailed Description
The invention provides a preparation method of a saturated polar polymer, which is characterized by comprising the following steps:
mixing an anionic surfactant, a metal ion salt and water to obtain a metal ion mixed solution;
mixing the metal ion mixed solution, the nonpolar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and carrying out hydrogenation reduction modification to obtain a hydrogenation reduction modified product;
and mixing the hydrogenation reduction modified product direct acrylonitrile monomer with a redox initiation system to carry out graft polymerization reaction to obtain the saturated polar polymer.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
The invention mixes the anion surface active agent, the metal ion salt and the water to obtain the metal ion mixed solution.
In the present invention, the metal ion salt preferably includes one or more of copper sulfate, copper chloride, copper nitrate, iron sulfate, iron chloride, zinc sulfate, zinc chloride, aluminum sulfate, aluminum chloride, neodymium chloride, cobalt sulfate, cadmium sulfate, and magnesium sulfate. When the metal ion salts are preferably a mixture, the specific type and amount of each metal ion salt in the mixture are not particularly limited, and the mixture can be used in any ratio. In the present invention, the metal ion salt serves to promote the generation of diimine, thereby improving the hydrogenation reaction efficiency.
In the present invention, the anionic surfactant is preferably sodium lauryl sulfate or sodium dodecylbenzenesulfonate. In the present invention, the anionic surfactant acts as a stabilizer.
The amount of water used in the present invention is not particularly limited, and the anionic surfactant and the metal ion salt can be completely dissolved.
After the mixed solution is obtained, the mixed solution, the nonpolar unsaturated polymer emulsion, the hydrazine hydrate and the hydrogen peroxide are mixed for hydrogenation reduction modification, and a hydrogenation reduction modified product is obtained.
In the present invention, the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion preferably includes one or more of natural rubber, isoprene rubber, a styrene-isoprene random copolymer, a styrene-isoprene block copolymer, a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a styrene-isoprene-butadiene random copolymer, and a styrene-isoprene-butadiene block copolymer. In the present invention, the natural rubber is preferably used in the form of natural latex, and the isoprene rubber is preferably used in the form of isoprene latex. In the present invention, the isoprene rubber is preferably trans-isoprene rubber, and the trans-isoprene rubber is preferably natural gutta percha or synthetic trans-isoprene rubber.
In the invention, the solid content of the nonpolar unsaturated polymer emulsion is preferably 5-60%, and more preferably 10-30%.
In the present invention, the molar amount of the metal ion salt is preferably 0.0001 to 0.01mmol in terms of the mass ratio of the nonpolar unsaturated polymer in the nonpolar unsaturated polymer emulsion: 1g, more preferably 0.001 to 0.008 mmol: 1g of the total weight of the composition.
In the present invention, the mass of the anionic surfactant is preferably 0.001 to 10% of the mass of the nonpolar unsaturated polymer in the nonpolar unsaturated polymer emulsion, and the mass of the anionic surfactant is not 0, and more preferably 0.01 to 1%.
In the invention, the molar ratio of hydrazine hydrate to carbon-carbon double bonds in the non-polar unsaturated polymer emulsion is preferably 1-10: 1. in the present invention, the hydrazine hydrate is preferably added in the form of a hydrazine hydrate solution, and the mass concentration of the hydrazine hydrate solution is preferably 80%.
In the invention, the molar ratio of the hydrogen peroxide to the hydrazine hydrate is preferably 1-5: 1, more preferably 0.5 to 4: 1. in the invention, the hydrogen peroxide is preferably added in the form of hydrogen peroxide, and the mass fraction of the hydrogen peroxide is preferably 30%. In the invention, the hydrogen peroxide is preferably continuously dripped into the reaction system at a constant speed, and the dripping time is preferably 0.5-6 h.
In the present invention, the mixing preferably comprises the steps of:
heating the nonpolar unsaturated polymer emulsion to a temperature of 30-60 ℃ and preserving heat;
sequentially adding an anionic surfactant, a metal ion salt solution and hydrazine hydrate into the heat-insulated nonpolar unsaturated polymer emulsion to obtain a mixed system;
and dropwise adding hydrogen peroxide into the mixed system.
In an embodiment of the present invention, the specific process of mixing preferably comprises the following steps:
placing the nonpolar unsaturated polymer emulsion in a four-neck flask provided with a condenser pipe, a constant-pressure funnel and a mechanical stirrer, and continuously stirring and heating to maintain the temperature at 30-60 ℃;
dissolving the anionic surfactant and the metal ion salt by using water, placing the dissolved anionic surfactant and the metal ion salt into a four-neck flask, uniformly stirring, and adding the hydrazine hydrate;
the hydrogen peroxide is added into a constant pressure funnel and is continuously dripped into a reaction system at a constant speed.
In the invention, the temperature of the hydrogenation reduction modification is preferably 30-60 ℃, and more preferably 40-50 ℃; the time is preferably 3-6 h, and the time is calculated from the uniform mixing of all the raw materials.
After the hydrogenation reduction modification, the invention preferably naturally cools the obtained product system to room temperature and then introduces nitrogen into the system to remove oxygen, thus obtaining the hydrogenation reduction modified product.
After obtaining the hydrogenation reduction modified product, the invention directly mixes the hydrogenation reduction modified product, the acrylonitrile monomer and the oxidation reduction initiation system to carry out graft polymerization reaction, thus obtaining the saturated polar polymer.
In the present invention, the amount of the acrylonitrile monomer is preferably 0.1 to 100phr, more preferably 20 to 70phr, based on the weight of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion.
In the present invention, the redox initiation system is preferably hydrogen peroxide/Fe2+Hydrogen peroxide/Cu+Potassium persulfate/Fe2+Cumene hydroperoxide/Fe2+T-butyl hydroperoxide/tetraethylenepentamine or cumene hydroperoxide/tetraethylenepentamine. In the present invention for said Fe2+And Cu+The source of (A) is not particularly limited, and any source known to those skilled in the art may be used.
In the present invention, the mass ratio of the molar amount of the oxidant component in the redox initiation system to the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion is preferably 0.02 to 0.2 mmol: 1g, the mass ratio of the molar weight of the reducing agent component in the redox initiation system to the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion is preferably 0.02-0.2 mmol: 1g of polymer, the molar ratio of the oxidant component to the reductant component preferably being 1: 1.
in the present invention, the mixing order of the acrylonitrile monomer, the hydrogenation reduction-modified product, and the redox initiation system is preferably: and sequentially adding an acrylonitrile monomer and an oxidant component in a redox initiation system into the hydrogenation reduction modified product, stirring for 20-24 h, and then adding a reducing agent component in the redox initiation system, wherein the oxidant component is added firstly to initiate free radical polymerization.
In the invention, the temperature of the graft polymerization reaction is preferably 10-30 ℃, and more preferably 15-25 ℃; the time is preferably 20-40 h, and the time of the graft polymerization reaction is calculated after the addition of the reducing agent component in the redox initiation system is completed. In the present invention, the graft polymerization reaction is preferably carried out in a protective atmosphere, which is preferably nitrogen.
After the graft polymerization reaction is completed, the invention preferably carries out reduced pressure distillation, flocculation, water washing, soaking, vacuum drying and purification on the obtained graft polymerization reaction product in sequence to obtain the polar polymer.
The parameters of the reduced pressure distillation are not specially limited, and the acrylonitrile monomer can be completely removed.
In the invention, the flocculation is preferably performed by using 2% of calcium chloride (CaCl)2) An aqueous solution.
In the present invention, the mass ratio of the calcium chloride aqueous solution to the polar polymer is preferably 0.001 to 0.5: 1. In the present invention, the aqueous calcium chloride solution is preferably added dropwise to the obtained substrate for reduced pressure distillation, and after the aqueous calcium chloride solution is added dropwise to the obtained substrate for reduced pressure distillation, the substrate for reduced pressure distillation flocculates into gel mass, and the gel mass and the solution are subjected to solid-liquid separation.
In the invention, the washing is preferably carried out for 3-5 times by using deionized water, and the washing has the function of removing components such as a water-soluble catalyst.
In the invention, the soaking time is preferably 24-48 h. In the present invention, the solvent for soaking is preferably deionized water, which serves to further remove components such as water-soluble catalyst.
In the present invention, the temperature of the vacuum drying is preferably 60 ℃ and the time is preferably 12 hours.
In the present invention, the purification is preferably carried out by cutting the obtained vacuum-dried gel mass into pieces, and subjecting the pieces to soxhlet extraction with a mixture of acetone and 2-butanone to remove free polyacrylonitrile, thereby obtaining the polar polymer material. In the present invention, the molar ratio of acetone to 2-butanone in the mixture of acetone and 2-butanone is preferably 3: 1. In the invention, the Soxhlet extraction condition preferably comprises the temperature of 55-80 ℃ and the time of 3-12 h.
The invention also provides a saturated polar polymer prepared by the preparation method in the technical scheme. In the present invention, the saturation degree of the saturated polar polymer is preferably 17% to 91%, and the graft ratio is preferably 5% to 34%.
In order to further illustrate the present invention, the following examples are given to describe the saturated polar polymer and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
The product parameters were tested in the following manner in the examples:
1. the grafting ratio is calculated by adopting the weight change before and after the unsaturated nonpolar polymer emulsion graft polymerization reaction according to the following formula:
Figure BDA0002873795670000071
wherein G is the graft ratio, W0 is the dry mass of the unsaturated nonpolar polymer latex, and Wg is the dry mass of the graft product.
2. The degree of saturation of the product obtained was determined by iodometry.
3. And (3) placing 10mg of the product obtained in the embodiment into a crucible under a nitrogen atmosphere by using a Q50 thermogravimetric analyzer, and testing the thermal decomposition temperature of the product under the conditions that the heating rate is 10 ℃/min, the temperature range is 50-600 ℃ and the nitrogen flow rate is 50 mL/min.
4. The mass change rate of the product obtained in the example in the IRM903 standard oil was tested according to GB/T1690-2010 standard.
Example 1
Placing 30g of natural latex into a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser, adding deionized water for dilution until the solid content of the latex is 15%, adding 0.23g of sodium dodecyl sulfate, stirring for 15min, and sequentially adding 0.008g of copper sulfate pentahydrate and 66.18g of hydrazine hydrate solution with the mass fraction of 80%; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 180g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing adding within 6h, continuing to react for 1h after dropwise adding, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 7.2g of acrylonitrile and 0.032g of tert-butyl hydroperoxide after 30min, stirring for 24h, then adding 0.068g of tetraethylenepentamine, reacting for 40h at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2Flocculating with water solution, washing flocculated gel block with deionized water for 3 times, soaking for 24 hr, and standing at 60 deg.CThe dried gel pieces were cut into small pieces and extracted in a Soxhlet apparatus with a mixture of acetone and 2-butanone (3: 1 molar ratio) to remove free polyacrylonitrile and obtain the product saturated polar polymer after vacuum drying in an air drying oven for 12 h.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of the graft polymerization reaction is indicated by the appearance of peaks.
The saturation of the product was 50%, the acrylonitrile graft ratio was 13%, the thermal decomposition temperature was 449.76 ℃, and the mass change rate in IRM903 at room temperature was 152% over 70 h.
Example 2
In the embodiment, 30g of natural latex is placed in a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser tube, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl sulfate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 66.18g of hydrazine hydrate solution with the mass fraction of 80% are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 180g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing adding within 6h, continuing to react for 1h after dropwise adding, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 12.6g of acrylonitrile and 0.16g of tert-butyl hydroperoxide after 30min, stirring for 24h, then adding 0.34g of tetraethylenepentamine, reacting for 40h at 25 ℃ under the protection of nitrogen, removing unreacted acrylonitrile by reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2Flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24h, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12h, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 60%, the acrylonitrile grafting rate is 22%, the thermal decomposition temperature is 459.13 ℃, and the mass change rate of 70h in IRM903 at room temperature is 126%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 3
In the embodiment, 30g of natural latex is placed in a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser tube, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl sulfate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 66.18g of hydrazine hydrate solution with the mass fraction of 80% are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 180g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6h, continuing to react for 1h after the dropwise adding is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 18.0g of acrylonitrile and 0.16g of tert-butyl hydroperoxide after 30min, stirring for 24h, then adding 0.34g of tetraethylenepentamine, reacting for 40h at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2And (2) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24h, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12h, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 61%, the acrylonitrile grafting rate is 34%, the thermal decomposition temperature is 459.95 ℃, and the mass change rate of the product in IRM903 at room temperature for 70h is 87%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 4
In the embodiment, 30g of natural latex is placed in a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser tube, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl sulfate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 16.54g of hydrazine hydrate solution with the mass fraction of 80% are sequentially added; heating in oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 300g of 30 percent hydrogen peroxide by mass through a separating funnel,controlling the dropping speed, finishing the addition within 6 hours, continuing the reaction for 1 hour after the dropping is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, adding 7.2g of acrylonitrile and 0.032g of tert-butyl hydroperoxide in sequence after 30 minutes, stirring for 24 hours, then adding 0.068g of tetraethylenepentamine, reacting for 40 hours at 25 ℃ under the protection of nitrogen, removing unreacted acrylonitrile by reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2And (2) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24h, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12h, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 17%, the acrylonitrile grafting rate is 15%, the thermal decomposition temperature is 395.56 ℃, and the mass change rate of 70h in IRM903 at room temperature is 147%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 5
In the embodiment, 30g of natural latex is placed in a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser tube, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl sulfate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 16.54g of hydrazine hydrate solution with the mass fraction of 80% are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 300g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6h, continuing to react for 1h after the dropwise adding is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 12.6g of acrylonitrile and 0.16g of tert-butyl hydroperoxide after 30min, stirring for 24h, then adding 0.34g of tetraethylenepentamine, reacting for 40h at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2Flocculating with water solution, washing flocculated gel block with deionized water for 3 times, soaking for 24 hr, vacuum drying in 60 deg.C vacuum drying oven for 12 hr, and dryingThe slabs were cut into small pieces and extracted in a soxhlet apparatus with a mixture of acetone and 2-butanone (3: 1 molar ratio) to remove free polyacrylonitrile to give a product with a saturation of 20%, acrylonitrile grafting of 28%, thermal decomposition temperature of 402.79 ℃ and mass change of 105% in IRM903 at room temperature for 70 h.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 6
In the embodiment, 30g of isoprene latex (with a solid content of 60%) is placed in a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser tube, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl benzene sulfonate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 99.26g of hydrazine hydrate solution with a mass fraction of 80% are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 270g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6h, continuing to react for 1h after the dropwise adding is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 12.6g of acrylonitrile and 0.16g of tert-butyl hydroperoxide after 30min, stirring for 24h, then adding 0.34g of tetraethylenepentamine, reacting for 40h at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2And (2) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24h, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12h, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 81%, the acrylonitrile grafting rate is 24%, the thermal decomposition temperature is 412.15 ℃, and the mass change rate of 70h in IRM903 at room temperature is 115%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is found to be 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 7
In this example, 30g of styrene-butadiene random copolymer latex (with a solid content of 30%, wherein the butadiene content is 77 wt%) is placed in a 500mL four-neck flask equipped with a stirring paddle, a separating funnel and a reflux condenser, deionized water is added for dilution until the solid content of the latex is 15%, 0.11g of sodium dodecyl sulfate is added, and after stirring for 15min, 0.004g of neodymium chloride and 72.19g of 80% hydrazine hydrate solution by mass are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 196.36g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6h, continuing to react for 1h after the dropwise adding is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 12.6g of acrylonitrile and 0.16g of tert-butyl hydroperoxide after 30min, stirring for 24h, then adding 0.34g of tetraethylenepentamine, reacting for 40h at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2And (2) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24 hours, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 93%, the acrylonitrile grafting rate is 5%, the thermal decomposition temperature is 460.93 ℃, and the mass change rate of 70 hours in IRM903 at room temperature is 168%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 8
In the embodiment, 30g of trans-isoprene rubber emulsion (with a solid content of 60%) is placed in a 500ml four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl benzene sulfonate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 72.19g of hydrazine hydrate solution with a mass fraction of 80% are sequentially added; heating in oil bath, maintaining the reaction temperature at 50 deg.C, and adding 180g of substance dropwise via separating funnelControlling the dropping speed of 30 percent hydrogen peroxide, finishing the adding within 6 hours, continuing to react for 1 hour after the dropping is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, adding 7.2g of acrylonitrile and 0.16g of tert-butyl hydroperoxide in sequence after 30 minutes, stirring for 24 hours, then adding 0.34g of tetraethylenepentamine, reacting for 40 hours at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile by reduced pressure distillation, and adopting CaCl calcium chloride with the mass concentration of 2 percent for latex2And (2) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24h, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12h, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 41%, the acrylonitrile grafting rate is 9%, the thermal decomposition temperature is 398.34 ℃, and the mass change rate of 70h in IRM903 at room temperature is 172%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 9
In this example, 30g of styrene-isoprene random copolymer emulsion (solid content is 30%, isoprene content is 80 wt%) is placed in a 500mL four-neck flask equipped with a stirring paddle, a separating funnel and a reflux condenser, deionized water is added for dilution until the solid content of the latex is 15%, 0.11g of sodium dodecylbenzenesulfonate is added, and after stirring for 15min, 0.004g of neodymium chloride and 59.56g of 80% hydrazine hydrate solution by mass are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 162g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6 hours, continuing to react for 1 hour after the dropwise adding is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 7.2g of acrylonitrile and 0.16g of tert-butyl hydroperoxide after 30 minutes, stirring for 24 hours, then adding 0.34g of tetraethylenepentamine, reacting for 40 hours at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2Flocculating the aqueous solution to obtain flocculated glueThe block was washed 3 times with deionized water, soaked for 24h, placed in a 60 ℃ vacuum oven for vacuum drying for 12h, the dried gum block was cut into small pieces, extracted in a soxhlet apparatus with a mixture of acetone and 2-butanone (molar ratio 3:1) to remove free polyacrylonitrile to give the product with a saturation of 89%, acrylonitrile grafting yield of 11%, thermal decomposition temperature of 469.71 ℃, and mass change rate of 70h in IRM903 at room temperature of 159%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Example 10
In this example, 30g of styrene-butadiene-isoprene random copolymer latex (with a solid content of 30%, wherein the butadiene content is 10 wt% and the isoprene content is 82 wt%) was placed in a 500mL four-neck flask equipped with a stirring paddle, a separating funnel and a reflux condenser, deionized water was added to dilute the latex until the solid content of the latex became 15%, 0.11g of sodium dodecylbenzenesulfonate was added, and after stirring for 15min, 0.004g of neodymium chloride and 70.41g of 80% by mass hydrazine hydrate solution were sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 191.51g of hydrogen peroxide with the mass fraction of 30% through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6 hours, continuing to react for 1 hour after the dropwise adding is finished, cooling to room temperature, introducing nitrogen into the system to remove oxygen, sequentially adding 7.2g of acrylonitrile and 0.08g of tert-butyl hydroperoxide after 30 minutes, stirring for 24 hours, then adding 0.17g of tetraethylenepentamine, reacting for 40 hours at 25 ℃ under the protection of nitrogen, then removing unreacted acrylonitrile through reduced pressure distillation, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2Flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24 hours, placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours, cutting the dried gel block into small pieces, extracting the small pieces in a Soxhlet device by using a mixture of acetone and 2-butanone (the molar ratio is 3:1) to remove free polyacrylonitrile to obtain a product, wherein the saturation degree of the product is 91%, the grafting rate of acrylonitrile is 7%, the thermal decomposition temperature is 478.31 ℃, and the mass change rate of 70 hours in IRM903 at room temperature is 162%.
The total reflection Fourier infrared spectrum test is carried out on the prepared saturated polar polymer, and the product is found to be 2235cm-1The occurrence of graft polymerization was confirmed by the appearance of peaks.
Comparative example 1
In this example, 30g of natural rubber latex is placed in a 500mL four-neck flask equipped with a stirring paddle, a separating funnel and a reflux condenser, deionized water is added for dilution until the solid content of the rubber latex is 15%, the rubber latex is heated by an oil bath to keep the temperature at 50 ℃ for 7 hours, and calcium chloride CaCl with the mass concentration of 2% is adopted as the rubber latex2And (3) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24 hours, and placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain a product, wherein the thermal decomposition temperature of the product is 392.14 ℃, and the mass change rate of the product in IRM903 at room temperature for 70 hours is 167%.
Comparative example 2
In the embodiment, 30g of natural latex is placed in a 500mL four-neck flask provided with a stirring paddle, a separating funnel and a reflux condenser tube, deionized water is added for dilution until the solid content of the latex is 15%, 0.23g of sodium dodecyl sulfate is added, and after stirring for 15min, 0.008g of copper sulfate pentahydrate and 66.18g of hydrazine hydrate solution with the mass fraction of 80% are sequentially added; heating in an oil bath, keeping the reaction temperature at 50 ℃, dropwise adding 180g of 30% hydrogen peroxide solution by mass through a separating funnel, controlling the dropwise adding speed, finishing the dropwise adding within 6 hours, continuing to react for 1 hour after the dropwise adding is finished, and adopting calcium chloride CaCl with the mass concentration of 2% as latex2And (3) flocculating the aqueous solution, washing the flocculated gel block for 3 times by using deionized water, soaking for 24h, and placing the gel block in a vacuum drying oven at 60 ℃ for vacuum drying for 12h to obtain a product, wherein the saturation of the product is 45%, the thermal decomposition temperature is 443.84 ℃, and the mass change rate of 70h in IRM903 at room temperature is 171%.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (8)

1. A method for preparing a saturated polar polymer, comprising the steps of:
mixing an anionic surfactant, a metal ion salt and water to obtain a metal ion mixed solution;
mixing the mixed solution, the nonpolar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and carrying out hydrogenation reduction modification to obtain a hydrogenation reduction modified product; the molar ratio of the hydrogen peroxide to the hydrazine hydrate is 1-5: 1;
directly mixing the hydrogenation reduction modified product with an acrylonitrile monomer and a redox initiation system to carry out graft polymerization reaction to obtain the saturated polar polymer; the amount of the acrylonitrile monomer is 0.1 to 100phr based on the weight of the nonpolar unsaturated polymer in the nonpolar unsaturated polymer emulsion.
2. The method of claim 1, wherein the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion comprises one or more of natural rubber, isoprene rubber, a random copolymer of styrene-isoprene, a block copolymer of styrene-isoprene, a random copolymer of styrene-butadiene, a block copolymer of styrene-butadiene, a random copolymer of styrene-isoprene-butadiene, and a block copolymer of styrene-isoprene-butadiene.
3. The method of claim 1, wherein the metal ion salt comprises one or more of copper sulfate, copper chloride, copper nitrate, iron sulfate, iron chloride, zinc sulfate, zinc chloride, aluminum sulfate, aluminum chloride, neodymium chloride, cobalt sulfate, cadmium sulfate, and magnesium sulfate.
4. The production method according to claim 1 or 3, wherein the mass ratio of the amount of the substance of the metal ion salt to the nonpolar unsaturated polymer in the nonpolar unsaturated polymer emulsion is 0.0001 to 0.01 mmol: 1g of the total weight of the composition.
5. The method according to claim 1, wherein the mass of the anionic surfactant is 0.001 to 10% of the mass of the nonpolar unsaturated polymer in the nonpolar unsaturated polymer emulsion.
6. The preparation method according to claim 1, wherein the molar ratio of hydrazine hydrate to carbon-carbon double bonds in the non-polar unsaturated polymer emulsion is 1-10: 1.
7. the method according to claim 1, wherein the temperature of the graft polymerization reaction is 10 to 30 ℃ and the time is 20 to 40 hours.
8. The method of any one of claims 1 to 7, wherein the saturated polar polymer has a saturation degree of 17 to 91%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4452950A (en) * 1983-02-22 1984-06-05 The Goodyear Tire & Rubber Company Process for hydrogenation of carbon-carbon double bonds in an unsaturated polymer in latex form
CN1974621A (en) * 2006-12-07 2007-06-06 武汉工程大学 Modified rubber powder and its prepn and use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4452950A (en) * 1983-02-22 1984-06-05 The Goodyear Tire & Rubber Company Process for hydrogenation of carbon-carbon double bonds in an unsaturated polymer in latex form
CN1974621A (en) * 2006-12-07 2007-06-06 武汉工程大学 Modified rubber powder and its prepn and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Preparation of hydrogenated natural rubber with nanomatrix structure;Thu Ha Nguyen;《Polymers for advanced technologies》;20190910;第31卷(第1期);87、89-90 *

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