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

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

A kind of saturated polar polymer and preparation method thereof

technical field

The invention relates to the technical field of modification, in particular to a saturated polar polymer and a preparation method thereof.

Background technique

At present, the commonly used highly saturated polar polymer material is hydrogenated nitrile butadiene rubber (HNBR). HNBR has both aging resistance and oil resistance, but its high price greatly limits its wide application in rubber products. Conjugated diene polymer materials, as one of the main raw materials in the rubber industry, have excellent comprehensive properties and are widely used. The attack of , oxygen, ozone, etc., causes the polymer molecular chain to age and degrade or cross-link, and the aging resistance is poor; and the non-polar characteristics of the conjugated diene polymer material have inherent defects in its oil resistance. The chemically active unsaturated carbon-carbon double bonds (C=C ) into a saturated structure with polar groups, which can further improve the aging resistance and oil resistance of the material on the basis of maintaining the original advantages of the conjugated diene polymer material, such as excellent performance and low cost.

Chinese patent CN110527004A discloses that natural rubber latex is grafted and modified by mercapto-ene click chemistry, and polar groups are introduced into its main chain to improve the oil resistance of natural rubber; at the same time, the functionalized natural rubber is hydrogenated by solution , eliminate the remaining unsaturated double bonds in the main chain, further improve its saturation, and prepare functionalized natural rubber with good oil resistance and excellent mechanical properties, which expands the application field and scope of natural rubber, but there is still polymer saturation. Poor degree of problem.

SUMMARY OF THE INVENTION

In view of this, the object of the present invention is to provide a saturated polar polymer and a preparation method thereof. The polymer obtained by the invention has high saturation.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a preparation method of a saturated polar polymer, comprising the following steps:

Mixing anionic surfactant, metal ion salt and water to obtain metal ion mixed solution;

Mixing the mixed solution, non-polar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide to carry out hydrogenation reduction modification to obtain a hydrogenation reduction modified product;

The polar polymer is obtained by directly mixing the hydrogenation reduction modified product with acrylonitrile monomer and a redox initiation system to carry out a graft polymerization reaction.

Preferably, the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion includes natural rubber, isoprene rubber, random copolymer of styrene-isoprene, styrene-isoprene block copolymers of styrene-butadiene, random copolymers of styrene-butadiene, block copolymers of styrene-butadiene, random copolymers of styrene-isoprene-butadiene and styrene- One or more of isoprene-butadiene block copolymers.

Preferably, the metal ion salts include copper sulfate, copper chloride, copper nitrate, ferric sulfate, ferric chloride, zinc sulfate, zinc chloride, aluminum sulfate, aluminum chloride, neodymium chloride, cobalt sulfate, cadmium sulfate and One or more of magnesium sulfate.

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 0.0001-0.01 mmol:1 g.

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 bond 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, based on the weight of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion, the amount of the acrylonitrile monomer used is 0.1-100 phr.

Preferably, the temperature of the graft polymerization reaction is 10-30° C., and the time is 20-40 h.

The present invention also provides a saturated polar polymer prepared by the preparation method described in the above technical solution, wherein the saturation degree of the saturated polar polymer is 17-91%.

The invention provides a method for preparing a saturated polar polymer, comprising the following steps: mixing an anionic surfactant, a metal ion salt and water to obtain a metal ion mixed solution; Saturated polymer emulsion, hydrazine hydrate and hydrogen peroxide are mixed, and hydrogenation reduction modification is carried out to obtain a hydrogenation reduction modified product; the hydrogenation reduction modification product is directly mixed with acrylonitrile monomer and a redox initiation system to carry out grafting A polymerization reaction is carried out to obtain the saturated polar polymer. In the present invention, hydrazine hydrate/metal ion salt is used as a catalytic system to carry out hydrogenation reduction modification on non-polar unsaturated polymers; then in the presence of a redox initiation system, acrylonitrile is grafted and polymerized to the polymer molecular chain, and the hydrogenation reduction modification is carried out. Properties and graft polymerization are carried out continuously, the production process is simple, the viscosity of emulsion polymerization is low, the heat transfer is fast and the polymerization rate is high, the graft polymerization is carried out in the emulsion, the system viscosity is low, the heat transfer is fast, the polymerization rate is high, and the grafting efficiency is high , and then the saturation of polar polymers can be effectively improved, the content and saturation of polar groups can be continuously adjusted, and the prepared polar polymers have excellent properties of oil resistance and aging resistance.

Moreover, in the present invention, the hydrogen source is diimine, a reaction product of hydrazine hydrate and hydrogen peroxide, without using hydrogen, the reaction operation is simple, the safety is improved, and the reaction is environmentally friendly.

Further, the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion of the present invention includes natural rubber, isoprene rubber, random copolymer of styrene-isoprene, styrene-isoprene Block copolymers of styrene, random copolymers of styrene-butadiene, block copolymers of styrene-butadiene, random copolymers of styrene-isoprene-butadiene, and styrene -One or more of isoprene-butadiene block copolymers, the raw materials are readily available and the cost is low.

Further, the present invention does not use organic solvents and rare metals, and the reaction is carried out under normal pressure;

Further, in the present invention, the grafting rate of acrylonitrile is controllable by regulating the temperature and time of the graft polymerization reaction and the amount of the acrylonitrile monomer.

Detailed ways

The invention provides a kind of preparation method of saturated polar polymer, it is characterized in that, comprises the following steps:

Mixing anionic surfactant, metal ion salt and water to obtain metal ion mixed solution;

Mixing the metal ion mixed solution, non-polar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and performing hydrogenation reduction modification to obtain a hydrogenation reduction modification product;

The hydrogenation reduction modified product is directly mixed with acrylonitrile monomer and a redox initiation system to carry out a graft polymerization reaction to obtain the saturated polar polymer.

In the present invention, unless otherwise specified, the raw materials used are all commercially available products in the field.

In the present invention, an anionic surfactant, a metal ion salt and water are mixed to obtain a metal ion mixed solution.

In the present invention, the metal ion salt preferably includes copper sulfate, copper chloride, copper nitrate, ferric sulfate, ferric chloride, zinc sulfate, zinc chloride, aluminum sulfate, aluminum chloride, neodymium chloride, cobalt sulfate, One or more of cadmium sulfate and magnesium sulfate. When the metal ion salt is preferably a mixture, the present invention does not specifically limit the specific type and amount of each metal ion salt in the mixture, and a mixture in any ratio can be used. In the present invention, the role of the metal ion salt is to promote the formation of diimine, thereby improving the efficiency of the hydrogenation reaction.

In the present invention, the anionic surfactant is preferably sodium dodecyl sulfate or sodium dodecylbenzenesulfonate. In the present invention, the anionic surfactant acts as a stabilizer.

The present invention has no special limitation on the amount of the water, as long as the anionic surfactant and the metal ion salt can be completely dissolved.

After the mixed solution is obtained, the present invention mixes the mixed solution, the non-polar unsaturated polymer emulsion, hydrazine hydrate and hydrogen peroxide, and performs hydrogenation reduction modification to obtain a hydrogenation reduction modified product.

In the present invention, the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion preferably includes natural rubber, isoprene rubber, random copolymer of styrene-isoprene, styrene-isoprene Block copolymers of pentadiene, random copolymers of styrene-butadiene, block copolymers of styrene-butadiene, random copolymers of styrene-isoprene-butadiene and One or more of the block copolymers of styrene-isoprene-butadiene. 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 eucommia gum or synthetic trans-isoprene rubber. The specific method is not particularly limited, and a method well known to those skilled in the art can be used.

In the present invention, the solid content of the non-polar unsaturated polymer emulsion is preferably 5-60%, more preferably 10-30%.

In the present invention, the molar ratio of the metal ion salt to the mass ratio of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion is preferably 0.0001-0.01 mmol: 1 g, more preferably 0.001-0.008 mmol : 1g.

In the present invention, the mass of the anionic surfactant is preferably 0.001-10% of the mass of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion, and the mass of the anionic surfactant is not 0 , more preferably 0.01 to 1%.

In the present invention, the molar ratio of the hydrazine hydrate to the carbon-carbon double bond 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 present invention, the molar ratio of the hydrogen peroxide to the hydrazine hydrate is preferably 1-5:1, more preferably 0.5-4:1. In the present 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 present invention, the hydrogen peroxide is preferably continuously added dropwise to the reaction system at a constant speed, and the dropwise addition time is preferably 0.5-6 h.

In the present invention, the mixing preferably comprises the following steps:

heating the non-polar unsaturated polymer emulsion to a temperature of 30 to 60 °C;

Adding anionic surfactant, metal ion salt solution, and hydrazine hydrate to the thermally insulated non-polar unsaturated polymer emulsion in turn to obtain a mixed system;

Hydrogen peroxide was added dropwise to the mixed system.

In an embodiment of the present invention, the specific process of mixing preferably includes the following steps:

The non-polar unsaturated polymer emulsion is placed in a four-necked flask equipped with a condenser tube, a constant pressure funnel and a mechanical stirrer, and the temperature is maintained at 30-60° C. with continuous stirring and heating;

The anionic surfactant and the metal ion salt are dissolved in water and placed in a four-necked flask, and after stirring evenly, the hydrazine hydrate is added;

The hydrogen peroxide was added to the constant pressure funnel, and was continuously added dropwise to the reaction system at a constant speed.

In the present invention, the temperature of the hydrogenation reduction modification is preferably 30-60°C, more preferably 40-50°C; the time is preferably 3-6h, and the time is calculated from the time when all the raw materials are uniformly mixed.

After the hydrogenation reduction modification, in the present invention, preferably, the obtained product system is naturally cooled to room temperature and then nitrogen gas is introduced into the system to remove oxygen to obtain a hydrogenation reduction modification product.

After the hydrogenation reduction modified product is obtained, the present invention directly mixes the hydrogenation reduction modified product, acrylonitrile monomer and a redox initiation system, and carries out a graft polymerization reaction to obtain the saturated polar polymer.

In the present invention, based on the weight of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion, the amount of the acrylonitrile monomer used is preferably 0.1-100 phr, more preferably 20-70 phr.

In the present invention, the redox initiation system is preferably hydrogen peroxide/Fe ²⁺ , hydrogen peroxide/Cu ⁺ , potassium persulfate/Fe ²⁺ , cumene hydrogen peroxide/Fe ²⁺ , tert-butyl Hydrogen peroxide/tetraethylenepentamine or cumene hydroperoxide/tetraethylenepentamine. The source of the Fe ²⁺ and Cu ⁺ is not particularly limited in the present invention, and sources well known to those skilled in the art can be used.

In the present invention, the molar ratio of the oxidant component in the redox initiation system to the mass ratio of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion is preferably 0.02-0.2 mmol: 1 g, so The molar ratio of the reducing agent component in the redox initiation system to the mass ratio of the non-polar unsaturated polymer in the non-polar unsaturated polymer emulsion is preferably 0.02-0.2 mmol: 1 g polymer, and the oxidizing agent group is The molar ratio of the component to the reducing agent component is preferably 1:1.

In the present invention, the mixing sequence of the acrylonitrile monomer, the hydrogenation reduction modified product and the redox initiation system is preferably as follows: the acrylonitrile monomer and the redox initiation system are sequentially added to the hydrogenation reduction modified product. The oxidant component is stirred for 20 to 24 hours, and then the reducing agent component in the redox initiation system is added, and the function of adding the oxidant component first is to initiate free radical polymerization.

In the present invention, the temperature of the graft polymerization reaction is preferably 10-30°C, more preferably 15-25°C; the time is preferably 20-40h, and the time of the graft polymerization reaction is based on the redox initiation system The calculation starts after the addition of the reducing agent component in . In the present invention, the graft polymerization reaction is preferably carried out in a protective atmosphere, and the protective atmosphere is preferably nitrogen.

After the graft polymerization reaction is completed, in the present invention, the obtained graft polymerization reaction product is preferably subjected to vacuum distillation, flocculation, water washing, soaking, vacuum drying and purification in sequence to obtain the polar polymer.

The parameters of the vacuum distillation are not particularly limited in the present invention, as long as the acrylonitrile monomer can be completely removed.

In the present invention, the flocculation is preferably performed with an aqueous calcium chloride (CaCl ₂ ) solution with a mass concentration of 2%.

In the present invention, the mass ratio of the calcium chloride aqueous solution to the polar polymer is preferably 0.001-0.5:1. In the present invention, the calcium chloride aqueous solution is preferably added dropwise to the obtained vacuum distillation substrate, and after the calcium chloride aqueous solution is added dropwise to the obtained vacuum distillation substrate, the vacuum distillation substrate is flocculated To form a gel block, the gel block can be separated from the solution by solid-liquid separation.

In the present invention, the water washing is preferably washed with deionized water for 3 to 5 times, and the function of the water washing is to remove components such as water-soluble catalysts.

In the present invention, the soaking time is preferably 24-48 hours. In the present invention, the soaking solvent is preferably deionized water, which acts to further remove components such as water-soluble catalysts.

In the present invention, the temperature of the vacuum drying is preferably 60°C, and the time is preferably 12h.

In the present invention, the purification is preferably performed by cutting the obtained glue block after vacuum drying into pieces, and performing Soxhlet extraction with a mixture of acetone and 2-butanone to remove free polyacrylonitrile to obtain the polar polymerization material. In the present invention, the molar ratio of acetone and 2-butanone in the mixture of acetone and 2-butanone is preferably 3:1. In the present invention, the conditions of the Soxhlet extraction preferably include a temperature of 55-80° C. and a time of 3-12 hours.

The present invention also provides the saturated polar polymer prepared by the preparation method described in the above technical solution. 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 saturated polar polymer provided by the present invention and its preparation method are described in detail below with reference to examples, but they should not be construed as limiting the protection scope of the present invention.

In the embodiment, the parameters of the product are tested in the following manner:

1. The calculation of the graft ratio adopts the following formula to calculate the weight change before and after the unsaturated non-polar polymer emulsion graft polymerization reaction:

In the formula, G is the graft ratio, W0 is the dry rubber mass of the unsaturated non-polar polymer latex, and Wg is the dry rubber mass of the grafted product.

2. The saturation of the obtained product was measured by the iodometric method.

3. Using a Q50 type thermogravimetric analyzer, under a nitrogen atmosphere, put 10 mg of the obtained product of the embodiment into a crucible, the heating rate is 10 ° C/min, the temperature range is 50 ~ 600 ° C, and the nitrogen flow rate is 50mL/min conditions The thermal decomposition temperature of the test product.

4. According to the GB/T 1690-2010 standard, test the mass change rate of the products obtained in the examples in IRM903 standard oil.

Example 1

Place 30g of natural latex in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, add deionized water to dilute to a latex solid content of 15%, and add 0.23g of sodium lauryl sulfate, After stirring for 15min, 0.008g of copper sulfate pentahydrate and 66.18g of hydrazine hydrate solution with a mass fraction of 80% were added in sequence; heated in an oil bath, keeping the reaction temperature at 50°C, 180g of hydrogen peroxide with a mass fraction of 30% was added dropwise through a separatory funnel to control The rate of addition was completed within 6 hours. After the addition was completed, the reaction was continued for 1 hour. The temperature was lowered to room temperature. Nitrogen was introduced into the system to remove oxygen. 24h, then add 0.068g tetraethylenepentamine, react at 25°C for 40h under nitrogen protection, then remove unreacted acrylonitrile by vacuum distillation, the latex is flocculated with a 2% mass concentration of calcium chloride ( _CaCl2) aqueous solution, The flocculated glue block was washed three times with deionized water, soaked for 24 hours, and then placed in a vacuum drying oven at 60 °C for 12 hours of vacuum drying. The dried glue block was cut into small pieces. The mixture of :1) is extracted in a Soxhlet device to remove free polyacrylonitrile to obtain the product saturated polar polymer.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

The saturation of the product was 50%, the grafting rate of acrylonitrile was 13%, the thermal decomposition temperature was 449.76°C, and the mass change rate in IRM903 at room temperature for 70 h was 152%.

Example 2

In this example, 30g of natural latex was placed in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, deionized water was added to dilute until the latex solid content was 15%, and 0.23g of dodecyl was added. Sodium sulfate, after stirring for 15min, add 0.008g copper sulfate pentahydrate and 66.18g 80% hydrazine hydrate solution in turn; heat in oil bath, keep the reaction temperature at 50 ℃, add 180g 30% hydrazine hydrate dropwise through a separatory funnel Hydrogen peroxide, controlled the rate of addition, added within 6 h, after the addition was completed, continued the reaction for 1 h, cooled to room temperature, passed nitrogen into the system to remove oxygen, and added 12.6 g of acrylonitrile and 0.16 g of tert-butyl peroxide in sequence after 30 min Hydrogen, stirred for 24h, then added 0.34g tetraethylenepentamine, reacted at 25°C for 40h under nitrogen protection, and then removed unreacted acrylonitrile by vacuum distillation, the latex was a 2% mass concentration of calcium chloride CaCl ₂ aqueous solution After flocculation, the flocculated glue block was washed 3 times with deionized water, soaked for 24 hours, placed in a vacuum drying oven at 60 °C for 12 hours, and the dried glue block was cut into small pieces. The mixture with a ratio of 3:1) was extracted in a Soxhlet device to remove free polyacrylonitrile to obtain a product with a saturation of 60%, acrylonitrile grafting rate of 22%, and a thermal decomposition temperature of 459.13°C, The mass change in IRM903 at room temperature for 70 h was 126%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 3

In this example, 30g of natural latex was placed in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, deionized water was added to dilute until the latex solid content was 15%, and 0.23g of dodecyl was added. Sodium sulfate, after stirring for 15min, add 0.008g copper sulfate pentahydrate and 66.18g 80% hydrazine hydrate solution in turn; heat in oil bath, keep the reaction temperature at 50 ℃, add 180g 30% hydrazine hydrate dropwise through a separatory funnel Hydrogen peroxide, controlled the rate of addition, added within 6h, after the addition, continued the reaction for 1h, cooled to room temperature, passed nitrogen into the system to remove oxygen, and added 18.0g acrylonitrile and 0.16g tert-butyl peroxide in sequence after 30min Hydrogen, stirred for 24h, then added 0.34g tetraethylenepentamine, reacted at 25°C for 40h under nitrogen protection, and then removed unreacted acrylonitrile by vacuum distillation, the latex was a 2% mass concentration of calcium chloride CaCl ₂ aqueous solution After flocculation, the flocculated glue block was washed 3 times with deionized water, soaked for 24 hours, placed in a vacuum drying oven at 60 °C for 12 hours, and the dried glue block was cut into small pieces. The mixture with a ratio of 3:1) was extracted in a Soxhlet device to remove free polyacrylonitrile to obtain a product with a saturation of 61%, acrylonitrile grafting rate of 34%, and a thermal decomposition temperature of 459.95°C, The mass change in IRM903 for 70 h at room temperature was 87%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 4

In this example, 30g of natural latex was placed in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, deionized water was added to dilute until the latex solid content was 15%, and 0.23g of dodecyl was added. Sodium sulfate, after stirring for 15min, add 0.008g copper sulfate pentahydrate and 16.54g 80% hydrazine hydrate solution in turn; heat in oil bath, keep the reaction temperature at 50 ℃, add 300g 30% hydrazine hydrate dropwise through a separatory funnel Hydrogen peroxide, controlled the rate of addition, added within 6h, after the addition was completed, continued the reaction for 1h, cooled to room temperature, passed nitrogen into the system to remove oxygen, and added 7.2g of acrylonitrile and 0.032g of tert-butyl peroxide in sequence after 30min Hydrogen, stirred for 24h, then added 0.068g tetraethylenepentamine, reacted at 25°C for 40h under nitrogen protection, and then removed unreacted acrylonitrile by vacuum distillation, the latex was a 2% mass concentration of calcium chloride CaCl ₂ aqueous solution After flocculation, the flocculated glue block was washed 3 times with deionized water, soaked for 24 hours, placed in a vacuum drying oven at 60 °C for 12 hours, and the dried glue block was cut into small pieces. The mixture with a ratio of 3:1) was extracted in a Soxhlet device to remove free polyacrylonitrile to obtain a product with a saturation of 17%, a graft ratio of acrylonitrile of 15%, and a thermal decomposition temperature of 395.56°C, The mass change in IRM903 for 70 h at room temperature was 147%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 5

In this example, 30g of natural latex was placed in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, deionized water was added to dilute until the latex solid content was 15%, and 0.23g of dodecyl was added. Sodium sulfate, after stirring for 15min, add 0.008g copper sulfate pentahydrate and 16.54g 80% hydrazine hydrate solution in turn; heat in oil bath, keep the reaction temperature at 50 ℃, add 300g 30% hydrazine hydrate dropwise through a separatory funnel Hydrogen peroxide, controlled the rate of addition, added within 6 h, after the addition was completed, continued the reaction for 1 h, cooled to room temperature, passed nitrogen into the system to remove oxygen, and added 12.6 g of acrylonitrile and 0.16 g of tert-butyl peroxide in sequence after 30 min Hydrogen, stirred for 24h, then added 0.34g tetraethylenepentamine, reacted at 25°C for 40h under nitrogen protection, and then removed unreacted acrylonitrile by vacuum distillation, the latex was a 2% mass concentration of calcium chloride CaCl ₂ aqueous solution After flocculation, the flocculated glue block was washed 3 times with deionized water, soaked for 24 hours, placed in a vacuum drying oven at 60 °C for 12 hours, and the dried glue block was cut into small pieces. The mixture with a ratio of 3:1) was extracted in a Soxhlet device to remove free polyacrylonitrile to obtain a product with a saturation of 20%, acrylonitrile grafting rate of 28%, and a thermal decomposition temperature of 402.79°C, The mass change in IRM903 for 70 h at room temperature was 105%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 6

In this example, 30 g of isoprene latex (solid content of 60%) was placed in a 500 mL four-necked flask equipped with a stirring paddle, a separatory funnel, and a reflux condenser, and deionized water was added to dilute until the solid content of the latex was 15%. Add 0.23g sodium dodecylbenzenesulfonate, and after stirring for 15min, add 0.008g copper sulfate pentahydrate and 99.26g hydrazine hydrate solution with a mass fraction of 80% in turn; heat in an oil bath, keep the reaction temperature at 50°C, and pass liquid separation 270g of hydrogen peroxide with a mass fraction of 30% was added dropwise to the funnel, the rate of addition was controlled, and the addition was completed within 6 hours. After the addition was completed, the reaction was continued for 1 hour, cooled to room temperature, and nitrogen was introduced into the system to remove oxygen. After 30 minutes, 12.6g of propylene was added in sequence Nitrile and 0.16g tert-butyl hydroperoxide were stirred for 24h, then 0.34g of tetraethylenepentamine was added, reacted at 25°C for 40h under nitrogen protection, and then the unreacted acrylonitrile was removed by vacuum distillation. The mass concentration of the latex was 2% calcium chloride ( _CaCl2) aqueous solution was used for flocculation. The flocculated glue block was washed three times with deionized water, soaked for 24 hours, and then placed in a vacuum drying box at 60 °C for 12 hours. The dried glue block was cut into small pieces. Extraction in a Soxhlet device with a mixture of acetone and 2-butanone (molar ratio of 3:1) to remove free polyacrylonitrile to obtain a product with a saturation of 81% and acrylonitrile graft ratio of 24 %, the thermal decomposition temperature is 412.15℃, and the mass change rate in IRM903 at room temperature for 70h is 115%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 7

In the present embodiment, 30g of styrene-butadiene random copolymer latex (solid content is 30%, wherein butadiene content is 77wt%) is placed in a 500mL four-port 500mL equipped with a stirring paddle, a separatory funnel and a reflux condenser. In the flask, add deionized water to dilute until the latex solid content is 15%, and add 0.11g of sodium dodecyl sulfate, after stirring for 15min, add 0.004g of neodymium chloride and 72.19g of hydrazine hydrate solution with a mass fraction of 80% in turn ; Heating in an oil bath, keeping the reaction temperature at 50 °C, adding 196.36 g of hydrogen peroxide with a mass fraction of 30% through a separatory funnel, controlling the rate of addition, and adding it within 6 hours. Nitrogen was introduced into the system to remove oxygen. After 30 min, 12.6 g of acrylonitrile and 0.16 g of tert-butyl hydroperoxide were added in sequence, stirred for 24 h, and then 0.34 g of tetraethylene pentamine was added to react at 25 °C for 40 h under nitrogen protection, and then Unreacted acrylonitrile was removed by distillation under reduced pressure. The latex was flocculated with an aqueous solution of calcium chloride (CaCl ₂ ) with a mass concentration of 2%. The flocculated rubber block was washed three times with deionized water, soaked for 24 hours, and then placed in a vacuum at 60 °C. Vacuum dry in a drying box for 12h, cut the dried glue block into small pieces, and extract in a Soxhlet device with a mixture of acetone and 2-butanone (molar ratio of 3:1) to remove free polyacrylonitrile to obtain the product , the saturation of the product is 93%, the grafting rate of acrylonitrile is 5%, the thermal decomposition temperature is 460.93℃, and the mass change rate in IRM903 at room temperature for 70h is 168%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 8

In this example, 30g of trans-isoprene rubber latex (solid content of 60%) was placed in a 500ml four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, and deionized water was added to dilute until the latex solid content was 15%, and add 0.23g sodium dodecylbenzenesulfonate, after stirring for 15min, add 0.008g copper sulfate pentahydrate and 72.19g hydrazine hydrate solution with a mass fraction of 80% in turn; heat in an oil bath to keep the reaction temperature at 50°C , 180g of hydrogen peroxide with a mass fraction of 30% was added dropwise through a separatory funnel to control the rate of addition, and the addition was completed within 6 hours. After the addition was completed, the reaction was continued for 1 hour, cooled to room temperature, and nitrogen was introduced into the system to remove oxygen. Add 7.2g acrylonitrile and 0.16g tert-butyl hydroperoxide, stir for 24h, then add 0.34g tetraethylenepentamine, react at 25℃ for 40h under nitrogen protection, then remove unreacted acrylonitrile by vacuum distillation, latex The mass concentration of 2% calcium chloride ( _CaCl2) aqueous solution was used for flocculation, and the flocculated glue block was washed with deionized water for 3 times, soaked for 24 hours, and then placed in a vacuum drying box at 60 °C for 12 hours. It was cut into small pieces and extracted in a Soxhlet apparatus with a mixture of acetone and 2-butanone (molar ratio of 3:1) to remove free polyacrylonitrile to obtain a product with a saturation of 41%, acrylonitrile connected The branch rate was 9%, the thermal decomposition temperature was 398.34℃, and the mass change rate in IRM903 at room temperature for 70h was 172%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 9

In this example, 30 g of styrene-isoprene random copolymer emulsion (solid content of 30% and isoprene content of 80% by weight) was placed in a 500-mL four-pack equipped with a stirring paddle, a separatory funnel and a reflux condenser. In the flask, add deionized water to dilute until the latex solid content is 15%, and add 0.11g of sodium dodecylbenzenesulfonate, after stirring for 15min, add 0.004g of neodymium chloride and 59.56g of 80% neodymium chloride in turn. Hydrazine hydrate solution; heated in an oil bath, keeping the reaction temperature at 50 °C, dropwise 162 g of hydrogen peroxide with a mass fraction of 30% through a separatory funnel, controlling the rate of addition, the addition is completed within 6 hours, after the dropwise addition is completed, continue to react for 1 hour, and cool to room temperature , nitrogen was introduced into the system to remove oxygen, 7.2g of acrylonitrile and 0.16g of tert-butyl hydroperoxide were added in sequence after 30min, stirred for 24h, then 0.34g of tetraethylenepentamine was added, and the reaction was carried out at 25°C for 40h under nitrogen protection Then, the unreacted acrylonitrile was removed by vacuum distillation. The latex was flocculated with an aqueous solution of calcium chloride (CaCl ₂ ) with a mass concentration of 2%. ℃ vacuum drying in a vacuum oven for 12h, cut the dried glue block into small pieces, and extract in a Soxhlet device with a mixture of acetone and 2-butanone (molar ratio of 3:1) to remove free polyacrylonitrile, The product was obtained, the saturation of the product was 89%, the graft ratio of acrylonitrile was 11%, the thermal decomposition temperature was 469.71°C, and the mass change rate in IRM903 at room temperature for 70 hours was 159%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Example 10

In this example, 30g of styrene-butadiene-isoprene random copolymer latex (solid content is 30%, wherein the butadiene content is 10wt%, and the isoprene content is 82wt%) is placed in the Into the 500mL four-necked flask of stirring paddle, separatory funnel and reflux condenser, add deionized water to dilute until the latex solid content is 15%, and add 0.11g of sodium dodecylbenzenesulfonate, after stirring for 15min, add 0.004 g neodymium chloride and 70.41 g hydrazine hydrate solution with a mass fraction of 80%; heating in an oil bath, keeping the reaction temperature at 50 °C, dropwise 191.51 g hydrogen peroxide with a mass fraction of 30% through a separatory funnel, controlling the rate of addition, and adding it within 6 h , after the dropwise addition, the reaction was continued for 1 h, cooled to room temperature, nitrogen was introduced into the system to remove oxygen, 7.2 g of acrylonitrile and 0.08 g of tert-butyl hydroperoxide were added in sequence after 30 min, stirred for 24 h, and then 0.17 g of tetrafluoroethylene was added. Ethylenepentamine was reacted at 25°C for 40h under nitrogen protection, and then unreacted acrylonitrile was removed by distillation under reduced pressure. The latex was flocculated with an aqueous solution of calcium chloride with a mass concentration of ₂ %, and the flocculated glue was used for Washed with ionized water for 3 times, soaked for 24 hours, placed in a vacuum drying oven at 60 °C for 12 hours, and cut the dried glue into small pieces. Extraction in the formula device to remove the free polyacrylonitrile to obtain the product, the saturation of the product is 91%, the grafting rate of acrylonitrile is 7%, the thermal decomposition temperature is 478.31 ℃, and the mass change rate in IRM903 at room temperature for 70h is 162%.

The obtained saturated polar polymer was tested by total reflection Fourier transform infrared spectroscopy, and it was found that the product peaked at about 2235 cm ^-1 , indicating that the graft polymerization reaction occurred.

Comparative Example 1

In this example, 30g of natural latex was placed in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel, and a reflux condenser, and deionized water was added to dilute until the latex solid content was 15%, and the oil bath heating maintained the temperature at 50°C , 7h, the latex was flocculated with an aqueous solution of calcium chloride ( _CaCl2) with a mass concentration of 2%. The flocculated rubber block was washed with deionized water for 3 times, soaked for 24h, and then placed in a vacuum drying box at 60 °C for 12h to obtain the product. , the thermal decomposition temperature of the product is 392.14℃, and the mass change rate in IRM903 at room temperature for 70h is 167%.

Comparative Example 2

In this example, 30g of natural latex was placed in a 500mL four-necked flask equipped with a stirring paddle, a separatory funnel and a reflux condenser, deionized water was added to dilute until the latex solid content was 15%, and 0.23g of dodecyl was added. Sodium sulfate, after stirring for 15min, add 0.008g copper sulfate pentahydrate and 66.18g 80% hydrazine hydrate solution in turn; heat in oil bath, keep the reaction temperature at 50 ℃, add 180g 30% hydrazine hydrate dropwise through a separatory funnel Hydrogen peroxide, control the dripping speed, add it within 6h, and continue the reaction for 1h after the dripping is completed. The latex is flocculated with an aqueous solution of calcium chloride with a mass concentration of ₂ %, and the flocculated rubber block is washed with deionized water 3 times. After soaking for 24 hours, the product was vacuum-dried in a 60°C vacuum drying oven for 12 hours to obtain a product with a saturation of 45%, a thermal decomposition temperature of 443.84°C, and a mass change rate of 171% in IRM903 at room temperature for 70 hours.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any form. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can also be made, and these improvements and modifications should also be regarded 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%.