CN113621138A - Claw-type polyvinyl silicone oil and preparation method thereof - Google Patents
Claw-type polyvinyl silicone oil and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract
The invention relates to claw-type polyvinyl silicone oil and a preparation method thereof, wherein the preparation method comprises the following steps: dimethyl siloxane ring bodies, methyl vinyl siloxane ring bodies and hexavinyl disiloxane), and the like, and the raw materials are subjected to water and impurity removal pretreatment, the pretreated materials are added into a stirring kettle in proportion, the constant temperature T = 30-70 ℃, the materials are pumped into a fluidized bed through a conveying pump and subjected to low-temperature reaction to obtain a crude polymer, the crude polymer enters a low-temperature removal system with the pressure of less than 50Pa and the temperature of 100-150 ℃, and the low-temperature removal system obtains the claw type polyvinyl silicone oil which has no peculiar smell, good appearance transparency and low silicon hydroxyl value. The claw-type polyvinyl silicone oil prepared by the low-temperature solid catalyst improves the use efficiency of the hexavinyl disiloxane, reduces the cost, does not additionally introduce metal ions, enriches the varieties of the vinyl silicone oil, and can greatly enhance the application performance indexes such as the linear expansion coefficient, the size change rate and the like of materials such as silica gel and the like.
Description
Technical Field
The invention relates to claw-type polyvinyl silicone oil and a preparation method thereof.
Background
The vinyl silicone oil is the main raw material of addition type silicone rubber, a reinforcing agent of high-temperature rubber, a modifier of other materials such as polyurethane, acrylic ester and the like, and has wide application fields. The polyvinyl silicone oil is polysiloxane which generally takes siloxane chain links as a main chain, a side chain or an end position and contains vinyl groups and has higher vinyl content, and mainly has the performances of increasing crosslinking density, improving hardness, tearing strength and the like.
Chinese patent document CN105482121A (application number: CN201511008606.0) discloses a synthetic method of polyvinyl silicone oil, which comprises the following steps: dimethyl cyclosiloxane mixture DMC and tetramethyl divinyl disiloxane are subjected to polymerization reaction under the action of an alkaline catalyst, after the reaction is finished, the temperature is increased to degrade the alkaline catalyst, low-boiling-point substances are removed by distillation, and finally the polyvinyl silicone oil is obtained. The alkaline catalyst in the process is tetramethylammonium hydroxide, the reaction temperature is 90-110 ℃, but the boiling point of tetramethyldivinyldisiloxane is 139 ℃, the tetramethyldivinyldisiloxane is volatile to generate higher saturated steam, and the effective utilization rate is low. The obtained polyvinyl silicone oil has polysiloxane as main chain and 1 equivalent of vinyl group at the end position, and the finished product has a large ammonia odor.
Chinese patent document CN105384936B discloses a preparation method of polyvinyl silicone oil, which comprises the following steps: adding a linear body, tetramethyltetravinylcyclotetrasiloxane and a capping agent into a reaction kettle, heating to 130-150 ℃, adding potassium hydroxide, stirring for reaction, keeping the temperature, vacuumizing, performing dehydration reaction, recovering normal pressure, adding phosphoric acid or silicon-based phosphate for neutralization, heating and removing low molecules under negative pressure to obtain the product. The end sealing agent is methyl silicone oil or single vinyl-terminated silicone oil with the polymerization degree of 2-5. The main chain of the product obtained by the method is polysiloxane, the terminal position is methyl or single vinyl group, the residual amount of potassium ions is high, and the potassium ions are difficult to remove, so that the application of the product in a scene with requirements on insulating property is limited.
The claw-type polyvinyl silicone oil containing 3 equivalent of vinyl groups at the end positions can improve the crosslinking density of materials such as silicon rubber and the like, greatly improve the application performances such as linear expansion coefficient, size change rate and the like of addition type silicon rubber and modified materials, and is particularly applied to aerospace and aviation neck materials. The polyvinyl silicone oil which takes polysiloxane as a main chain and contains 3 equivalent of vinyl groups at the end position and the preparation method thereof are reported, so that the development of the synthetic method of the claw-type polyvinyl silicone oil has important significance.
Disclosure of Invention
In order to prepare the claw-type polyvinyl silicone oil, the ammonia odor is eliminated, the potassium ion content in the product is greatly reduced, the application performance of the product is improved, and the application scene is not influenced. In order to achieve the purpose, the invention provides the following technical scheme:
the molecular formula of the claw-type polyvinyl silicone oil is shown as follows,
wherein m is 1-250, n is 0-50, and m and n are integers.
A preparation method of claw-type polyvinyl silicone oil comprises the following steps:
(1) raw material pretreatment, namely water and impurity removal pretreatment of dimethyl siloxane ring (DMC) and hexavinyl disiloxane (HVDS);
(2) adding the pretreated DMC and the pretreated HVDS into a stirring kettle in proportion, and heating to the temperature T-30-70 ℃ to obtain a mixed material A;
(3) pumping the mixed material A into a fluidized bed with a constant temperature of T +/-2 ℃ by a material delivery pump, filling a resin catalyst B into the fluidized bed, and allowing the material to pass through the fluidized bed for 5min to 24h to obtain a crude polymer C;
(4) and (3) removing the crude polymer C to obtain a finished product D under the conditions that the pressure is less than 50Pa and the temperature is 100-150 ℃.
The pre-treatment of the DMC, the VMC and the HVDS is at least one stage of bag filter and one stage of membrane filter, wherein the DMC is dehydrated for 0.5 to 6.0 hours in a dehydration kettle with the pressure less than 200Pa and the temperature of 40 to 80 ℃ after the filtration, the VMC and the HVDS are respectively adsorbed by a molecular sieve packed tower, and the purity of the DMC is more than or equal to 99.999 percent and the water content is less than 20ppm after the treatment; HVDS purity is greater than or equal to 99.9%, and water content is less than 20 ppm.
In the addition amounts of the dimethyl siloxane ring body and the hexavinyl disiloxane in the step (2), the DMC accounts for 64.0-98.5 wt%, and the HVDS accounts for 1.5-36.0%.
And (2) adding methylvinylsiloxane ring bodies (VMC), wherein the VMC is pretreated by filtering through at least a first-stage bag filter and a first-stage membrane filter, the VMC is respectively adsorbed by a molecular sieve packed tower, and the purity of the VMC is more than or equal to 99.99% and the water content of the VMC is less than 20ppm after treatment.
The proportions of DMC, VMC and HVDS are that DMC accounts for 64.0-97.5 wt%, VMC accounts for 1-10.0% and HVDS accounts for 1.5-36.0%.
The resin catalyst in the step (3) is polystyrene cation exchange resin loaded with acid sites, wherein the concentration of the acid sites is more than or equal to 5.0mmol/g, the effective particle size is 0.50-2.00 mm, the uniformity coefficient is less than or equal to 1.50, and the water content is less than or equal to 0.5%.
Through the technical scheme, the invention has the following technical effects:
1. the raw materials are pretreated by removing water and impurities, so that the purity of the raw materials is improved, side reactions are reduced, and a target product is purified.
2. The boiling point of the hexavinyl disiloxane is 119 ℃, the volatile component is volatile, the reaction temperature T +/-2 (T is 30-70 ℃) is adopted, the saturated vapor pressure of the hexavinyl disiloxane during the reaction is greatly reduced, and the use efficiency of the hexavinyl disiloxane is improved.
3. The invention adopts porous particles such as polystyrene with higher loading acid site concentration, not only does not have the decomposition of temporary catalyst of tetramethylammonium hydroxide and residual ammonia odor, but also can avoid the ion residue introduced outside the catalyst such as potassium hydroxide and the like which need to be neutralized.
4. The fluidized bed is a double-layer inner and outer cylinder structure, the inner cylinder can rotate, the inner cylinder wall is treated by three prevention and the like, the adhesion of raw and auxiliary materials on the inner wall is greatly reduced, the raw and auxiliary materials are in dynamic balance, and the reaction stability and the material utilization efficiency are improved.
The claw type polyvinyl silicone oil prepared by the method has no peculiar smell, good appearance transparency, turbidity less than 0.5NTU and relative value of silicon hydroxyl group less than 1.050. The reaction temperature is lower, the energy consumption and the carbon emission are reduced, the saturated vapor pressure of the materials is reduced, and the utilization efficiency of the materials is improved.
Detailed Description
Example 1
100kg of dimethyl siloxane ring body (DMC) is filtered by a first-stage bag filter and a first-stage membrane filter, enters a glass fiber reinforced plastic dehydration kettle, is heated to 70 ℃, is vacuumized under 100Pa, and is dehydrated for 4 hours to obtain DMC-1 with the purity of 99.9995 percent and the water content of 15ppm for later use.
10kg of hexavinyl disiloxane (HVDS) is filtered by a first-stage bag filter and a first-stage membrane filter respectively, and then enters a packed tower filled with molecular sieves for treatment for 18h respectively to obtain HVDS-1 with the purity of 99.92% and the water content of 12ppm for later use.
Catalyst: the acid site-loaded polystyrene cation exchange resin has the acid site concentration of 5.1mmol/g, the effective particle size of 0.50-1.00 mm, the uniformity coefficient of less than or equal to 0.50 and the water content of less than or equal to 0.15 percent.
1950g of DMC-1 and 50g of HVDS-1 were added to a stirred tank made of glass fiber reinforced plastic, and the mixture was stirred at low speed for 1 hour while the temperature was raised to 70. + -. 2 ℃ to obtain mixture A1. The mixture raw material A1 was pumped into a fluidized bed with an inner cylinder rotatable at 68. + -. 2 ℃ by a transfer pump, the residence time of the catalyst in the fluidized bed was controlled to about 1h to obtain crude polymer C1, viscosity 145cP, and conversion rate 88.8%. And (3) feeding the crude polymer C1 into a reducing system with the pressure of 35-45 Pa and the temperature of 130 ℃ to obtain a finished product D1. The finished product D1 has a molecular formula of m being 100-150 and n being 0, is colorless and transparent in appearance, has a volatile component of 0.75%, has a viscosity of 236cP, and has a silicon hydroxyl relative value of 1.023.
Example 2
The procedure and the procedure were the same as in example 1 except that the residence time in the fluidized bed was controlled to about 4 hours, to obtain crude polymer C2 and finished product D2, respectively. Crude polymer C2, viscosity 185cP, conversion 89.1%. And a finished product D2, wherein m is 140-190 and n is 0 in the molecular formula, the finished product is colorless and transparent in appearance, the volatile component is 0.80%, the viscosity is 304cP, and the relative value of silicon hydroxyl is 1.028.
Example 3
The procedure and procedure were the same as in example 1 except that the constant temperature in the stirred tank was 40. + -. 2 ℃ and the constant temperature in the fluidized bed was 35. + -. 2 ℃ to obtain crude polymer C3 and finished product D3, respectively. Crude polymer C3, viscosity 125cP, conversion 84.1%. The finished product D3 has a molecular formula that m is 800-135 and n is 0, is colorless and transparent in appearance, has 0.78% of volatile components, has the viscosity of 190cP, and has the relative value of silicon hydroxyl of 1.020.
Example 4
The other processes and steps are the same as the example 1 except that the pressure is reduced by 25-30 Pa and the temperature is 110 +/-2 ℃, and a crude polymer C4 and a finished product D4 are respectively obtained. Crude polymer C4, viscosity 147cP, conversion 88.6%. And the finished product D4 has a molecular formula of m being 100-150 and n being 0, is colorless and transparent in appearance, has a volatile component of 1.50%, has a viscosity of 212cP and has a silicon hydroxyl relative value of 1.022.
Example 5
100kg of dimethyl siloxane ring body (DMC) is filtered by a first-stage bag filter and a first-stage membrane filter, enters a glass fiber reinforced plastic dehydration kettle, is heated to 70 ℃, is vacuumized under 100Pa, and is dehydrated for 4 hours to obtain DMC-5 with the purity of 99.9995 percent and the water content of 15ppm for later use. 10kg of methyl vinyl siloxane ring body (VMC) and 10kg of hexavinyl disiloxane (HVDS) are respectively filtered by a first-stage bag filter and a first-stage membrane filter, and then respectively enter a packed tower filled with molecular sieves for treatment for 18h to respectively obtain VMC-5 with the purity of 99.992 percent, the water content of 10ppm, HVDS-5 with the purity of 99.92 percent and the water content of 12ppm for later use. 1850g of DMC-5, 80g of VMC-5 and 70g of HVDS-5 were added to a stirred tank made of glass fiber reinforced plastics, the temperature was raised to 70. + -. 2 ℃ and stirred at low speed for 1 hour to obtain mixture A5. The mixture raw material A5 is pumped into a fluidized bed with a rotatable inner cylinder at 68 +/-2 ℃ by a delivery pump, the concentration of the acid site of the catalyst in the fluidized bed is 5.6mmol/g (the effective particle size is 0.80-1.20 mm, the uniformity coefficient is less than or equal to 0.60, and the water content is less than or equal to 0.20%), the retention time is controlled for about 1h, and the crude polymer C5, the viscosity is 80cP, and the conversion rate is 87.5% are obtained. And (3) feeding the crude polymer C5 into a reducing system with the pressure of 35-45 Pa and the temperature of 130 ℃ to obtain a finished product D5. And (3) a finished product D5, wherein m is 70-130 and n is 3-8 in the molecular formula, the finished product is colorless and transparent in appearance, the volatile component is 1.25%, the viscosity is 128cP, and the relative value of silicon hydroxyl is 1.027.
Example 6
The procedure and the procedure were the same as in example 5 except that the residence time in the fluidized bed was controlled to about 6 hours, to obtain crude polymer C6 and finished product D6, respectively. Crude polymer C6, viscosity 105cP, conversion 88.2%. And (3) a finished product D6, wherein m is 80-140 and n is 3-8 in the molecular formula, the finished product is colorless and transparent in appearance, the volatile component is 1.28%, the viscosity is 156cP, and the relative value of silicon hydroxyl is 1.030.
Example 7
The procedure and procedure were the same as in example 5 except that the temperature in the stirred tank was kept constant at 55. + -. 2 ℃ and that in the fluidized bed at 50. + -. 2 ℃ to obtain crude polymer C7 and finished product D7, respectively. Crude polymer C7, viscosity 73cP, conversion 84.7%. And the finished product D7 has a molecular formula of m being 70-130 and n being 3-8, is colorless and transparent in appearance, has 0.75% of volatile matter, has viscosity of 126cP and has a silicon hydroxyl relative value of 1.026.
Example 8
The procedure and the steps are the same as those in example 5 except that the pressure is reduced to 25-30 Pa, and crude polymer C8 and finished product D8 are obtained respectively. Crude polymer C8, viscosity 79cP, conversion 87.6%. And the finished product D8 has a molecular formula of 70-130 m and 3-8 n, is colorless and transparent in appearance, has 0.52% of volatile components, has a viscosity of 130cP and has a silicon hydroxyl relative value of 1.021.
Comparative example 1
The concentration of the acid sites of the catalyst in the fluidized bed is 3.2mmol/g (the effective particle size is 0.50-1.00 mm, the uniformity coefficient is less than or equal to 0.50, and the water content is less than or equal to 0.15%), other processes and steps are the same as those in example 1, and a crude polymer C1-1 and a finished product D1-1 are respectively obtained. Crude Polymer C1-1, viscosity 81cP, conversion 62.5%. The finished product D1-1 has a molecular formula that m is 90-160 and n is 0, is colorless and transparent in appearance, has 0.85% of volatile components, has the viscosity of 228cP and has the silicon hydroxyl relative value of 1.021.
Comparative example 2
The procedure and the procedure were the same as in example 1 except that the temperature in the stirred tank was kept constant at 110. + -. 2 ℃ and the temperature in the fluidized bed was kept constant at 105. + -. 2 ℃ to obtain crude polymer C1-2 and finished product D1-2, respectively. Crude Polymer C1-2, viscosity 320cP, conversion 89.4%. The finished product D1-2 has a molecular formula that m is 230-300 and n is 0, is colorless and transparent in appearance, has 0.75% of volatile components, has the viscosity of 589cP and has the silicon hydroxyl relative value of 1.019.
Comparative example 3
The concentration of the acid sites of the catalyst in the fluidized bed is 4.5mmol/g, the effective particle size is 0.50-1.00 mm, the uniformity coefficient is less than or equal to 1.0, the water content is less than or equal to 0.2 percent, and other processes and steps are the same as those in example 1, so that a crude polymer C1-3 and a finished product D1-3 are respectively obtained. Crude polymer C1-3, viscosity 146cP, conversion 88.7%. The finished product D1-3 has a molecular formula that m is 100-150 and n is 0, is colorless and transparent in appearance, has 0.75% of volatile components, has the viscosity of 238cP and has the silicon hydroxyl relative value of 1.020.
Comparative example 4
The procedure and the steps are the same as those in example 1 except that the pressure is reduced by 180 to 200pa, and a crude polymer C1-4 and a finished product D1-4 are obtained respectively. Crude polymer C1-3, viscosity 142cP, conversion 88.3%. And (3) a finished product D1-4, wherein m is 100-150 and n is 0 in the molecular formula, the finished product is colorless and transparent in appearance, the volatile component is 2.83%, the viscosity is 218cP, and the relative value of silicon hydroxyl is 1.025.
Comparative example 5
The procedure and the procedure were the same as in example 1 except that the amount of DMC-1 used was 1300g and that of HVDS-1 used was 700g, to obtain crude polymer C1-5 and finished product D1-5, respectively. Crude polymer C1-5, viscosity 3.1cP, conversion 78.3%. And (3) a finished product D1-5, wherein m is 7-12, n is 0, the appearance is colorless and transparent, the volatile component is 4.60%, the viscosity is 5.4cP, and the relative value of silicon hydroxyl is 1.019.
Comparative example 6
The procedure and procedure were the same as in example 5 except that the temperature was 190 ℃ to obtain crude polymer C5-6 and finished product D5-6, respectively. Crude polymer C5-6, viscosity 80cP, conversion 87.7%. The finished product D5-6 has a molecular formula of 70-130 m and 3-8 n, is light yellow and transparent in appearance, has a volatile component of 0.43%, has a viscosity of 135cP and has a silicon hydroxyl relative value of 1.023.
Comparative example 7
The procedure and procedure were the same as in example 5 except that DMC, VMC and HVDS were not subjected to impurity removal, to obtain crude polymer C5-7 and finished product D5-7, respectively. Crude Polymer C5-7, viscosity 53cP, conversion 85.7%. The finished product D5-7 has a molecular formula of m being 50-110 and n being 3-8, is turbid in appearance, has a volatile component of 1.05%, has a viscosity of 109cP and has a silicon hydroxyl relative value of 1.078.
Comparative example 8
Adding 1850g of dimethyl siloxane ring body, 80g of VMC and 70g of HVDS into a stainless steel reaction kettle (DMC, VMC and HVDS are not subjected to impurity removal treatment), stirring, heating to 130 ℃, adding 0.052g of potassium hydroxide, keeping the temperature, stirring for reaction for 3 hours, adding 0.062g of phosphoric acid for neutralization for 0.5 hour, and obtaining a crude polymer C5-8 with the viscosity of 79cP and the conversion rate of 85.6 percent after the neutralization is finished. And (3) removing the crude polymer C5-8 in a removing system with the constant temperature of 180 +/-2 ℃ and the pressure of 3kPa to obtain the polyvinyl silicone oil D5-8. The polyvinyl silicone oil D5-8 has a molecular formula that m is 70-130, n is 3-10, the appearance is yellow and slightly turbid, the volatile matter is 2.60%, the relative value of silicon hydroxyl is 1.17, and the viscosity is 131 cP.
Comparative example 9
Adding 1850g of dimethyl siloxane ring body, 80g of VMC and 70g of HVDS into a stainless steel reaction kettle (DMC, VMC and HVDS are not subjected to impurity removal treatment), stirring, heating to 100 ℃, adding 0.110g of tetramethylammonium hydroxide, keeping the temperature, stirring for reaction for 3h, heating to 150 ℃ to degrade alkaline catalyst tetramethylammonium hydroxide for 6h, and decomposing the catalyst for 3h at 140 +/-2 ℃ to obtain crude polymer C5-9 with the viscosity of 74cP and the conversion rate of 83.6%. And (3) removing the low-temperature polyvinyl silicone oil by a removing system with the constant temperature of 140 +/-2 ℃ and the pressure of 500Pa to obtain the polyvinyl silicone oil D5-9. The polyvinyl silicone oil D5-9 has a molecular formula of m being 70-130 and n being 3-10, has a large ammonia odor, is colorless and transparent in appearance, contains 2.50% of volatile components, has a relative value of silicon hydroxyl of 1.21, and has a viscosity of 119 cP.
Comparative example 10
DMC, VMC and HVDS pretreatment, addition proportions were the same as in example 5, except that: adding the materials into a stainless steel reaction kettle, stirring, heating to 100 ℃, adding 0.110g of tetramethylammonium hydroxide, keeping the temperature, stirring for reacting for 3 hours, heating to 150 ℃, degrading an alkaline catalyst tetramethylammonium hydroxide for 6 hours, and decomposing the catalyst at 170 +/-2 ℃ to obtain a crude polymer C5-10, wherein the viscosity is 89cP and the conversion rate is 86.9%. And (3) removing the crude polymer C5-10 in a removing system with the constant temperature of 170 +/-2 ℃ and the pressure of 200Pa to obtain the polyvinyl silicone oil D5-10. The polyvinyl silicone oil D5-10 has a molecular formula of m being 70-130 and n being 3-10, has a large ammonia odor, a light yellow and transparent appearance, a volatile component of 0.76%, a relative value of silicon hydroxyl of 1.018 and a viscosity of 126 cP.
Claims (7)
1. The claw type polyvinyl silicone oil is characterized in that the claw type polyvinyl silicone oil has a simple structure as follows:
wherein m is 1-250, n is 0-50, and m and n are integers.
2. A preparation method of claw-type polyvinyl silicone oil comprises the following steps:
(1) pretreating raw materials, namely performing water removal and impurity removal pretreatment on dimethyl siloxane ring bodies and hexavinyl disiloxane;
(2) adding the pretreated dimethyl siloxane ring body and hexavinyl disiloxane into a stirring kettle in proportion, and heating to the temperature T of 30-70 ℃ to obtain a mixed material A;
(3) pumping the mixed material A into a fluidized bed with a constant temperature of T +/-2 ℃ by a material delivery pump, filling a resin catalyst B into the fluidized bed, and allowing the material to stay in the fluidized bed for 5 min-24 h to obtain a crude polymer C;
(4) and (3) removing the crude polymer C at the pressure of less than 50Pa and the temperature of 100-150 ℃ to obtain the finished claw-shaped polyvinyl silicone oil, wherein the claw-shaped polyvinyl silicone oil has a simple structure formula as follows:
wherein m is 1-250, n is 0-50, and m and n are integers.
3. The method for preparing claw-type polyvinyl silicone oil according to claim 2, wherein the dimethyl siloxane ring body in step (1) has a purity of not less than 99.999% and a water content of less than 20 ppm; the purity of the hexavinyl disiloxane is more than or equal to 99.9 percent, and the water content is less than 20 ppm.
4. The method for preparing claw type polyvinyl silicone oil according to claim 2, wherein in the addition amount of dimethyl siloxane ring body and hexavinyl disiloxane in the step (2), DMC accounts for 64.0-98.5 wt%, and HVDS accounts for 1.5-36.0%.
5. The method for preparing claw-type polyvinyl silicone oil according to claim 2, wherein methyl vinyl siloxane ring bodies are further added in the step (2), the purity of the methyl vinyl siloxane ring bodies is more than or equal to 99.99%, and the water content is less than 20 ppm.
6. The method for preparing claw-type polyvinyl silicone oil according to claim 5, wherein the proportions of the dimethylsiloxane rings, the methylvinylsiloxane rings and the hexavinyldisiloxane in step (2) are 64.0-97.5 wt% for the dimethylsiloxane rings, 1-10.0% for the methylvinylsiloxane rings and 1.5-36.0% for the hexavinyldisiloxane.
7. The method for preparing claw-type polyvinyl silicone oil according to claim 2, wherein the resin catalyst in step (3) is polystyrene cation exchange resin loaded with acid sites, wherein the concentration of the acid sites is not less than 5.0mmol/g, the effective particle size is 0.50-2.00 mm, the uniformity coefficient is not more than 1.50, and the water content is not more than 0.5%.
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