CN113881072B - Molecular weight controllable polysulfate crosslinking method - Google Patents
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- 238000004132 cross linking Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 31
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008213 purified water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- -1 diphenyl dichlorobenzyl chloride Chemical group 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JSOKQUGAHOSRLB-UHFFFAOYSA-N 2,5-dichloro-5-(chloromethyl)cyclohexa-1,3-diene Chemical compound ClC1(CCl)CC=C(C=C1)Cl JSOKQUGAHOSRLB-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- XGCDHPDIERKJPT-UHFFFAOYSA-N [F].[S] Chemical group [F].[S] XGCDHPDIERKJPT-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005935 Sulfuryl fluoride Substances 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 2
- YYGRHZGRPBCGKN-UHFFFAOYSA-N ClC1=C(C=CC=C1)Cl.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound ClC1=C(C=CC=C1)Cl.C1(=CC=CC=C1)C1=CC=CC=C1 YYGRHZGRPBCGKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
Abstract
The invention discloses a molecular weight controllable polysulfate crosslinking method, which comprises the following steps: (1) Heating and fully dissolving the polysulfate into dichloroethane; (2) In the presence of a cross-linking agent and a catalyst, the polysulfate undergoes a cross-linking reaction to obtain a cross-linked mixture; (3) Separating out the crosslinked polymer in the crosslinked mixture, and recovering and recycling dichloroethane; (4) Purifying the precipitated crosslinked polymer to obtain the crosslinked polysulfate. The invention can realize mass industrialized production, the production raw materials can be recovered, the post-treatment process is simple, and the pollution is small.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a molecular weight controllable polysulfate crosslinking method.
Background
The fluorine sulfur exchange (SuFEx) click reaction is a new generation of click chemistry reported by the sharp professor 2014. The system adopts cheap industrial pesticide sulfuryl fluoride (SO) 2 F 2 ) And reacting with a phenolic compound to prepare a substrate for a SuFEx click reaction. The synthesized polysulfate material has acid and alkali resistance, higher glass transition temperature and excellent mechanical property.
The high-valence main group fluoride has high chemical stability, but the activation under specific conditions can realize extremely efficient chemical bond conversion and linkage, and the combination of the special stability and reactivity determines that the compound has unique potential application in organic synthetic chemistry, material chemistry, chemical biology and pharmaceutical chemistry. The success of the hexavalent sulfur fluorine exchange reaction (SuFEx) is precisely that of utilizing this particular reactivity of the hexavalent sulfur fluorine bonds. Since 2014, sharp professor (angel. Chem. Int. Ed.2014, 9430) first proposed and successfully realized hexavalent sulfur fluorine exchange reaction, the reaction has been widely focused on organic synthetic chemistry, material chemistry, pharmaceutical chemistry, chemical biology, especially protein molecule selective marking and modification, and the like, and has shown a good application prospect, and is called new generation click chemistry, becoming a new hot spot of current fluorochemical research, compared with polycarbonate and polyester materials, the corresponding polysulfate and polysulfonate materials have higher chemical stability and excellent mechanical properties, and the special toughness and impact resistance make the novel thermoplastic materials likely to be applied in the fields of automobile manufacturing, aerospace, electronic equipment, building, packaging materials, and the like.
In the preparation process of the polysulfate, the phenomenon that the molecular weight is difficult to be increased in the later period of reaction exists, so that a polymer with large molecular weight cannot be produced, the application field of the polymer is limited, and in order to solve the problem, a molecular weight controllable polysulfate crosslinking method is provided.
Disclosure of Invention
The invention aims to provide a molecular weight controllable polysulfate crosslinking method, which solves the problems of difficult promotion of mechanical and other properties caused by difficult promotion of the molecular weight of polysulfate, has simple and stable reaction process, economical and economical materials, recoverable raw materials, small environmental pollution, higher heat-resistant temperature, better electrical insulation and low dielectric loss, and has wide application prospect in the fields of aviation, communication, electronics and microelectronics.
In order to achieve the above object, the present invention provides a molecular weight-controllable polysulfate crosslinking method, comprising the steps of:
(1) Heating and fully dissolving the polysulfate into dichloroethane;
(2) In the presence of a cross-linking agent and a catalyst, the polysulfate undergoes a cross-linking reaction to obtain a cross-linked mixture;
(3) Separating out the crosslinked polymer in the crosslinked mixture, and recovering and recycling dichloroethane;
(4) Purifying the precipitated crosslinked polymer to obtain the crosslinked polysulfate.
The molecular weight controllable polysulfate crosslinking method of the invention is preferable, the molecular weight of the polysulfate is 20000-100000, and the structural formula is:
wherein R is 1 is-Me, -Et, -Ph, -iPr, -H, or is absent; r is R 2 is-Me, -Et, -Ph, -iPr or-H; x is-C, -Si, -O or absent; n=10 to 1000.
In the molecular weight-controllable polysulfate crosslinking method of the invention, the catalyst is preferably at least one selected from ferric trichloride, aluminum trichloride and zinc chloride.
According to the molecular weight-controllable polysulfate crosslinking method, preferably, the crosslinking agent is diphenyl dichlorobenzyl, p-dichlorobenzyl or dichloroethane, and the molecular weight-controllable polysulfate crosslinking method has the following structure:
the molecular weight-controllable polysulfate crosslinking method of the invention is preferably characterized in that the method for separating out the crosslinked polymer comprises the following steps: the crosslinked mixture is settled into a solvent which is miscible with dichloroethane, wherein the solvent is at least one of a methanol solution and an ethanol solution.
The molecular weight-controllable polysulfate crosslinking method of the invention, preferably, the step (4) specifically comprises: dissolving, settling and crosslinking the polysulfate by using an organic solvent, and then removing residual catalyst by using purified water at high temperature to obtain purified crosslinked polysulfate; the organic solvent is methanol or ethanol solution; the high temperature is 110-140 ℃.
In the molecular weight-controllable polysulfate crosslinking method of the invention, preferably, in the step (1), the heating temperature is 60-80 ℃.
In the molecular weight-controllable polysulfate crosslinking method, preferably, in the step (1), the mass ratio of the polysulfate to the dichloroethane is 1:5-10.
In the molecular weight-controllable polysulfate crosslinking method of the invention, preferably, in the step (2), the mass ratio of the polysulfate to the catalyst is 1:0.005-0.3.
In the molecular weight-controllable polysulfate crosslinking method of the invention, preferably, in the step (2), the crosslinking reaction temperature is 60-80 ℃ and the time is 0.5-6 hours.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. the method for crosslinking the polysulfate can obviously improve the molecular weight of the polysulfate.
2. The method for crosslinking the polysulfate solves the problems that the molecular weight of the polysulfate is unstable and the molecular weight is difficult to raise in the later period of polymerization.
3. The method for crosslinking the polysulfate takes the dichloroethane as the solvent and simultaneously takes the dichloroethane as the crosslinking agent, the reaction condition is mild and easy to control, the reaction flow is simple, the operation is easy, the economy and the economy are realized, the byproducts are few, and the industrial production is easy.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Example 1
1. Preparation of polysulfates
(1) Firstly, 5 kg of bisphenol A type polysulfate is put into a 50L autoclave, and the mixture is boiled in high-purity water at 120 ℃; for 4 hours. After cooling, the mixture was discharged and the aqueous phase tds=252 was measured.
(2) The polysulfate was filtered off and dried at 80℃to give a moisture content of 0.1%. The molecular weight mn= 38856 was measured.
2. Cross-linking of polysulfates
(1) 500g of the treated bisphenol A type polysulfate was taken, 5L of dichloroethane solvent was added thereto, and the mixture was stirred at 80℃for 2 hours with heating, thereby sufficiently dissolving the polysulfate.
(2) To the solution obtained in (1) was added 2g of biphenyl dichlorobenzene as a crosslinking agent and stirred for 30 minutes.
(3) To the solution obtained in (2) was added 10g of iron trichloride catalyst with stirring, and the catalyst was added after being dispersed with dichloroethane. Heated with stirring at 80℃for 1 hour.
(4) Pouring the solution obtained in the step (3) into 5L of methanol for sedimentation and taking out.
(5) Adding the crosslinked polysulfate obtained in the step (4) into a 10L autoclave, adding 4L of purified water, boiling for 5 hours at 120 ℃ for 1 time, repeatedly boiling for one time at 100 ℃ by using 4L of methanol solution after drying, and drying to obtain the crosslinked polysulfate.
(6) The crosslinked polysulfate obtained in (5) was sampled and tested for molecular weight, and crosslinked polysulfate mn= 95553 was obtained.
Example two
(1) 500g of the treated bisphenol A type polysulfate is taken, 5L of solvent dichloroethane is added and simultaneously used as a solvent and a crosslinking agent, and the mixture is heated and stirred at 80 ℃ for 2 hours to fully dissolve the polysulfate.
(2) To the solution obtained in (1) was added 10g of iron trichloride catalyst with stirring, and the catalyst was added after being dispersed with dichloroethane. Heated with stirring at 80℃for 1 hour.
(3) Pouring the solution obtained in the step (2) into 5L of methanol for sedimentation and taking out.
(4) Adding the crosslinked polysulfate obtained in the step (3) into a 10L autoclave, adding 4L of purified water, boiling for 5 hours at 120 ℃ for 1 time, repeatedly boiling for one time at 100 ℃ by using 4L of methanol solution after drying, and drying to obtain the crosslinked polysulfate.
(5) The crosslinked polysulfate obtained in (4) was sampled and tested for molecular weight, and crosslinked polysulfate mn= 202722 was obtained.
Example III
(1) 500g of the treated bisphenol A type polysulfate was taken, 5L of dichloroethane solvent was added thereto, and the mixture was stirred at 80℃for 2 hours with heating, thereby sufficiently dissolving the polysulfate.
(2) To the solution obtained in (1) was added 2g of p-dichlorobenzyl as a crosslinking agent and stirred for 30 minutes.
(3) To the solution obtained in (2) was added 10g of iron trichloride catalyst with stirring, and the catalyst was added after being dispersed with dichloroethane. Heated with stirring at 80℃for 1 hour.
(4) Pouring the solution obtained in the step (3) into 5L of methanol for sedimentation and taking out.
(5) Adding the crosslinked polysulfate obtained in the step (4) into a 10L autoclave, adding 4L of purified water, boiling for 5 hours at 120 ℃ for 1 time, repeatedly boiling for one time at 100 ℃ by using 4L of methanol solution after drying, and drying to obtain the crosslinked polysulfate.
(6) And (3) sampling and detecting the molecular weight of the crosslinked polysulfate obtained in the step (5), and measuring the Mn=163892 of the crosslinked polysulfate.
Example IV
(1) 500g of the treated bisphenol A type polysulfate was taken, and 4L of dichloroethane was added as a solvent and a crosslinking agent, followed by stirring at 80℃for 2 hours, thereby sufficiently dissolving the polysulfate.
(2) To the solution obtained in (1) was added 10g of aluminum trichloride as a catalyst with stirring, and the catalyst was added after being dispersed with dichloroethane. Heated with stirring at 80℃for 1 hour.
(3) Pouring the solution obtained in the step (2) into 5L of methanol for sedimentation and taking out.
(4) Adding the crosslinked polysulfate obtained in the step (3) into a 10L autoclave, adding 4L of purified water, boiling for 5 hours at 120 ℃ for 1 time, repeatedly boiling for one time at 100 ℃ by using 4L of methanol solution after drying, and drying to obtain the crosslinked polysulfate.
(5) The crosslinked polysulfate obtained in (4) was sampled and tested for molecular weight, and crosslinked polysulfate mn= 123923 was obtained.
Example five
(1) 500g of the treated bisphenol A type polysulfate was taken, and 4L of dichloroethane was added as a solvent and a crosslinking agent, followed by stirring at 80℃for 2 hours, thereby sufficiently dissolving the polysulfate.
(2) To the solution obtained in (1) was added the catalyst zinc chloride with stirring, and the catalyst was added after being dispersed with dichloroethane. Heated with stirring at 80℃for 1 hour.
(3) Pouring the solution obtained in the step (2) into 5L of methanol for sedimentation and taking out.
(4) Adding the crosslinked polysulfate obtained in the step (3) into a 10L autoclave, adding 4L of purified water, boiling for 5 hours at 120 ℃ for 1 time, repeatedly boiling for one time at 100 ℃ by using 4L of methanol solution after drying, and drying to obtain the crosslinked polysulfate.
(5) The crosslinked polysulfate obtained in (4) was sampled and tested for molecular weight, and crosslinked polysulfate mn= 99865 was obtained.
Example six
1. Preparation of polysulfates
(1) Firstly adding 5 kg of diphenyl ether polysulfate into a 50L autoclave, and boiling with high-purity water at 100 ℃; for 4 hours. After cooling, the aqueous phase tds=239 was measured.
(2) The polysulfate was filtered off and dried at 70℃to give a moisture content of 0.1%. Measured molecular weight mn= 67925
2. Cross-linking of polysulfates
(1) 500g of the treated diphenyl ether polysulfate is taken, 4L of solvent dichloroethane is added and simultaneously used as a solvent and a cross-linking agent, and the mixture is heated and stirred for 1 hour at 80 ℃ to fully dissolve the polysulfate.
(2) To the solution obtained in (1) was added 5g of iron trichloride as a catalyst with stirring, and the catalyst was added after being dispersed with dichloroethane. Heated with stirring at 80℃for 1 hour.
(3) Pouring the solution obtained in the step (2) into 5L of methanol solution, settling and taking out.
(4) Adding the crosslinked polysulfate obtained in the step (3) into a 10L autoclave, adding 4L of purified water, boiling for 5 hours at 120 ℃ for 1 time, repeatedly boiling for one time at 100 ℃ by using 4L of methanol solution after drying, and drying to obtain the crosslinked polysulfate.
(5) The crosslinked polysulfate obtained in (4) was sampled and tested for molecular weight, and crosslinked polysulfate mn= 109522 was obtained.
Comparative example one
(1) Firstly adding 5 kg of diphenyl ether polysulfate into a 50L autoclave, and boiling with high-purity water at 100 ℃; for 4 hours. After cooling, the aqueous phase tds=239 was measured.
(2) The polysulfate was filtered off and dried at 70℃to give a moisture content of 0.1%. Measured molecular weight mn= 67925
Comparative example two
(1) Firstly, 5 kg of bisphenol A type polysulfate is put into a 50L autoclave, and the mixture is boiled in high-purity water at 120 ℃; for 4 hours. After cooling, the mixture was discharged and the aqueous phase tds=252 was measured.
(2) The polysulfate was filtered off and dried at 80℃to give a moisture content of 0.1%. The molecular weight mn= 38856 was measured.
After the polymer prepared by the invention was processed, the mechanical properties were measured, and the results are shown in Table 1 below.
TABLE 1 mechanical Property results
| Project | Molecular weight | Tensile Strength (Mpa) | Impact Strength (KJ/m) 2 ) |
| Example 1 | 95553 | 25.4 | 2.46 |
| Example two | 202722 | 49.22 | 2.81 |
| Example III | 163892 | 59.49 | 2.33 |
| Example IV | 123923 | 55.48 | 2.48 |
| Example five | 99865 | 50.07 | 2.79 |
| Example six | 109522 | 42.29 | 2.93 |
| Comparative example one | 67925 | 19.8 | 2.15 |
| Comparative example two | 38856 | 15.1 | 2.25 |
As can be seen from Table 1, the tensile properties of the polysulfate are greatly improved after crosslinking. The proper crosslinking is carried out on the polysulfate material, so that the shock resistance of the material can be improved, and the polysulfate material can be better applied to the field of engineering plastics.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (7)
1. A method for crosslinking a polysulfate of controlled molecular weight comprising the steps of:
(1) Heating and dissolving polysulfate in dichloroethane;
(2) In the presence of a cross-linking agent and a catalyst, the polysulfate undergoes a cross-linking reaction to obtain a cross-linked mixture;
(3) Separating out crosslinked polymer in the crosslinked mixture, and recovering dichloroethane for reuse;
(4) Purifying the precipitated crosslinked polymer to obtain crosslinked polysulfate;
wherein the molecular weight of the polysulfate is 20000-100000, and the structural formula is as follows:
wherein R is 1 is-Me, -Et, -Ph, -iPr, -H, or is absent; r is R 2 is-Me, -Et, -Ph, -iPr, -H, or is absent; x is-C, -Si or-O; n=10 to 1000;
the catalyst is at least one of ferric trichloride, aluminum trichloride and zinc chloride;
the cross-linking agent is diphenyl dichlorobenzyl chloride, p-dichlorobenzyl chloride or dichloroethane.
2. The method for crosslinking a polysulfate of claim 1, wherein the method for precipitating the crosslinked polymer is: the crosslinked mixture is settled into a solvent which is miscible with dichloroethane, wherein the solvent is at least one of a methanol solution and an ethanol solution.
3. The molecular weight controllable polysulfate crosslinking process of claim 1, wherein step (4) is specifically: dissolving, settling and crosslinking the polysulfate by using an organic solvent, and then removing residual catalyst by using purified water at high temperature to obtain purified crosslinked polysulfate; the organic solvent is methanol or ethanol; the high temperature is 110-140 ℃.
4. The method of crosslinking a polysulfate of claim 1, wherein the heating temperature in step (1) is from 60 ℃ to 80 ℃.
5. The molecular weight controllable polysulfate crosslinking process of claim 1, wherein in step (1), the mass ratio of polysulfate to dichloroethane is 1:5-10.
6. The molecular weight controllable polysulfate crosslinking process of claim 1, wherein in step (2), the mass ratio of polysulfate to catalyst is 1:0.005-0.3.
7. The method for crosslinking a polysulfate of claim 1, wherein the crosslinking reaction is carried out at a temperature of 60 to 80℃for a period of 0.5 to 6 hours in step (2).
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| CN112898571A (en) * | 2021-01-29 | 2021-06-04 | 苏州大学 | Porous cross-linked material and preparation method and application thereof |
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| CN104059228A (en) * | 2013-10-25 | 2014-09-24 | 陈元文 | Bisphenol A type poly sulfuric acid (ammonia) ester compound and synthetic method thereof |
| CN110540647A (en) * | 2018-04-16 | 2019-12-06 | 白银图微新材料科技有限公司 | Polymerization method of sulfuric acid (amine) ester linker polymer |
| CN110804183A (en) * | 2019-12-09 | 2020-02-18 | 白银图微新材料科技有限公司 | Copolymerized polysulfate and preparation method thereof |
| CN112898571A (en) * | 2021-01-29 | 2021-06-04 | 苏州大学 | Porous cross-linked material and preparation method and application thereof |
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