CN113896891A - Method for end-capping modified poly (amino) sulfate - Google Patents
Method for end-capping modified poly (amino) sulfate Download PDFInfo
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- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical class NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- VPSPMKQOKBYPON-UHFFFAOYSA-N ethyl carbamate;sulfuric acid Chemical compound OS(O)(=O)=O.CCOC(N)=O VPSPMKQOKBYPON-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002635 polyurethane Polymers 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- JVNCFFFHVBWVBR-UHFFFAOYSA-N 2-(1-hydroxyethyl)phenol Chemical compound CC(O)C1=CC=CC=C1O JVNCFFFHVBWVBR-UHFFFAOYSA-N 0.000 claims description 2
- ZOWWQFKBWKBYAE-UHFFFAOYSA-N 2-(3-phenylprop-2-enyl)phenol Chemical compound OC1=CC=CC=C1CC=CC1=CC=CC=C1 ZOWWQFKBWKBYAE-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical group 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000203 mixture Substances 0.000 description 11
- 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 10
- 238000009835 boiling Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- -1 hydroxyl compound Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920002578 polythiourethane polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical class [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/24—Polysulfonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/30—Polysulfonamides; Polysulfonimides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a method for end-capping modified poly (amino) sulfate. The method modifies poly (amino) sulfate by an end-capping agent, and comprises the following steps: dissolving the poly (amino) sulfate in a solvent, adding a basic catalyst and a hydroxyl-containing end-capping reagent for reaction, after the phase conversion of the polymer is finished, washing and drying to obtain the end-capped poly (amino) sulfate. The method provided by the invention has the advantages of simple and stable process, capability of realizing large-scale industrial production, recoverable by-products and low pollution, and the modified poly (urethane) sulfate material has better thermal stability, aging resistance, excellent acid and alkali resistance and solvent resistance and wide application prospect.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a method for end-capping modified poly (ammonia) sulfate.
Background
With the continuous progress of science and technology, the polyester industry has been rapidly developed in recent years as one of important chemical synthetic materials. At present, polyester materials are widely applied to the fields of fiber manufacturing, packaging, engineering plastics, electronic and electric products, medical materials, buildings, automobiles and the like. Compared with the prior art, the polyester material has the advantages of simpler and easier synthesis, high utilization rate of raw material monomers, lower cost and the like. Therefore, polyester-based materials have been widely used in industrial production and daily life of people. And the special fields, such as aerospace, electronic communication, microelectronics and the like, have higher requirements on materials. Therefore, it is one of the targets of the research and research of materials scientists to research and discover polyester materials with better overall performance, such as uniform polymerization degree, high purity, good tolerance (acid and alkali) and good wear resistance.
Poly (amino) sulfate is used; compared with the traditional Polycarbonate (PC), the poly (amino) sulfate has the advantages of better thermal stability, better aging resistance, excellent acid and alkali resistance, excellent solvent resistance and the like; meanwhile, the preparation condition is milder, no special reaction device is needed, and the method is very favorable for large-scale industrial production. But the properties such as high temperature resistance, toughness and the like are insufficient, and the development of the composite material is influenced.
Disclosure of Invention
Based on the above, the invention aims to disclose a method for end-capping modified poly (amino) sulfate, which has simple and stable process, can realize large-scale industrial production, can recover byproducts and has little pollution; in addition, the end-capped modified poly (amino) sulfate obtained by the method has better thermal stability, aging resistance, excellent acid and alkali resistance and solvent resistance, and wide application prospect.
To this end, the invention provides a method for end-capping modified poly (urethane) sulfate, comprising the steps of: dissolving 1eq of poly (amino) sulfate in a solvent, adding 0.1eq-1eq of an alkaline catalyst and 0.1eq-1eq of a hydroxyl-containing end-capping agent for reaction, after the phase conversion of the polymer is completed, washing and drying to obtain the end-capped poly (amino) sulfate. Wherein eq represents the equivalent of the reaction substrate, and 1eq represents 1 time the amount of the reaction substrate substance.
In the method for end-capping modified poly (amino) sulfate according to the present invention, it is preferable that the reaction conditions are as follows: the temperature is 100-200 ℃, the further optimization is 140-160 ℃, and the time is 1-10 h, the further optimization is 2-5 h.
In the method for end-capping modified poly (urethane) sulfate according to the present invention, it is preferable that the poly (urethane) sulfate has the following structural formula:
in the formula R1is-Me, -Et, -Ph, -ipr or-H;
R2is-Me, -Et, -Ph, -ipr or-H;
x is-C-, -Si-;
X1is-C-, -Si-;
n is an integer of 10 to 1000.
The method for end-capping modified poly (amino) sulfate according to the present invention, wherein preferably, the solvent is at least one selected from the group consisting of N, N dimethylformamide, dimethyl sulfoxide, sulfolane, and N-methylpyrrolidone; further preferably, the solvent is at least one selected from the group consisting of sulfolane and N-methylpyrrolidone.
In the method for end-capping modified poly (amino) sulfate according to the present invention, it is preferable that the hydroxyl group in the hydroxyl group-containing end-capping agent is an alcoholic hydroxyl group and/or a phenolic hydroxyl group.
In the method for end-capping modified poly (amino) sulfate according to the present invention, it is preferable that the end-capping agent containing a hydroxyl group is at least one selected from the group consisting of phenol, cresol, cinnamyl phenol, p-hydroxyphenylethanol, o-hydroxyphenylethanol, resorcinol, 1, 3, 5-benzenetriol, hydroquinone, catechol, and naphthol; further preferably, the hydroxyl-containing blocking agent is at least one selected from the group consisting of p-hydroxyphenylethanol, phenol, and hydroquinone.
In the method for end-capping modified poly (amino) sulfate according to the present invention, it is preferable that the basic catalyst is an organic base and/or an inorganic base.
In the method for end-capping modified poly (amino) sulfate according to the present invention, it is preferable that the basic catalyst is at least one selected from triethylamine, potassium carbonate, calcium chloride, sodium carbonate, and sodium bicarbonate.
In the method for end-capping modified poly (amino) sulfate according to the present invention, it is preferable that the basic catalyst is at least one selected from triethylamine, sodium carbonate and potassium carbonate.
The method for end-capping modified poly (amino) sulfate of the present invention is preferably that the washing process is: distilling in water at 70-150 deg.C for 1-7 times, and distilling in ethanol at 70-120 deg.C for 1-5 times.
The technical scheme of the invention specifically comprises the following steps:
(1) 1eq of poly (amino) sulfate was dissolved in a solvent at a certain temperature with stirring.
(2) Then 0.1eq-1eq of alkaline catalyst is added to react with 0.1eq-1eq of alcoholic hydroxyl compound or phenolic hydroxyl compound for 1h-10 h.
(3) The polymer completes the phase inversion.
(4) Washing and drying to obtain the end-capped poly (amino) sulfate.
The invention has the following beneficial effects:
(1) the end-capping reagent can be directly added in the reaction process, and the process is very simple.
(2) The toughness and temperature resistance of the modified poly (amino) sulfate are greatly improved, and the acid and alkali resistance of the modified poly (amino) sulfate is not influenced.
(3) The modified poly (amino) sulfate has better performance than the polysulfone engineering plastics.
In conclusion, the method provided by the invention has the advantages of simple and stable process, capability of realizing large-scale industrial production, recoverable by-products and low pollution, and the modified poly (amino) sulfate has better thermal stability, aging resistance, excellent acid and alkali resistance and solvent resistance and wide application prospect.
Drawings
FIG. 1 is a graph of a secondary temperature-rising curve-DSC of example 1;
FIG. 2 is a graph of a secondary temperature-rising curve-DSC of example 5.
FIG. 3 is a graph of a secondary temperature-rising curve-DSC of comparative example 1.
FIG. 4 is a graph of a secondary temperature-rising curve-DSC of comparative example 2.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
Preparing a capped modified polysulfate by the following steps:
weighing 1kg of bisphenol A, 1.71kg of bisphenol A disulfoyl fluoride, 464g of sodium hydroxide and 2kg of N-methylpyrrolidone, adding the mixture into a 10L reaction kettle, reacting for 2h at 150 ℃, adding 822g of end-capping reagent phenol, continuing the reaction for 30min, pouring the mixture into water, precipitating, crushing, boiling for 1h in 100 ℃ water, and then boiling for 1h in 80 ℃ ethanol to obtain end-capped modified polysulfate (Mn 30000 g/mol).
Example 2
Weighing 1kg of bisphenol A polysulfate (Mn is 30000g/mol), 3kg of N-methyl pyrrolidone, adding 822g of end-capping reagent phenol and 500g of sodium hydroxide into a 10L reaction kettle, reacting at 150 ℃ for 2h, pouring into water for precipitation, crushing, boiling in 100 ℃ water for 1h, and then boiling in 80 ℃ ethanol for 1h to obtain the end-capped modified polysulfate.
Example 3
Weighing 1kg of bisphenol A polysulfate (Mn is 30000g/mol), 3kg of N-methylpyrrolidone, 482g of hydroquinone and 500g of sodium hydroxide, putting the materials into a 10L reaction kettle, reacting at 150 ℃ for 2h, pouring the materials into water for precipitation, crushing the materials, boiling the materials in water at 100 ℃ for 1h, and then boiling the materials in ethanol at 80 ℃ for 1h to obtain the end-capped modified polysulfate.
Example 4
Weighing 1kg of bisphenol A polysulfate (Mn is 30000g/mol), 3kg of N-methylpyrrolidone, 605g of p-hydroxyphenylethanol and 500g of sodium hydroxide, putting the mixture into a 10L reaction kettle, reacting at 150 ℃ for 2h, pouring the mixture into water for precipitation, crushing the mixture, boiling the mixture for 1h in water at 100 ℃, and then boiling the mixture for 1h in ethanol at 80 ℃ to obtain the end-capped modified polysulfate.
Example 5
Weighing 1kg of 4, 4-diaminodiphenyl ether, 1.5kg of 4, 4-diaminodiphenyl ether dithio fluoride, 529g of sodium hydroxide and 1.75kg of N-methylpyrrolidone, adding the mixture into a 10L reaction kettle, reacting for 3h at 130 ℃, adding 940g of end-capping agent phenol, continuing to react for 30min, pouring the mixture into water for separation, crushing, boiling the mixture for 1h in 100 ℃ water, and then boiling the mixture for 1h in 80 ℃ ethanol to obtain the end-capped modified polythiourethane.
Comparative example 1
1kg of bisphenol a, 1.71kg of bisphenol a bissulfuryl fluoride, 464g of sodium hydroxide and 2kg of n-methylpyrrolidone were weighed into a 10L reaction kettle, reacted at 150 ℃ for 2 hours, poured into water to precipitate, pulverized, boiled in water at 100 ℃ for 1 hour, and then boiled in ethanol at 80 ℃ for 1 hour to obtain a polysulfate (Mn 30000 g/mol).
Comparative example 2
1kg of 4, 4-diaminodiphenyl ether, 1.5kg of 4, 4-diaminodiphenyl ether dithio fluoride, 529g of sodium hydroxide and 1.75kg of N-methylpyrrolidone are weighed into a 10L reaction kettle, reacted at 130 ℃ for 3 hours, poured into water to be precipitated, crushed, boiled in 100 ℃ water for 1 hour, and then boiled in 80 ℃ ethanol for 1 hour to obtain the polythiourethane (Mn 30000 g/mol).
The performance tests are shown in the following table:
(1) test for solvent resistance
TABLE 1
(2) Mechanical Property test
TABLE 2
| Material(s) | AverageImpact Strength (J) | Tensile Strength (mpa) |
| Example 1 | 1.173 | 55.31 |
| Example 2 | 1.171 | 55.30 |
| Example 3 | 1.016 | 52.56 |
| Example 4 | 1.231 | 50.15 |
| Example 5 | 1.113 | 53.21 |
| Comparative example 1 | 0.878 | 44.46 |
| Comparative example 2 | 0.732 | 41.82 |
| Polysulfone | 0.986 | 47.35 |
As can be seen from Table 1, the solvent resistance of the poly (urethane) sulfate is obviously improved after the end capping modification.
As can be seen from Table 2, the average impact strength of the poly (urethane) sulfate after the end capping modification is more than ten times that before the end capping modification, which shows that the toughness is far better than that before the end capping modification, the tensile strength is also slightly improved, and the material performance is comparable to that of polysulfone.
As can be seen from FIGS. 1 and 2, the glass transition temperature of the modified polysulfuric acid (ammonia) is also greatly increased, so that the application range of the material is wider.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (10)
1. A method for end-capping a modified poly (amino) sulfate, comprising the steps of: dissolving 1eq of poly (amino) sulfate in a solvent, adding 0.1eq-1eq of an alkaline catalyst and 0.1eq-1eq of a hydroxyl-containing end-capping agent for reaction, after the phase conversion of the polymer is completed, washing and drying to obtain the end-capped poly (amino) sulfate.
2. The method of end-capping modified poly (amino) sulfate according to claim 1, wherein the reaction conditions are: the temperature is 100-200 ℃, preferably 140-160 ℃, and the time is 1-10 h, preferably 2-5 h.
3. The method of end-capping modified poly (urethane) sulfate according to claim 1, wherein the poly (urethane) sulfate has the following general structural formula:
in the formula R1is-Me, -Et, -Ph, -ipr or-H;
R2is-Me, -Et, -Ph, -ipr or-H；
X is-C-, -Si-;
X1is-C-, -Si-;
n is an integer of 10 to 1000.
4. The method for end-capping modified poly (amino) sulfate according to claim 1, wherein the solvent is selected from at least one of N, N dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone; preferably, the solvent is at least one selected from sulfolane and N-methyl pyrrolidone.
5. The method for end-capping modified poly (amino) sulfate according to claim 1, wherein the hydroxyl group in the hydroxyl group-containing end-capping agent is an alcoholic hydroxyl group and/or a phenolic hydroxyl group.
6. The method for end-capping modified poly (amino) sulfate according to claim 5, wherein the end-capping agent containing hydroxyl group is at least one selected from phenol, cresol, cinnamyl phenol, p-hydroxyphenylethanol, o-hydroxyphenylethanol, resorcinol, 1, 3, 5-benzenetriol, hydroquinone, catechol, naphthol; preferably, the hydroxyl-containing blocking agent is at least one selected from the group consisting of p-hydroxyphenylethanol, phenol, and hydroquinone.
7. The method of end-capping modified poly (amino) sulfate according to claim 1, wherein the basic catalyst is an organic base and/or an inorganic base.
8. The method for end-capping modified poly (amino) sulfate according to claim 6, wherein the basic catalyst is at least one selected from triethylamine, potassium carbonate, calcium chloride, sodium carbonate, and sodium bicarbonate.
9. The method of end-capping modified poly (amino) sulfate according to claim 7, wherein the basic catalyst is at least one selected from triethylamine, sodium carbonate and potassium carbonate.
10. The method of end-capping modified poly (amino) sulfate according to claim 1, wherein the washing is performed by: distilling in water at 70-150 deg.C for 1-7 times, and distilling in ethanol at 70-120 deg.C for 1-5 times.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110917909A (en) * | 2019-12-27 | 2020-03-27 | 白银图微新材料科技有限公司 | Method for preparing separation membrane by using poly (amino) sulfate polymer and modified polymer thereof as membrane preparation material |
| CN112495198A (en) * | 2019-09-12 | 2021-03-16 | 白银图微新材料科技有限公司 | Technology for preparing film by using poly (amino) sulfate polymer and application |
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2021
- 2021-11-05 CN CN202111307989.7A patent/CN113896891A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112495198A (en) * | 2019-09-12 | 2021-03-16 | 白银图微新材料科技有限公司 | Technology for preparing film by using poly (amino) sulfate polymer and application |
| 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 |
| CN110917909A (en) * | 2019-12-27 | 2020-03-27 | 白银图微新材料科技有限公司 | Method for preparing separation membrane by using poly (amino) sulfate polymer and modified polymer thereof as membrane preparation material |
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