CN101885843A - Water-soluble polyphenylene sulfide and its preparation method - Google Patents

Abstract

，该聚苯硫醚溶于水和饱和食盐水，不溶于甲基吡咯烷酮、二甲基乙酰胺、四氢呋喃、甲苯、丙酮、氯仿和乙醇，或，该聚苯硫醚溶于水和饱和食盐水，微溶于甲基吡咯烷酮、二甲基乙酰胺和乙醇，不溶于四氢呋喃、甲苯、丙酮和氯仿，其中R为N⁺(CH₃)₃Cl^-、NH⁺(CH₃)₂Cl^-、N⁺(CH₂CH₂OH)₃Cl^-、NH⁺(CH₂CH₂OH)₂Cl^-或

。本发明还公开了上述水溶性聚苯硫醚的制备方法。本发明制备的聚苯硫醚具有良好的水溶性、耐温抗盐性，不仅有望拓展聚苯硫醚在水溶性功能高分子领域的应用，还可有望应用于油田、造纸、废水处理等工作环境较恶劣的领域。The water-soluble polyphenylene sulfide disclosed by the present invention has a general structural formula as follows:

, the polyphenylene sulfide is soluble in water and saturated saline, insoluble in methylpyrrolidone, dimethylacetamide, tetrahydrofuran, toluene, acetone, chloroform and ethanol, or , the polyphenylene sulfide is soluble in water and saturated saline, slightly soluble in methylpyrrolidone, dimethylacetamide and ethanol, insoluble in tetrahydrofuran, toluene, acetone and chloroform, where R is N ⁺ (CH ₃ ) ₃ Cl ^- , NH ⁺ (CH ₃ ) ₂ Cl ^- , N ⁺ (CH ₂ CH ₂ OH) ₃ Cl ^- , NH ⁺ (CH ₂ CH ₂ OH) ₂ Cl ^- or

. The invention also discloses a preparation method of the above-mentioned water-soluble polyphenylene sulfide. The polyphenylene sulfide prepared by the present invention has good water solubility, temperature resistance and salt resistance, and is not only expected to expand the application of polyphenylene sulfide in the field of water-soluble functional polymers, but also expected to be applied to oil fields, papermaking, wastewater treatment, etc. Areas with harsh environments.

Description

Water-soluble polyphenylene sulfide and its preparation method

technical field

The invention belongs to the technical field of polyphenylene sulfide and its preparation, and in particular relates to a water-soluble polyphenylene sulfide and a preparation method thereof.

Background technique

Water-soluble amphoteric polymers (water-soluble amphoteric polymers) are water-soluble polymers containing positive and negative charge groups on the molecular chain. Compared with water-soluble anionic or cationic polymers containing only one charge, Their properties are relatively unique (Zang Qingda, Li Zhuomei. Journal of Functional Polymers, 1994, 7(1): 90.). For example, in terms of the nature of the force between molecules and within the molecular chain, for polyelectrolytes containing only one charge, the electrostatic force is only electrostatic repulsion, while for amphoteric polymers, the electrostatic force can be either repulsive or attractive, specifically Whether it is repulsion or attraction depends on the relative number of positive and negative charges in the molecular chain. In terms of solution properties, the viscosity of amphoteric polymers with zero net charge of macromolecules or equal number of positive and negative charge groups on the molecular chain will increase instead of decrease in viscosity in saline solution, showing a very obvious "reverse polymerization". Electrolyte Effect".

Because of this unique property endows the amphoteric polymer with unique functions, it can be widely used in many fields, such as: it can be used as an ion exchanger for the selective separation of metal ions; it can be used as an effective flocculant, coagulant and Complexing agent (Kawaguchi, H.; Hoshino, H. and Ohtsuka, J.J Appl Polym Sci 1981, 26(6): 2015.); can play a catalytic role and has the properties of a biocatalyst-enzyme; can be used as a drug carrier-high Molecular storage, microcapsules, rubber pulp, etc., and it has been increasingly widely used in petroleum engineering, papermaking, environmental protection and other industries, and has become an important material and admixture in many industrial sectors. For example, as a new oilfield polymer chemical agent, it is mainly used abroad as a new drilling fluid viscosifier (Peiffer D.G. et al. US 4637882, 1987.), a fracturing fluid additive (Li Xiuhua, Chen Jinfu, Tong Manli. Petroleum and Natural Gas Chemical Industry , 1995, 24(1): 12.), cementing admixture (Peiffer D.G. et al. US 4626285, 1986.) and enhanced oil recovery and oil displacement agent (Edited by [US] W E Haines, translated by Jin Jingzhi et al. Papers on the Development of Oilfield Chemistry. Beijing: Petroleum Industry Press, 1991: 60.); while it is mainly used as a strong inhibitor in China (Li Jian, Xiang Xingjin, Luo Pingya, etc. Natural Gas Industry, 1991, 11(5) : 42.), multifunctional new drilling fluid viscosity reducer (Yan Jienian, Huang Linji. Drilling fluid optimization design and application technology. Shandong: Petroleum University Press, 1993: 123.), shale hydration inhibitor (Niu Yabin , Zhang Daming, etc. Oilfield Chemistry, 1994, 11(4): 273.), fluid loss control agent and a new type of water plugging and profile control agent with excellent preparation performance (Sheng Yaping, Xi Cunrong. Oilfield Chemistry, 1993, 10(1): 19. )wait.

In recent years, due to the extreme environment in some industries, such as the ultra-high temperature and high salt environment of ultra-deep wells in oil fields, the strong acid and strong alkali environment in wastewater treatment, and the strong acid and alkali and high temperature and high salt environment of flocculants, the amphoteric water-soluble polymer The use of materials puts forward higher and more stringent requirements, that is, amphoteric polymer materials should also have excellent high temperature resistance, salt resistance, strong acid resistance and strong alkali resistance. At present, in domestic research, most scholars (Sheng Yaping, Xi Cunrong. Oilfield Chemistry, 1993, 10 (1): 19; C.J. Thaemlitz, A.D. Patel. SPE57715, 1999; Wang Zhonghua et al. Research on AMPS polymer and drilling fluid system and application [J]. Petroleum and Natural Gas Chemical Industry, 2001, 30(3): 138-140; Xu Juan et al. Synthesis and performance of anti-high temperature fluid loss reducer PAX. Journal of Southwest Petroleum Institute, 2004, 26(2): 57-59; Yang Xiaohua, Wang Zhonghua. Research and Application of Vinyl Sulfonate Polymer and Drilling Fluid System [J]. Zhengzhou University Journal, 2001, 33(2): 89-91). Copolymerization of temperature-resistant and salt-resistant monomers. On the basis of obtaining higher molecular weight polymers, hydration groups such as sulfonic acid groups and carboxyl groups are introduced into the molecular structure to achieve the purpose of high temperature resistance and salt resistance. Unfortunately, due to the limitation of high temperature resistance and strong acid and alkali resistance of the main chain, this type of polymer is difficult to meet the harsh working environment that requires amphoteric water-soluble polymers, such as deep wells or ultra-deep wells in oil and gas field exploration and development. Harsh environment with high temperature, high pressure and high salinity.

Polyphenylene sulfide (PPS), also known as polyphenylene ether and polyphenylene sulfide, is a macromolecular linear rigid material composed of benzene rings connected to sulfur atoms at the para position, and has excellent heat resistance. Its melting point is as high as 280-290°C, and it begins to decompose above 430-460°C in the air. Its thermal stability far exceeds engineering plastics such as PA, PBT, POM and PEFE; Tetrafluoroethylene (PTFE) is similar, that is, it is not corroded by most other acids, alkalis and salts except for strong oxidizing acids, alkalis and salts, such as concentrated sulfuric acid, nitric acid and aqua regia. Although polyphenylene sulfide has good potential application value in the above fields due to its excellent chemical resistance and thermal stability, it loses the possibility of application in the above fields because it does not dissolve in aqueous solution.

Contents of the invention

One of the purposes of the present invention is to solve the problems existing in the prior art, to provide a kind of water-soluble polyphenylene sulfide which not only has the characteristics of amphoteric polymer, but also can be dissolved in water, so as to endow polyphenylene sulfide with the advantages in certain fields. potential application value.

Another object of the present invention is to provide a method for preparing the above-mentioned water-soluble polyphenylene sulfide.

The water-soluble polyphenylene sulfide provided for reaching the purpose of the present invention has the general structural formula as follows:

该聚苯硫醚溶于水和饱和食盐水，不溶于甲基吡咯烷酮、二甲基乙酰胺、四氢呋喃、甲苯、丙酮、氯仿和乙醇，或Where R is N ⁺ (CH ₃ ) ₃ Cl ^- , NH ⁺ (CH ₃ ) ₂ Cl ^- , N ⁺ (CH ₂ CH ₂ OH) ₃ Cl ^- , NH ⁺ (CH ₂ CH ₂ OH) ₂ Cl ^- or

The polyphenylene sulfide is soluble in water and saturated saline, insoluble in methylpyrrolidone, dimethylacetamide, tetrahydrofuran, toluene, acetone, chloroform and ethanol, or

该聚苯硫醚溶于水和饱和食盐水，微溶于甲基吡咯烷酮、二甲基乙酰胺和乙醇，不溶于四氢呋喃、甲苯、丙酮和氯仿。Where R is N ⁺ (CH ₃ ) ₃ Cl ^- , NH ⁺ (CH ₃ ) ₂ Cl ^- , N ⁺ (CH ₂ CH ₂ OH) ₃ Cl ^- , NH ⁺ (CH ₂ CH ₂ OH) ₂ Cl ^- or

The polyphenylene sulfide is soluble in water and saturated saline, slightly soluble in methylpyrrolidone, dimethylacetamide and ethanol, and insoluble in tetrahydrofuran, toluene, acetone and chloroform.

The method for preparing the above-mentioned water-soluble polyphenylene sulfide provided by the present invention, the process steps and conditions of the method are as follows:

1) Sulfonate polyphenylene sulfide at 80-105°C for 2-12 hours with sulfuric acid with a fuming amount of 20-25%, and then lower the temperature of the mixture to room temperature, wherein the fuming sulfuric acid and polyphenylene sulfide The volume-to-weight ratio is 10-20ml/g;

2) When the temperature of the mixed solution is 15°C, first add the Lewis catalyst which is 2-6% according to the mass fraction of sulfonated polyphenylene sulfide, and then add dropwise to it according to the weight of sulfonated polyphenylene sulfide while stirring: The volume of chloromethylation reagent is 1g/3-7ml of chloromethylation reagent, and it is reacted at 0-30°C for 4-12h, then purified with ice-water mixture with 4% salt content and washed repeatedly until the pH value of the filtrate is 7. The obtained solid was dried to constant weight;

3) First, add the obtained chloromethylated polyphenylene sulfide solid into a quaternizing agent or a tertiary ammonizing agent or 1-pyrrolidone with a concentration of 2-5 mol/L and stir to dissolve, then adjust the pH to 4.0-10.0, and React at 20-80°C for 7-10 hours, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times, and dry the obtained solid to constant weight to obtain the water-soluble polyphenylene with the general structural formula [I] Thioether, wherein the ratio of chloromethylated polyphenylene sulfide to quaternizing agent or tertiary ammonizing agent or 1-pyrrolidone is 1g/3-7mL, or

1) Sulfonate polyphenylene sulfide at 80-105°C for 2-12 hours with sulfuric acid with a smoke emission of 20-25%, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether for precipitation and suction filtration , the obtained solid is washed with acetone until the pH value of the filtrate is 7, and then dried to a constant weight, wherein the volume-to-weight ratio of oleum to polyphenylene sulfide is 10-20ml/g;

2) In the obtained sulfonated polyphenylene sulfide solid, add a polar aprotic solvent with a weight-to-volume ratio of 1 g/5-15 mL to the sulfonated polyphenylene sulfide and calculate the mass fraction of sulfonated polyphenylene sulfide as 2 -6% Lewis catalyst, stirred and dissolved at 30-70°C and mixed evenly, then added dropwise to it while stirring the bromine ethanol solution according to the weight of sulfonated polyphenylene sulfide: the volume of bromine ethanol solution was 1g/5-10ml , the volume concentration of the bromine ethanol solution is 1%, and the reaction is 2-12h after the dropwise addition;

3) Adjust the pH of the obtained mixed solution to 4.0-10.0, then add 1 g of quaternizing agent or tertiary ammonizing agent or 1-pyrrolidone at a concentration of 2-5 mol/L according to the weight of brominated polyphenylene sulfide in the mixed solution /3-7mL, stirred and mixed, and reacted at 20-80°C for 7-10h, then added absolute ethanol for precipitation, suction filtration, and repeated washing with absolute ethanol for 4-5 times, then Soxhlet extraction for 24h, and the obtained solid was dried to constant The water-soluble polyphenylene sulfide with general structure formula [II] can be obtained after weighting.

The weight-to-volume ratio of the materials used in the above method can be increased or decreased in the same proportion.

The Lewis catalyst used in the above method is any one of iron trichloride, tin tetrachloride or aluminum trichloride.

The polar aprotic solvent used in the above method is preferably any one of dimethylsulfoxide (DMSO), dimethylacetamide (DMAc) or dimethylformamide (DMF), more preferably dimethylsulfoxide .

The chloromethylation reagent used in the above method is preferably 1,4-dichloromethoxybutane or chloromethoxyoctane.

The quaternization reagent used in the above method is preferably trimethylamine aqueous solution or triethanolamine; the tertiary ammonization reagent is preferably dimethylamine aqueous solution or dimethylamine.

Compared with the prior art, the present invention has the following advantages:

1) Since the polyphenylene sulfide provided by the present invention introduces a large number of sulfonic acid groups, hydroxyl groups, quaternary ammonium groups or tertiary ammonium groups and other strong hydrophilic groups on its main chain aromatic ring, the originally insoluble polyphenylene sulfide becomes An amphoteric polyelectrolyte polymer was developed, which not only endows it with water solubility, but also ensures its ability to resist low molecular electrolytes, breaking the conventional rule that polyphenylene sulfide is insoluble in any solvent at room temperature.

2) Since the polyphenylene sulfide provided by the present invention has good water solubility (salt resistance) against low-molecular electrolytes, and its main chain is a macromolecular linear structure composed of a benzene ring connected to a sulfur atom at the para-position Rigid materials have good thermal stability, so it is not only expected to expand the application of polyphenylene sulfide in the field of water-soluble functional polymers, but also with its excellent performance of temperature and salt resistance, it is expected to be used in oil fields, papermaking, waste water Handling and other areas where the working environment is harsh.

3) Due to directly adopting fuming sulfuric acid as the sulfonating reagent and solvent of polyphenylene sulfide in the method of the present invention, then directly adopting the solvent and catalyst of chloromethylation to carry out chloromethylation to sulfonated polyphenylene sulfide, Therefore, the preparation steps are skillfully reduced, the preparation materials are saved, and the cost is reduced.

4) Since the method of the present invention adopts 1,4-dichloromethoxybutane as the chloromethylation reagent, the carcinogenic problem usually caused by the chloromethylation of formaldehyde and hydrogen chloride is avoided.

5) The preparation method provided by the invention is simple and easy to operate and control.

Description of drawings

Fig. 1 is the infrared spectrum of the sulfonated polyphenylene sulfide prepared in the first step of the inventive method;

Fig. 2 is the infrared spectrum of the chloromethylated polyphenylene sulfide prepared in the second step of the first method of the present invention, in which SPPS is sulfonated polyphenylene sulfide, and CMPPS is chloromethylated polyphenylene sulfide;

Fig. 3 is the infrared spectrum of chloromethylated polyphenylene sulfide, quaternized and tertiary ammonized polyphenylene sulfide prepared by the first method of the present invention, in which a represents chloromethylated polyphenylene sulfide, and b represents Quaternized polyphenylene sulfide, c represents tertiary ammonized polyphenylene sulfide;

Fig. 4 is the infrared spectrum of brominated polyphenylene sulfide, quaternized and tertiary ammonized polyphenylene sulfide prepared by the second method of the present invention, in which a represents brominated polyphenylene sulfide, and b represents quaternized polyphenylene sulfide. Phenyl sulfide, c represents tertiary ammonium polyphenylene sulfide;

Fig. 5 is the TGA curve of polyphenylene sulfide, quaternized amphoteric polyphenylene sulfide and tertiary ammonized amphoteric polyphenylene sulfide in the air in the general structural formula I prepared by the present invention, wherein a is polyphenylene sulfide, b is quaternized polyphenylene sulfide, and c is tertiary ammonized polyphenylene sulfide;

Fig. 6 shows the viscosities of sulfonated polyphenylene sulfide prepared by the present invention and the quaternized amphoteric polyphenylene sulfide and tertiary ammonium amphoteric polyphenylene sulfide in the general structural formula I in different salt concentrations at the isoelectric point position , where a is sulfonated polyphenylene sulfide, b is quaternized amphoteric polyphenylene sulfide, and c is tertiary ammonium amphoteric polyphenylene sulfide;

Fig. 7 is the TGA curve of polyphenylene sulfide, quaternized amphoteric polyphenylene sulfide and tertiary ammonized amphoteric polyphenylene sulfide in the air in the general structural formula II prepared by the present invention, wherein a is polyphenylene sulfide, b is tertiary ammonium polyphenylene sulfide, c is quaternized polyphenylene sulfide;

Fig. 8 shows the viscosities of sulfonated polyphenylene sulfide prepared by the present invention and its quaternized amphoteric polyphenylene sulfide and tertiary ammonium amphoteric polyphenylene sulfide in the general structural formula II at different salt concentrations at the isoelectric point position The change curve, where a is quaternized amphoteric polyphenylene sulfide, b is tertiary ammonium amphoteric polyphenylene sulfide, and c is sulfonated polyphenylene sulfide.

Detailed ways

The following examples are provided to specifically describe the present invention. It should be pointed out that the following examples can not be interpreted as limiting the protection scope of the present invention. Those skilled in the art will make some non-essential contributions to the present invention according to the above-mentioned contents of the present invention. Improvements and adjustments still belong to the protection scope of the present invention.

Example 1

Sulfonate 10g of polyphenylene sulfide with 200ml of sulfuric acid with a fume content of 20-25% at 105°C for 4h, then when the temperature of the mixture is lowered to 15°C, first add the sulfonated polyphenylene sulfide The mass fraction is counted as 3% iron trichloride catalyst, and then 30ml of 1,4-dichloromethoxybutane is added dropwise thereto while stirring, and reacted for 4h at 30°C, and then use a salt content of 4% The ice-water mixture was purified and washed repeatedly until the pH value of the filtrate was 7, and the obtained solid was dried to constant weight; first, the obtained chloromethylated polyphenylene sulfide solid was added into 70 mL of trimethylamine aqueous solution with a concentration of 2 mol/L and stirred to dissolve, and then Adjust the pH to 4.0-5.0, and react at 20°C for 7 hours, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol 4-5 times, and dry the obtained solid at 80-90°C to constant weight to obtain the general structure In the formula [I], R is N ⁺ (CH ₃ ) ₃ Cl ^- water-soluble polyphenylene sulfide.

Example 2

Sulfonate 10g of polyphenylene sulfide with 150ml of sulfuric acid with a fume content of 20-25% at 80°C for 4 hours, then when the temperature of the mixture is lowered to 15°C, first add the sulfonated polyphenylene sulfide The mass fraction is counted as 5% ferric chloride catalyst, and then 50ml of 1,4-dichloromethoxybutane is added dropwise to it while stirring, and reacted for 6h at 15°C, and then use a salt content of 4% The ice-water mixture was purified and washed repeatedly until the pH value of the filtrate was 7, and the obtained solid was dried to constant weight; first, the obtained chloromethylated polyphenylene sulfide solid was added into 60 mL of diethanolamine aqueous solution with a concentration of 5 mol/L and stirred to dissolve, and then Adjust the pH to 8.0-9.0, react at 40°C for 10 hours, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times, and dry the obtained solid at 80-90°C to constant weight to obtain the structure Water-soluble polyphenylene sulfide of NH ⁺ (CH ₂ CH ₂ OH) ₂ Cl ^- in formula [I].

Example 3

Sulfonate 10g of polyphenylene sulfide with 130ml of sulfuric acid with a fume content of 20-25% at 105°C for 2 hours, then when the temperature of the mixture is lowered to 15°C, first add the sulfonated polyphenylene sulfide The mass fraction is counted as 2% ferric chloride catalyst, then 70ml of chloromethoxyoctane is added dropwise to it while stirring, and reacted for 12h at 0°C, and then purified with an ice-water mixture with a salt content of 4%. And repeatedly washed until the pH value of the filtrate was 7, and the obtained solid was dried to constant weight; first, the obtained chloromethylated polyphenylene sulfide solid was added into 50 mL of trimethylamine aqueous solution with a concentration of 5 mol/L and stirred to dissolve, and then the pH was adjusted to 9.0- 10.0, and react at 20°C for 7h, add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol 4-5 times, and dry the obtained solid at 80-90°C to constant weight to obtain the general structure [I] R is N ⁺ (CH ₃ ) ₃ Cl ^- water-soluble polyphenylene sulfide.

Example 4

Sulfonate 10g of polyphenylene sulfide with 100ml of sulfuric acid with a fume content of 20-25% at 105°C for 6 hours, then when the temperature of the mixture is lowered to 15°C, first add the sulfonated polyphenylene sulfide The mass fraction of the ferric chloride catalyst is 6%, and then 40ml of chloromethoxybutane is added dropwise while stirring, and reacted for 10h at 20°C, and then purified with an ice-water mixture with a salt content of 4%. and repeatedly washed until the pH value of the filtrate was 7, and the obtained solid was dried to constant weight; first, the obtained chloromethylated polyphenylene sulfide solid was added into 50 mL of dimethylamine aqueous solution with a concentration of 3 mol/L and stirred to dissolve, and then the pH was adjusted to 7.0 -8.0, and react at 80°C for 8h, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol 4-5 times, and dry the obtained solid at 80-90°C to constant weight to obtain the general structural formula [I] R is NH ⁺ (CH ₃ ) ₂ Cl ^- water-soluble polyphenylene sulfide.

Example 5

Sulfonate 10g of polyphenylene sulfide with 150ml of sulfuric acid with a fume content of 20-25% at 100°C for 10h, then when the temperature of the mixture is lowered to 15°C, first add the sulfonated polyphenylene sulfide The mass fraction is counted as 4% tin tetrachloride catalyst, and then 50ml of 1,4-dichloromethoxybutane is added dropwise thereto while stirring, and reacted for 12h at 25°C, and then use a salt content of 4% The ice-water mixture was purified and washed repeatedly until the pH value of the filtrate was 7, and the obtained solid was dried to constant weight; first, the obtained chloromethylated polyphenylene sulfide solid was added into 30 mL of trimethylamine aqueous solution with a concentration of 4 mol/L and stirred to dissolve, and then Adjust the pH to 4.0-5.0, react at 40°C for 8 hours, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times, and dry the obtained solid at 80-90°C to constant weight to obtain the general structure In the formula [I], R is N ⁺ (CH ₃ ) ₃ Cl ^- water-soluble polyphenylene sulfide.

Example 6

的水溶性聚苯硫醚。Sulfonate 10g of polyphenylene sulfide with 150ml of sulfuric acid with a fume content of 20-25% at 90°C for 12 hours, then when the temperature of the mixture is lowered to 15°C, first add the sulfonated polyphenylene sulfide The mass fraction is calculated as 4% aluminum trichloride catalyst, and then 60ml of 1,4-dichloromethoxybutane is added dropwise to it while stirring, and reacted at 10°C for 8h, and then the salt content is 4% The ice-water mixture was purified and washed repeatedly until the pH value of the filtrate was 7, and the obtained solid was dried to constant weight; first, the obtained chloromethylated polyphenylene sulfide solid was added into 40 mL of 1-pyrrolidone aqueous solution with a concentration of 2 mol/L and stirred to dissolve, Then adjust the pH to 6.0-7.0, react at 60°C for 9 hours, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times, and dry the obtained solid at 80-90°C to constant weight to obtain the structure R in the general formula [I] is

water-soluble polyphenylene sulfide.

Example 7

Sulfonate 10g of polyphenylene sulfide with 200ml of sulfuric acid with a fume content of 20-25% at 105°C for 4h, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether for precipitation and suction filtration to obtain The solid was washed with acetone until the pH value of the filtrate was 7, and then dried to constant weight; 50 mL of dimethyl sulfoxide and 3% of sulfonated polyphenylene sulfide were added to the obtained sulfonated polyphenylene sulfide solid Ferric chloride catalyst, stir and dissolve at 40°C and mix evenly, then add dropwise 100ml of bromine ethanol solution with a volume concentration of 1% while stirring, and react for 5h after the dropwise addition; first adjust the pH of the resulting mixed solution to 4.0 -5.0, then add 50mL trimethylamine aqueous solution with a concentration of 2mol/L, stir and mix, and react at 60°C for 7h, then add absolute ethanol for precipitation, filter with suction, wash repeatedly with absolute ethanol for 4-5 times and then Soxhlet extraction After 24 hours, the obtained solid was dried to constant weight to obtain a water-soluble polyphenylene sulfide in which R in the general structural formula [II] is N ⁺ (CH ₃ ) ₃ Cl ^- .

Example 8

Sulfonate 10g of polyphenylene sulfide with 150ml of sulfuric acid with a fume content of 20-25% at 80°C for 4h, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether for precipitation and suction filtration to obtain The solid was washed with acetone until the pH value of the filtrate was 7, and then dried to constant weight; 130 mL of dimethylformamide and 4% of dimethylformamide were added to the obtained sulfonated polyphenylene sulfide solid Tin tetrachloride catalyst, stir and dissolve at 30°C and mix evenly, then add dropwise 50ml of bromine ethanol solution with a volume concentration of 1% while stirring, and react for 12h after the dropwise addition; first adjust the pH of the obtained mixed solution to 9.0 -10.0, then add 30mL trimethylamine aqueous solution with a concentration of 4mol/L, stir and mix, and react at 20°C for 10h, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times, then Soxhlet extraction After 24 hours, the obtained solid was dried to constant weight to obtain a water-soluble polyphenylene sulfide in which R in the general structural formula [II] is N ⁺ (CH ₃ ) ₃ Cl ^- .

Example 9

Sulfonate 10g of polyphenylene sulfide with 130ml of sulfuric acid with a fume content of 20-25% at 105°C for 2h, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether to precipitate and suction filter to obtain The solid was washed with acetone until the pH value of the filtrate was 7, and then dried to constant weight; 100 mL of dimethylacetamide and 2% of dimethylacetamide were added to the obtained sulfonated polyphenylene sulfide solid Ferric chloride catalyst, stirred and dissolved at 70°C and mixed evenly, then dropwise added 80ml of bromine ethanol solution with a volume concentration of 1% to it while stirring, and reacted for 7h after the dropwise addition; first adjust the pH of the resulting mixed solution to 7.0 -8.0, then add 40 mL of dimethylamine aqueous solution with a concentration of 5 mol/L, stir and mix, and react at 80°C for 7 hours, then add absolute ethanol for precipitation, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times before Soxhlet extraction After extracting for 24 hours, the obtained solid was dried to constant weight to obtain the water-soluble polyphenylene sulfide in which R in the general structural formula [II] is NH ⁺ (CH ₃ ) ₂ Cl ^- .

Example 10

Sulfonate 10g of polyphenylene sulfide with 100ml of sulfuric acid with a fume content of 20-25% at 105°C for 6h, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether for precipitation and suction filtration to obtain The solid was washed with acetone until the pH value of the filtrate was 7, and then dried to constant weight; 120 mL of dimethyl sulfoxide and 6% of sulfonated polyphenylene sulfide were added to the obtained sulfonated polyphenylene sulfide solid Ferric chloride catalyst, stirred and dissolved at 50°C and mixed evenly, then dropwise added 60ml of bromine ethanol solution with a volume concentration of 1% while stirring, and reacted for 7h after the dropwise addition; first adjust the pH of the resulting mixed solution to 6.0 -7.0, then add 70 mL of triethanolamine aqueous solution with a concentration of 3 mol/L, stir and mix, and react at 30°C for 8 hours, then add absolute ethanol to precipitate, filter with suction, wash repeatedly with absolute ethanol for 4-5 times, and then Soxhlet extraction After 24 hours, the obtained solid was dried to constant weight to obtain a water-soluble polyphenylene sulfide in which R in the general structural formula [II] is N ⁺ (CH ₂ CH ₂ OH) ₃ Cl ^- .

Example 11

Sulfonate 10g of polyphenylene sulfide with 150ml of sulfuric acid with a fume content of 20-25% at 100°C for 10h, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether for precipitation and suction filtration to obtain The solid was washed with acetone until the pH value of the filtrate was 7, and then dried to constant weight; 150 mL of dimethylacetamide and 4% of dimethylacetamide were added to the obtained sulfonated polyphenylene sulfide solid Ferric chloride catalyst, stir and dissolve at 60°C and mix evenly, then add dropwise 70ml of bromine ethanol solution with a volume concentration of 1% while stirring, and react for 2h after the dropwise addition; first adjust the pH of the resulting mixed solution to 4.0 -5.0, then add 60 mL of diethanolamine aqueous solution with a concentration of 5 mol/L, stir and mix, and react at 40°C for 8 hours, then add absolute ethanol to precipitate, filter with suction, and wash repeatedly with absolute ethanol for 4-5 times, then Soxhlet extraction After 24 hours, the obtained solid was dried to constant weight to obtain a water-soluble polyphenylene sulfide in which R in the general structural formula [II] is NH ⁺ (CH ₂ CH ₂ OH) ₂ Cl ^- .

Example 12

的水溶性聚苯硫醚。Sulfonate 10 g of polyphenylene sulfide with 150 ml of sulfuric acid with a fume content of 20-25% at 90°C for 12 hours, then lower the temperature of the mixture to room temperature and pour it into anhydrous ether for precipitation and suction filtration to obtain The solid was washed with acetone until the pH value of the filtrate was 7, and then dried to constant weight; 130 mL of dimethylformamide and 4% of dimethylformamide were added to the obtained sulfonated polyphenylene sulfide solid Aluminum trichloride catalyst, stir and dissolve at 40°C and mix evenly, then dropwise add 70ml of bromine ethanol solution with a volume concentration of 1% to it while stirring, and react for 10h after the dropwise addition; first adjust the pH of the obtained mixed solution to 5.0 -6.0, then add 60mL of 1-pyrrolidone aqueous solution with a concentration of 4mol/L, stir and mix, and react at 40°C for 9h, then add absolute ethanol to precipitate, filter with suction, wash repeatedly with absolute ethanol for 4-5 times, and then Soxhlet Extract 24h, the gained solid is dried to constant weight and promptly obtains in the general structure formula [II] R is

water-soluble polyphenylene sulfide.

In order to investigate the relevant properties of the prepared polyphenylene sulfide, the present invention firstly tested its solubility in various solvents, and the test results are shown in Table 1.

Table 1

Note: In this test, 2% (weight percent) polymer is added to the corresponding solution, heated to 70°C and dissolved for one hour, then cooled to room temperature, and then observed. In the table, + means completely dissolved, one means insoluble, ± means slightly soluble; PPS: polyphenylene sulfide; QAPPS (I): water-soluble polyphenylene sulfide corresponding to the general structural formula (I); QAPPS (II): The water-soluble polyphenylene sulfide corresponding to the general structural formula (II).

From the solubility test results of Table 1, the water-soluble polyphenylene sulfide corresponding to the general structural formula (I) can be dissolved in water, and the water-soluble polyphenylene sulfide corresponding to the general structural formula (II) can not only Soluble in water, and slightly soluble in methylpyrrolidone, dimethylacetamide and ethanol.

Secondly, the present invention also separately analyzes the degree of sulfonation of sulfonated polyphenylene sulfide, the degree of bromination of brominated-sulfonated polyphenylene sulfide and the chlorine content of chloromethyl-sulfonated polyphenylene sulfide prepared in some examples. According to acid-base titration method (Wu Xuemei. Research on sulfonated polyarylether sulfone ketone and its modified proton exchange membrane. Doctoral dissertation of Dalian University of Technology), combustion with oxygen bottle (Jiang Xiaohui, Wang Chunmei, Hou Xuewei. Brominated polystyrene The mensuration of bromine content) the bromine of combined state is converted into ionic state earlier, adopts silver nitrate solution to carry out titration again (Dong Yanming. Practical analysis technology of macromolecule material [M]. Beijing: China Petrochemical Press, 2005.) Measured, The measurement results are shown in Tables 2, 3, and 4.

Table 2

Note: ^a is the mass (g) of polyphenylene sulfide in the reaction; ^b is the volume (mL) of fuming sulfuric acid in the reaction; ^c is the sulfonation of sulfonated polyphenylene sulfide under different reaction conditions by acid-base titration Spend.

From the test results in Table 2, it can be seen that polyphenylene sulfide has been transformed into sulfonated polyphenylene sulfide.

table 3

Note: ^a is the mass of sulfonated polyphenylene sulfide in the reaction; ^b is the mass fraction of ferric chloride (FeCl ₃ ) in polyphenylene sulfide in the reaction.

From the test results in Table 3, it can be seen that sulfonated polyphenylene sulfide has been converted into brominated-sulfonated polyphenylene sulfide, and in the subsequent reaction, it is substituted by quaternary ammonium group, tertiary amine group or pyrrolidone group again Use the oxygen bottle combustion method and the silver nitrate titration method to determine the bromine content in it, and the bromine content is basically zero.

Table 4

Note: ^a is the mass of sulfonated polyphenylene sulfide in the reaction; ^b is the mass fraction of ferric chloride (FeCl ₃ ) in polyphenylene sulfide in the reaction.

From the test results in Table 4, it can be seen that sulfonated polyphenylene sulfide has been transformed into chloromethylated-sulfonated polyphenylene sulfide, and is substituted by quaternary amine groups, tertiary amine groups or pyrrolidone groups in the subsequent reaction Then use the oxygen cylinder combustion method and the silver nitrate titration method to measure the chlorine content therein again, and the chlorine content is basically zero.

In addition, in order to investigate the grafting situation of the prepared sulfonated polyphenylene sulfide, the quaternized amphoteric polyphenylene sulfide in the general structural formulas I and II, and the grafting of the tertiary ammonium amphoteric polyphenylene sulfide, as well as the temperature and salt resistance properties, this paper Invention also carried out infrared spectrum test and temperature and salt resistance performance test on it, the results are shown in Figures 1 to 8 respectively.

Among Fig. 1, 3420cm-1 is the O-H stretching vibration peak of sulfonic acid group-SO3H; 1230cm-1 and 1188cm-1 are the S=O stretching vibration peak of sulfonic acid group-SO3H; 1030cm-1 is the stretching vibration peak of C-N; 890cm -1 and 811cm-1 are the characteristic absorption peaks of the three substitutions of the benzene ring; the characteristic absorption peak at 620cm-1 is the stretching vibration peak of the S-O bond; from the infrared spectrum, it can be proved that the sulfonate group has been successfully grafted onto polyphenylene sulfide .

In Figure 2, 2967cm ^-1 and 2866cm ^-1 are the symmetric and asymmetric stretching vibration peaks of methylene on chloromethyl; 1440cm ^-1 is the scissor vibration peak of methylene; the peak CMPPS at 621cm ^-1 is obviously stronger In SPPS, the presence of a C-Cl bond is stated. It can be seen from this map that chloromethyl has been attached to sulfonated polyphenylene sulfide.

It can be seen from Figure 3 that 2920cm ^-1 and 2810cm ^-1 in the b curve are the absorption peaks formed by the symmetrical and asymmetric stretching vibration of the methyl group on the quaternary ammonium group; 3189cm-1 in the c curve is the characteristic absorption of the tertiary amine-NH The peak, 2810cm-1, is the absorption peak formed by the stretching vibration of the methyl group on the tertiary ammonium; and the 3050cm-1 and 3040cm-1 in the b and c curves are both the skeleton vibration peaks of the benzene ring, and the vibration peaks are due to the The vibration of the N atom directly connected to the benzene ring is enhanced, which is observed in curves b and c. In curve a, it is difficult to observe the skeleton vibration peak of the benzene ring due to the interference of the hydroxyl peak.

It can be seen from Figure 4 that the characteristic frequency peak 935cm ^- 1 of the benzene ^ring caused by bromine is not obvious in the b and c curves; and the absorption peak caused by asymmetric stretching vibration; 3189cm-1 in c is the characteristic absorption peak of tertiary amine-NH, and 2810cm-1 is caused by the stretching vibration of the methyl group on tertiary ammonium; and 3050cm-1 in the curves of b and c Both 1 and 3040cm-1 are the skeleton vibration peaks of the benzene ring, and this vibration peak is observed in the b and c curves because of the influence of the N atom directly connected to the benzene ring, and the vibration is enhanced, and it is observed in the a curve Due to the interference of the hydroxyl peak, it is difficult to observe the skeleton vibration peak of the benzene ring.

As can be seen from Figure 5, because polyphenylene sulfide itself has excellent high temperature resistance, it does not undergo obvious decomposition until about 500 ° C in the air; Phenyl sulfide and tertiary ammonium amphoteric polyphenylene sulfide show a large mass loss before 300°C due to the evaporation of water, because amphoteric polyphenylene sulfide has very excellent water absorption properties, and between 300-400°C The main performance is the decomposition of sulfonic acid groups, and then the relative decomposition quality of the main chain and quaternary and tertiary ammonium groups is gradually lost. However, compared with the existing water-soluble polymers whose use temperature is limited to about 200°C, its high temperature resistance has been greatly improved, especially the quaternized amphoteric polyphenylene sulfide, which has a temperature of about 350°C , the quality retention rate is still about 80%.

It can be seen from Figure 6 that amphoteric polyphenylene sulfide has good solubility in pure water, and from the comparison of the three curves, it can be seen that amphoteric polyphenylene sulfide has better solubility than sulfonated polyphenylene sulfide with a single charge. Salt resistance, and with the increase of salt concentration, its molecular chain is more extended in water, showing the increase of viscosity. However, with the increase of salt concentration, the viscosity of sulfonated polyphenylene sulfide decreases sharply, and finally precipitates. Since the polymer flocculation effect, sewage treatment effect, and fluid loss reduction effect are closely related to the stretching state of the polymer chain, maintaining the stretching state of the polymer chain is the basic condition for quality assurance. Compared with polymers with a flexible main chain, its semi-rigid main chain makes the stretchability of the polymer itself show obvious advantages.

It can be seen from Figure 7 that because polyphenylene sulfide itself has excellent high temperature resistance, it does not undergo obvious decomposition until about 500 ° C in the air; Phenyl sulfide and tertiary ammonium amphoteric polyphenylene sulfide show a large mass loss before 300°C due to the evaporation of water, because amphoteric polyphenylene sulfide has very excellent water absorption properties, and between 300-400°C The main performance is the decomposition of the sulfonic acid group, and then along with the main chain and the quaternary, the relative decomposition quality of the tertiary ammonium group is gradually lost. However, compared with the existing water-soluble polymers whose use temperature is limited to about 200°C, its high temperature resistance has been greatly improved, especially the quaternized amphoteric polyphenylene sulfide, which has a temperature of about 350°C , the quality retention rate is still about 80%.

It can be seen from Figure 8 that amphoteric polyphenylene sulfide has good solubility in pure water, and the comparison of the three curves shows that amphoteric polyphenylene sulfide has better solubility than sulfonated polyphenylene sulfide with a single charge. Salt resistance, and with the increase of salt concentration, its molecular chain is more extended in water, showing the increase of viscosity. However, with the increase of salt concentration, the viscosity of sulfonated polyphenylene sulfide decreases sharply, and finally precipitates. Since the polymer flocculation effect, sewage treatment effect, and fluid loss reduction effect are closely related to the stretching state of the polymer chain, maintaining the stretching state of the polymer chain is the basic condition for quality assurance. Compared with polymers with a flexible main chain, its semi-rigid main chain makes the stretchability of the polymer itself show obvious advantages.

Claims (8)

1. water-solubility polyphenylene sulfide, its general structure is as follows:

Wherein R is N ⁺(CH ₃) ₃Cl ^-, NH ⁺(CH ₃) ₂Cl ^-, N ⁺(CH ₂CH ₂OH) ₃Cl ^-, NH ⁺(CH ₂CH ₂OH) ₂Cl ^-Or

Water-soluble and the saturated aqueous common salt of this polyphenylene sulfide is insoluble to methyl-2-pyrrolidone, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), toluene, acetone, chloroform and ethanol, or

Wherein R is N ⁺(CH ₃) ₃Cl ^-, NH ⁺(CH ₃) ₂Cl ^-, N ⁺(CH ₂CH ₂OH) ₃Cl ^-, NH ⁺(CH ₂CH ₂OH) ₂Cl ^-Or

Water-soluble and the saturated aqueous common salt of this polyphenylene sulfide is slightly soluble in methyl-2-pyrrolidone, N,N-DIMETHYLACETAMIDE and ethanol, is insoluble to tetrahydrofuran (THF), toluene, acetone and chloroform.

2. method for preparing the described water-solubility polyphenylene sulfide of claim 1, the processing step and the condition of this method are as follows:

1) with the amount of being fuming be the sulfuric acid of 20-25% at 80-105 ℃ of following p-poly-phenyl thioether sulfonation 2-12h, then the temperature of this mixed solution is reduced to room temperature, wherein the envelope-bulk to weight ratio of oleum and polyphenylene sulfide is 10-20ml/g;

2) when mixeding liquid temperature is 15 ℃, add the Lewis catalyzer of counting 2-6% by the massfraction of sulfonated polyphenyl thioether earlier, then while stirring to wherein dripping by sulfonated polyphenyl thioether weight: the chloromethylation reagent volume is the chloromethylation reagent of 1g/3-7ml, and in 0-30 ℃ of reaction 4-12h, mixture of ice and water purification and repetitive scrubbing with saltiness 4% is 7 to filtrate pH value again, and the gained solid drying is to constant weight;

3) earlier gained chloromethylation polyphenylene sulfide solid is added stirring and dissolving in quaternizing agent that concentration is 2-5mol/L or tertiary amine reagent or the 1-pyrrolidone, regulating pH then is 4.0-10.0, and at 20-80 ℃ of reaction 7-10h, add dehydrated alcohol precipitation, suction filtration again, and with dehydrated alcohol repetitive scrubbing 4-5 time, the gained solid is dried to constant weight in 80-90 ℃ and promptly gets the water-solubility polyphenylene sulfide of general structure for [I], wherein the proportioning of chloromethylation polyphenylene sulfide and quaternizing agent or tertiary amine reagent or 1-pyrrolidone is 1g/3-7mL, or

1) be that the sulfuric acid of 20-25% is at 80-105 ℃ of following p-poly-phenyl thioether sulfonation 2-12h with the amount of being fuming, then the temperature of this mixed solution is reduced to room temperature and pour into and precipitate suction filtration in the anhydrous diethyl ether, gained solids washed with acetone to filtrate pH value is 7, be dried to constant weight again, wherein the envelope-bulk to weight ratio of oleum and polyphenylene sulfide is 10-20ml/g;

2) weightmeasurement ratio of adding and sulfonated polyphenyl thioether is the polar aprotic solvent of 1g/5-15mL and the Lewis catalyzer of counting 2-6% by the massfraction of sulfonated polyphenyl thioether in gained sulfonated polyphenyl thioether solid, mix in 30-70 ℃ of stirring and dissolving, then while stirring to wherein dripping by sulfonated polyphenyl thioether weight: the chloromethylation reagent volume is the bromine ethanolic soln of 1g/5-10ml, the volumetric concentration of this bromine ethanolic soln is 1%, drips afterreaction 2-12h;

3) pH of adjusting gained mixed solution is 4.0-10.0 earlier, adding quaternizing agent that concentration is 2-5mol/L or tertiary amine reagent or 1-pyrrolidone 1g/3-7mL by the weight of brominated polyphenylene thioether in the mixed solution then mixes, and in 20-80 ℃ of reaction 7-10h, add dehydrated alcohol precipitation, suction filtration again, and with the cable-styled extracting 24h in dehydrated alcohol repetitive scrubbing 4-5 time back, gained solid drying to constant weight promptly get the water-solubility polyphenylene sulfide that general structure is [II].

3. the preparation method of water-solubility polyphenylene sulfide according to claim 2, used Lewis catalyzer is an iron trichloride in this method, any in tin tetrachloride or the aluminum chloride.

4. according to the preparation method of claim 2 or 3 described water-solubility polyphenylene sulfides, used polar aprotic solvent is any in dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE or the dimethyl formamide in this method.

5. according to the preparation method of claim 2 or 3 described water-solubility polyphenylene sulfides, used chloromethylation reagent is 1 in this method, 4-dichloro methyl butyl ether or chlorine methoxyl group octane.

6. the preparation method of water-solubility polyphenylene sulfide according to claim 4, used chloromethylation reagent is 1 in this method, 4-dichloro methyl butyl ether or chlorine methoxyl group octane.

7. according to the preparation method of claim 2 or 3 described water-solubility polyphenylene sulfides, used quaternizing agent is trimethylamine aqueous solution or trolamine in this method; Tertiary amine reagent is dimethylamine agueous solution or dimethanolamine.

8. the preparation method of water-solubility polyphenylene sulfide according to claim 6, used quaternizing agent is trimethylamine aqueous solution or trolamine in this method; Tertiary amine reagent is dimethylamine agueous solution or dimethanolamine.

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