CN111363115A - Water-soluble high polymer material and preparation method and application thereof - Google Patents
Water-soluble high polymer material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble polymer material, which is prepared from the following raw materials: 200 parts of polyethylene glycol, 20-50 parts of hydroxyl-terminated polyether mixed diol, 3-7 parts of trimethylolpropane, 154-203 parts of diisocyanate, 2-5 parts of biomass melanin and 25-31 parts of N-methyldiethanolamine; the hydroxyl-terminated polyether mixed diol is prepared by mixing polytetrahydrofuran diol and polypropylene oxide diol in a ratio of 1: 0.9-1.1. The preparation method comprises the steps of mixing polyethylene glycol, hydroxyl-terminated polyether mixed glycol, trimethylolpropane and biomass melanin, dehydrating, adding diisocyanate, reacting, adding N-methyldiethanolamine, and carrying out die pressing vulcanization to obtain the product. The water-soluble polymer material disclosed by the invention has high strength, good elasticity and sealing property, and excellent water solubility, can be widely applied to underground tools such as bridge plugs, packers and the like, and realizes the technical characteristic that a sealing element does not need to be fished.
Description
Technical Field
The invention relates to a water-soluble polymer material, a preparation method thereof and application thereof in preparing a sealing element, belonging to the technical field of functional materials.
Background
After the traditional sealing element used for the fracturing process is operated, the sealing element of the packer needs to be lifted out of an oil well, the sealing element is broken in the operation, the lifting-out difficulty is caused, and the operation cost of the oil extraction process is increased. The traditional material of the current oil production tool gradually develops from drillable to soluble direction, and the matched packer sealing element is required to be rapidly dissolved in water while the bridge plug can be rapidly dissolved in water.
At present, foreign soluble composite material downhole tools for fracturing are mature, a soluble fracturing ball seat, a soluble fracturing bridge plug and other tools are formed, and used soluble sealing elements are oil-soluble sealing element materials and water-soluble sealing element materials. However, the literature data of the water-soluble high-performance elastomer is only rarely reported at home and abroad, and no patent publication and literature report of the preparation technology of the water-soluble rubber elastomer are found. The research in the field is relatively late in China, and although certain results are achieved in the aspect of soluble fracturing balls, the research on water-soluble rubber is blank.
Disclosure of Invention
In view of the prior art, the invention provides a water-soluble polymer material and a preparation method thereof. The water-soluble polymer material can be used for preparing a sealing element. The water-soluble polymer material is a rubber elastomer composite material, has high strength, and has excellent performance after being prepared into a sealing element; meanwhile, the sealing element can be quickly dissolved in clear water and alkaline water media, so that the sealing element can be automatically dissolved in the water media after the fracturing process is finished, the sealing element is prevented from being lifted out, the subsequent treatment of tools is avoided, the construction procedures are reduced, the construction time is shortened, the construction cost is reduced, and the technical characteristic that the sealing element does not need to be fished is realized.
The invention is realized by the following technical scheme:
a water-soluble high polymer material is prepared from the following raw materials in parts by weight: 200 parts of polyethylene glycol, 20-50 parts of hydroxyl-terminated polyether mixed glycol, 3-7 parts of trimethylolpropane (cross-linking agent), 154-203 parts of diisocyanate, 2-5 parts of biomass melanin (reinforcing agent) and 25-31 parts of N-methyldiethanolamine (chain extender);
the hydroxyl-terminated polyether mixed glycol is formed by physically mixing polytetrahydrofuran glycol and polypropylene oxide glycol, and the mass ratio of the polytetrahydrofuran glycol to the polypropylene oxide glycol is 1: 0.9-1.1.
Further, the polyethylene glycol has a relative molecular mass of 1800 to 2000g/mol, a viscosity of 5.0 to 6.7mPa · s, and a hydroxyl value of 51 to 62mg KOK/g. PEG-2000 is preferred.
Preferably, the polytetrahydrofuran diol is selected from PTMG-1000 (referred to product specification).
Preferably, the polypropylene oxide glycol is selected from N-210 (product specification), and has a number average molecular weight of 1000, a functionality of 2, and a hydroxyl number of 112 mgKOH/g.
Preferably, the diisocyanate is selected from any one or a combination of two or more of isophorone diisocyanate (IPDI), Toluene Dicyanate (TDI), 4-diisocyanate diphenylmethane (MDI), 1, 6-Hexamethylene Diisocyanate (HDI), and Naphthalene Diisocyanate (NDI), preferably isophorone diisocyanate.
Preferably, the biomass melanin is squid melanin.
The preparation method of the water-soluble polymer material comprises the following steps: mixing polyethylene glycol, hydroxyl-terminated polyether mixed glycol, a cross-linking agent trimethylolpropane and a reinforcing agent biomass melanin in a reaction container, and dehydrating for 50-70 minutes at 95-105 ℃; then cooling to 55-65 ℃, adding diisocyanate, and reacting for 1.5-2.5 hours at the reaction temperature of 70-80 ℃ (the synthesis reaction is exothermic); after the reaction is finished, vacuumizing and defoaming for 10-30 minutes to prepare a biomass hybrid polyurethane prepolymer (NCO functional group terminated prepolymer); then, adding a chain extender, quickly and uniformly stirring, pouring into a mold (preheated to 95-105 ℃ in advance), closing the mold when the mixture is in a gel state (does not flow or is not sticky), and placing the mold on a flat vulcanizing machine for mold pressing and vulcanizing, wherein the vulcanizing conditions are as follows: 8-12 MPa, 95-105 ℃ and 50-70 minutes to obtain the water-soluble polymer material.
The water-soluble polymer material is a rubber elastomer composite material, has high strength, good elasticity and sealing property and excellent water solubility, and can be widely applied to underground tools such as bridge plugs, packers and the like. The sealing element prepared from the water-soluble high polymer material can be automatically dissolved in a water medium, is free from lifting, avoids the subsequent treatment of tools, reduces the construction procedures, shortens the construction time, reduces the construction cost and realizes the technical characteristic that the sealing element does not need to be salvaged.
The various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
The polyethylene glycol used in the following examples, which was PEG-2000 in specification, was commercially available.
The polytetrahydrofuran diol used in the following examples, having a PTMG-1000 specification, is commercially available in a conventional manner.
The polypropylene oxide glycol used in the following examples, having a specification of N-210, is commercially available.
Example 1 preparation of Water-soluble Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 20g of hydroxyl-terminated polyether mixed glycol (prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1: 1), 3g of trimethylolpropane and 2g of biomass enhancer squid ink melanin are placed in a 500mL three-neck flask, and dehydration treatment is carried out for 1h at 100 ℃; cooling to 60 ℃, adding 172.9g of isophorone diisocyanate, and controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5 h; after the reaction is finished, vacuumizing and removing bubbles for 30 minutes to prepare the prepolymer terminated by the NCO functional group.
100g of the prepared polyurethane prepolymer is placed in a 200mL beaker, 25.47g of chain extender N-methyldiethanolamine is added, after the mixture is rapidly and uniformly stirred, the mixture is poured into a preheated mold at 100 ℃, when the mixture is in a gel state (non-flowing or non-sticky), the mold is closed, the mold is placed on a flat vulcanizing machine for mold pressing and vulcanizing, and the vulcanizing condition is 10MPa × 100 ℃ and × 1 h.
Taking out the material from the mold after the material is completely cured to obtain the water-soluble high polymer material, standing the material at room temperature for 24h, respectively placing the material in 100 ℃ water media with pH values of 6 and 9 for dissolution experiment evaluation, periodically fishing out the material from the water media and weighing the material until the material is completely dissolved in water, and recording the dissolution time.
Example 2 preparation of Water-soluble Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 30g of hydroxyl-terminated polyether mixed glycol (prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol in a mass ratio of 1: 1), 3g of trimethylolpropane and 2g of biomass enhancer squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 182.8g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant temperature reaction for 2.5h, and after the reaction is finished, vacuumizing is carried out for debubbling for 30 min, so as to prepare the NCO functional group terminated prepolymer.
120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine chain extender is added into the beaker, the mixture is poured into a preheated mold at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky (gel), the mold is closed, the mold is placed on a flat-plate vulcanizing machine for mold pressing and vulcanizing, and the vulcanizing condition is × 1 hours at 10MPa × 100 ℃.
And taking the material out of the mold after the material is completely cured, standing the material at room temperature for 24 hours, and respectively testing the mechanical property and the solubility in an aqueous medium of the material.
Example 3 preparation of Water-soluble Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 40g of hydroxyl-terminated polyether mixed glycol (prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol in a mass ratio of 1: 1), 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 192.6g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant temperature reaction for 2.5h, and after the reaction is finished, vacuumizing is carried out for debubbling for 30 min, so as to prepare the NCO functional group terminated prepolymer.
120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine chain extender is added into the beaker, the mixture is poured into a preheated mold at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky (gel), the mold is closed, the mold is placed on a flat-plate vulcanizing machine for mold pressing and vulcanizing, and the vulcanizing condition is × 1 hours at 10MPa × 100 ℃.
And taking the material out of the mold after the material is completely cured, standing the material at room temperature for 24 hours, and respectively testing the mechanical property and the solubility in an aqueous medium of the material.
Example 4 preparation of Water-soluble Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol (prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol in a mass ratio of 1: 1), 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 202.5g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant temperature reaction for 2.5h, and after the reaction is finished, vacuumizing is carried out for defoaming for 30 min, so that an NCO functional group-terminated prepolymer is prepared.
120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine chain extender is added into the beaker, the mixture is poured into a preheated mold at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky (gel), the mold is closed, the mold is placed on a flat-plate vulcanizing machine for mold pressing and vulcanizing, and the vulcanizing condition is × 1 hours at 10MPa × 100 ℃.
And taking the material out of the mold after the material is completely cured, standing the material at room temperature for 24 hours, and respectively testing the mechanical property and the solubility in an aqueous medium of the material.
Example 5 preparation of Water-soluble Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol (prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol in a mass ratio of 1: 1), 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 147.9g of toluene dicyanate is added, the reaction temperature is controlled at 75 ℃ for constant temperature reaction for 2.5h, and after the reaction is finished, vacuumizing and defoaming are carried out for 30 min, so that the NCO functional group terminated prepolymer is prepared.
120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine chain extender is added into the beaker, the mixture is poured into a preheated mold at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky (gel), the mold is closed, the mold is placed on a flat-plate vulcanizing machine for mold pressing and vulcanizing, and the vulcanizing condition is × 1 hours at 10MPa × 100 ℃.
And taking the material out of the mold after the material is completely cured, standing the material at room temperature for 24 hours, and respectively testing the mechanical property and the solubility in an aqueous medium of the material.
Example 6 preparation of Water-soluble Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol (prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol in a mass ratio of 1: 1), 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 157.5g of isophorone diisocyanate and 24.7g of toluenedicyanide are added, the reaction temperature is controlled at 75 ℃ for constant temperature reaction for 2.5h, and after the reaction is finished, vacuum pumping is carried out for defoaming for 30 min, so that the NCO functional group terminated prepolymer is prepared.
120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine chain extender is added into the beaker, the mixture is poured into a preheated mold at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky (gel), the mold is closed, the mold is placed on a flat-plate vulcanizing machine for mold pressing and vulcanizing, and the vulcanizing condition is × 1 hours at 10MPa × 100 ℃.
And taking the material out of the mold after the material is completely cured, standing the material at room temperature for 24 hours, and respectively testing the mechanical property and the solubility in an aqueous medium of the material.
Comparative example preparation of Polymer Material
The method comprises the following steps: 200g of polyethylene glycol, 3g of trimethylolpropane and 2g of biomass enhancer squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, cooling is carried out to 60 ℃, 154.1g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant temperature reaction for 2.5h, and after the reaction is finished, vacuumizing and defoaming are carried out for 30 min, so as to prepare the prepolymer with the end capped NCO functional group.
Taking 110g of the prepared polyurethane prepolymer, putting the 110g of the prepared polyurethane prepolymer into a 200mL beaker, adding 28.02g N-methyldiethanolamine chain extender, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture does not flow or is not sticky (gel-like), and putting the mold on a flat-plate vulcanizing machine for mold pressing and vulcanizing under the vulcanizing condition of 10MPa × 100 ℃ and × 1 h.
And taking the material out of the mold after the material is completely cured, standing the material at room temperature for 24 hours, and respectively testing the mechanical property and the solubility in an aqueous medium of the material.
Performance testing
The performance test of the soluble polymer materials obtained in the above examples 1 to 6 and comparative example 1 was carried out by the following method:
mechanical properties: the test was carried out according to the national Standard test GB/T16584-. The stretching rate is 500mm min-1。
Hardness: the Shore A hardness of the material is tested according to GB/T531-1999 by adopting a KYLX-A type rubber hardness tester produced by open source test machinery factories in Yangtze City.
Evaluation of solubility: two 10g portions of the water-soluble polymer material prepared in example 1 were placed in 200mL portions of aqueous media of 100 deg.C, 120 deg.C and 150 deg.C, pH 6 and 9 were respectively, and the water-soluble polymer material was periodically removed from the aqueous media and weighed until it was completely dissolved in water, and the dissolution time was recorded, wherein the pH of the aqueous media was adjusted by acetic acid and sodium carbonate, respectively, for the aqueous media of pH 6 and 9. The same treatment was carried out for the products prepared in the other examples and comparative examples.
The 100 ℃ results are shown in Table 1.
TABLE 1 mechanical Properties and solubility evaluation of soluble Polymer materials
As can be seen from the table, the increase of the usage amount of the polyether mixed glycol with different terminal hydroxyl groups improves the mechanical property of the water-soluble polymer material, and the complete dissolution time is also prolonged; this is because the addition of the hydroxyl-terminated polyether mixed diol increases the elastic modulus of the material, and the mechanical properties are improved more and more with more usage, so that the dissolution time is gradually prolonged in an aqueous medium due to the improvement of the mechanical properties.
Example 7 preparation of Water-soluble Polymer Material
The preparation method comprises the following steps of putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol formed by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:0.9, 3g of trimethylolpropane and 5g of biomass reinforcing agent squid ink melanin into a 500mL three-neck flask, carrying out dehydration treatment for 50 minutes at 100 ℃, cooling to 60 ℃, adding 203g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 1.5 hours, vacuumizing and degassing for 10 minutes after the reaction is finished, preparing a prepolymer with an end capped with NCO functional groups, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 25g N-methyldiethanolamine, rapidly and uniformly stirring, pouring the mixture into a mold preheated at 100 ℃, closing the mold when the mixture is in a gel state, putting the mold on a flat plate vulcanizing machine for vulcanizing and molding, and obtaining the polyurethane prepolymer with the vulcanizing condition of 8MPa × 105 ℃ for × 70 minutes.
Example 8 preparation of Water-soluble Polymer Material
The preparation method comprises the following steps of putting 200g of polyethylene glycol, 20g of hydroxyl-terminated polyether mixed glycol formed by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1.1, 7g of trimethylolpropane and 2g of squid ink melanin serving as a biomass reinforcing agent into a 500mL three-neck flask, carrying out dehydration treatment at 100 ℃ for 70 minutes, cooling to 60 ℃, adding 154g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2 hours, vacuumizing and degassing for 20 minutes after the reaction is finished, preparing a prepolymer with an end-capped NCO functional group, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 31g N-methyldiethanolamine, rapidly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is in a gel state, putting the mold on a flat plate vulcanizing machine for vulcanizing, and carrying out × 50 minutes under the condition of 12MPa × 95 ℃ and 3995 ℃ of vulcanization molding pressure, thus obtaining the polyurethane.
Example 9 preparation of Water-soluble Polymer Material
The preparation method comprises the following steps of putting 200g of polyethylene glycol, 40g of hydroxyl-terminated polyether mixed glycol formed by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 5g of trimethylolpropane and 4g of biomass reinforcing agent squid ink melanin into a 500mL three-neck flask, carrying out dehydration treatment at 100 ℃ for 70 minutes, cooling to 60 ℃, adding 180g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2 hours, vacuumizing and degassing for 30 minutes after the reaction is finished, preparing a prepolymer with an end capped by NCO functional groups, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 28g N-methyldiethanolamine, rapidly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is in a gel state, putting the mold on a flat plate vulcanizing machine for mold pressing and vulcanizing, wherein the vulcanizing condition is 10MPa, × 100 ℃, 100 ℃ and × 60 minutes, and obtaining the polyurethane prepolymer.
Example 10 preparation of Water-soluble Polymer Material
The preparation method comprises the following steps of putting 200g of polyethylene glycol, 30g of hydroxyl-terminated polyether mixed glycol formed by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 5g of trimethylolpropane and 4g of biomass reinforcing agent squid melanin into a 500mL three-neck flask, carrying out dehydration treatment at 100 ℃ for 70 minutes, cooling to 60 ℃, adding 170g of 4, 4-diisocyanate diphenylmethane, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2 hours, after the reaction is finished, vacuumizing and removing bubbles for 30 minutes to prepare an NCO functional group-terminated prepolymer, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 27g N-methyldiethanolamine, rapidly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is in a gel state, putting the mold on a flat plate vulcanizing machine for vulcanizing, and carrying out × 60 minutes under the condition of 10MPa × 100 ℃ of vulcanization molding pressure, thus obtaining the polyurethane prepolymer.
Example 11 preparation of Water-soluble Polymer Material
The preparation method comprises the following steps of putting 200g of polyethylene glycol, 25g of hydroxyl-terminated polyether mixed glycol formed by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 6g of trimethylolpropane and 3g of biomass reinforcing agent squid ink melanin into a 500mL three-neck flask, carrying out dehydration treatment at 100 ℃ for 70 minutes, cooling to 60 ℃, adding 190g of 1, 6-hexamethylene diisocyanate, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2 hours, vacuumizing and degassing for 30 minutes after the reaction is finished, preparing NCO functional group-terminated prepolymer, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30g of N-methyldiethanolamine, rapidly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is in a gel state, putting the mold on a flat plate vulcanizing machine for molding and vulcanizing, wherein the vulcanization condition is 10MPa × 100 ℃ for × 60 minutes, and obtaining the polyurethane prepolymer.
Example 12 preparation of Water-soluble Polymer Material
The preparation method comprises the following steps of putting 200g of polyethylene glycol, 35g of hydroxyl-terminated polyether mixed diol prepared by mixing polytetrahydrofuran diol and polypropylene oxide diol according to the mass ratio of 1:1, 4g of trimethylolpropane and 3g of biomass reinforcing agent squid ink melanin into a 500-mL three-neck flask, carrying out dehydration treatment at 100 ℃ for 70 minutes, cooling to 60 ℃, adding 160g of naphthalene diisocyanate, controlling the reaction temperature at 75 ℃ for carrying out constant-temperature reaction for 2 hours, vacuumizing and degassing for 30 minutes after the reaction is finished, preparing a prepolymer with an end capped by an NCO functional group, putting 120g of the prepared polyurethane prepolymer into a 200-mL beaker, adding 27g N-methyldiethanolamine, rapidly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is gelatinous, putting the mold on a flat plate vulcanizing machine for vulcanizing and molding under the vulcanizing condition of × 60 minutes at 10MPa × 100 ℃ to obtain the polyurethane prepolymer.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. A water-soluble polymer material, characterized in that: is prepared from the following raw materials in parts by weight: 200 parts of polyethylene glycol, 20-50 parts of hydroxyl-terminated polyether mixed diol, 3-7 parts of trimethylolpropane, 154-203 parts of diisocyanate, 2-5 parts of biomass melanin and 25-31 parts of N-methyldiethanolamine;
the hydroxyl-terminated polyether mixed glycol is formed by physically mixing polytetrahydrofuran glycol and polypropylene oxide glycol, and the mass ratio of the polytetrahydrofuran glycol to the polypropylene oxide glycol is 1: 0.9-1.1.
2. The water-soluble polymer material according to claim 1, wherein: the polyethylene glycol is selected from PEG-2000.
3. The water-soluble polymer material according to claim 1, wherein: the polytetrahydrofuran diol is selected from PTMG-1000;
or/and: the polypropylene oxide dihydric alcohol is selected from N-210.
4. The water-soluble polymer material according to claim 1, wherein: the diisocyanate is selected from any one or the combination of more than two of isophorone diisocyanate, toluene dicyanate, 4-diisocyanate diphenylmethane, 1, 6-hexamethylene diisocyanate and naphthalene diisocyanate.
5. The water-soluble polymer material according to claim 1, wherein: the biomass melanin is squid ink melanin.
6. The water-soluble polymer material according to any one of claims 1 to 5, wherein: is prepared by the following method: mixing polyethylene glycol, hydroxyl-terminated polyether mixed glycol, trimethylolpropane and biomass melanin in a reaction container, and dehydrating for 50-70 minutes at 95-105 ℃; then cooling to 55-65 ℃, adding diisocyanate, and reacting at the reaction temperature of 70-80 ℃ for 1.5-2.5 hours; after the reaction is finished, vacuumizing and removing bubbles for 10-30 minutes to prepare a biomass hybrid polyurethane prepolymer; then adding N-methyldiethanolamine, stirring uniformly rapidly, pouring into a mold preheated to 95-105 ℃ in advance, closing the mold when the mixture is in a gel state, placing the mold on a flat vulcanizing machine for mold pressing vulcanization, wherein the vulcanization conditions are as follows: 8-12 MPa, 95-105 ℃ and 50-70 minutes to obtain the water-soluble polymer material.
7. The water-soluble polymer material according to claim 6, wherein: is prepared by the following method:
placing 200g of polyethylene glycol, 20g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid ink melanin in a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 172.9g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ and reacting for 2.5h at constant temperature, vacuumizing and defoaming for 30 min after the reaction is finished, preparing a prepolymer with an end capped by NCO functional groups, placing 100g of the prepared polyurethane prepolymer in a 200mL beaker, adding 25.47g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is in a gel state, placing the mold on a flat plate vulcanizing machine for vulcanizing, wherein the vulcanizing molding condition is × 100 ℃ at 100 ℃ and × 1h, and obtaining the polyurethane prepolymer;
or 200g of polyethylene glycol, 30g of hydroxyl-terminated polyether mixed diol prepared by mixing polytetrahydrofuran diol and polypropylene oxide diol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 182.8g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant-temperature reaction for 2.5h, after the reaction is finished, the vacuum pumping is carried out for removing bubbles for 30 min, NCO functional group-terminated prepolymer is prepared, 120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine is added, the mixture is poured into a preheated mould at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky, the mould is closed, the mould is placed on a flat plate vulcanizing machine for mould pressing and vulcanizing, and the vulcanization condition is 10 × 100 ℃ × 1 MPa, so as to obtain the polyurethane prepolymer;
or 200g of polyethylene glycol, 40g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 192.6g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant-temperature reaction for 2.5h, after the reaction is finished, vacuumizing is carried out for removing bubbles for 30 min, NCO functional group-terminated prepolymer is prepared, 120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine is added, the mixture is poured into a preheated mould at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or does not stick to the hand, the mould is closed, the mould is placed on a flat plate vulcanizing machine for mould pressing and vulcanizing, and the vulcanization condition is 10 × 100 ℃ × 1 MPa, so as to obtain the polyurethane prepolymer;
or putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment into a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 202.5g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5h, vacuumizing for defoaming for 30 min after the reaction is finished, preparing NCO functional group-terminated prepolymer, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30.57g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture does not flow or stick to the hand, putting the mold on a flat plate vulcanizing machine for mold pressing and vulcanizing, wherein the vulcanization condition is 10 × 100 ℃ and × 1 MPa, and obtaining the polyurethane prepolymer;
or putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment into a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 147.9g of toluenedicyanide ester, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5h, vacuumizing and removing bubbles for 30 min after the reaction is finished, preparing NCO functional group end-capped prepolymer, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30.57g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture does not flow or is not handled, putting the mold on a flat vulcanizing machine for mold pressing and vulcanizing under the vulcanizing condition of 10MPa × 100 ℃ for × 1h, and obtaining the polyurethane prepolymer;
or putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment into a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 157.5g of isophorone diisocyanate and 24.7g of toluenedicyanide, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5h, vacuumizing and defoaming for 30 min after the reaction is finished, preparing a prepolymer with an end capped NCO functional group, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30.57g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a mold preheated at 100 ℃, closing the mold when the mixture does not flow or is not sticky, pressing the mold, putting the mold on a flat plate vulcanizing machine for vulcanizing, wherein the vulcanization condition is 10MPa × 100 ℃ for × 1 h;
the polyethylene glycol is selected from PEG-2000; the polytetrahydrofuran diol is selected from PTMG-1000; the polypropylene oxide dihydric alcohol is selected from N-210.
8. A method for producing a water-soluble polymer material according to any one of claims 1 to 6, characterized in that: mixing polyethylene glycol, hydroxyl-terminated polyether mixed glycol, trimethylolpropane and biomass melanin in a reaction container, and dehydrating for 50-70 minutes at 95-105 ℃; then cooling to 55-65 ℃, adding diisocyanate, and reacting at the reaction temperature of 70-80 ℃ for 1.5-2.5 hours; after the reaction is finished, vacuumizing and removing bubbles for 10-30 minutes to prepare a biomass hybrid polyurethane prepolymer; then adding N-methyldiethanolamine, stirring uniformly rapidly, pouring into a mold preheated to 95-105 ℃ in advance, closing the mold when the mixture is in a gel state, placing the mold on a flat vulcanizing machine for mold pressing vulcanization, wherein the vulcanization conditions are as follows: 8-12 MPa, 95-105 ℃ and 50-70 minutes to obtain the water-soluble polymer material.
9. The method for producing a water-soluble polymer material according to claim 8, wherein: the method comprises the following steps:
placing 200g of polyethylene glycol, 20g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid ink melanin in a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 172.9g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ and reacting for 2.5h at constant temperature, vacuumizing and defoaming for 30 min after the reaction is finished, preparing a prepolymer with an end capped by NCO functional groups, placing 100g of the prepared polyurethane prepolymer in a 200mL beaker, adding 25.47g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture is in a gel state, placing the mold on a flat plate vulcanizing machine for vulcanizing, wherein the vulcanizing molding condition is × 100 ℃ at 100 ℃ and × 1h, and obtaining the polyurethane prepolymer;
or 200g of polyethylene glycol, 30g of hydroxyl-terminated polyether mixed diol prepared by mixing polytetrahydrofuran diol and polypropylene oxide diol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 182.8g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant-temperature reaction for 2.5h, after the reaction is finished, the vacuum pumping is carried out for removing bubbles for 30 min, NCO functional group-terminated prepolymer is prepared, 120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine is added, the mixture is poured into a preheated mould at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or is not sticky, the mould is closed, the mould is placed on a flat plate vulcanizing machine for mould pressing and vulcanizing, and the vulcanization condition is 10 × 100 ℃ × 1 MPa, so as to obtain the polyurethane prepolymer;
or 200g of polyethylene glycol, 40g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment are placed in a 500mL three-neck flask, dehydration treatment is carried out for 1h at 100 ℃, the temperature is cooled to 60 ℃, 192.6g of isophorone diisocyanate is added, the reaction temperature is controlled at 75 ℃ for constant-temperature reaction for 2.5h, after the reaction is finished, vacuumizing is carried out for removing bubbles for 30 min, NCO functional group-terminated prepolymer is prepared, 120g of the prepared polyurethane prepolymer is taken in a 200mL beaker, 30.57g N-methyldiethanolamine is added, the mixture is poured into a preheated mould at 100 ℃ after being rapidly and uniformly stirred, when the mixture does not flow or does not stick to the hand, the mould is closed, the mould is placed on a flat plate vulcanizing machine for mould pressing and vulcanizing, and the vulcanization condition is 10 × 100 ℃ × 1 MPa, so as to obtain the polyurethane prepolymer;
or putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment into a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 202.5g of isophorone diisocyanate, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5h, vacuumizing for defoaming for 30 min after the reaction is finished, preparing NCO functional group-terminated prepolymer, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30.57g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture does not flow or stick to the hand, putting the mold on a flat plate vulcanizing machine for mold pressing and vulcanizing, wherein the vulcanization condition is 10 × 100 ℃ and × 1 MPa, and obtaining the polyurethane prepolymer;
or putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment into a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 147.9g of toluenedicyanide ester, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5h, vacuumizing and removing bubbles for 30 min after the reaction is finished, preparing NCO functional group end-capped prepolymer, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30.57g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a preheated mold at 100 ℃, closing the mold when the mixture does not flow or is not handled, putting the mold on a flat vulcanizing machine for mold pressing and vulcanizing under the vulcanizing condition of 10MPa × 100 ℃ for × 1h, and obtaining the polyurethane prepolymer;
or putting 200g of polyethylene glycol, 50g of hydroxyl-terminated polyether mixed glycol prepared by mixing polytetrahydrofuran glycol and polypropylene oxide glycol according to the mass ratio of 1:1, 3g of trimethylolpropane and 2g of biomass reinforcing agent squid pigment into a 500mL three-neck flask, dehydrating for 1h at 100 ℃, cooling to 60 ℃, adding 157.5g of isophorone diisocyanate and 24.7g of toluenedicyanide, controlling the reaction temperature at 75 ℃ for constant-temperature reaction for 2.5h, vacuumizing and defoaming for 30 min after the reaction is finished, preparing a prepolymer with an end capped NCO functional group, putting 120g of the prepared polyurethane prepolymer into a 200mL beaker, adding 30.57g N-methyldiethanolamine, quickly and uniformly stirring, pouring the mixture into a mold preheated at 100 ℃, closing the mold when the mixture does not flow or is not sticky, pressing the mold, putting the mold on a flat plate vulcanizing machine for vulcanizing, wherein the vulcanization condition is 10MPa × 100 ℃ for × 1 h;
the polyethylene glycol is selected from PEG-2000; the polytetrahydrofuran diol is selected from PTMG-1000; the polypropylene oxide dihydric alcohol is selected from N-210.
10. Use of the water-soluble polymer material according to claim 1 for producing a bridge plug or a packer or a seal.
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