CN115304741B - Polyurethane anti-seepage sealing ring and preparation method thereof - Google Patents
Polyurethane anti-seepage sealing ring and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
Abstract
The invention discloses a polyurethane anti-seepage sealing ring and a preparation method thereof, wherein the polyurethane anti-seepage sealing ring is prepared by reacting a heat-resistant modifier, polyethylene glycol 2000, isophorone diisocyanate and a chain extender, hydroxyl groups on the heat-resistant modifier and the polyethylene glycol 2000 react with isocyanate groups on the isophorone diisocyanate to form an isocyanate group-terminated prepolymer, the prepolymer further reacts with the chain extender to enable the hydroxyl groups on the chain extender to react with the isocyanate groups on the prepolymer to form a grid structure, the molecular chain of the heat-resistant modifier contains a large number of imide structures and organic silicon structures, the high temperature resistant effect of a polyurethane material can be effectively improved, and meanwhile, the chain extender contains a large number of organic phosphorus structures, so that the endowed polyurethane material has good flame retardant effect, and a carbon layer is formed on the surface of the material during combustion, so as to prevent dripping.
Description
Technical Field
The invention relates to the technical field of sealing ring preparation, in particular to a polyurethane anti-seepage sealing ring and a preparation method thereof.
Background
Polyurethane is a widely used organic polymer material and is known as the fifth plastic. Polyurethane materials are various, including polyurethane elastomer, polyurethane foam, polyurethane adhesive, polyurethane paint and the like, and have been widely used in the fields of daily life, industrial and agricultural production, medical materials and the like due to the advantages of excellent material properties, strong structural designability and the like. The porous polyurethane belongs to a polyurethane material with wide application, the relation between the structure and the performance is similar to that of other polyurethane types, the porous polyurethane is derived from a special molecular chain structure of polyurethane, polyurethane molecules contain two chain segment components of soft and hard, and a special microphase separation structure can be formed, so that polyurethane resin has excellent wear resistance, bending resistance, ageing resistance and bonding fastness, and meanwhile, the polyurethane material is flexible and rich in rigidity, has a plurality of advantages such as good mechanical property, and is used as a raw material of a sealing ring, but the high temperature resistant effect of the polyurethane material is poor, the mechanical property of the polyurethane material can be obviously reduced under the high temperature condition, and the sealing effect is greatly reduced.
Disclosure of Invention
The invention aims to provide a polyurethane anti-seepage sealing ring and a preparation method thereof, which solve the problems that the high-temperature resistant effect of polyurethane is poor and the sealing effect is reduced under the high-temperature condition at the present stage.
The aim of the invention can be achieved by the following technical scheme:
a polyurethane impervious sealing ring is prepared from heat-resistant modifier, polyethylene glycol 2000, isophorone diisocyanate and chain extender through reaction.
Further, the heat-resistant modifier is prepared by the following steps:
step A1: uniformly mixing benzene tetracarboxylic dianhydride, p-methylaniline, boric acid and dimethylbenzene, introducing nitrogen for protection, reacting for 7-9 hours at the temperature of 125-135 ℃ under the condition that the rotating speed is 200-300r/min, cooling to room temperature, filtering the filtrate with the removal rate to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide and carbon tetrachloride, and reacting for 2-3 hours under the condition that the rotating speed is 150-200r/min to obtain an intermediate 2;
the reaction process is as follows:
step A2: uniformly mixing potassium carbonate, triethylbenzyl ammonium chloride, deionized water, phenylmethane and an intermediate 2, carrying out reflux reaction for 2-4 hours at the rotation speed of 200-300r/min and the temperature of 115-120 ℃ to obtain an intermediate 3, uniformly mixing the intermediate 3, dimethyl dichlorosilane, pyridine and tetrahydrofuran, carrying out reaction for 3-5 hours at the rotation speed of 150-200r/min and the temperature of 40-50 ℃, adding diphenyl silicon glycol, continuing to react for 5-7 hours, adding deionized water, standing for layering, removing a water layer, and distilling an organic phase to remove a solvent to obtain the heat-resistant modifier.
The reaction process is as follows:
further, the molar ratio of benzene tetracarboxylic dianhydride to p-methylaniline in the step A1 is 1:2, and the molar ratio of the intermediate 1 to the N-bromosuccinimide is 1:2.
Further, the dosage ratio of the potassium carbonate, the triethylbenzyl ammonium chloride, the deionized water and the intermediate 2 in the step A2 is 8g to 1g to 80mL to 5g, and the molar ratio of the intermediate 3 to the dimethyldichlorosilane to the diphenylsilandiol is 1:2:1.5.
Further, the chain extender is prepared by the following steps:
step B1: dissolving neopentyl glycol in chloroform, stirring at a rotating speed of 150-200r/min and a temperature of 20-25 ℃, adding phosphorus oxychloride, heating to a temperature of 60-70 ℃, reacting for 5-7h to obtain an intermediate 4, dissolving the intermediate 4 in acetonitrile, adding resorcinol, adding pyridine under the condition of ice-water bath, and reacting for 8-10h to obtain an intermediate 5;
the reaction process is as follows:
step B2: uniformly mixing the intermediate 5, epoxy chloropropane, aluminum trichloride and tetrahydrofuran, stirring for 3-5 hours at the rotating speed of 200-300r/min and the temperature of 10-15 ℃, heating to 35-45 ℃, and continuing to react for 2-3 hours to obtain an intermediate 6;
the reaction process is as follows:
step B3: and (3) uniformly mixing diaminobenzophenone and DOPO, reacting for 2-4 hours at the rotation speed of 150-200r/min and the temperature of 185-195 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 6, the intermediate 7 and N, N-dimethylformamide, and reacting for 8-10 hours at the temperature of 20-25 ℃ and the pH value of 10-11 to obtain the chain extender.
The reaction process is as follows:
further, the molar ratio of neopentyl glycol to phosphorus oxychloride described in step B1 is 1:1, and the molar ratio of intermediate 4 to resorcinol is 2:1.
Further, the molar ratio of the intermediate 5 to the epichlorohydrin in the step B2 is 1:1.
Further, the molar ratio of diaminobenzophenone to DOPO described in step B3 is 1:2 and the molar ratio of intermediate 6 to intermediate 7 is 4:1.
The preparation method of the polyurethane anti-seepage sealing ring specifically comprises the following steps:
step S1: uniformly mixing a heat-resistant modifier, polyethylene glycol 2000 and tetrahydrofuran, stirring at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, heating to the temperature of 80-85 ℃, reacting for 3-5h, cooling to the temperature of 40-50 ℃, adding triethylamine, and continuously stirring for 10-15min to obtain a prepolymer;
step S2: mixing the prepolymer, the chain extender and chloroform uniformly, stirring for 1-1.5h at the rotation speed of 150-200r/min and the temperature of 30-40 ℃, vacuum drying, adding into a mould, and curing at the temperature of 80-85 ℃ to obtain the polyurethane anti-seepage sealing ring.
Further, the molar ratio of the heat-resistant modifier to the polyethylene glycol 2000 to the isophorone diisocyanate in the step S1 is 1:1:3, and the dosage of the dibutyltin dilaurate is 1-3 per mill of the total mass of the reactants.
Further, the molar ratio of the prepolymer to the chain extender in step S2 is 1:2.
The invention has the beneficial effects that: according to the invention, a heat-resistant modifier, polyethylene glycol 2000, isophorone diisocyanate and a chain extender are reacted to prepare a polyurethane anti-seepage sealing ring, wherein the heat-resistant modifier takes benzene tetracarboxylic dianhydride as a raw material to react with p-methylaniline to prepare an intermediate 1, the intermediate 1 is subjected to bromination treatment by using N-bromosuccinimide to prepare an intermediate 2, the intermediate 2 is hydrolyzed to prepare an intermediate 3, the intermediate 3 and dimethyl dichlorosilane are reacted and then reacted with diphenyl silicon glycol to prepare the heat-resistant modifier, the chain extender takes neopentyl glycol as a raw material to react with phosphorus oxychloride to prepare an intermediate 4, the intermediate 4 is reacted with resorcinol to prepare an intermediate 5, the intermediate 5 is subjected to friedel-crafts reaction with epoxy chloropropane to prepare an intermediate 6, and diaminobenzophenone and DOPO are reacted to prepare an intermediate 7, the intermediate 6 and the intermediate 7 are reacted, so that epoxy groups on the intermediate 6 react with amino groups on the intermediate 7 to prepare the chain extender, hydroxyl groups on the heat-resistant modifier and the polyethylene glycol 2000 react with the hydroxyl groups on the isocyanate groups on the polyol and the polyol diisocyanate to form a pre-isocyanate structure, and the polyurethane anti-seepage sealing ring can further react with the epoxy isocyanate on the surface of the polyurethane anti-seepage sealing ring, and the flame-retardant structure is formed on the surface of the polyurethane anti-seepage sealing ring is well.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the polyurethane anti-seepage sealing ring specifically comprises the following steps:
step S1: uniformly mixing a heat-resistant modifier, polyethylene glycol 2000 and tetrahydrofuran, stirring at a rotating speed of 200r/min and a temperature of 60 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, heating to a temperature of 80 ℃, reacting for 3 hours, cooling to a temperature of 40 ℃, adding triethylamine, and continuously stirring for 10 minutes to obtain a prepolymer;
step S2: and (3) uniformly mixing the prepolymer and the chain extender, stirring for 1h at the rotation speed of 150r/min and the temperature of 30 ℃, vacuum drying, adding into a die, and curing at the temperature of 80 ℃ to obtain the polyurethane anti-seepage sealing ring.
The mol ratio of the heat-resistant modifier to the polyethylene glycol 2000 to the isophorone diisocyanate in the step S1 is 1:1:3, and the dosage of the dibutyltin dilaurate is 1 per mill of the total mass of the reactants.
The molar ratio of the prepolymer to the chain extender in the step S2 is 1:2.
The heat-resistant modifier is prepared by the following steps:
step A1: uniformly mixing benzene tetracarboxylic dianhydride, p-methylaniline, boric acid and dimethylbenzene, introducing nitrogen for protection, reacting for 7 hours at the rotation speed of 200r/min and the temperature of 125 ℃, cooling to room temperature, filtering the filtrate with the removal rate to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide and carbon tetrachloride, and reacting for 2 hours under the illumination condition at the rotation speed of 150r/min to obtain an intermediate 2;
step A2: uniformly mixing potassium carbonate, triethylbenzyl ammonium chloride, deionized water, phenylmethane and an intermediate 2, carrying out reflux reaction for 2 hours at the rotation speed of 200r/min and the temperature of 115 ℃ to obtain an intermediate 3, uniformly mixing the intermediate 3, dimethyl dichlorosilane, pyridine and tetrahydrofuran, carrying out reaction for 3 hours at the rotation speed of 150r/min and the temperature of 40 ℃, adding diphenyl silicon glycol, continuously carrying out reaction for 5 hours, adding deionized water, standing for layering, removing a water layer, and distilling an organic phase to remove a solvent to obtain the heat-resistant modifier.
The molar ratio of benzene tetracarboxylic dianhydride to p-methylaniline in the step A1 is 1:2, and the molar ratio of the intermediate 1 to the N-bromosuccinimide is 1:2.
The dosage ratio of the potassium carbonate, the triethylbenzyl ammonium chloride, the deionized water and the intermediate 2 in the step A2 is 8g to 1g to 80mL to 5g, and the molar ratio of the intermediate 3 to the dimethyldichlorosilane to the diphenylsilanediol is 1 to 2 to 1.5.
The chain extender is prepared by the following steps:
step B1: dissolving neopentyl glycol in chloroform, stirring at a rotating speed of 150r/min and a temperature of 20 ℃, adding phosphorus oxychloride, heating to a temperature of 60 ℃, reacting for 5 hours to obtain an intermediate 4, dissolving the intermediate 4 in acetonitrile, adding resorcinol, adding pyridine under the condition of ice-water bath, and reacting for 8 hours to obtain an intermediate 5;
step B2: uniformly mixing the intermediate 5, epoxy chloropropane, aluminum trichloride and tetrahydrofuran, stirring for 3 hours at the rotating speed of 200r/min and the temperature of 10 ℃, heating to the temperature of 35 ℃, and continuing to react for 2 hours to obtain an intermediate 6;
step B3: and (3) uniformly mixing diaminobenzophenone and DOPO, reacting for 2 hours at the rotation speed of 150r/min and the temperature of 185 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 6 and the intermediate 7, and reacting for 8 hours at the temperature of 20-25 ℃ and the pH value of 10 to obtain the chain extender.
The mole ratio of neopentyl glycol to phosphorus oxychloride in step B1 is 1:1, and the mole ratio of intermediate 4 to resorcinol is 2:1.
The mol ratio of the intermediate 5 to the epichlorohydrin in the step B2 is 1:1.
The molar ratio of diaminobenzophenone to DOPO in step B3 is 1:2 and the molar ratio of intermediate 6 to intermediate 7 is 4:1.
Example 2
The preparation method of the polyurethane anti-seepage sealing ring specifically comprises the following steps:
step S1: uniformly mixing a heat-resistant modifier, polyethylene glycol 2000 and tetrahydrofuran, stirring at a rotating speed of 200r/min and a temperature of 65 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, heating to 83 ℃, reacting for 4 hours, cooling to 45 ℃, adding triethylamine, and continuously stirring for 15 minutes to obtain a prepolymer;
step S2: and (3) uniformly mixing the prepolymer and the chain extender, stirring for 1.3 hours at the rotation speed of 180r/min and the temperature of 35 ℃, vacuum drying, adding into a die, and curing at the temperature of 83 ℃ to obtain the polyurethane anti-seepage sealing ring.
The mol ratio of the heat-resistant modifier to the polyethylene glycol 2000 to the isophorone diisocyanate in the step S1 is 1:1:3, and the dosage of the dibutyltin dilaurate is 2 per mill of the total mass of the reactants.
The molar ratio of the prepolymer to the chain extender in the step S2 is 1:2.
The heat-resistant modifier is prepared by the following steps:
step A1: uniformly mixing benzene tetracarboxylic dianhydride, p-methylaniline, boric acid and dimethylbenzene, introducing nitrogen for protection, reacting for 8 hours at the rotation speed of 200r/min and the temperature of 130 ℃, cooling to room temperature, filtering the filtrate with the removal rate to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide and carbon tetrachloride, and reacting for 2.5 hours under the illumination condition at the rotation speed of 180r/min to obtain an intermediate 2;
step A2: uniformly mixing potassium carbonate, triethylbenzyl ammonium chloride, deionized water, phenylmethane and an intermediate 2, carrying out reflux reaction for 3 hours at the rotation speed of 300r/min and the temperature of 118 ℃ to obtain an intermediate 3, uniformly mixing the intermediate 3, dimethyl dichlorosilane, pyridine and tetrahydrofuran, carrying out reaction for 4 hours at the rotation speed of 180r/min and the temperature of 45 ℃, adding diphenyl silicon glycol, continuously carrying out reaction for 6 hours, adding deionized water, standing for layering, removing a water layer, and distilling an organic phase to remove a solvent to obtain the heat-resistant modifier.
The molar ratio of benzene tetracarboxylic dianhydride to p-methylaniline in the step A1 is 1:2, and the molar ratio of the intermediate 1 to the N-bromosuccinimide is 1:2.
The dosage ratio of the potassium carbonate, the triethylbenzyl ammonium chloride, the deionized water and the intermediate 2 in the step A2 is 8g to 1g to 80mL to 5g, and the molar ratio of the intermediate 3 to the dimethyldichlorosilane to the diphenylsilanediol is 1 to 2 to 1.5.
The chain extender is prepared by the following steps:
step B1: dissolving neopentyl glycol in chloroform, stirring at a rotating speed of 180r/min and a temperature of 23 ℃, adding phosphorus oxychloride, heating to a temperature of 65 ℃, reacting for 6 hours to obtain an intermediate 4, dissolving the intermediate 4 in acetonitrile, adding resorcinol, adding pyridine under the condition of ice-water bath, and reacting for 9 hours to obtain an intermediate 5;
step B2: uniformly mixing the intermediate 5, epoxy chloropropane, aluminum trichloride and tetrahydrofuran, stirring for 4 hours at the temperature of 13 ℃ at the rotating speed of 200r/min, heating to the temperature of 40 ℃, and continuing to react for 2.5 hours to obtain an intermediate 6;
step B3: and (3) uniformly mixing diaminobenzophenone and DOPO, reacting for 3 hours at the rotation speed of 180r/min and the temperature of 190 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 6 and the intermediate 7, and reacting for 9 hours at the temperature of 23 ℃ and the pH value of 10 to obtain the chain extender.
The mole ratio of neopentyl glycol to phosphorus oxychloride in step B1 is 1:1, and the mole ratio of intermediate 4 to resorcinol is 2:1.
The mol ratio of the intermediate 5 to the epichlorohydrin in the step B2 is 1:1.
The molar ratio of diaminobenzophenone to DOPO in step B3 is 1:2 and the molar ratio of intermediate 6 to intermediate 7 is 4:1.
Example 3
The preparation method of the polyurethane anti-seepage sealing ring specifically comprises the following steps:
step S1: uniformly mixing a heat-resistant modifier, polyethylene glycol 2000 and tetrahydrofuran, stirring at a rotating speed of 300r/min and a temperature of 70 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, heating to a temperature of 85 ℃, reacting for 5 hours, cooling to a temperature of 50 ℃, adding triethylamine, and continuously stirring for 15 minutes to obtain a prepolymer;
step S2: and (3) uniformly mixing the prepolymer and the chain extender, stirring for 1.5 hours at the rotation speed of 200r/min and the temperature of 40 ℃, vacuum drying, adding into a die, and curing at the temperature of 85 ℃ to obtain the polyurethane anti-seepage sealing ring.
The mol ratio of the heat-resistant modifier to the polyethylene glycol 2000 to the isophorone diisocyanate in the step S1 is 1:1:3, and the dosage of the dibutyltin dilaurate is 3 per mill of the total mass of the reactants.
The molar ratio of the prepolymer to the chain extender in the step S2 is 1:2.
The heat-resistant modifier is prepared by the following steps:
step A1: uniformly mixing benzene tetracarboxylic dianhydride, p-methylaniline, boric acid and dimethylbenzene, introducing nitrogen for protection, reacting for 9 hours at the rotation speed of 300r/min and the temperature of 135 ℃, cooling to room temperature, filtering the filtrate with the removal rate to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide and carbon tetrachloride, and reacting for 3 hours under the illumination condition at the rotation speed of 200r/min to obtain an intermediate 2;
step A2: uniformly mixing potassium carbonate, triethylbenzyl ammonium chloride, deionized water, phenylmethane and an intermediate 2, carrying out reflux reaction for 4 hours at the rotation speed of 300r/min and the temperature of 120 ℃ to obtain an intermediate 3, uniformly mixing the intermediate 3, dimethyl dichlorosilane, pyridine and tetrahydrofuran, carrying out reaction for 5 hours at the rotation speed of 200r/min and the temperature of 50 ℃, adding diphenyl silicon glycol, continuously carrying out reaction for 7 hours, adding deionized water, standing for layering, removing a water layer, and distilling an organic phase to remove a solvent to obtain the heat-resistant modifier.
The molar ratio of benzene tetracarboxylic dianhydride to p-methylaniline in the step A1 is 1:2, and the molar ratio of the intermediate 1 to the N-bromosuccinimide is 1:2.
The dosage ratio of the potassium carbonate, the triethylbenzyl ammonium chloride, the deionized water and the intermediate 2 in the step A2 is 8g to 1g to 80mL to 5g, and the molar ratio of the intermediate 3 to the dimethyldichlorosilane to the diphenylsilanediol is 1 to 2 to 1.5.
The chain extender is prepared by the following steps:
step B1: dissolving neopentyl glycol in chloroform, stirring at a rotating speed of 200r/min and a temperature of 25 ℃, adding phosphorus oxychloride, heating to a temperature of 70 ℃, reacting for 7 hours to obtain an intermediate 4, dissolving the intermediate 4 in acetonitrile, adding resorcinol, adding pyridine under the condition of ice-water bath, and reacting for 10 hours to obtain an intermediate 5;
step B2: uniformly mixing the intermediate 5, epoxy chloropropane, aluminum trichloride and tetrahydrofuran, stirring for 5 hours at the rotation speed of 300r/min and the temperature of 15 ℃, heating to the temperature of 45 ℃, and continuing to react for 3 hours to obtain an intermediate 6;
step B3: and (3) uniformly mixing diaminobenzophenone and DOPO, reacting for 4 hours at the rotation speed of 200r/min and the temperature of 195 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 6 and the intermediate 7, and reacting for 10 hours at the temperature of 25 ℃ and the pH value of 11 to obtain the chain extender.
The mole ratio of neopentyl glycol to phosphorus oxychloride in step B1 is 1:1, and the mole ratio of intermediate 4 to resorcinol is 2:1.
The mol ratio of the intermediate 5 to the epichlorohydrin in the step B2 is 1:1.
The molar ratio of diaminobenzophenone to DOPO in step B3 is 1:2 and the molar ratio of intermediate 6 to intermediate 7 is 4:1.
Comparative example 1
The comparative example is polyurethane material prepared by Chinese patent CN 113861372A.
Comparative example 2
The comparative example is polyurethane material prepared by Chinese patent CN 113549194A.
Comparative example 3
The comparative example is polyurethane material prepared by Chinese patent CN 113527624A.
The polyurethane materials prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for tensile strength according to the GB/T528-2009 standard, and then tested for tensile strength at 120℃and limiting oxygen index to test patterns, the results of which are shown in the following table;
the polyurethane materials prepared in examples 1-3 show that the tensile strength is not obviously changed under the condition of 120 ℃, and the limiting oxygen index is 42-43, so that the polyurethane materials have good high temperature resistance and flame retardant effect.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (4)
1. The utility model provides a polyurethane prevention of seepage sealing washer which characterized in that: is prepared by the reaction of a heat-resistant modifier, polyethylene glycol 2000, isophorone diisocyanate and a chain extender;
the heat-resistant modifier is prepared by the following steps:
step A1: benzene tetracarboxylic dianhydride, p-methylaniline, boric acid and dimethylbenzene are mixed for reaction, then the temperature is reduced to room temperature, filtrate with the removal rate is filtered to prepare an intermediate 1, and the intermediate 1, N-bromosuccinimide and carbon tetrachloride are mixed for reaction to prepare an intermediate 2;
step A2: mixing potassium carbonate, triethylbenzyl ammonium chloride, deionized water, phenylmethane and an intermediate 2, carrying out reflux reaction to obtain an intermediate 3, mixing the intermediate 3, dimethyl dichlorosilane, pyridine and tetrahydrofuran, adding diphenyl silicon glycol, continuing the reaction, adding deionized water, standing for layering, removing a water layer, and distilling an organic phase to remove a solvent to obtain a heat-resistant modifier;
the molar ratio of benzene tetracarboxylic dianhydride to p-methylaniline in the step A1 is 1:2, and the molar ratio of the intermediate 1 to N-bromosuccinimide is 1:2;
the dosage ratio of the potassium carbonate, the triethylbenzyl ammonium chloride, the deionized water and the intermediate 2 in the step A2 is 8g to 1g to 80mL to 5g, and the molar ratio of the intermediate 3 to the dimethyldichlorosilane to the diphenylsilandiol is 1 to 2 to 1.5;
the chain extender is prepared by the following steps:
step B1: dissolving neopentyl glycol in chloroform, stirring, adding phosphorus oxychloride, heating for reaction to obtain an intermediate 4, dissolving the intermediate 4 in acetonitrile, adding resorcinol, adding pyridine under the condition of ice-water bath, and reacting to obtain an intermediate 5;
step B2: mixing and stirring the intermediate 5, epoxy chloropropane, aluminum trichloride and tetrahydrofuran, and heating to continue the reaction to obtain an intermediate 6;
step B3: mixing diaminobenzophenone with DOPO to prepare an intermediate 7, and mixing and reacting the intermediate 6, the intermediate 7 and N, N-dimethylformamide to prepare a chain extender;
the mole ratio of the neopentyl glycol to the phosphorus oxychloride in the step B1 is 1:1, and the mole ratio of the intermediate 4 to the resorcinol is 2:1;
the mol ratio of the intermediate 5 to the epichlorohydrin in the step B2 is 1:1;
the molar ratio of diaminobenzophenone to DOPO in step B3 is 1:2 and the molar ratio of intermediate 6 to intermediate 7 is 4:1.
2. The method for preparing the polyurethane anti-seepage sealing ring according to claim 1, which is characterized in that: the method specifically comprises the following steps:
step S1: mixing and stirring a heat-resistant modifier, polyethylene glycol 2000 and tetrahydrofuran, adding isophorone diisocyanate and dibutyltin dilaurate, heating to react, cooling, adding triethylamine, and continuously stirring for 10-15min to obtain a prepolymer;
step S2: mixing and stirring the prepolymer, the chain extender and chloroform, vacuum drying, adding into a mould, and curing to obtain the polyurethane anti-seepage sealing ring.
3. The method for preparing the polyurethane anti-seepage sealing ring according to claim 2, which is characterized in that: the mol ratio of the heat-resistant modifier to the polyethylene glycol 2000 to the isophorone diisocyanate in the step S1 is 1:1:3, and the dosage of the dibutyl tin dilaurate is 1-3 per mill of the total mass of the reactants.
4. The method for preparing the polyurethane anti-seepage sealing ring according to claim 2, which is characterized in that: the molar ratio of the prepolymer to the chain extender in the step S2 is 1:2.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259577A (en) * | 1995-03-20 | 1996-10-08 | Daihachi Chem Ind Co Ltd | Production of condensed phosphoric ester containing halogen |
| US5852197A (en) * | 1995-07-17 | 1998-12-22 | Hoechst Aktiengellschaft | Cyclic disphosphoric esters, a process for their preparation and their use |
| JPH111612A (en) * | 1998-06-01 | 1999-01-06 | Daihachi Chem Ind Co Ltd | Flame-retardant polyurethane foam composition |
| JP2004292476A (en) * | 2003-03-25 | 2004-10-21 | Fuji Photo Film Co Ltd | Two-photon absorption polymerizable composition and method for polymerizing the same |
| JP2008242444A (en) * | 2007-02-27 | 2008-10-09 | Jsr Corp | Liquid crystal aligning agent and liquid crystal display element |
| WO2009101895A1 (en) * | 2008-02-12 | 2009-08-20 | Fujifilm Corporation | Polymer, composition, cured product, method for producing the polymer and method for producing the cured product |
| CN103980231A (en) * | 2014-06-04 | 2014-08-13 | 中国科学院上海有机化学研究所 | Synthetic method of pentafluorphenyl epoxypropane |
| JP2015157926A (en) * | 2013-04-19 | 2015-09-03 | 三洋化成工業株式会社 | Polyurethane (urea) resin for actuator, and actuator using the same |
| CN108997714A (en) * | 2018-07-23 | 2018-12-14 | 深圳职业技术学院 | Reactive flame retardant and its fire retarding epoxide resin for epoxy resin |
| JP2020033421A (en) * | 2018-08-28 | 2020-03-05 | 株式会社カネカ | Polyimide resin and method for producing the same, polyimide solution, polyimide film and method for producing the same and method for producing tetracarboxylic acid dianhydride |
| CN112384489A (en) * | 2018-07-05 | 2021-02-19 | 尤尼吉可株式会社 | Method for producing organic compound |
| JP2021042136A (en) * | 2019-09-06 | 2021-03-18 | 旭化成株式会社 | Diamine compound and method for producing the same |
| CN113402814A (en) * | 2021-08-10 | 2021-09-17 | 江阴市嘉宇新材料有限公司 | PP (polypropylene) backing plate for slicing single/polycrystalline silicon rod and preparation method thereof |
-
2022
- 2022-08-30 CN CN202211044910.0A patent/CN115304741B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259577A (en) * | 1995-03-20 | 1996-10-08 | Daihachi Chem Ind Co Ltd | Production of condensed phosphoric ester containing halogen |
| US5852197A (en) * | 1995-07-17 | 1998-12-22 | Hoechst Aktiengellschaft | Cyclic disphosphoric esters, a process for their preparation and their use |
| JPH111612A (en) * | 1998-06-01 | 1999-01-06 | Daihachi Chem Ind Co Ltd | Flame-retardant polyurethane foam composition |
| JP2004292476A (en) * | 2003-03-25 | 2004-10-21 | Fuji Photo Film Co Ltd | Two-photon absorption polymerizable composition and method for polymerizing the same |
| JP2008242444A (en) * | 2007-02-27 | 2008-10-09 | Jsr Corp | Liquid crystal aligning agent and liquid crystal display element |
| WO2009101895A1 (en) * | 2008-02-12 | 2009-08-20 | Fujifilm Corporation | Polymer, composition, cured product, method for producing the polymer and method for producing the cured product |
| JP2015157926A (en) * | 2013-04-19 | 2015-09-03 | 三洋化成工業株式会社 | Polyurethane (urea) resin for actuator, and actuator using the same |
| CN103980231A (en) * | 2014-06-04 | 2014-08-13 | 中国科学院上海有机化学研究所 | Synthetic method of pentafluorphenyl epoxypropane |
| CN112384489A (en) * | 2018-07-05 | 2021-02-19 | 尤尼吉可株式会社 | Method for producing organic compound |
| CN108997714A (en) * | 2018-07-23 | 2018-12-14 | 深圳职业技术学院 | Reactive flame retardant and its fire retarding epoxide resin for epoxy resin |
| JP2020033421A (en) * | 2018-08-28 | 2020-03-05 | 株式会社カネカ | Polyimide resin and method for producing the same, polyimide solution, polyimide film and method for producing the same and method for producing tetracarboxylic acid dianhydride |
| JP2021042136A (en) * | 2019-09-06 | 2021-03-18 | 旭化成株式会社 | Diamine compound and method for producing the same |
| CN113402814A (en) * | 2021-08-10 | 2021-09-17 | 江阴市嘉宇新材料有限公司 | PP (polypropylene) backing plate for slicing single/polycrystalline silicon rod and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Thermal stability and flame retardancy of novel phloroglucinol based organo phosphorus compound;Hai Vothi，等;《Polymer Degradation and Stability》;第95卷;1092-1098 * |
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