CN113308110A - Polyurethane rubber-lined composite pipeline and preparation method thereof - Google Patents
Polyurethane rubber-lined composite pipeline and preparation method thereof Download PDFInfo
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- CN113308110A CN113308110A CN202110817733.4A CN202110817733A CN113308110A CN 113308110 A CN113308110 A CN 113308110A CN 202110817733 A CN202110817733 A CN 202110817733A CN 113308110 A CN113308110 A CN 113308110A
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- polyurethane
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- lined composite
- polyurethane rubber
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 91
- 239000004814 polyurethane Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 10
- 239000010959 steel Substances 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ASJCSAKCMTWGAH-SYDPRGILSA-N (1r,2s)-cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)[C@H]1CCC[C@H]1C(O)=O ASJCSAKCMTWGAH-SYDPRGILSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 11
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention discloses a polyurethane rubber-lined composite pipeline and a preparation method thereof, and relates to the field of pipelines, polytetrahydrofuran is added into a three-neck flask, a catalyst and sodium hydroxide are added, epoxy chloropropane is dripped into the three-neck flask to obtain an intermediate A, the intermediate A is added into distilled water, concentrated sulfuric acid is added to obtain an intermediate B, and the intermediate B, 1, 4-butanediol and toluene diisocyanate are uniformly stirred; the problems that the existing pipeline lining material is poor in toughness and low in tear strength in the using process, and the pipeline lining material is easy to damage, so that a steel pipe is corroded, the material leaks, the aging is easy, and the wear resistance is poor are solved; the modified polyurethane has the advantages that the number of macromolecular chains is increased, chain segments are increased, the macromolecular chains and a cross-linked network structure form a semi-interpenetrating polymer network structure, cracks are prevented from being generated and enlarged, and the purposes of improving the wear resistance and the aging resistance of the material are achieved.
Description
Technical Field
The invention relates to the field of pipelines, in particular to a polyurethane rubber-lined composite pipeline and a preparation method thereof.
Background
The anti-corrosion wear-resistant pipeline is an ideal conveying pipeline in the liquid-solid and gas-solid conveying industry, the inner surface of the metal pipeline is lined with a layer of anti-corrosion wear-resistant material, so that the anti-corrosion wear-resistant pipeline has the strength of the metal pipeline and excellent anti-corrosion wear-resistant performance, and is widely applied to a process pipeline of a metallurgical mine, a conveying pipeline of tailings, a process pipeline of a coal preparation plant, a deashing conveying pipeline of a thermal power plant, a process pipeline of a chemical water workshop, a desulfurization dust removal pipeline, a process pipeline of a non-metal mine and a municipal water supply and drainage buried pipeline;
in the using process, the pipeline needs to bear higher load and friction force, but the existing pipeline lining material has poor toughness and low tear strength in the using process, and when materials are conveyed, the inner layer material of the pipeline is easy to damage, so that a steel pipe is corroded, the materials are leaked, and the pipeline lining material is easy to age and has poor wear resistance;
therefore, how to improve the problems that the existing pipeline lining material has poor toughness, low tear strength, easy aging and poor wear resistance is needed to be solved by the invention.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a polyurethane rubber-lined composite pipeline and a preparation method thereof:
(1) adding polytetrahydrofuran into a three-neck flask, adding a catalyst and sodium hydroxide, dropwise adding epoxy chloropropane into the three-neck flask to obtain an intermediate A, adding the intermediate A into distilled water, adding concentrated sulfuric acid to obtain an intermediate B, and uniformly stirring the intermediate B, 1, 4-butanediol and toluene diisocyanate to obtain the modified polyurethane, so that the problems that the existing pipeline lining material is poor in toughness and low in tear strength in the using process, and when the material is conveyed, the inner layer material of a pipeline is easy to damage, so that a steel pipe is corroded, and the material is leaked are solved;
(2) the plasticizer is prepared by adding cis-cyclopentane-1, 2-dicarboxylic acid into a three-neck flask, adding polyethylene glycol, adding a solvent toluene solution, adding a catalyst to obtain an intermediate C, adding diethylene glycol monobutyl ether into the intermediate C, and adding the catalyst to solve the problems that the existing pipeline lining material is easy to age and poor in wear resistance.
The purpose of the invention can be realized by the following technical scheme:
a polyurethane rubber-lined composite pipeline is prepared by the following steps:
s1: weighing 90-100 parts of modified polyurethane and 1-10 parts of plasticizer according to the parts by weight, and uniformly mixing for later use;
s2: putting the mixture obtained in the step S1 into an injection molding machine, heating and melting, injecting into a mold, and cooling to obtain a polyurethane pipeline;
s3: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s4: and introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain the polyurethane rubber-lined composite pipeline.
As a further scheme of the invention: the binder is one of polyisocyanate adhesives and hydroxyl-containing polyurethane adhesives.
As a further scheme of the invention: the preparation steps of the modified polyurethane are as follows:
s31: adding polytetrahydrofuran into a three-neck flask, adding a catalyst and sodium hydroxide, starting mechanical stirring, controlling the temperature to be 40-50 ℃, dropwise adding epoxy chloropropane into the three-neck flask by using a dropping funnel, controlling the dropwise adding speed to be 1-2 drops/s, raising the temperature to 55-65 ℃, stirring for 1-2 hours, cooling, carrying out suction filtration, adjusting to be neutral by using sulfuric acid, and removing precipitates by reduced pressure distillation to obtain an intermediate A;
the reaction principle is as follows:
s32: adding the intermediate A into distilled water, adding concentrated sulfuric acid, hydrolyzing at room temperature for 3-4h, adjusting to neutrality with sodium carbonate solution, distilling under reduced pressure, and filtering to remove precipitate to obtain an intermediate B;
the reaction principle is as follows:
s33: and uniformly stirring the intermediate B, 1, 4-butanediol and toluene diisocyanate, pouring into a polytetrafluoroethylene mold, putting the mold into a vacuum drying oven, vacuumizing by using an oil pump, defoaming for 30-60min, and curing for 10-20h to obtain the modified polyurethane.
The reaction principle is as follows:
as a further scheme of the invention: in step S31, the catalyst is tetra-n-butylammonium bromide, and the molar ratio of the polytetrahydrofuran, the epichlorohydrin, the catalyst and the sodium hydroxide is 1: 2.5: 0.03: 3.
as a further scheme of the invention: in the step S32, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the sodium carbonate solution is 38%.
As a further scheme of the invention: in the step S33, the dosage ratio of the intermediate B, the 1, 4-butanediol and the toluene diisocyanate is 10 g: 4 g: 11 g.
As a further scheme of the invention: the preparation steps of the plasticizer are as follows:
s71: adding cis-cyclopentane-1, 2-dicarboxylic acid into a three-neck flask provided with a stirrer, a water separator and a condenser, adding polyethylene glycol, adding a solvent toluene solution, starting the stirrer, heating to 190 ℃ for 180 ℃ for reflux reaction for 1-2h, adding a catalyst, heating to 210 ℃ for reflux reaction for 2-3h, and obtaining an intermediate C;
the reaction principle is as follows:
s72: adding diethylene glycol monobutyl ether into the intermediate C, adding a catalyst, controlling the temperature at 200-230 ℃, reacting for 2-3h, and carrying out reduced pressure distillation to obtain the plasticizer.
The reaction principle is as follows:
as a further scheme of the invention: in the step S71, the catalyst is tetrabutyl titanate, the amount of the catalyst is 0.4% of the total mass of the cis-cyclopentane-1, 2-dicarboxylic acid and the polyethylene glycol, and the molar ratio of the cis-cyclopentane-1, 2-dicarboxylic acid to the polyethylene glycol is 6: 5.
as a further scheme of the invention: in the step S72, the catalyst is tetrabutyl titanate, the mass of the catalyst is 0.5% of the total mass of the intermediate C and the diethylene glycol monobutyl ether, and the molar ratio of the intermediate C to the diethylene glycol monobutyl ether is 1: 0.5.
as a further scheme of the invention: a preparation method of a polyurethane rubber-lined composite pipeline comprises the following preparation processes:
s1: uniformly mixing modified polyurethane and a plasticizer, putting the mixture into an injection molding machine, heating and melting the mixture, injecting the mixture into a mold, and cooling the mold to obtain a polyurethane pipeline;
s2: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s3: and introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain the polyurethane rubber-lined composite pipeline.
The invention has the beneficial effects that:
the invention adds polytetrahydrofuran into a three-mouth flask, adds catalyst and sodium hydroxide, adds epichlorohydrin into the three-mouth flask to obtain an intermediate A, adds the intermediate A into distilled water, adds concentrated sulfuric acid to obtain an intermediate B, uniformly stirs the intermediate B, 1, 4-butanediol and toluene diisocyanate to obtain the modified polyurethane, introduces epoxy groups through the reaction of polytetrahydrofuran and epichlorohydrin, and then opens a ring to form a polyhydroxy structure, the polyurethane formed by polymerization presents a three-dimensional shape in space, and can be self-cured without adding a micromolecular cross-linking agent, thereby avoiding the defect that the micromolecular cross-linking agent is easy to migrate, the polyhydroxy structure polymerizes the toluene diisocyanate, so that the number of macromolecular chains of the modified polyurethane is increased, chain segments are increased, and the macromolecular chains and a cross-linked network structure form a semi-interpenetrating polymer network structure, the physical crosslinking structure is increased, the generation and the expansion of cracks are prevented, and the wear resistance and the heat resistance of the modified polyurethane are improved, so that the aims of improving the wear resistance and the aging resistance of the material are fulfilled;
cis-cyclopentane-1, 2-dicarboxylic acid is added into a three-neck flask, polyethylene glycol is added, a solvent toluene solution is added, a catalyst is added to obtain an intermediate C, diethylene glycol monobutyl ether is added into the intermediate C, a catalyst is added to obtain the plasticizer, the plasticizer is inserted between modified polyurethane molecular chains, van der Waals force between the modified polyurethane molecules can be weakened, mobility of the modified polyurethane molecular chains is increased, crystallinity of the modified polyurethane molecular chains is reduced, plasticity of the modified polyurethane is improved, tensile strength and tear resistance of the modified polyurethane are improved, softening temperature and brittle temperature of the modified polyurethane material are reduced, an ether group and an ester group are contained in a molecular structure, the ester group is introduced to enable the modified polyurethane material to have good compatibility with an ether bond, and the modified polyurethane material has flexibility, toughness and toughness, The plasticizer has the advantages of oil resistance and static resistance, large interaction between a macromolecular chain and a chain of the plasticizer in the using process, low extraction and migration, and increased durability of the modified polyurethane material, has the performances of high temperature resistance and low toxicity, and protects the ecological environment, thereby achieving the purpose of improving the toughness.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment is a polyurethane rubber-lined composite pipeline, which is prepared by the following steps:
s1: weighing 90 parts of modified polyurethane and 10 parts of plasticizer according to parts by weight, and uniformly mixing for later use;
s2: putting the mixture obtained in the step S1 into an injection molding machine, heating and melting, injecting into a mold, and cooling to obtain a polyurethane pipeline;
s3: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s4: introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain a polyurethane rubber-lined composite pipeline;
the preparation method of the modified polyurethane comprises the following steps:
s31: adding polytetrahydrofuran into a three-neck flask, adding a catalyst and sodium hydroxide, starting mechanical stirring, controlling the temperature to be 50 ℃, dropwise adding epoxy chloropropane into the three-neck flask by using a dropping funnel, controlling the dropwise adding speed to be 1 drop/s, raising the temperature to 55 ℃, stirring for 1h, cooling, performing suction filtration, adjusting the temperature to be neutral by using sulfuric acid, and performing reduced pressure distillation to obtain an intermediate A;
s32: adding the intermediate A into distilled water, adding concentrated sulfuric acid, hydrolyzing at room temperature for 3h, adjusting to neutral with sodium carbonate solution, distilling under reduced pressure, and filtering to obtain an intermediate B;
s33: uniformly stirring the intermediate B, 1, 4-butanediol and toluene diisocyanate, pouring into a polytetrafluoroethylene mold, putting the mold into a vacuum drying oven, vacuumizing by using an oil pump, defoaming for 30min, and curing for 10h to obtain the modified polyurethane;
the preparation steps of the plasticizer are as follows:
s71: adding cis-cyclopentane-1, 2-dicarboxylic acid into a three-neck flask provided with a stirrer, a water separator and a condenser, adding polyethylene glycol, adding a solvent toluene solution, starting the stirrer, heating to 180 ℃, carrying out reflux reaction for 1h, adding a catalyst, heating to 200 ℃, and carrying out reflux reaction for 2h to obtain an intermediate C;
s72: adding diethylene glycol monobutyl ether into the intermediate C, adding a catalyst, controlling the temperature at 200 ℃, reacting for 2 hours, and distilling under reduced pressure to obtain the plasticizer.
Example 2:
the embodiment is a polyurethane rubber-lined composite pipeline, which is prepared by the following steps:
s1: weighing 90 parts of modified polyurethane and 10 parts of plasticizer according to parts by weight, and uniformly mixing for later use;
s2: putting the mixture obtained in the step S1 into an injection molding machine, heating and melting, injecting into a mold, and cooling to obtain a polyurethane pipeline;
s3: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s4: introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain a polyurethane rubber-lined composite pipeline;
the preparation method of the modified polyurethane comprises the following steps:
s31: adding polytetrahydrofuran into a three-neck flask, adding a catalyst and sodium hydroxide, starting mechanical stirring, controlling the temperature to be 40 ℃, dropwise adding epoxy chloropropane into the three-neck flask by using a dropping funnel, controlling the dropwise adding speed to be 1 drop/s, raising the temperature to 55 ℃, stirring for 1h, cooling, performing suction filtration, adjusting the temperature to be neutral by using sulfuric acid, and performing reduced pressure distillation to obtain an intermediate A;
s32: adding the intermediate A into distilled water, adding concentrated sulfuric acid, hydrolyzing at room temperature for 3h, adjusting to neutral with sodium carbonate solution, distilling under reduced pressure, and filtering to obtain an intermediate B;
s33: uniformly stirring the intermediate B, 1, 4-butanediol and toluene diisocyanate, pouring into a polytetrafluoroethylene mold, putting the mold into a vacuum drying oven, vacuumizing by using an oil pump, defoaming for 30min, and curing for 10h to obtain the modified polyurethane;
the preparation steps of the plasticizer are as follows:
s71: adding cis-cyclopentane-1, 2-dicarboxylic acid into a three-neck flask provided with a stirrer, a water separator and a condenser, adding polyethylene glycol, adding a solvent toluene solution, starting the stirrer, heating to 180 ℃, carrying out reflux reaction for 1h, adding a catalyst, heating to 200 ℃, and carrying out reflux reaction for 3h to obtain an intermediate C;
s72: adding diethylene glycol monobutyl ether into the intermediate C, adding a catalyst, controlling the temperature at 230 ℃, reacting for 3 hours, and distilling under reduced pressure to obtain the plasticizer.
Example 3:
the embodiment is a polyurethane rubber-lined composite pipeline, which is prepared by the following steps:
s1: weighing 100 parts of modified polyurethane and 10 parts of plasticizer according to parts by weight, and uniformly mixing for later use;
s2: putting the mixture obtained in the step S1 into an injection molding machine, heating and melting, injecting into a mold, and cooling to obtain a polyurethane pipeline;
s3: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s4: introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain a polyurethane rubber-lined composite pipeline;
the preparation method of the modified polyurethane comprises the following steps:
s31: adding polytetrahydrofuran into a three-neck flask, adding a catalyst and sodium hydroxide, starting mechanical stirring, controlling the temperature to be 50 ℃, dropwise adding epoxy chloropropane into the three-neck flask by using a dropping funnel, controlling the dropwise adding speed to be 2 drops/s, raising the temperature to 65 ℃, stirring for 2 hours, cooling, performing suction filtration, adjusting the temperature to be neutral by using sulfuric acid, and performing reduced pressure distillation to obtain an intermediate A;
s32: adding the intermediate A into distilled water, adding concentrated sulfuric acid, hydrolyzing at room temperature for 4h, adjusting to neutrality with sodium carbonate solution, distilling under reduced pressure, and vacuum filtering to obtain an intermediate B;
s33: uniformly stirring the intermediate B, 1, 4-butanediol and toluene diisocyanate, pouring into a polytetrafluoroethylene mold, putting the mold into a vacuum drying oven, vacuumizing by using an oil pump, carrying out defoaming treatment for 60min, and curing for 20h to obtain the modified polyurethane;
the preparation steps of the plasticizer are as follows:
s71: adding cis-cyclopentane-1, 2-dicarboxylic acid into a three-neck flask provided with a stirrer, a water separator and a condenser, adding polyethylene glycol, adding a solvent toluene solution, starting the stirrer, heating to 190 ℃, carrying out reflux reaction for 2 hours, adding a catalyst, heating to 210 ℃, and carrying out reflux reaction for 3 hours to obtain an intermediate C;
s72: adding diethylene glycol monobutyl ether into the intermediate C, adding a catalyst, controlling the temperature at 230 ℃, reacting for 3 hours, and distilling under reduced pressure to obtain the plasticizer.
Comparative example 1:
compared with the example 3, the comparative example does not add the plasticizer, and the rest steps are the same;
comparative example 2:
this comparative example used a high strength rubber lining formulation as disclosed in chinese patent CN201210302377.3 to prepare a composite pipe;
cutting dumbbell-shaped test pieces of the polyurethane linings of the composite pipelines of the examples 1-3 and the comparative examples 1-2 by a cutter, and measuring the tensile strength and the elongation at break by a WSM type universal electronic tensile tester, wherein a 500N sensor is adopted during the test, the tensile rate is 100mm/min, and the specification of the test pieces is 20mm multiplied by 4mm multiplied by 2 mm;
the results are shown in the following table:
| sample (I) | Tensile strength/MPa | Elongation at break/% |
| Experimental example 1 | 12.63 | 385 |
| Experimental example 2 | 14.11 | 397 |
| Experimental example 3 | 13.12 | 389 |
| Comparative example 1 | 6.52 | 221 |
| Comparative example 2 | 10.29 | 256 |
As can be seen from the above table, under the same test conditions, the tensile strength of the experimental example reaches 12.63MPa, the tensile strength of the comparative example 1 without the plasticizer is 6.52MPa, the tensile strength of the comparative example 2 using the high-strength rubber lining formula disclosed in the Chinese patent CN201210302377.3 is 10.29MPa, the elongation at break of the experimental example reaches 385-397%, the elongation at break of the comparative example 1 without the plasticizer is 221%, the elongation at break of the comparative example 2 using the high-strength rubber lining formula disclosed in the Chinese patent CN201210302377.3 is 256%, and the data of the experimental example are obviously better than those of the comparative examples, which indicates that the mechanical properties of the material are improved by using the modified polyurethane and the plasticizer.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. The polyurethane rubber-lined composite pipeline is characterized by being prepared by the following steps:
s1: weighing 90-100 parts of modified polyurethane and 1-10 parts of plasticizer according to the parts by weight, and uniformly mixing for later use;
s2: putting the mixture obtained in the step S1 into an injection molding machine, heating and melting, injecting into a mold, and cooling to obtain a polyurethane pipeline;
s3: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s4: and introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain the polyurethane rubber-lined composite pipeline.
2. The polyurethane-lined composite pipe of claim 1, wherein the adhesive is one of a polyisocyanate adhesive and a hydroxyl-containing polyurethane adhesive.
3. The polyurethane rubber-lined composite pipeline according to claim 1, wherein the preparation steps of the modified polyurethane are as follows:
s31: adding polytetrahydrofuran into a three-neck flask, adding a catalyst and sodium hydroxide, starting mechanical stirring, controlling the temperature to be 40-50 ℃, dropwise adding epoxy chloropropane into the three-neck flask by using a dropping funnel, controlling the dropwise adding speed to be 1-2 drops/s, raising the temperature to 55-65 ℃, stirring for 1-2 hours, cooling, carrying out suction filtration, adjusting to be neutral by using sulfuric acid, and carrying out reduced pressure distillation to obtain an intermediate A;
s32: adding the intermediate A into distilled water, adding concentrated sulfuric acid, hydrolyzing at room temperature for 3-4h, adjusting to neutral with sodium carbonate solution, distilling under reduced pressure, and vacuum filtering to obtain an intermediate B;
s33: and uniformly stirring the intermediate B, 1, 4-butanediol and toluene diisocyanate, pouring into a polytetrafluoroethylene mold, putting the mold into a vacuum drying oven, vacuumizing by using an oil pump, defoaming for 30-60min, and curing for 10-20h to obtain the modified polyurethane.
4. The polyurethane rubber-lined composite pipe according to claim 3, wherein the catalyst in step S31 is tetra-n-butylammonium bromide, and the molar ratio of the polytetrahydrofuran, the epichlorohydrin, the catalyst and the sodium hydroxide is 1: 2.5: 0.03: 3.
5. the polyurethane rubber-lined composite pipeline according to claim 3, wherein the mass fraction of the concentrated sulfuric acid in step S32 is 98%, and the mass fraction of the sodium carbonate solution is 38%.
6. The polyurethane rubber-lined composite pipe according to claim 3, wherein the intermediate B, 1, 4-butanediol and toluene diisocyanate are used in a ratio of 10g in step S33: 4 g: 11 g.
7. The polyurethane rubber-lined composite pipe according to claim 1, wherein the plasticizer is prepared by the following steps:
s71: adding cis-cyclopentane-1, 2-dicarboxylic acid into a three-neck flask provided with a stirrer, a water separator and a condenser, adding polyethylene glycol, adding a solvent toluene solution, starting the stirrer, heating to 190 ℃ for 180 ℃ for reflux reaction for 1-2h, adding a catalyst, heating to 210 ℃ for reflux reaction for 2-3h, and obtaining an intermediate C;
s72: adding diethylene glycol monobutyl ether into the intermediate C, adding a catalyst, controlling the temperature at 200-230 ℃, reacting for 2-3h, and carrying out reduced pressure distillation to obtain the plasticizer.
8. The polyurethane rubber-lined composite pipe according to claim 7, wherein the catalyst in step S71 is tetrabutyl titanate, the amount of the catalyst is 0.4% of the total mass of the cis-cyclopentane-1, 2-dicarboxylic acid and the polyethylene glycol, and the molar ratio of the cis-cyclopentane-1, 2-dicarboxylic acid to the polyethylene glycol is 6: 5.
9. the polyurethane rubber-lined composite pipe according to claim 7, wherein in step S72, the catalyst is tetrabutyl titanate, the mass of the catalyst is 0.5% of the total mass of the intermediate C and the diethylene glycol monobutyl ether, and the molar ratio of the intermediate C to the diethylene glycol monobutyl ether is 1: 0.5.
10. the preparation method of the polyurethane rubber-lined composite pipeline according to claim 1, characterized by comprising the following preparation processes:
s1: uniformly mixing modified polyurethane and a plasticizer, putting the mixture into an injection molding machine, heating and melting the mixture, injecting the mixture into a mold, and cooling the mold to obtain a polyurethane pipeline;
s2: coating the outer wall of the polyurethane pipeline with a binder, and pushing the polyurethane pipeline into a steel pipe pipeline matrix;
s3: and introducing nitrogen into the polyurethane pipeline, and pressurizing to obtain the polyurethane rubber-lined composite pipeline.
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