CN112646104A - Preparation process of polyurethane resin - Google Patents
Preparation process of polyurethane resin Download PDFInfo
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- CN112646104A CN112646104A CN202011608196.4A CN202011608196A CN112646104A CN 112646104 A CN112646104 A CN 112646104A CN 202011608196 A CN202011608196 A CN 202011608196A CN 112646104 A CN112646104 A CN 112646104A
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000728 polyester Polymers 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims 8
- 239000003054 catalyst Substances 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 238000004886 process control Methods 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—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
- C08G63/66—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
- C08G63/785—Preparation processes characterised by the apparatus used
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation process of polyurethane resin, which comprises the following steps: step 1: uniformly mixing polyol, oxalic acid and an antioxidant, adding into a reaction kettle, and stirring; step 2: condensing the water evaporated from the reaction kettle and then feeding the water into a wastewater collection system; and step 3: opening vacuum and gradually reducing the pressure to-0.09 MPa; and 4, step 4: stopping vacuumizing and recovering the normal pressure in the reaction kettle to obtain polyester dihydric alcohol which is put into a polyester intermediate tank; and 5: adding an organic solvent or water into a polymerization kettle, and adding polyester dihydric alcohol and special PE in an intermediate tank; step 6: adding diisocyanate, and slowly stirring to perform polymerization reaction; and 7: adding a terminator, and filling to obtain a polyurethane resin finished product. The invention uses polycondensation and polymerization reaction method to prepare polyurethane resin, and has the advantages of simple process control, strong product controllability, and the like.
Description
Technical Field
The invention relates to the technical field of biology, in particular to a preparation process of polyurethane resin.
Background
Polyurethane is one of synthetic resins having excellent comprehensive properties. Because of the multiple synthetic monomer varieties, mild reaction conditions, specificity, controllability, large formula adjustment scope and the microstructure characteristics of high polymer materials, the polyurethane resin can be widely used for coatings, adhesives, foamed plastics, synthetic fibers and elastomers, becomes one of the essential materials in the fields of clothing, food, live, operation and high and new technology, and forms a multi-variety and multi-series material family to form a complete polyurethane industrial system which is not possessed by other resins. Polyurethane (PU) resins are polymers with repeating structural units of urethane segments made by reacting isocyanates with polyols. Is prepared by polymerizing long-chain raw materials and short-chain raw materials and is a block polymer. Generally, the long-chain diols constitute the soft segments, while the hard segments are composed of polyisocyanates and chain extenders. The types of the soft segment and the hard segment affect the hardness, strength and other properties of the material. The factors influencing the performance of various polyurethane products are many, and the basic factors influencing the performance are cohesive energy, hydrogen bonds, crystallinity, crosslinking degree, molecular weight and temperature of groups. The soft segment accounts for a large part of the polyurethane, and the molecular weight of the soft segment has an influence on the mechanical properties of the polyurethane. The structure of the isocyanate affects the rigidity of the polyurethane. The polyurethane material is a material with comprehensive performance, has the advantages of good physical and mechanical properties, excellent weather resistance, small change of elasticity and hardness with temperature and the like, and is widely applied to many fields such as coating, adhesive, printing ink and the like.
However, in the preparation process of polyurethane resin, because the crosslinking effect of polyurethane is destroyed at high temperature, the hysteresis loss is large, and the production cost is easily too high, the design of a preparation process of polyurethane resin is urgently needed.
Disclosure of Invention
The present invention is directed to a process for preparing a polyurethane resin, which solves the above problems of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation process of polyurethane resin comprises the following steps:
step 1: adding polyol into a reaction kettle, stirring, adding oxalic acid and an antioxidant, and uniformly mixing to obtain a first mixed solution;
step 2: when the temperature in the reaction kettle is 140-160 ℃, condensing the water evaporated from the reaction kettle, then feeding the condensed water into a wastewater collection system, and continuing to keep the temperature to react the first mixed solution after no water is separated out;
and step 3: when the first mixed solution reacts in the reaction kettle, when the acid value is between 6.0 and 8.0, the vacuum is started to gradually reduce the pressure to-0.09 MPa, and the temperature in the reaction kettle is 220-;
and 4, step 4: when the acid value and the hydroxyl value of the first mixed solution are qualified, reducing the temperature in the reaction kettle to be below 80 ℃, stopping vacuumizing, recovering the normal pressure in the reaction kettle, and putting the obtained polyester dihydric alcohol into a polyester intermediate tank;
and 5: adding an organic solvent or water into a polymerization kettle, adding polyester diol, special PE and a chain extender in an intermediate tank, starting a stirrer for stirring to obtain a second mixed solution;
step 6: when the temperature in the polymerization kettle is 55-65 ℃, adding diisocyanate into the second mixed solution, and slowly stirring to perform polymerization reaction to obtain a third mixed solution;
and 7: adding a terminator into the third mixed solution, stopping the polymerization reaction, naturally cooling to 10-40 ℃, and filling to obtain a polyurethane resin finished product.
Preferably, in step 1, the polyol comprises one or a mixture of two or more of ethylene glycol, diethylene glycol or 1, 4-butanediol.
Preferably, in step 2, the water evaporated from the reaction kettle is condensed and then enters a wastewater collection system to obtain condensed water, the collected condensed water is evaporated, and the excessive dihydric alcohol in the condensed water is collected.
Preferably, in step 5, the organic solvent comprises one or a mixture of more than two of toluene, butanone or DMF.
Preferably, in step 6, the polymerization temperature is 65 to 90 ℃.
Preferably, in step 7, the terminating agent is ethylene glycol.
Preferably, in step 1, a hoisting component is adopted when the polyol, the oxalic acid and the antioxidant are added into the reaction kettle.
Preferably, the hoist and mount subassembly includes base, first guard plate, second guard plate, third guard plate, lifting hook, baffle, fork truck hole and division board, the front side, rear side and the right side of base top are all located perpendicularly to first guard plate, second guard plate, third guard plate, the left side of base top is equipped with the baffle perpendicularly, the upper surface middle part of first guard plate, second guard plate, third guard plate all is equipped with the lifting hook, all be equipped with the fork truck hole around the base, the upper surface of base is equipped with the division board.
Preferably, one end of the partition plate is connected with the middle part of the inner wall of the baffle, and the other end of the partition plate is connected with the middle part of the inner wall of the third protection plate.
Preferably, the height of the baffle is smaller than the heights of the first protection plate, the second protection plate and the third protection plate.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses polycondensation and polymerization reaction method to prepare polyurethane resin, has the advantages of simple process control, strong product controllability and the like, the product adjusts the performance of the resin by controlling the temperature and the vacuum pressure of the soft section and the hard section in the reaction kettle and the polymerization kettle, the prepared polyurethane resin has good storage property and heat resistance, and meets the diversified requirements; simultaneously, the raw materials are added into the reaction kettle by arranging the hoisting assembly, so that the operation is strong.
Drawings
FIG. 1 is a schematic flow chart of steps 1 to 4;
FIG. 2 is a schematic flow chart of step 5 to step 7;
FIG. 3 is a front view of the hoist assembly;
figure 4 is a top view of the hoist assembly.
In the figure: 1-hoisting the assembly; 101-a base; 102-a first guard plate; 103-a second guard plate; 104-a third prevention plate; 105-a hook; 106-a baffle; 107-forklift holes; 108-separation plate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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:
referring to fig. 1-4, the present invention provides a technical solution: a preparation process of polyurethane resin comprises the following steps:
step 1: adding polyol into a reaction kettle, stirring, adding oxalic acid and an antioxidant, and uniformly mixing to obtain a first mixed solution;
step 2: when the temperature in the reaction kettle is 140 ℃, condensing the water evaporated from the reaction kettle, then feeding the condensed water into a wastewater collection system, and continuously preserving the heat to react the first mixed solution after no water is separated out;
and step 3: when the first mixed solution is reacted in a reaction kettle, when the acid value is pH =6.0, starting vacuum and gradually reducing the pressure to-0.09 MPa, wherein the temperature in the reaction kettle is 220 ℃;
and 4, step 4: when the acid value and the hydroxyl value of the first mixed solution are qualified, reducing the temperature in the reaction kettle to be below 80 ℃, stopping vacuumizing, recovering the normal pressure in the reaction kettle, and putting the obtained polyester dihydric alcohol into a polyester intermediate tank;
and 5: adding an organic solvent or water into a polymerization kettle, adding polyester diol, special PE and a chain extender in an intermediate tank, starting a stirrer for stirring to obtain a second mixed solution;
step 6: when the temperature in the polymerization kettle is 55 ℃, adding diisocyanate into the second mixed solution, and slowly stirring to perform polymerization reaction to obtain a third mixed solution;
and 7: and adding a terminator into the third mixed solution, stopping the polymerization reaction, naturally cooling to 10 ℃, and filling to obtain a polyurethane resin finished product.
In step 1, the polyhydric alcohol comprises one or a mixture of more than two of ethylene glycol, diethylene glycol or 1, 4-butanediol.
In the step 2, the water evaporated from the reaction kettle is condensed and then enters a wastewater collection system to obtain condensed water, the collected condensed water is evaporated, and excessive dihydric alcohol in the condensed water is collected.
In step 5, the organic solvent comprises one or a mixture of more than two of toluene, butanone or DMF.
In step 6, the temperature of the polymerization reaction was 65 ℃.
In step 7, the terminating agent is ethylene glycol.
Example 2:
referring to fig. 1-4, the present invention provides a technical solution: a preparation process of polyurethane resin comprises the following steps:
step 1: adding polyol into a reaction kettle, stirring, adding oxalic acid and an antioxidant, and uniformly mixing to obtain a first mixed solution;
step 2: when the temperature in the reaction kettle is 150 ℃, condensing the water evaporated from the reaction kettle, then feeding the condensed water into a wastewater collection system, and continuously preserving the heat to react the first mixed solution after no water is separated out;
and step 3: when the first mixed solution is reacted in a reaction kettle, when the acid value is pH =7.0, starting vacuum and gradually reducing the pressure to-0.09 MPa, wherein the temperature in the reaction kettle is 220 ℃;
and 4, step 4: when the acid value and the hydroxyl value of the first mixed solution are qualified, reducing the temperature in the reaction kettle to be below 80 ℃, stopping vacuumizing, recovering the normal pressure in the reaction kettle, and putting the obtained polyester dihydric alcohol into a polyester intermediate tank;
and 5: adding an organic solvent or water into a polymerization kettle, adding polyester diol, special PE and a chain extender in an intermediate tank, starting a stirrer for stirring to obtain a second mixed solution;
step 6: when the temperature in the polymerization kettle is 60 ℃, adding diisocyanate into the second mixed solution, and slowly stirring to perform polymerization reaction to obtain a third mixed solution;
and 7: and adding a terminator into the third mixed solution, stopping the polymerization reaction, naturally cooling to 30 ℃, and filling to obtain a polyurethane resin finished product.
In step 1, the polyhydric alcohol comprises one or a mixture of more than two of ethylene glycol, diethylene glycol or 1, 4-butanediol.
In the step 2, the water evaporated from the reaction kettle is condensed and then enters a wastewater collection system to obtain condensed water, the collected condensed water is evaporated, and excessive dihydric alcohol in the condensed water is collected.
In step 5, the organic solvent comprises one or a mixture of more than two of toluene, butanone or DMF.
In step 6, the polymerization temperature was 80 ℃.
In step 7, the terminating agent is ethylene glycol.
Example 3:
referring to fig. 1-4, the present invention provides a technical solution: a preparation process of polyurethane resin comprises the following steps:
step 1: adding polyol into a reaction kettle, stirring, adding oxalic acid and an antioxidant, and uniformly mixing to obtain a first mixed solution;
step 2: when the temperature in the reaction kettle is 160 ℃, condensing the water evaporated from the reaction kettle, then feeding the condensed water into a wastewater collection system, and continuously preserving the heat to react the first mixed solution after no water is separated out;
and step 3: when the first mixed solution is reacted in a reaction kettle, when the acid value is pH =8.0, starting vacuum and gradually reducing the pressure to-0.09 MPa, wherein the temperature in the reaction kettle is 225 ℃;
and 4, step 4: when the acid value and the hydroxyl value of the first mixed solution are qualified, reducing the temperature in the reaction kettle to be below 80 ℃, stopping vacuumizing, recovering the normal pressure in the reaction kettle, and putting the obtained polyester dihydric alcohol into a polyester intermediate tank;
and 5: adding an organic solvent or water into a polymerization kettle, adding polyester diol, special PE and a chain extender in an intermediate tank, starting a stirrer for stirring to obtain a second mixed solution;
step 6: when the temperature in the polymerization kettle is 65 ℃, adding diisocyanate into the second mixed solution, and slowly stirring to perform polymerization reaction to obtain a third mixed solution;
and 7: and adding a terminator into the third mixed solution, stopping the polymerization reaction, naturally cooling to 40 ℃, and filling to obtain a polyurethane resin finished product.
In step 1, the polyhydric alcohol comprises one or a mixture of more than two of ethylene glycol, diethylene glycol or 1, 4-butanediol.
In the step 2, the water evaporated from the reaction kettle is condensed and then enters a wastewater collection system to obtain condensed water, the collected condensed water is evaporated, and excessive dihydric alcohol in the condensed water is collected.
In step 5, the organic solvent comprises one or a mixture of more than two of toluene, butanone or DMF.
In step 6, the temperature of the polymerization reaction was 90 ℃.
In step 7, the terminating agent is ethylene glycol.
In the step 1 of the three groups of embodiments, a hoisting component 1 is adopted when polyol, oxalic acid and antioxidant are added into a reaction kettle, the hoisting component 1 comprises a base 101, a first protection plate 102, a second protection plate 103, a third protection plate 104, a lifting hook 105, a baffle 106, fork holes 107 and a partition plate 108, the first protection plate 102, the second protection plate 103 and the third protection plate 104 are vertically arranged on the front side, the rear side and the right side above the base 101, the baffle 106 is vertically arranged on the left side above the base 101, the lifting hook 105 is arranged in the middle of the upper surfaces of the first protection plate 102, the second protection plate 103 and the third protection plate 104, the fork holes 107 are arranged around the base 101, the partition plate 108 is arranged on the upper surface of the base 101, one end of the partition plate 108 is connected with the middle of the inner wall of the baffle 106, the other end of the partition plate 108 is connected with the middle of the inner wall of the third protection plate 104, the height of second protection plate 103, third protection plate 104, division board 108 can be used for saying that base 101 falls into two parts, places different former storage bucket, and baffle 106 can protect former storage bucket can not drop. The embodiment adopts the polycondensation and polymerization reaction method to prepare the polyurethane resin, has the advantages of simple process control, strong product controllability and the like, the product regulates the performance of the resin by controlling the temperature and the vacuum pressure of a soft section and a hard section in a reaction kettle and a polymerization kettle, and the prepared polyurethane resin has good storage property and heat resistance and meets the diversified requirements; meanwhile, the hoisting component 1 is arranged to add raw materials into the reaction kettle, so that the operation is strong.
Application method
1. Preparation of polyester diols
(1) The reaction principle is as follows:
(2) the process is briefly described as follows:
firstly, dihydric alcohol (such as ethylene glycol, diethylene glycol, 1, 4-butanediol and the like) is pumped into a polycondensation reaction kettle, a stirrer is started to stir, then adipic acid and an antioxidant are manually added and weighed, and after the feeding is finished, a manhole cover is locked.
And introducing heat conducting oil into the outer coil pipe for heating, heating and melting to perform polycondensation reaction, separating out moisture when the temperature in the reaction kettle reaches about 150 ℃, condensing evaporated water through a condenser, then feeding the condensed water into a collecting tank, and sending the condensed water to a wastewater system for treatment. After the anhydrous components are separated out, continuously preserving the heat for reaction; sampling and analyzing at different times during the reaction period, starting vacuum to gradually reduce the pressure to-0.09 MPa when the acid value meets the specified range, simultaneously increasing the circulation temperature of the heat-conducting oil, and controlling the temperature in the reaction kettle to be 220-225 ℃; in the process, the change conditions of the acid value and the hydroxyl value of the system are analyzed by time-sharing sampling, and the reaction is basically finished when the analysis result is qualified; opening a condensation collecting pipeline, evaporating and collecting the excessive dihydric alcohol, and reusing the excessive dihydric alcohol for the reaction of the next batch; and after the recovery is finished, stopping heating the coil pipe, introducing circulating cooling water, and stopping vacuumizing to recover the normal pressure of the system after the temperature is reduced to be below 80 ℃. The obtained polyester diol is put into a polyester intermediate tank for standby through a pipeline when the polyester diol is hot.
2. Preparation of polyurethane resin
(1) The reaction principle is as follows:
(2) the process is briefly described as follows:
firstly, pumping metered water or organic solvent (toluene, butanone and DMF) into a polymerization kettle through a pipeline, starting a stirrer, metering and pumping polyester dihydric alcohol in an intermediate tank, manually adding weighed special PE for stirring, introducing steam into a coil pipe for heating to 60 ℃, then adding weighed diisocyanate (such as TDI material pumping and MDI manual adding), and slowly stirring for polymerization reaction; gradually raising the heating temperature along with the reaction, and controlling the reaction temperature to be less than 90 ℃; pumping a small amount of terminating agent (ethylene glycol) after reacting for a period of time to stop the reaction, and naturally cooling to below 40 ℃ to fill into a barrel to obtain a finished product when-NCO in the sampling analysis system is completely reacted to indicate that the reaction is finished.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation process of polyurethane resin is characterized by comprising the following steps:
step 1: adding polyol into a reaction kettle, stirring, adding oxalic acid and an antioxidant, and uniformly mixing to obtain a first mixed solution;
step 2: when the temperature in the reaction kettle is 140-160 ℃, condensing the water evaporated from the reaction kettle, then feeding the condensed water into a wastewater collection system, and continuing to keep the temperature to react the first mixed solution after no water is separated out;
and step 3: when the first mixed solution reacts in the reaction kettle, when the acid value is between 6.0 and 8.0, the vacuum is started to gradually reduce the pressure to-0.09 MPa, and the temperature in the reaction kettle is 220-;
and 4, step 4: when the acid value and the hydroxyl value of the first mixed solution are qualified, reducing the temperature in the reaction kettle to be below 80 ℃, stopping vacuumizing, recovering the normal pressure in the reaction kettle, and putting the obtained polyester dihydric alcohol into a polyester intermediate tank;
and 5: adding an organic solvent or water into a polymerization kettle, adding polyester diol, special PE and a chain extender in an intermediate tank, starting a stirrer for stirring to obtain a second mixed solution;
step 6: when the temperature in the polymerization kettle is 55-65 ℃, adding diisocyanate into the second mixed solution, and slowly stirring to perform polymerization reaction to obtain a third mixed solution;
and 7: adding a terminator into the third mixed solution, stopping the polymerization reaction, naturally cooling to 10-40 ℃, and filling to obtain a polyurethane resin finished product.
2. The process according to claim 1, wherein the reaction mixture comprises: in step 1, the polyhydric alcohol comprises one or a mixture of more than two of ethylene glycol, diethylene glycol or 1, 4-butanediol.
3. The process according to claim 1, wherein the reaction mixture comprises: in the step 2, the water evaporated from the reaction kettle is condensed and then enters a wastewater collection system to obtain condensed water, the collected condensed water is evaporated, and excessive dihydric alcohol in the condensed water is collected.
4. The process according to claim 1, wherein the reaction mixture comprises: in step 5, the organic solvent comprises one or a mixture of more than two of toluene, butanone or DMF.
5. The process according to claim 1, wherein the reaction mixture comprises: in step 6, the polymerization temperature is 65-90 ℃.
6. The process according to claim 1, wherein the reaction mixture comprises: in step 7, the terminating agent is ethylene glycol.
7. The process according to claim 1, wherein the reaction mixture comprises: in the step 1, a hoisting component is adopted when the polyol, the oxalic acid and the antioxidant are added into the reaction kettle.
8. The process according to claim 7, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: hoist and mount subassembly includes base, first guard plate, second guard plate, third guard plate, lifting hook, baffle, fork truck hole and division board, the front side, rear side and the right side of base top are all located perpendicularly to first guard plate, second guard plate, third guard plate, the left side of base top is equipped with the baffle perpendicularly, the upper surface middle part of first guard plate, second guard plate, third guard plate all is equipped with the lifting hook, all be equipped with the fork truck hole around the base, the upper surface of base is equipped with the division board.
9. The process according to claim 8, wherein the reaction mixture comprises: one end of the partition plate is connected with the middle part of the inner wall of the baffle, and the other end of the partition plate is connected with the middle part of the inner wall of the third protection plate.
10. The process according to claim 9, wherein the reaction mixture comprises: the height of baffle is less than the height of first guard plate, second guard plate, third guard plate.
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| CN202011608196.4A CN112646104A (en) | 2020-12-30 | 2020-12-30 | Preparation process of polyurethane resin |
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| CN202011608196.4A CN112646104A (en) | 2020-12-30 | 2020-12-30 | Preparation process of polyurethane resin |
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Cited By (1)
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| CN113786790A (en) * | 2021-08-31 | 2021-12-14 | 台州禾欣高分子新材料有限公司 | Polyurethane resin stirring device for leather and preparation process thereof |
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