CN109575868B - Method for continuously producing moisture-curing polyurethane adhesive - Google Patents
Method for continuously producing moisture-curing polyurethane adhesive Download PDFInfo
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- CN109575868B CN109575868B CN201811319492.5A CN201811319492A CN109575868B CN 109575868 B CN109575868 B CN 109575868B CN 201811319492 A CN201811319492 A CN 201811319492A CN 109575868 B CN109575868 B CN 109575868B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 51
- 239000004814 polyurethane Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000013008 moisture curing Methods 0.000 title claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 57
- 150000003077 polyols Chemical class 0.000 claims abstract description 57
- 230000003068 static effect Effects 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 238000001723 curing Methods 0.000 claims abstract description 21
- 238000003860 storage Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 229920005906 polyester polyol Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005057 refrigeration Methods 0.000 claims description 6
- 239000011552 falling film Substances 0.000 claims description 4
- 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 description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 9
- 239000004744 fabric Substances 0.000 description 12
- 239000004753 textile Substances 0.000 description 12
- 239000000498 cooling water Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010923 batch production Methods 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012941 solvent-based polyurethane adhesive Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
-
- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/70—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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a method for continuously producing moisture-curing polyurethane adhesive, which comprises the steps of feeding polyol which is accurately measured and dehydrated into a group of static mixers with controllable temperature, mixing the polyol with isocyanate and reacting the polyol with the isocyanate, controlling the reaction process of materials by controlling the temperature of different static mixers, and then feeding the materials into a constant temperature reactor to cure the materials, thus obtaining the moisture-curing polyurethane adhesive product. By adopting the method of the invention to continuously produce the moisture-curing polyurethane adhesive, the temperature of each reaction section is accurately controlled, the process repeatability is high, the stability of the product is greatly improved, and the viscosity error of the product reaches +/-15% of the set viscosity; the constant-temperature reactor is adopted for curing, so that the reaction is more thorough, the viscosity increase rate in one month is not more than 15%, the viscosity increase rate in storage is lower than 25%, and convenience is provided for users to use; meanwhile, the continuous production mode also greatly improves the production capacity of equipment and reduces the investment of manpower, equipment and plants.
Description
Technical Field
The invention relates to a method for continuously producing moisture-curing polyurethane adhesives.
Technical Field
In recent years, polyurethane adhesives have been developed in the fields of wood manufacturing, car decorations, textile processing, and the like, because of their high strength and ease of application. Polyurethane adhesives fall into two broad categories, namely two-component adhesives and one-component adhesives, with the one-component polyurethane adhesives being more convenient to use and therefore more widely used.
At present, the single-component polyurethane adhesive is mainly a solvent-type adhesive, is easy to store and convenient to process, and is a main polyurethane adhesive variety supplied in the market. However, with the increasing awareness of environmental protection, national requirements for environmental protection are becoming more stringent, and solvent-based polyurethane adhesives are gradually being replaced by solvent-free moisture-curable polyurethane adhesives (i.e., PURs).
At present, PUR is produced by a batch kettle type production method, and the problem of poor heat conduction in the reaction process is solved due to high reaction speed and high heat release. In order to prevent the local temperature from being overhigh, manufacturers only need to control the yield of a single batch to be below 2t, and only can repeatedly build a plurality of devices if the yield is improved, so that the investment of personnel, equipment, land and the like is increased, and the operating conditions are difficult to repeat. An important index for product control is viscosity, which is up to + -40% given by each company due to the difficult repetition of operating conditions, causing great trouble for users, even if it cannot be used due to the generation of a large amount of gel due to temperature runaway.
Disclosure of Invention
The invention aims to provide a method for continuously producing a moisture-curing polyurethane adhesive, aiming at solving the problems of poor product quality stability, low equipment efficiency, large production line investment, large occupied area and the like caused by the conventional intermittent production mode of the moisture-curing polyurethane adhesive.
The invention relates to a method for continuously producing a moisture-curing polyurethane adhesive, which is characterized in that polyol which is accurately measured and dehydrated is sent into a group of static mixers with controllable temperature to be mixed with isocyanate and react, the reaction process of materials is controlled by controlling the temperature of different static mixers, and then the materials are sent into a constant temperature reactor to be cured, so that a moisture-curing polyurethane adhesive product can be obtained.
Wherein: the polyol is one or more of polyether polyol and polyester polyol; the isocyanate is one or more of 4, 4-diphenyl methylene diisocyanate (4,4-MDI), liquefied MDI and toluene-2, 4-diisocyanate (TDI). More specifically, the present invention relates to a method for continuously producing a moisture-curable polyurethane adhesive, comprising the steps of:
(1) feeding the polyol which is accurately metered into a static mixer by a metering pump and uniformly mixing; then sending the mixture into an evaporator, and removing water in the mixed polyol at the temperature of 150-200 ℃ under a vacuum condition; when the water content of the mixed polyol is not more than 200ppm, cooling to 50-80 ℃;
(2) feeding the dehydrated mixed polyol obtained in the step (1) into a group of static mixer groups with controllable temperature, uniformly mixing the dehydrated mixed polyol with isocyanate with the temperature of 35-50 ℃, reacting, and controlling the temperature of the static mixer groups in sections to ensure that the polyol and the isocyanate in the materials are fully reacted;
(3) the reacted material is sent into a constant temperature reactor for curing, and a small amount of unreacted polyhydric alcohol is further reacted continuously, so that the viscosity is not increased excessively in the storage process, and the moisture-curing polyurethane adhesive product can be obtained.
Wherein: the polyol is one or more of polyether polyol and polyester polyol; the isocyanate is one or more of 4, 4-diphenyl methylene diisocyanate (4,4-MDI), liquefied MDI and toluene-2, 4-diisocyanate (TDI).
Further, the vacuum condition in the step (1) is that the absolute pressure is in the range of 5-15 Pa.
Further, the evaporator in the step (1) is one of a scraper evaporator, a falling film evaporator or a molecular evaporator.
Further, the static mixer group described in step (2) is formed by connecting 3 or more than 3 static mixers in series, the number of the static mixers in series depends on the magnitude of the exothermic heat of the reaction, and the number of the static mixers in series can be increased properly when the exothermic heat is large, and preferably is formed by 3 to 5 static mixers, wherein: the mixing uniformity temperature of the mixed polyol and the isocyanate in the 1 st static mixer is controlled to be 55-70 ℃, the rest static mixers are main reaction sections, and the material temperature is controlled to be 90-120 ℃ in sections.
Further, the curing in the step (3) is performed for 2-6 hours at the temperature of 105-115 ℃ in a constant temperature reactor.
Further, the method for continuously producing the moisture-curable polyurethane adhesive of the present invention further comprises the filling and storing processes of: and (3) feeding the cured material into a nitrogen protection filling machine, filling according to the weight required by a customer, and feeding the product barrel into a 15-25 ℃ refrigeration house for storage.
The filling machine is a continuous liquid filling machine, quickly cools and stores the products after being filled, and can keep the viscosity stable.
According to the method for continuously producing the moisture-curing polyurethane adhesive, the reactor adopts the static mixer, the diameter of the static mixer is only 25-250 mm, and the guide fluid in the static mixer ensures that the reactor has no radial temperature difference, so that the reaction heat can be transferred in time, and the reaction temperature is controlled very stably. The equipment related in the method can be purchased in the market, and the process equipment, instruments and pipeline installation belong to normal chemical equipment installation.
By adopting the method of the invention to continuously produce the moisture-curing polyurethane adhesive, the continuous process can ensure that the product is produced under a repeatable process condition, and the stability of the product can be maintained; because the materials are uniformly distributed, the temperature control of each reaction section is accurate, the process repeatability is high, the stability of the product is greatly improved, and the viscosity error of the product reaches +/-15% of the set viscosity; the constant-temperature reactor is adopted for curing, so that the reaction is more thorough, the viscosity increase rate in one month is not more than 15%, the viscosity increase rate in storage is lower than 25%, and convenience is provided for users to use; meanwhile, the continuous production mode also greatly improves the production capacity of equipment and reduces the investment of manpower, equipment and plants.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and the non-mentioned parts of the examples are handled by common sense and general technique.
Example 1
The 6000t wet-curing polyurethane adhesive continuous production line (designed by 6000h year-by-year operation) is used for producing the textile cloth film wet-curing polyurethane adhesive, and the target viscosity is 4000cps (90 ℃).
(1) 3 kinds of polyether polyols and 2 kinds of polyester polyols which are accurately metered are sent into a static mixer with the diameter of 25mm and the length of 1m by a metering pump to be uniformly mixed; then the mixture is sent into a scraper evaporator (the area is 20 square meters), and the water in the mixed polyol is removed under the conditions of 185 ℃ and 10Pa absolute vacuum; when the water content of the mixed polyol is not more than 200ppm, the temperature is reduced to 55 ℃.
(2) Sending the dehydrated mixed polyol with the temperature of 55 ℃ obtained in the step (1) into a group of temperature-controllable static mixer groups (formed by sequentially connecting 3 static mixers in series), uniformly mixing the dehydrated mixed polyol with isocyanate (4,4-MDI) with the temperature of 45 ℃ in the 1 st static mixer (with the diameter of 25mm and the length of 2m), keeping the temperature at 55 ℃, reacting the polyol with the isocyanate in the 2 nd static mixer and the 3 rd static mixer (with the diameter of 150mm and the length of 2m), and respectively controlling the reaction temperature at 100-105 ℃ and 105-115 ℃.
(3) The reacted materials are sent into a cooling pipe with a stirring and temperature control jacket and an inner disc and the volume of the cooling pipe is 4m3Curing the mixture for 2 hours at the temperature of 115 ℃ in a constant temperature reactor to obtain the moisture-curing polyurethane adhesive product.
And (3) feeding the cured product into a nitrogen protection filling machine, filling (200 KG per barrel) according to the weight required by a customer, and feeding the product barrel into a 15-DEG C refrigeration house for storage.
Example 2
10000t of wet curing polyurethane adhesive continuous production line (designed by 6000h of annual operation) is produced for producing the wet curing polyurethane adhesive of the textile cloth film, and the target viscosity is 6000cps (90 ℃).
(1) Feeding the 3 polyether polyols which are accurately metered into a static mixer with the diameter of 40mm and the length of 1m by a metering pump, and uniformly mixing; then sending into a falling film evaporator (with the area of 40 square meters), and removing water in the mixed polyol under the conditions of 150 ℃ and absolute vacuum of 5 Pa; when the water content of the mixed polyol is not more than 200ppm, the temperature is reduced to 50 ℃.
(2) Feeding the dehydrated mixed polyol with the temperature of 50 ℃ obtained in the step (1) into a group of temperature-controllable static mixers (consisting of 4 static mixers which are connected in series in sequence), uniformly mixing the dehydrated mixed polyol with isocyanate (TDI) with the temperature of 40 ℃ in a 1 st static mixer (with the diameter of 65mm and the length of 2m), keeping the temperature at 65 ℃, reacting the polyol with the isocyanate in 2 nd to 4 th static mixers (with the diameter of 200mm and the length of 2m), and respectively controlling the reaction temperature at 100-105 ℃, 105-115 ℃ and 115-120 ℃.
(3) The reacted materials are sent into a cooling pipe with a stirring and temperature control jacket and an inner disc and the volume of the cooling pipe is 8m3Curing for 4 hours at the temperature of 110 ℃ in the constant temperature reactor to obtain the moisture-curing polyurethane adhesive product.
And (3) feeding the cured product into a nitrogen protection filling machine, filling (200 KG per barrel) according to the weight required by a customer, and feeding the product barrel into a cold storage at 25 ℃ for storage.
Example 3
The 6000t wet-curing polyurethane adhesive continuous production line (designed by 6000h year-by-year operation) is used for producing the textile cloth film wet-curing polyurethane adhesive, and the target viscosity is 4000cps (90 ℃).
(1) 2 polyether polyols after accurate measurement are sent into a static mixer with the diameter of 25mm and the length of 1m by a measuring pump to be mixed evenly; then sending into a scraper evaporator (with the area of 20 square meters), and removing water in the mixed polyol under the conditions of 200 ℃ and absolute vacuum of 15 Pa; when the water content of the mixed polyol is not more than 200ppm, the temperature is reduced to 80 ℃.
(2) Sending the dehydrated mixed polyol with the temperature of 55 ℃ obtained in the step (1) into a group of temperature-controllable static mixer groups (consisting of 4 static mixers which are connected in series in sequence), uniformly mixing the dehydrated mixed polyol with isocyanate (liquefied MDI) with the temperature of 50 ℃ in the 1 st static mixer (with the diameter of 25mm and the length of 1m), keeping the temperature at 55 ℃, reacting the polyol with the isocyanate in the 2 nd to 4 th static mixers (with the diameter of 150mm and the length of 2m), and respectively controlling the reaction temperature at 100-105 ℃, 105-115 ℃ and 115-118 ℃.
(3) The reacted materials are sent into a cooling pipe with a stirring and temperature control jacket and an inner disc and the volume of the cooling pipe is 4m3Curing the mixture for 6 hours at the temperature of 105 ℃ in a constant temperature reactor to obtain the moisture-curing polyurethane adhesive product.
And (3) feeding the cured product into a nitrogen protection filling machine, filling (200 KG per barrel) according to the weight required by a customer, and feeding the product barrel into a refrigeration house at 20 ℃ for storage.
Example 4
12000t of wet-curing polyurethane adhesive continuous production line (designed according to 6000h of annual operation) is produced annually, and is used for producing the wet-curing polyurethane adhesive of cloth pasting sponge for textiles, and the target viscosity is 12000cps (110 ℃).
(1) 3 kinds of polyether polyols and 2 kinds of polyester polyols which are accurately metered are sent into a static mixer with the diameter of 80mm and the length of 1m by a metering pump to be uniformly mixed; then sending into a molecular evaporator (area is 20 square meters), and removing water in the mixed polyol under the conditions of 200 ℃ and absolute vacuum of 10 Pa; when the water content of the mixed polyol is not more than 200ppm, the temperature is reduced to 80 ℃.
(2) Sending the dehydrated mixed polyol with the temperature of 55 ℃ obtained in the step (1) into a group of temperature-controllable static mixer groups (formed by sequentially connecting 5 static mixers in series), uniformly mixing the dehydrated mixed polyol with isocyanate (liquefied MDI) with the temperature of 50 ℃ in a 1 st static mixer (with the diameter of 50mm and the length of 2m), keeping the temperature at 65 ℃, reacting the polyol with the isocyanate in 2 nd to 5 th static mixers (with the diameter of 200mm and the length of 4m), and respectively controlling the reaction temperature at 90-95 ℃, 95-105 ℃, 100-110 ℃ and 115-120 ℃.
(3) The reacted materials are sent into a cooling pipe with a stirring and temperature control jacket and an inner disc and the volume of the cooling pipe is 8m3Curing the mixture for 3 hours at the temperature of 110 ℃ in a constant temperature reactor to obtain the moisture-curing polyurethane adhesive product.
And (3) feeding the cured product into a nitrogen protection filling machine, filling (200 KG per barrel) according to the weight required by a customer, and feeding the product barrel into a refrigeration house at 20 ℃ for storage.
Example 5
The continuous production line of the moisture-curing polyurethane adhesive with 1000t per year (designed to run for 3000 hours per year) is used for producing the moisture-curing polyurethane adhesive for the cloth pasting of the textile, and the target viscosity is 15000cps (120 ℃).
(1) 3 kinds of polyether polyols and 2 kinds of polyester polyols which are accurately metered are sent into a static mixer with the diameter of 25mm and the length of 1m by a metering pump to be uniformly mixed; then sending into a falling film evaporator (square meter with area of 10), and removing water in the mixed polyol under the conditions of 200 ℃ and absolute vacuum of 10 Pa; when the water content of the mixed polyol is not more than 200ppm, the temperature is reduced to 80 ℃.
(2) And (2) sending the dehydrated mixed polyol with the temperature of 55 ℃ obtained in the step (1) into a group of temperature-controllable static mixer groups (formed by sequentially connecting 3 static mixers in series), uniformly mixing the dehydrated mixed polyol with isocyanate (liquefied MDI) with the temperature of 50 ℃ in the 1 st static mixer (with the diameter of 50mm and the length of 2m), keeping the temperature at 70 ℃, reacting the polyol with the isocyanate in the 2 nd and 3 rd static mixers (with the diameter of 200mm and the length of 2m), and respectively controlling the reaction temperature at 105-110 ℃ and 110-115 ℃.
(3) The reacted materials are sent into a cooling pipe with a stirring and temperature control jacket and an inner disc and the volume of the cooling pipe is 2m3Curing the mixture for 3 hours at the temperature of 110 ℃ in a constant temperature reactor to obtain the moisture-curing polyurethane adhesive product.
And (3) feeding the cured product into a nitrogen protection filling machine, filling (200 KG per barrel) according to the weight required by a customer, and feeding the product barrel into a refrigeration house at 20 ℃ for storage.
Comparative example 1
The wet-curing polyurethane adhesive intermittent production device for 6000t textiles produced annually (6000 h of design running annually) is used for producing the cloth film wet-curing polyurethane adhesive for textiles, and the target viscosity is 4000cps (90 ℃).
3 polyether polyols and 2 polyester polyols are metered according to the formula requirements and then added into a polymerization reaction kettle one by one, the temperature of the materials is raised to 120 ℃, the materials are vacuumized to 100Pa, and the materials are dehydrated for 2-3 hours to be less than 0.02 percent.
Cooling water is introduced into a jacket of the reaction kettle to reduce the temperature of the materials to 70-72 ℃, then 4.4-MDI is quantitatively added, the temperature of the materials is gradually increased from 70 ℃ to 105 ℃, the time is counted for 3 hours from the beginning, and the temperature is controlled between 105 ℃ and 115 ℃.
Cooling water is introduced into a jacket of the reaction kettle to reduce the temperature of the materials to 90 ℃ for packaging.
Comparative example 2
10000t of moisture-curing polyurethane adhesive for textiles produced annually (6000 h of design), the process is used for producing the moisture-curing polyurethane adhesive for cloth pasting of textiles, and the target viscosity is 6000cps (90 ℃).
3 polyether polyols are added into a polymerization reaction kettle (3 m) one by one according to the formula requirement after being metered3X 10) is added, the temperature of the material is raised to 120 ℃, the material is vacuumized to 100Pa, and the material is dehydrated for 2 to 3 hours until the pressure is less than 0.02 percent.
Cooling water is introduced into a jacket of the reaction kettle to reduce the temperature of the materials to 70-72 ℃, then 4.4-MDI is quantitatively added, the temperature of the materials is gradually increased from 70 ℃ to 105 ℃, the time is counted for 3 hours from the beginning, and the temperature is controlled between 105 ℃ and 115 ℃.
Cooling water is introduced into a jacket of the reaction kettle to reduce the temperature of the materials to 90 ℃ for packaging.
Comparative example 3
12000t of wet-cured polyurethane adhesive for textiles produced annually is intermittently produced by a device (designed by 6000h of annual operation), and the process is used for producing the wet-cured polyurethane adhesive for cloth pasting sponge for textiles, wherein the target viscosity is 12000cps (110 ℃).
3 polyether polyols and 2 polyester polyols are metered according to the formula requirements and then are added into a polymerization reaction kettle (3 m)3X 12 stations), heating the materials to 120 ℃, vacuumizing to 100Pa, and dehydrating for 2-3h until the pressure is less than 0.02 percent.
Cooling water is introduced into a jacket of the reaction kettle to reduce the temperature of the materials to 70-72 ℃, then 4.4-MDI is quantitatively added, the temperature of the materials is gradually increased from 70 ℃ to 105 ℃, the time is counted for 3 hours from the beginning, and the temperature is controlled between 105 ℃ and 115 ℃.
Cooling water is introduced into a jacket of the reaction kettle to reduce the temperature of the materials to 90 ℃ for packaging.
Note: the various devices mentioned above are commercially available in the country and the specific equipment operating requirements can be customized to the equipment manufacturer.
Effects of the embodiment
The viscosity, the viscosity stability, the equipment number and the floor area of the moisture-curing polyurethane adhesive prepared by a continuous method and an intermittent method are compared according to three brands of fabric film, fabric cloth and fabric sponge.
Comparison table for products prepared by different production methods
Note: 1. examples 1, 2,4 were run continuously for 48h, with samples taken every four hours to determine the viscosity range
2. Comparative examples 1, 2 and 3 the viscosity range of 5 continuous kettles was determined at the end of the reaction
3. The main equipment refers to the reactor part, and does not comprise a raw material storage tank.
As can be seen from the comparison table:
the main control indicators for the production of moisture-curing polyurethane adhesives by the continuous and batch processes-viscosity (viscosity at the end of polymerization) -the deviations from the target value 4000 for examples 1, 2,4 are-12% to + 14.1%, -9.6% to + 10.9%, -9.6% to + 8%, respectively, and the deviations from the batch process ratios 1, 2, 3 are-10.5% to + 88.6%, -27.4% to + 64%, respectively-21% to + 36.9%. The viscosity deviation of the batch method is 4 times that of the continuous method, and the viscosity deviation is over 40 percent, so that the batch method cannot be normally used by users.
The viscosity increasing rate of 24h (the viscosity increasing rate is the viscosity increasing rate of all the examination samples after being stored for 24 h) is 8 percent in the average value of the examples 1, 2 and 4, the synchronous increasing rate of the batch method product is 18 percent, and the low viscosity increasing rate of 24h indicates that the reaction is carried out completely, thereby being beneficial to controlling the production end point and ensuring the stability of the quality.
The viscosity increase after one month (% increase in viscosity of all the examined samples after one month of storage) is compared, and the viscosity increases of examples 1, 2 and 4 are 8.7%, 6% and 10.4%, respectively, while those of comparative examples 1, 2 and 4 are 14.8%, 10% and 20.5%, respectively. The sample of the product prepared by the continuous method with the viscosity increase rate of one month is obviously lower than that of the product prepared by the batch method, thereby being beneficial to the long-time storage of the product.
It can be seen from the table that the same throughput, the volume of the main equipment required for continuous production of moisture-curable polyurethane adhesives is 25% to 35% of the batch process, and the floor area is 20% to 25% of the batch process.
Claims (6)
1. A method for continuously producing a moisture-curing polyurethane adhesive, comprising the steps of:
(1) feeding the polyol which is accurately metered into a static mixer by a metering pump and uniformly mixing; then sending the mixture into an evaporator, and removing water in the mixed polyol at the temperature of 150-200 ℃ under a vacuum condition; when the water content of the mixed polyol is not more than 200ppm, cooling to 50-80 ℃;
(2) feeding the dehydrated mixed polyol obtained in the step (1) into a group of static mixer groups with controllable temperature, uniformly mixing the dehydrated mixed polyol with isocyanate with the temperature of 35-50 ℃, reacting, and controlling the temperature of the static mixer groups in sections to ensure that the polyol and the isocyanate in the materials are fully reacted;
(3) the reacted materials are sent into a constant temperature reactor for curing, and a moisture-curing polyurethane adhesive product can be obtained;
static mixer group, form by 3 ~ 5 static mixers series connection, wherein: uniformly mixing the mixed polyol and the isocyanate in a 1 st static mixer, controlling the temperature to be 55-70 ℃, taking the rest static mixers as main reaction sections, and controlling the material temperature to be 90-120 ℃ in sections; and (4) curing in the step (3) for 2-6 hours at 105-115 ℃ in a constant temperature reactor.
2. The method of claim 1, wherein the polyol is one or more of a polyether polyol and a polyester polyol; the isocyanate is one or more of 4, 4-diphenyl methylene diisocyanate, liquefied MDI and toluene-2, 4-diisocyanate.
3. The method for continuously producing a moisture-curable polyurethane adhesive according to claim 1, wherein the vacuum condition in the step (1) is an absolute pressure in the range of 5 to 15 Pa.
4. The method for continuously producing a moisture-curable polyurethane adhesive according to claim 1, wherein the evaporator in the step (1) is one of a scraper evaporator, a falling film evaporator or a molecular evaporator.
5. The method for continuously producing a moisture-curing polyurethane adhesive as set forth in claim 1, further comprising a filling and storing process of: and (3) feeding the cured material into a nitrogen protection filling machine, filling according to the weight required by a customer, and feeding the product barrel into a 15-25 ℃ refrigeration house for storage.
6. The method of claim 5, wherein the filling machine is a continuous liquid filling machine, and the packaged product is stored at a rapid cooling rate.
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