CN114316175A - Solvent-containing isocyanate curing agent and preparation method thereof - Google Patents
Solvent-containing isocyanate curing agent and preparation method thereof Download PDFInfo
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- CN114316175A CN114316175A CN202111638731.5A CN202111638731A CN114316175A CN 114316175 A CN114316175 A CN 114316175A CN 202111638731 A CN202111638731 A CN 202111638731A CN 114316175 A CN114316175 A CN 114316175A
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- polyol
- isocyanate
- solvent
- curing agent
- isocyanate curing
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 64
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 239000002904 solvent Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 34
- 150000003077 polyols Chemical class 0.000 claims abstract description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920005903 polyol mixture Polymers 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000000053 physical method Methods 0.000 claims abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 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 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- 239000007787 solid Substances 0.000 abstract description 11
- 230000006378 damage Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- RVKPQXGYBPTWPT-UHFFFAOYSA-N 3-methylhexane-2,2-diol Chemical compound CCCC(C)C(C)(O)O RVKPQXGYBPTWPT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of chemical raw materials, in particular to an isocyanate curing agent containing a solvent and a preparation method thereof. The raw materials of the isocyanate curing agent containing the solvent mainly comprise polyol D or polyol mixture containing the polyol D and isocyanate according to a molar ratio of 1: (2-10), wherein the polyol D is polyether polyol obtained by copolymerizing one or a mixture of more of glycerol, trimethylolethane and trimethylolpropane with ethylene oxide or/and propylene oxide; the isocyanate is one or more of aromatic isocyanate, aliphatic isocyanate and alicyclic isocyanate. The preparation method of the isocyanate curing agent can be a physical method through a film evaporator or a chemical method for reducing the content of free isocyanate, the obtained curing agent has low viscosity and low content of free isocyanate, meets the requirements of high solid content and low viscosity in the industry, and effectively reduces the harm to human bodies and the pollution to the environment.
Description
Technical Field
The invention relates to the technical field of chemical raw materials, in particular to an isocyanate curing agent containing a solvent and a preparation method thereof.
Background
Environmental protection is the development trend of the coating. At present, the national environmental protection is upgraded, and more attention is paid to the emission of the solvent with the Volatile Organic Compound (VOC) as the index. At present, water-based paint and high-solid low-viscosity paint are the main approaches for reducing VOC, but the physical property and water resistance of the water-based paint cannot meet the requirements of high-performance paint, and the high-solid low-viscosity paint reduces VOC emission on the basis of considering the performance of the paint, thereby becoming an effective development way of environment-friendly paint.
The polyurethane material prepared by taking the polyisocyanate curing agent as one of the components has the advantages of high hardness, good toughness, strong chemical resistance, quick drying and the like, and is widely used as a raw material of the two-component wood lacquer and used as a polyurethane two-component adhesive and an elastomer. The polyurethane two-component paint or adhesive is prepared by the reaction of hydroxyl-containing resin such as alkyd resin, polyester resin, acrylic resin and the like and an addition product of micromolecular alcohol and isocyanate or isocyanate trimer. The Toluene Diisocyanate (TDI) is used as a curing agent, and compared with other curing agents, the Toluene Diisocyanate (TDI) has the advantages of high curing speed, high hydrolysis resistance, corrosion resistance and thermal stability, so that the Toluene Diisocyanate (TDI) is widely applied. While much research has been devoted to the preparation of low free isocyanate solvent-based curing agents by physical or chemical methods, little has been mentioned about how to reduce the viscosity of the isocyanate curing agent itself, thereby reducing the VOC of downstream coatings and adhesives.
The existing isocyanate curing agent has some defects in practical use, such as: in the process of matching with resin for use, the added solvent is volatilized in a large amount, so that the construction environment is large in irritation and toxicity, and the damage to a human body is large.
Disclosure of Invention
The high-solid low-viscosity type curing agent only has 1/3-1/2 of the viscosity of a common curing agent, has good compatibility when being matched with resin, can greatly reduce the using amount of a dilute solvent, has small solvent volatilization amount in the construction process, and effectively reduces the harm to human bodies and the pollution to the environment.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a solvent-containing isocyanate curing agent is prepared by mixing polyol D or a polyol mixture containing polyol D and isocyanate according to a molar ratio of 1: (2-10), wherein the polyol D is polyether polyol obtained by copolymerizing one or a mixture of more of glycerol, trimethylolethane and trimethylolpropane with ethylene oxide or/and propylene oxide.
Preferably, the starting material consists essentially of polyol D or a polyol mixture containing polyol D and isocyanate in a molar ratio of 1: (3-7); more preferably, the molar ratio of 1: (3-5).
The preferred polyol D has a molecular weight of 200-1000 and a theoretical functionality of 3, with the molecular weight of 220-480 being particularly preferred.
The other component in the polyol mixture containing the polyol D is polyether polyol with the functionality of less than 3 and the molecular weight of 200-1000, and the proportion of the polyether polyol is less than 20 percent of the total amount of the polyol containing the polyether polyol D. Preferably, the isocyanate is one or more of aromatic isocyanate, aliphatic isocyanate and alicyclic isocyanate.
Preferably, the isocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimide-modified diphenylmethane diisocyanate.
Preferably, the isocyanate is 2,4 toluene diisocyanate and/or 2,6 toluene diisocyanate.
More preferably, the isocyanate is 2,4 toluene diisocyanate.
Preferably, the raw material also comprises one or more small molecular alcohols or a mixture of small molecular alcohols.
Preferably, the small molecule alcohol or the mixture of small molecule alcohols is one or more of ethylene glycol, 1, 3-propylene glycol, methyl propylene glycol, 1, 3-butanediol, 1, 4-butanediol, dipropylene glycol, diethylene glycol, neopentyl glycol, methyl pentanediol, glycerol, trimethylolpropane and pentaerythritol.
More preferably, the small molecule alcohol is one or more of ethylene glycol, neopentyl glycol, methyl pentanediol and glycerol.
Preferably, the mass ratio of the small molecule alcohol or the mixture of small molecule alcohols to the polyol D is (0-50): 100, more preferably, the mass ratio is (5-30): 100, particularly preferably (5-20): 100.
a preparation method of a solvent-containing isocyanate curing agent comprises the following steps: weighing raw materials, carrying out addition reaction, removing redundant isocyanate by a physical method or a chemical method to obtain a product, and adding a solvent to dissolve the product to obtain the isocyanate-terminated polyurethane resin. Preferably, the solvent is one or more of ethyl acetate, propyl acetate and butyl acetate, and ethyl acetate and/or butyl acetate are/is preferably used as the solvent.
Further, the physical method comprises the following steps:
s1: uniformly mixing alcohol raw materials, and dehydrating in vacuum at the temperature of below 100 ℃ for 4-8h until the water content of a system is below 200 ppm;
s2: adding isocyanate and an antioxidant into a reaction kettle, uniformly stirring, heating to 65-75 ℃, dropwise adding a product obtained in the step S1 into the reaction kettle within 1-4h, and reacting for 4-8 h;
s3: injecting the reaction product obtained in the step S2 into a feed chute of a laboratory film evaporator in batches, setting the feed temperature to be 60-70 ℃, maintaining the main body of the instrument in a vacuum state at the temperature of 100-;
s4: the heavy component of step S3 was dissolved in ethyl acetate to prepare a uniform curing agent solution.
Further, the chemical method comprises the following steps:
p1: uniformly mixing alcohol raw materials, and dehydrating in vacuum at the temperature of below 100 ℃ for 4-8h until the water content of a system is below 200 ppm;
p2: adding isocyanate, ethyl acetate and an antioxidant into a reaction kettle, uniformly stirring, heating to 60-80 ℃, adding the product obtained in the step P1 into the reaction kettle at one time, and reacting for 4-8 hours;
p3: adding a catalyst, continuing to react for 4-8h, and then adding phosphoric acid or benzoyl chloride to stop the reaction, wherein the obtained product is a uniform curing agent solution.
Compared with the prior art, the solvent-containing isocyanate curing agent and the preparation method thereof have the following advantages: the obtained curing agent has very low viscosity, good compatibility with resin and less solvent used in the thinning process, so that the obtained coating or adhesive has less solvent volatilization and plays a role in protecting the environment and human bodies.
Detailed Description
Example 1
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: 123 parts of glycerol polyether (MW 150, NJ-301), 28.6 parts of ethylene glycol, 33.5 parts of propylene glycol and 50.1 parts of diethylene glycol are uniformly mixed, and the mixture is dehydrated for 4 to 8 hours under the vacuum condition of 5Torr at the temperature of below 100 ℃ until the moisture of the system reaches below 200ppm, and is placed for 24 hours to be cooled to the normal temperature;
step two: adding TDI-80900 parts and 5 parts of antioxidant into a reaction kettle, uniformly stirring, heating to 65 ℃, dropwise adding the product obtained in the step one within 1.5h, and reacting for 6h to obtain a white waxy solid at normal temperature;
step three: injecting 1000 parts of the reactant in the second step into a feeding groove of a laboratory film evaporator in batches, setting the feeding temperature to be 65 ℃ and the feeding speed to be 300 mL/h; the vacuum degree of the main body of the instrument is 0.25mbar, the temperature is 130 ℃, and the rotating speed is 300 r/min; the temperature of a main body cooling system and the discharge of light components is 5 ℃, and a cold trap before a pump is protected by a dry ice solvent bath; the discharge temperature of the heavy component is more than 100 ℃, 750 parts of the heavy component is obtained, and the heavy component is viscous liquid at normal temperature;
step four: 750 parts of the heavies from step three were dissolved in 250 parts of ethyl acetate at 70 ℃ to provide a homogeneous curative solution, recorded as A.
Example 2
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: uniformly mixing 64 parts of glycerol polyether (MW 220, NJ-302) and 16 parts of ethylene glycol, dehydrating at the temperature of below 100 ℃ under vacuum of 5Torr for 4-8 hours until the water content of the system is below 200ppm, standing for 24 hours, and cooling to the normal temperature;
step two: adding TDI-80190 parts, ethyl acetate 114 parts and antioxidant 2 parts into a reaction kettle, uniformly stirring, heating to 60 ℃, adding the product obtained in the first step into the reaction kettle for reaction for 6 hours;
step three: adding DMP-300.016 parts, cooling to 50 ℃, continuing to react for 6 hours, then adding 0.4 part of phosphoric acid or benzoyl chloride to terminate the reaction, and obtaining a uniform curing agent solution, which is recorded as B.
Example 3
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: 145 parts of glycerol polyether (MW 250, NJ-303) and 25 parts of ethylene glycol are uniformly mixed, the mixture is dehydrated for 4 to 8 hours under the vacuum condition of 5Torr at the temperature of below 100 ℃ until the moisture of the system reaches below 200ppm, and the mixture is placed for 24 hours and cooled to the normal temperature;
step two: adding TDI-80650 parts into a reaction kettle, stirring uniformly, heating to 65 ℃, dropwise adding the component A within 4 hours, and reacting for 7 hours to obtain a reaction product which is a viscous light yellow liquid (NCO% 25.4, viscosity 33569);
step three: injecting 100 parts of the reactant in the second step into a feeding groove of a laboratory film evaporator in batches, setting the feeding temperature to be 70 ℃ and the feeding speed to be 500 mL/h; the vacuum degree of the main body of the instrument is 0.25mbar, the temperature is 150 ℃, and the rotating speed is 500 r/min; the temperature of a main body cooling system and the discharge of light components is 5 ℃, and a cold trap before a pump is protected by a dry ice solvent bath; the discharge temperature of the heavy component is more than 100 ℃, 75 parts of the heavy component is obtained, and the heavy component is thick liquid which is almost solid at normal temperature.
Step four: 75 parts of the heavies from step three were dissolved in 25 parts of ethyl acetate at 70 ℃ to give a homogeneous curative solution, reported as C.
Example 4
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: dehydrating 400 parts of alkoxy adduct (MW 260) of trimethylolpropane for 4-8 hours at 120 ℃ under vacuum of 5Torr until the water content of the system reaches below 200ppm, and placing the system in a constant-temperature storage tank at 40 ℃ under the protection of nitrogen for cooling;
step two: adding TDI-801200 parts into a reaction kettle, uniformly stirring, heating to 70 ℃, dropwise adding the component A within 4 hours, and reacting for 8 hours to obtain a reactant which is a yellow waxy solid with NCO% of 24.5;
step three: injecting 1000 parts of the reactant in the second step into a feeding groove of a laboratory film evaporator in batches, setting the feeding temperature to be 65 ℃ and the feeding speed to be 100 mL/h; the vacuum degree of the main body of the instrument is 0.25mbar, the temperature is 100 ℃, and the rotating speed is 200 r/min; the temperature of a main body cooling system and the discharge of light components is 5 ℃, and a cold trap before a pump is protected by a dry ice solvent bath; the discharge temperature of the heavy component is more than 100 ℃, 750 parts of the heavy component is obtained, and the heavy component is waxy solid at normal temperature;
step four: dissolving 750 parts of the heavy component obtained in the third step into 250 parts of ethyl acetate at 70 ℃, wherein the obtained product is a uniform curing agent solution and is recorded as D;
example 5
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: 355 parts of trimethylolpropane, 600 parts of alkoxy adduct (MW 260) of trimethylolpropane, 1000 parts of polyether polyol (NJ 202) which is initiated by propylene glycol and has the molecular weight of 200, 645 parts of neopentyl glycol and 40 parts of propylene glycol are uniformly mixed, dehydrated for 4 to 8 hours under the vacuum condition of 5Torr at the temperature of below 100 ℃ until the moisture of the system reaches below 200ppm, and placed for 24 hours and cooled to the normal temperature;
step two: adding 9218 parts of TDI-65 and 20 parts of antioxidant into a reaction kettle, uniformly stirring, heating to 62 ℃, gradually adding the product obtained in the step one into the reaction kettle, and reacting for 6 hours;
step three: adding DMP-302.2 parts, cooling to 50 ℃, continuing to react for 6 hours, then adding 0.4 part of phosphoric acid or benzoyl chloride to terminate the reaction, and obtaining a uniform curing agent solution, which is recorded as E.
Reference ratio 1
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: uniformly mixing 110 parts of trimethylolpropane, 17 parts of dimethyl pentanediol and 30 parts of dipropylene glycol, dehydrating the mixture for 4 to 8 hours at the temperature of below 100 ℃ under vacuum of 5Torr until the water content of the system is below 200ppm, and placing the mixture in a constant-temperature storage tank at the temperature of 40 ℃ under the protection of nitrogen for cooling;
step two: adding TDI-80920 parts and 6 parts of antioxidant into a reaction kettle, uniformly stirring, heating to 65 ℃, keeping the product obtained in the step one at 70 ℃ for 2-3 hours, and dropwise adding the product to react for 6 hours to obtain a white waxy solid;
step three: injecting 100 parts of the reactant in the second step into a feeding groove of a laboratory film evaporator in batches, setting the feeding temperature to be 65 ℃ and the feeding speed to be 300 mL/h; the vacuum degree of the main body of the instrument is 0.25mbar, the temperature is 125 ℃, and the rotating speed is 300 r/min; the temperature of a main body cooling system and the discharge of light components is 5 ℃, and a cold trap before a pump is protected by a dry ice solvent bath; the discharge temperature of the heavy component is more than 100 ℃, 75 parts of the heavy component is obtained and is solid at normal temperature;
step four: 750 parts of the heavies were dissolved in 250 parts of ethyl acetate at 70 deg.C, and the resulting product was a homogeneous curative solution, recorded as F.
Reference ratio 2
A preparation method of a solvent-containing isocyanate curing agent comprises the following steps:
the method comprises the following steps: dehydrating 134.17 parts of trimethylolpropane in a vacuum condition of 5Torr at the temperature of below 100 ℃ for 4-8 hours until the moisture of the system reaches below 200ppm, and placing the system in a constant-temperature storage tank at the temperature of 40 ℃ under the protection of nitrogen for cooling;
step two: adding TDI-80522.48 parts and 4.4 parts of antioxidant into a reaction kettle, uniformly stirring, heating to 65 ℃, adding the product obtained in the first step into the reaction kettle for 10 hours, and obtaining a uniform curing agent solution, wherein the record is G.
Test example 1
The isocyanate curing agents obtained in examples 1 to 5, reference example 1 and reference example 2 were subjected to performance tests, and the results are shown in Table 1:
TABLE 1
Reference example 1 and reference example 2 are conventional isocyanate curing agent production methods, and it can be seen from table 1 that the isocyanate curing agents prepared in examples 1 to 5 of the present invention can achieve lower viscosity than conventional isocyanate curing agents with the same solvent dosage, and can achieve performance, even partial performance superior to that of the conventional isocyanate curing agents with larger solvent dosage. The invention has high solid content and low viscosity, excellent performance and less solvent volatilization, and plays a role in protecting the environment and human body.
The above embodiments are only specific examples of the present invention, and the protection scope of the present invention includes but is not limited to the product forms and styles of the above embodiments, and any suitable changes or modifications made by those skilled in the art according to the claims of the present invention shall fall within the protection scope of the present invention.
Claims (11)
1. A solvent-containing isocyanate curing agent characterized by: the raw materials mainly comprise polyol D or a polyol mixture containing the polyol D and isocyanate according to a molar ratio of 1: (2-10), wherein the polyol D is polyether polyol obtained by copolymerizing one or a mixture of more of glycerol, trimethylolethane and trimethylolpropane with ethylene oxide or/and propylene oxide.
2. A solvent-containing isocyanate curing agent according to claim 1, wherein: the raw material mainly comprises polyol D and isocyanate, wherein the molecular weight of the polyol D is 200-480, the theoretical functionality is 3, and the molecular weight of the polyol D is preferably 220-480.
3. A solvent-containing isocyanate curing agent according to claim 1, wherein: the raw materials mainly comprise a polyol mixture containing polyol D and isocyanate, wherein the average molecular weight of all polyether polyols in the polyol mixture containing polyol D is 200-1000, and the functionality is 2-3.
4. A solvent-containing isocyanate curing agent according to claim 1 or 3, wherein: the other component in the polyol mixture containing the polyol D is polyether polyol with the functionality of less than 3 and the molecular weight of 200-1000, and the proportion of the polyether polyol is less than 20 percent of the total amount of the polyol containing the polyether polyol D.
5. A solvent-containing isocyanate curing agent according to claim 1, wherein: the isocyanate is one or more of aromatic isocyanate, aliphatic isocyanate and alicyclic isocyanate.
6. A solvent-containing isocyanate curing agent according to claim 1 or 5, wherein: the isocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate and carbodiimide modified diphenylmethane diisocyanate; toluene diisocyanate is preferred, and 2, 4-toluene diisocyanate is particularly preferred.
7. A solvent-containing isocyanate curing agent according to claim 1, wherein: the raw material also comprises one or more small molecular alcohols or a mixture of small molecular alcohols.
8. A solvent-containing isocyanate curing agent according to claim 7, wherein: the small molecular alcohol or the mixture of the small molecular alcohols is one or more of ethylene glycol, 1, 3-propylene glycol, methyl propylene glycol, 1, 3-butanediol, 1, 4-butanediol, dipropylene glycol, diethylene glycol, neopentyl glycol, methyl pentanediol, glycerol, trimethylolpropane and pentaerythritol.
9. A solvent-containing isocyanate curing agent according to claim 7, wherein: the mass ratio of the small molecular alcohol or the mixture of the small molecular alcohols to the polyol D is (0-50): 100.
10. the method for producing a solvent-containing isocyanate curing agent according to claim 1 or 7, wherein: weighing raw materials, carrying out addition reaction, removing redundant isocyanate by a physical method or a chemical method to obtain a product, and adding a solvent to dissolve the product to obtain the isocyanate-terminated polyurethane resin.
11. The method of claim 10, wherein the solvent is one or more of ethyl acetate, propyl acetate, and butyl acetate, and preferably ethyl acetate and/or butyl acetate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5442028A (en) * | 1993-08-20 | 1995-08-15 | Morton International, Inc. | Curatives for aqueous adhesives |
| CN107880249A (en) * | 2017-11-24 | 2018-04-06 | 鹤山市信兴化工有限公司 | A kind of polyurethane curing agent and preparation method thereof |
| CN112029063A (en) * | 2020-09-07 | 2020-12-04 | 江苏湘园化工有限公司 | Liquid polyurethane curing agent composition and application method thereof |
-
2021
- 2021-12-29 CN CN202111638731.5A patent/CN114316175A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5442028A (en) * | 1993-08-20 | 1995-08-15 | Morton International, Inc. | Curatives for aqueous adhesives |
| CN107880249A (en) * | 2017-11-24 | 2018-04-06 | 鹤山市信兴化工有限公司 | A kind of polyurethane curing agent and preparation method thereof |
| CN112029063A (en) * | 2020-09-07 | 2020-12-04 | 江苏湘园化工有限公司 | Liquid polyurethane curing agent composition and application method thereof |
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