CN110982045A - Low-viscosity and low-color-number isocyanate curing agent, and preparation method and application thereof - Google Patents
Low-viscosity and low-color-number isocyanate curing agent, and preparation method and application thereof Download PDFInfo
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- CN110982045A CN110982045A CN201911145009.0A CN201911145009A CN110982045A CN 110982045 A CN110982045 A CN 110982045A CN 201911145009 A CN201911145009 A CN 201911145009A CN 110982045 A CN110982045 A CN 110982045A
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- 239000012948 isocyanate Substances 0.000 title claims abstract 18
- 150000002513 isocyanates Chemical class 0.000 title claims abstract 18
- 239000003795 chemical substances by application Substances 0.000 title claims abstract 16
- 238000002360 preparation method Methods 0.000 title claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 14
- 238000000034 method Methods 0.000 claims abstract 11
- 238000006243 chemical reaction Methods 0.000 claims abstract 7
- 150000002978 peroxides Chemical class 0.000 claims abstract 6
- 239000003054 catalyst Substances 0.000 claims abstract 4
- 125000002723 alicyclic group Chemical group 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims abstract 2
- -1 hydroxyalkyl ammonium Chemical class 0.000 claims 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 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 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 229910052751 metal Chemical class 0.000 claims 2
- 239000002184 metal Chemical class 0.000 claims 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 238000005070 sampling Methods 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims 2
- 238000004448 titration Methods 0.000 claims 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims 1
- AJEUSSNTTSVFIZ-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCCO AJEUSSNTTSVFIZ-UHFFFAOYSA-M 0.000 claims 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims 1
- 230000010933 acylation Effects 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000002168 alkylating agent Substances 0.000 claims 1
- 229940100198 alkylating agent Drugs 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical group ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims 1
- 229940011051 isopropyl acetate Drugs 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 235000011056 potassium acetate Nutrition 0.000 claims 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims 1
- 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 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 claims 1
- DWBDUFAECGEQOS-UHFFFAOYSA-M triethyl(3-hydroxypropyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCCO DWBDUFAECGEQOS-UHFFFAOYSA-M 0.000 claims 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 2
- 150000002191 fatty alcohols Chemical class 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 229920001228 polyisocyanate Polymers 0.000 abstract 1
- 239000005056 polyisocyanate Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
Classifications
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08G2115/00—Oligomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides an isocyanate curing agent with low viscosity and low color number, a preparation method and application thereof, wherein the method comprises the following steps: a) long-chain alcohol is taken as a modified raw material, and the content of peroxide in the long-chain alcohol is controlled to be less than or equal to 500 ppm; b) mixing isocyanate, long-chain alcohol and a catalyst for reaction; c) and detecting the NCO content, and terminating the reaction when the NCO content reaches the control standard. The invention can effectively reduce the polarity of polyisocyanate by using long-chain fatty alcohol or alicyclic alcohol with higher molecular weight for modification, thereby reducing the viscosity of the curing agent, and in addition, some long-chain fatty alcohol used plays a role of a surfactant to a certain extent, thereby improving the tolerance of dimethylbenzene. In addition, the invention can prepare the isocyanate curing agent with low viscosity and low color number by controlling the contents of peroxide and double bonds in the long-chain alcohol, thereby being beneficial to improving the storage stability of the curing agent.
Description
Technical Field
The invention relates to an isocyanate curing agent, in particular to an isocyanate curing agent with low viscosity and low color number, a preparation method and application thereof, belonging to the technical field of isocyanate derivatives.
Background
Polyurethane prepared by taking a 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 paint raw material and a polyurethane elastomer and polyurethane foam. 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. The polyisocyanate curing agent has a certain amount of isocyanate monomer residues in the preparation process, and the free TDI limit value after paint preparation is less than or equal to 0.4% specified in Chinese standard GB1858-2009 harmful substance limit in indoor decoration and finishing material solvent type wood lacquer coating, which indicates that the free TDI monomer content in the curing agent must be less than 0.8% to reach the Chinese national standard, so that the isocyanate content needs to be reduced before the curing agent is used to meet the standard requirement.
The existing curing agent isocyanate content treatment modes mainly comprise a physical method and a chemical method. The physical method is represented by a film evaporation method, namely a film evaporator and a high vacuum system are adopted, under the high temperature and negative pressure, the prepolymer rapidly passes through a tower plate in a film state, a free isocyanate monomer is evaporated, for example, Chinese patent publication CN1793194A separates the free isocyanate in the polyurethane addition product through single-stage film evaporation, and the content of the free TDI in the finally obtained product is lower than 0.5 wt%.
The chemical reaction method mainly adds catalysts such as amine, quaternary ammonium base, metal soap and the like to enable isocyanate to be self-polymerized to reduce the content of free TDI, and has the advantages of simple synthesis process, no need of additional separation operation and low cost, but the content of the monomer of the curing agent prepared by the chemical method is 0.5-1.0 wt%, and the reduction of the monomer needs to be realized by increasing the reaction degree and changing the formula, so that the color number of the product is increased, the NCO content is lower, the viscosity is increased, and the miscibility with the hydroxyl resin is reduced.
Chinese patent publication CN105026454A discloses that the low-color isocyanate curing agent is prepared by controlling the content of CIMCH (2-chloro-6-isocyanato-methylcyclohexadiene) in TDI and then removing free TDI through the catalytic action of a catalyst, wherein the final TDI content is less than 0.1 percent, but the viscosity is more than 1000cP, the color number is 50-80Hazen, and the color number viscosity is higher.
In the Chinese patent publication CN106084183A, micromolecular alcohol is adopted for modification, the prepared color number is less than 20Hazen, but the viscosity is 600cP, and the viscosity is still higher;
the U.S. published patent No. 4814103A improves the color number of the product by adding hindered phenolic substances and epoxy compounds as additives into the product, and does not fundamentally eliminate the influence of possible color-causing substances.
The idea of the above patent is to improve the color number of the product by controlling the preparation process and post-treatment process of the polyisocyanate curing agent in the process of preparing the isocyanate curing agent, but the concept is to inhibit the side reaction of initiating the color number of the product in the reaction process, but the influence of the color-causing substances can not be fundamentally eliminated, thereby possibly causing the stability of the product to be poor.
Disclosure of Invention
The invention aims to provide an isocyanate curing agent with low viscosity and low color number, a preparation method and application thereof, wherein the method reduces the viscosity of the isocyanate curing agent by adding long-chain alcohol and improves the compatibility of the isocyanate curing agent; the color number of the product is effectively reduced by controlling the content of peroxide in the long-chain alcohol; further, the continuous generation of peroxide is fundamentally reduced by controlling the content of double bonds in the long-chain alcohol; the isocyanate curing agent with low viscosity, low free monomer, high compatibility and low color number can be prepared by the method, and can be applied to a cross-linking agent in a bi-component polyurethane paint.
Higher molecular weight long chain fatty or alicyclic alcohols generally contain a certain amount of double bonds, the unsaturated double bond content of which can be expressed by iodine number. The double bond structure in the alcohol can be acted by oxygen in the air, and an addition reaction is carried out to generate peroxide, and the inventor surprisingly discovers that the peroxide can be continuously decomposed or oxidized in a curing agent to generate lower aldehyde and carboxylic acid, so that the prepared product has higher color number.
Based on the theory and discovery, the invention provides a method for controlling the color number of a polyisocyanate curing agent product with different ideas, the method reduces the content of peroxide in alcohol by purifying the alcohol, so as to prepare the isocyanate curing agent with low viscosity and low color number, and in the purification process, the content of double bonds is also controlled, so that the generation of the peroxide in the storage period is reduced, and the storage stability of the curing agent is further improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a low-viscosity and low-color-number isocyanate curing agent comprises the following steps:
a) long-chain alcohol is taken as a modified raw material, and the content of peroxide in the long-chain alcohol is controlled to be less than or equal to 500 ppm;
b) mixing isocyanate, long-chain alcohol and a catalyst for reaction;
c) and detecting the NCO content, and terminating the reaction when the NCO content reaches the control standard.
Further, the structural general formula of the long-chain alcohol is R- (OH)nWherein R is an aliphatic chain or alicyclic chain of C6-22, and n is 1-3; the long-chain alcohol is preferably one or more of octanol, isooctanol, dodecanol, tetradecanol and octadecanol.
Further, the addition amount of the long-chain alcohol and the isocyanate is 1:10 to 30, preferably 1: 15-25; the dosage of the catalyst is 0.01-1%, preferably 0.05-0.1% of the mass of the isocyanate monomer.
Further, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate and cyclohexane dimethylene diisocyanate, preferably toluene diisocyanate, more preferably one or two of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate;
the catalyst is Mannich base, hydroxide of hydroxyalkyl ammonium, phosphorus compound or metal salt of alkyl carboxylic acid, preferably Mannich base;
the hydroxide of the hydroxyalkyl ammonium is preferably one or more of trimethyl hydroxypropyl ammonium hydroxide, trimethyl hydroxyethyl ammonium hydroxide, triethyl hydroxypropyl ammonium hydroxide and triethyl hydroxyethyl ammonium hydroxide; the phosphorus compound is preferably tributyl phosphine; the metal salt of the alkyl carboxylic acid is preferably one or more of potassium acetate, tin octoate, zinc octoate and tin acetate;
the reaction terminator is a protonic acid, an acylation reagent or an alkylation reagent; the protonic acid is preferably one or more of phosphoric acid, hydrochloric acid and sulfuric acid; the acylating agent is preferably benzoyl chloride; the alkylating agent is preferably one or two of methyl p-toluenesulfonate and di-n-butyl phosphate.
Further, a solvent is added in the step b); the solvent is preferably one or more of toluene, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and propylene glycol methyl ether acetate.
Further, the reaction temperature of the step b) is 20-90 ℃, and preferably 20-50 ℃; the reaction time is 5 to 40 hours, preferably 10 to 30 hours.
Further, the step c) is terminated when the NCO content reaches 7.0-8.0%.
Further, the removal process of the peroxide in the long-chain alcohol is one or two of rectification and distillation; the control mode of the peroxide content is interval sampling titration test;
preferably, before controlling the peroxide in the long-chain alcohol, firstly controlling the content of double bonds in the long-chain alcohol to be less than or equal to 10 ppm; more preferably, the double bond content control process is one or two of rectification and distillation; the control mode of the double bond content is interval sampling titration test.
The double bond in the alcohol compound can reduce the boiling point of the alcohol, and the peroxide can increase the boiling point of the alcohol, so that the long-chain alcohol can be purified by distillation or rectification treatment according to different boiling points, and the contents of the peroxide and the double bond in the alcohol can be controlled.
The isocyanate curing agent is used as a cross-linking agent in a two-component polyurethane paint.
The invention can effectively reduce the polarity of polyisocyanate by using long-chain fatty alcohol or alicyclic alcohol with higher molecular weight for modification, thereby reducing the viscosity of the curing agent, and in addition, some long-chain fatty alcohol used plays a role of a surfactant to a certain extent, thereby improving the tolerance of dimethylbenzene. In addition, the invention can prepare the isocyanate curing agent with low viscosity and low color number by controlling the contents of peroxide and double bonds in the long-chain alcohol, thereby being beneficial to improving the storage stability of the curing agent.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples presented, but also encompasses any other known modification within the scope of the claims, the specific application of the invention is not limited to the examples described, and a person skilled in the art can apply the inventive concept within the scope of the claims.
The raw materials and sources of the product are as follows:
dodecanol, tianjin sun cure, lot 201808240;
octanol, tianjin optical rehabilitation, lot No. 201705140;
hexadecanol, tianjin photofrivolysis, lot No. 201703210;
octadecanol, tianjin sun-cured chemical, lot number 201605040;
toluene diisocyanate, Vanhua Chemicals, batch No. 020181124
Isophorone diisocyanate, Vanhua Chemicals, batch No. 020160321
Diphenylmethane diisocyanate, Vanhua Chemicals, batch No. 020190111
Xylylene diisocyanate, Vanhua Chemicals, batch No. 020190324
Hexamethylene diisocyanate, Wanhua chemical, Lot 020180524
Mannich base catalyst: (1) mannich bases based on bisphenol a/formalin (Fomalin)/dimethylamine, cf synthesis in US 4115373, pages six, lines 5-10; (2) mannich bases based on phenol/formalin (Fomalin)/dimethylamine are synthesized according to US 4115373, page eight, lines 5-40.
Other raw materials and reagents may be commercially available unless otherwise specified.
The analysis and test method adopted by the embodiment of the invention is as follows:
the NCO content test is according to the standard GB/T12009.4;
the content test of the free isocyanate monomer adopts the national 10 standard GB/T18446-;
dynamic viscosity was measured at 25 ℃ using a spindle viscometer (Brookfield DV-II);
hazen colour number was determined using a colour number measuring device (BYK LCS IV);
solids content was tested according to GB/T2793-1995;
the content of free TDI is tested according to GB/T18446-2009;
the peroxide content is tested according to GB/T32102-2015;
the iodine value content is tested according to GB/T5532-2008, and then converted into the double bond content, and the conversion formula is as follows: double bond content 254 iodine value;
and the xylene tolerance is measured by xylene titration, namely the ratio of the mass of the xylene to the mass of the sample when turbid and insoluble substances appear.
[ example 1 ]
Firstly, carrying out reduced pressure distillation treatment on dodecanol (the initial peroxide content is 1224ppm, the double bond content is 254ppm), controlling the distillation temperature to be 105 ℃, the pressure to be 1pa, testing the double bond content of the dodecanol in a kettle every 1 hour, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1 hour and stopping distillation when the peroxide content is less than or equal to 500ppm, finally obtaining the dodecanol with the peroxide content of 20ppm and the double bond content of 5ppm, adding 10kg of toluene diisocyanate and 11kg of butyl acetate into the reaction kettle under the protection of nitrogen, stirring uniformly, then adding 1425g of dodecanol (the molar ratio of hydroxyl groups to isocyanate groups is 1:15) into the reaction kettle, adding 250g of catalyst solution (the solution is a butyl acetate solution of Mannich base, wherein the concentration of the Mannich base based on bisphenol A/formalin/dimethylamine is 20 wt%) after reacting for half an hour at 30 ℃ to initiate trimerization, when NCO% (% 7.5%), 100g of dibutyl phosphate was added to terminate the reaction.
[ example 2 ]
Firstly, carrying out reduced pressure distillation treatment on octanol (the initial peroxide content is 1011ppm, the double bond content is 127ppm), controlling the distillation temperature to be 95 ℃, the pressure to be 1pa, testing the double bond content of the octanol in a kettle every 1h, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1h, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain dodecanol with the peroxide content of 500ppm and the double bond content of 10ppm, adding 10kg of isophorone diisocyanate and 11kg of ethyl acetate into the reaction kettle under the protection of nitrogen, stirring uniformly, then adding 1169g of octanol (the molar ratio of hydroxyl to isocyanate is 1:10) into the reaction kettle, reacting for half an hour at the temperature of 50 ℃, adding 1g of tributyl phosphine to initiate trimerization, and adding 40g of methyl p-toluenesulfonate to terminate the reaction when the NCO% is 7.46%.
[ example 3 ]
Firstly, carrying out reduced pressure distillation treatment on tetradecanol (the initial peroxide content is 1534ppm, the double bond content is 305ppm), controlling the distillation temperature at 120 ℃, the pressure at 1pa, testing the double bond content of the tetradecanol in a kettle every 1h, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the distillate every 1h, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain tetradecanol with the peroxide content of 50ppm and the double bond content of 6ppm, under the protection of nitrogen, 10k of diphenylmethane diisocyanate and 11kg of propylene glycol monomethyl ether acetate are added into a reaction kettle, stirred uniformly, 571g of tetradecanol (the molar ratio of hydroxyl to isocyanate groups is 1:30) is added into the reaction kettle, after reacting for half an hour at 40 ℃, 5g of trimethyl hydroxypropyl ammonium hydroxide is added to initiate trimerization, and when the NCO% is 7.6%, 100g of benzoyl chloride is added to terminate the reaction.
[ example 4 ]
Firstly, carrying out reduced pressure distillation treatment on dodecanol (the initial peroxide content is 1224ppm, the double bond content is 254ppm), controlling the distillation temperature to be 105 ℃, the pressure to be 1pa, testing the double bond content of the dodecanol in a kettle every 1 hour, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1 hour, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain the dodecanol with the peroxide content of 150ppm and the double bond content of 7ppm, adding 15kg of toluene diisocyanate and 15kg of butyl acetate into the reaction kettle under the protection of nitrogen, uniformly stirring, then adding 1027g of dodecanol (the molar ratio of hydroxyl to isocyanate is 1:25) into the reaction kettle, reacting for half an hour at 30 ℃, adding 375g of catalyst solution (the solution is a butyl acetate solution of Mannich base based on bisphenol A/formalin/dimethylamine, wherein the concentration of the Mannich base is 20 wt%), when NCO% (% 7.42%), 500g of phosphoric acid was added to terminate the reaction.
[ example 5 ]
Firstly, carrying out reduced pressure distillation treatment on hexadecanol (the initial peroxide content is 2675ppm, the double bond content is 252ppm), controlling the distillation temperature at 130 ℃, the pressure at 1pa, testing the double bond content of the hexadecanol in a kettle every 1 hour, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1 hour, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain the hexadecanol with the peroxide content of 125ppm and the double bond content of 2ppm, adding 10kg of xylylene diisocyanate and 11kg of n-propyl acetate into the reaction kettle under the protection of nitrogen, stirring uniformly, then adding 1287g of the hexadecanol (the molar ratio of hydroxyl to isocyanate is 1:20) into the reaction kettle, reacting for half an hour at 60 ℃, adding 100g of lithium acetate to initiate trimerization, and adding 200g of n-octyl phosphate to terminate the reaction when the NCO% is 7.43%.
[ example 6 ]
Firstly, carrying out reduced pressure distillation treatment on octadecanol (the initial peroxide content is 2415ppm, the double bond content is 381ppm), controlling the distillation temperature at 140 ℃, the pressure at 1pa, testing the double bond content of the dodecanol in a kettle every 1h, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1h, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain the dodecanol with the peroxide content of 100ppm and the double bond content of 4ppm, adding 15kg of hexamethylene diisocyanate and 15kg of butyl acetate into the reaction kettle under the protection of nitrogen, uniformly stirring, then adding 4200g of octadecanol (the molar ratio of hydroxyl to isocyanate is 1:11.5) into the reaction kettle, reacting for half an hour at 45 ℃, adding 75g of catalyst solution (the solution is a Mannich base butyl acetate solution of Mannich base, wherein the concentration of the Mannich base based on bisphenol A/formalin/dimethylamine is 20 wt%), when NCO% (% 7.51), 80g of dibutyl phosphate was added to terminate the reaction.
[ example 7 ]
Firstly, carrying out reduced pressure distillation treatment on dodecanol (the initial peroxide content is 1224ppm, the double bond content is 254ppm), controlling the distillation temperature to be 105 ℃, the pressure to be 1pa, testing the double bond content of the dodecanol in a kettle every 1 hour, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1 hour, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain the dodecanol with the peroxide content of 450ppm and the double bond content of 8ppm, adding 12kg of toluene diisocyanate and 12kg of butyl acetate into the reaction kettle under the protection of nitrogen, uniformly stirring, then adding 820g of dodecanol (the molar ratio of hydroxyl to isocyanate is 1:30) into the reaction kettle, adding 200g of catalyst solution (the solution is a butyl acetate solution of Mannich base, wherein the concentration of the Mannich base based on bisphenol A/formalin (Fomalin)/dimethylamine is 20 wt%) into the reaction kettle after reacting for half an hour at 30 ℃, when NCO%. was 7.48%, 150g of ethyl p-toluenesulfonate was added to terminate the reaction.
[ example 8 ]
Firstly, carrying out reduced pressure distillation treatment on tetradecanol (initial peroxide content is 1534ppm, double bond content is 305ppm), controlling distillation temperature at 130 ℃, pressure at 1pa, testing double bond content of dodecanol in a kettle every 1h, collecting fractions when the double bond content is less than or equal to 10ppm, then testing peroxide content of the fractions every 1h, stopping distillation when the peroxide content is less than or equal to 500ppm to obtain tetradecanol with peroxide content of 300ppm and double bond content of 6ppm, adding 12kg of toluene diisocyanate and 12kg of isopropyl acetate into the reaction kettle under the protection of nitrogen, stirring uniformly, then adding 1500g of dodecanol (molar ratio of hydroxyl group to isocyanate group is 1:17) into the reaction kettle, reacting for half an hour at 80 ℃, adding 120g of catalyst solution (the solution is a Mannich base butyl acetate solution of Mannich base, wherein the concentration of the Mannich base based on bisphenol A/formalin/dimethylamine is 20 wt%), when NCO%. was 7.45%, 120g of isooctyl phosphate was added to terminate the reaction.
[ example 9 ]
Firstly rectifying dodecanol (initial peroxide content: 1224ppm and double bond content: 254ppm), controlling the temperature at the top of a tower to be 95 ℃, the extraction temperature to be 95 ℃, the temperature at the bottom of the tower to be 110 ℃, the pressure in the tower to be absolute pressure 10Pa, testing the double bond content of dodecanol at the bottom of the tower every 1 hour, collecting fractions when the double bond content is less than or equal to 10ppm, then testing the peroxide content of the fractions every 1 hour, stopping rectification when the peroxide content is less than or equal to 500ppm, obtaining decanol with the peroxide content of 460ppm and the double bond content of 7ppm, adding 12kg of toluene diisocyanate and 12kg of butyl acetate into a reaction kettle under the protection of nitrogen, stirring uniformly, then adding 2000g of decanol (the molar ratio of hydroxyl to isocyanate is 1:11) into the reaction kettle, adding 65g of a Mannich base catalyst solution (the solution is a butyl acetate solution of Mannich base after reacting for half an hour at 35 ℃, wherein the concentration of mannich base based on bisphenol a/formalin (Fomalin)/dimethylamine was 20 wt%, and when NCO% >, 7.50%, 100g dibutyl phosphate was added to terminate the reaction.
Comparative example 1
The preparation process and the conditions were the same as in example 1, except that tetradecanol (initial peroxide content 1534ppm, double bond content 304.8ppm) which had not been subjected to distillation or rectification was used as the starting material. The reaction was terminated when NCO% >, 7.20%.
Comparative example 2
The preparation process and conditions were the same as in example 1, except that dodecanol (initial peroxide content 1224ppm, double bond content 254ppm) which had not been subjected to distillation or rectification was used as the starting material. The reaction was terminated when NCO% >, 7.80%.
Comparative example 3
Preparing an isocyanate curing agent by modifying small molecular alcohol:
to a stirrer, a thermometer and a nitrogen introducing pipe2A protected 500mL four-necked flask was charged with 800g TDI, 150g n-butanol, 5g catalyst solution (based on bisphenol A/dimethylamine/formaldehyde, a 50% by mass dilution of a Mannich base butyl acetate mixture (40% DMF dilution)), 10g antioxidant trioctyl phosphite, and 1000g butyl acetate, heated in a water bath to 30 ℃ and sampled every 0.5h to measure NCO. And when the trimerization conversion rate reaches 65%, adding 1g of polymerization inhibitor di-n-butyl phosphate, continuing to perform heat preservation reaction for 0.5h, adding 150g of hexadecanol, continuing to perform reaction for 2h, stopping the reaction, cooling and discharging, wherein the detected NCO percent is 530 percent.
The isocyanate curing agents prepared in the examples and comparative examples were measured for properties such as viscosity, xylene tolerance, solid content, color number, etc., and the results are shown in Table 1.
TABLE 1 measurement results of isocyanate curing agent Properties
It can be seen from the examples and comparative examples 1-2 that the color number of the isocyanate curing agent can be significantly reduced by reducing the peroxide content. It can be seen from the examples and comparative example 3 that the use of the treated long-chain alcohols significantly increases the tolerance of the isocyanate curing agent.
To test the storage stability of the curing agent of the present invention, the isocyanate curing agents prepared in each example and comparative example were stored in an oven at 50 ℃ for several weeks and periodically checked for a period of time, and the results of color number change are shown in Table 2.
TABLE 2 qualitative test results at 50 ℃ for isocyanate compositions
It can be seen from Table 2 that the isocyanate curing agent prepared by the present invention has better storage stability.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a low-viscosity and low-color-number isocyanate curing agent is characterized by comprising the following steps:
a) long-chain alcohol is taken as a modified raw material, and the content of peroxide in the long-chain alcohol is controlled to be less than or equal to 500 ppm;
b) mixing isocyanate, long-chain alcohol and a catalyst for reaction;
c) and detecting the NCO content, and terminating the reaction when the NCO content reaches the control standard.
2. The method for preparing a low viscosity and low color number isocyanate curing agent according to claim 1, wherein the long chain alcohol has a general structural formula of R- (OH)nWherein R is an aliphatic chain or alicyclic chain of C6-22, and n is 1-3; the long-chain alcohol is preferably one or more of octanol, isooctanol, dodecanol, tetradecanol and octadecanol.
3. The method for preparing a low viscosity and low color number isocyanate curing agent according to claim 2, wherein the long chain alcohol and the isocyanate are added in an amount of 1:10 to 30, preferably 1: 15-25; the dosage of the catalyst is 0.01-1%, preferably 0.05-0.1% of the mass of the isocyanate monomer.
4. The method of preparing a low viscosity and low color number isocyanate curing agent according to claim 3, wherein the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and cyclohexanedimethylene diisocyanate, preferably toluene diisocyanate, more preferably one or two of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate;
the catalyst is Mannich base, hydroxide of hydroxyalkyl ammonium, phosphorus compound or metal salt of alkyl carboxylic acid, preferably Mannich base;
the hydroxide of the hydroxyalkyl ammonium is preferably one or more of trimethyl hydroxypropyl ammonium hydroxide, trimethyl hydroxyethyl ammonium hydroxide, triethyl hydroxypropyl ammonium hydroxide and triethyl hydroxyethyl ammonium hydroxide; the phosphorus compound is preferably tributyl phosphine; the metal salt of the alkyl carboxylic acid is preferably one or more of potassium acetate, tin octoate, zinc octoate and tin acetate;
the reaction terminator is a protonic acid, an acylation reagent or an alkylation reagent; the protonic acid is preferably one or more of phosphoric acid, hydrochloric acid and sulfuric acid; the acylating agent is preferably benzoyl chloride; the alkylating agent is preferably one or two of methyl p-toluenesulfonate and di-n-butyl phosphate.
5. The method for preparing a low viscosity and low color number isocyanate curing agent according to claim 4, wherein a solvent is added in the step b); the solvent is preferably one or more of toluene, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and propylene glycol methyl ether acetate.
6. The method for preparing a low viscosity and low color number isocyanate curing agent according to any one of claims 1 to 5, wherein the reaction temperature of step b) is 20 to 90 ℃, preferably 20 to 50 ℃; the reaction time is 5 to 40 hours, preferably 10 to 30 hours.
7. The method for preparing a low viscosity and low color number isocyanate curing agent according to any one of claims 1 to 6, wherein the step c) terminates the reaction when NCO content reaches 7.0 to 8.0%.
8. The method for preparing the isocyanate curing agent with low viscosity and low color number according to any one of claims 1 to 7, wherein the process for removing the peroxide in the long-chain alcohol is one or two of rectification and distillation; the control mode of the peroxide content is interval sampling titration test;
preferably, before controlling the peroxide in the long-chain alcohol, firstly controlling the content of double bonds in the long-chain alcohol to be less than or equal to 10 ppm; more preferably, the double bond content control process is one or two of rectification and distillation; the control mode of the double bond content is interval sampling titration test.
9. An isocyanate curing agent prepared by the method of any one of claims 1 to 8.
10. Use of an isocyanate curing agent prepared according to any one of claims 1 to 8 as a cross-linking agent in a two-component polyurethane paint.
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