CN107868225A - A kind of preparation method of the TDI tripolymer light curing agent of low free monomer content - Google Patents
A kind of preparation method of the TDI tripolymer light curing agent of low free monomer content Download PDFInfo
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- CN107868225A CN107868225A CN201610852581.0A CN201610852581A CN107868225A CN 107868225 A CN107868225 A CN 107868225A CN 201610852581 A CN201610852581 A CN 201610852581A CN 107868225 A CN107868225 A CN 107868225A
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- tdi
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- curing agent
- paint
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
Abstract
The present invention relates to a kind of preparation method of the TDI tripolymer light curing agent of low free monomer content, its formula components is：2,4 toluene di-isocyanate(TDI)s, PPG, long-chain alcohol, urge agent A, n-butanol, catalyst B, polymerization inhibitor, antioxidant and solvent；The TDI tripolymer light curing agent of low free monomer content made from invention, solid content is that 50 ± 2%, nco value is 7.5 ± 0.3%, viscosity (applying 4 glasss) 25~35s, free TDI≤0.5%, toluene tolerance >=2, aromatic-free, has the characteristics that environmental protection, scratch resistance is good, gloss is high, the transparency is good；The polyurethane paint prepared with hydroxy component has high glaze, high rigidity, high transparency, paint film scratch resistance is good, levelability is good, the features such as high intermiscibility of richness is wide, it is to be used for the environment-friendlycuring curing agents such as various bi-component polyester paints, polyurethane paint, decorative paint, floor paint, the priming paint such as woodenware, metal, plastics.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane curing agent, more particularly to a kind of low free monomer content
TDI tripolymer light curing agent.
Background technology
Bicomponent polyurethane coating is usually to be made up of isocyanate prepolymer and hydroxy-containing resin two parts, commonly referred to as
Curing agent component and host component, acroleic acid polyurethane, alcohol acid and polyurethane, polyester can be divided into according to the difference of hydroxy-containing component and gathered
The kinds such as urethane, polyether-polyurethane, epoxy polyurethane, typically all with film-forming temperature is low, adhesive force is strong, hardness is big, wearability
The superior functions such as good and chemicals-resistant, good weatherability, it is a kind of coating most widely used at present, is mainly used in original factory of vehicle
The side such as paint, plastic paint, woodcare paint, industrial paint, anticorrosive paint floor paint, electronic paint, fabric leather coating, printing-ink industry
Face.In China, polyurethane coating accounts for 75% or so the market share in woodwork coating, and it is left that 40% is accounted in car refinishing paint
The right market share, also increasingly wider in the application of other field such as anticorrosive paint, plastic paint etc., the market share is about
10%.
The TDI curing agent commonly used on the market at present has TDI tripolymers, TDI-TMP addition products, and produces the main of curing agent
Raw material is exactly toluene di-isocyanate(TDI) (abbreviation TDI), and TDI is a kind of volatilizable noxious material, and it can be with the protein of human body
Reaction makes albuminous degeneration, therefore the maximum of human body is endangered.TDI steam has strong lacrimation, and breathing is stimulated after suction
System, causes dry cough, laryngalgia, headache, bronchitis and asthma, and serious meeting causes death.In order to avoid isocyanate-monomer
Harm to human body, each state all work out the limitation of polyurethane products free monomers；The European Community provide, containing TDI, HDI, IPDI,
The container outer wall of the chemicals such as HMDI must put up mark：Diisocyanate free monomer mass fraction person below 0.5%, outside
Wall indicates " containing isocyanates ", is environment-friendly products；Free monomer content indicates " harmful " caution sign 0.5%~2.0%
And " containing isocyanates "；Free monomer content person more than 2%, except " containing isocyanates " is indicated, it must also indicate " poisonous " and attached
There is human skeleton bones of the dead mark.
Country has formulated mandatory standard in terms of coating environmental protection in recent years, in standard GB/T 18581-2009《It is indoor
Limits of harmful substances in decorating and renovating material solvent wood coatings》In define VOC in polyurethane paint
(VOC) content≤670g/L, benzene content≤0.3%, toluene, dimethylbenzene, ethylene total content≤30%, free TDI, | HDI contents
Summation≤0.4%.
Reducing polyurethane curing agent free TDI content of monomer turns into the direction of domestic coated sand intensifier industry emphasis tackling key problem, from
From the point of view of technical principle, chemical method and physical method can be divided into by reducing the technological approaches of free TDI, including：It is direct synthesis technique, molten
Agent extraction, high vacuum film evaporation method, molecularly distilled and chemical catalysis method for refining etc..Large-scale industrial production at present
It is mostly offshore company, such as Bayer companies, Rhodia companies, Nippon Polyurethane Industry Co., Ltd., minimizing technology Gao Zhen
Empty film evaporation method.But high vacuum film evaporation method, investment is excessive, process control needs are high, domestic at present to remove work to the method
Skill and plant issue never solve well, and the free isocyanate monomer content in most of domestic TDI curing agent is tight
Weight is exceeded, and TDI content is difficult to accomplish within 0.5%, mostly 1% or so.
A kind of film evaporation method processing solidification is all disclosed in Chinese patent literature CN1793194A, CN101717571A
The method of free toluene diisocyanate in agent addition product, it is by the way of multiple-effect thin film evaporation, at high temperature by true
Empty mode evaporates free toluene di-isocyanate(TDI), and the content of free TDI is between 0.15~0.5%.
Chinese patent literature CN 100439414C disclose a kind of preparation method of low-free TDI trimer curing agent,
It includes：By in TDI, solvent S, catalyst A input reactors, antioxidant and long-chain alcohol are added, heating and thermal insulation, detects nco value；
When nco value reaches 20~40%, Phase transfer solvent X and catalyst B is added, when nco value reaches 10~15%, adds resistance
Poly- agent stopped reaction；Supplementing solvent S, it is evaporated under reduced pressure and removes Phase transfer solvent X.Wherein solvent S be ethyl acetate, butyl acetate,
And its mixture；Phase transfer solvent X is petroleum ether, dimethyl carbonate, normal hexane, thiacyclohexane or its any mixture；Catalyst
A, catalyst B is all lithium acetate, KOH, NaOH, tributylphosphine, triethylenediamine and its any mixture；Obtained product
For TDI tripolymers, 45% ＜ containing free TDI content 0.5% admittedly.The method is the improved process of solvent extraction, unreacted trip
Free isocyanate monomer-soluble solution in hydrocarbon mixture (such as petroleum ether, dimethyl carbonate, n-hexane, hexamethylene benzene or its mixture),
And curing agent polymer is then unable to solution modeling in bottom, then on upper strata, mixing hydrocarbon solvent continues to add catalyst reaction, still
It is difficult to which its reaction of control, easily produces high polymer, or even gel in the case of stirring in a kettle；It is lower free without stirring
Isocyanate-monomer is difficult that reaction is complete.And ethyl acetate, butyl acetate low boiling point, azeotropic mixture easily is formed with hydrocarbon mixture,
Conventional vacuum distillation is difficult to remove hydrocarbon mixture, then constantly adds and waste substantial amounts of ethyl acetate, butyl acetate；And decompression is steamed
Temperature will be improved when evaporating, the time is grown, and the curing agent in kettle is not just known whether under catalyst, high temperature or curing agent；Separately
Containing ester, free monomer in the solvent distilled outside, it can neither use, can not discharge, storage is all problematic, therefore how
Recycling design is difficult.Both made method feasible, it is also not possible to eliminate the mixing hydrocarbon solvent remained in curing agent, eventually influence
Properties of product.
The content of the invention
A kind of the present invention is intended to provide preparation method of the TDI tripolymer light curing agent of low free monomer content.
The present invention is that TDI trimer curing agents are raw material using 2,4- toluene di-isocyanate(TDI)s, avoids 2,6- toluene two
NCO on isocyanates 2,6 left behind because steric hindrance is difficult to react；Conventional TDI trimer curing agents one
As it is all more crisp, pliability, glossiness and resistance to marring are all poor, and tolerance of the curing agent to toluene can be improved using long-chain alcohol
Degree and the fragility for improving film；With modified by polyether glycol TDI trimer curing agents can improve the pliability of film, glossiness and
Resistance to marring.
TDI trimer catalysts are using DMP-30, triazine (PC-41), double (dimethylaminoethyl) ethers, triethylene two
Amine, isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, zinc naphthenate or its mixture.
Later stage, the present invention used the hydroxy compounds n-butanol of small molecule free TDI to be converted into nontoxic material
The free TDI content of monomer that can be effectively reduced in the presence of catalyst in curing agent；Reduce the catalyst of free TDI content
For isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, zinc naphthenate one kind.
Because benzene kind solvent toxicity is big, the present invention is using the ethyl acetate, butyl acetate, dimethyl carbonate of low toxicity as anti-
The solvent and diluted solvent answered.
In order to solve the problems, such as techniques as described above, the present invention takes following technical scheme：The present invention relates to a kind of low trip
From the TDI tripolymer light curing agent of content of monomer, it is characterised in that：By weight percentage, its formula composition is：2,4- first
Phenylene diisocyanate 46.0~52.0%, PPG 1.0~2.0%, long-chain alcohol 3.0~5.0%, catalyst A 0.1~
0.3%th, n-butanol 1.5~3.0%, catalyst B 0.05~0.1%, polymerization inhibitor 0.15~0.30%, antioxidant 0.2~
0.4%th, solvent 40~52%；Described PPG is 210 polyethers, one kind of 220 polyethers；Described long-chain alcohol is bay
One or more of combinations of alcohol, 16 carbon alcohol, octadecanol；Described catalyst A is DMP-30, triazine (PC-41), double
A kind of and isooctyl acid potassium of (dimethylaminoethyl) ether or triethylenediamine, zinc Isoocatanoate, the one of potassium acetate or zinc naphthenate
The composition of kind and solvent；Described catalyst B is isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, the one or more of zinc naphthenate
Combination；Described polymerization inhibitor is one kind of phosphoric acid, hypophosphorous acid or chlorobenzoyl chloride；Described antioxidant be BHT, BHEB, DBEP,
1331st, 1010,1098 or UV-P one or more of combinations；Described solvent is ethyl acetate, butyl acetate, carbonic acid diformazan
One or more of combinations of ester；Described PPG, long-chain alcohol, n-butanol or solvent is beforehand with dewater treatment.
The present invention proposes a kind of preparation method of the TDI tripolymer light curing agent of low free monomer content, and its feature exists
In：Comprise the following steps：
1), 2,4 toluene diisocyanate, PPG, long-chain alcohol, solvent are put into respectively by weight percentage
In reactor, lead to N2 protections, be warming up to 75~80 DEG C, after being incubated 0.5~1h, cool to 55 DEG C, what then addition had compounded urges
Agent A, control temperature start to detect NCO, detect a nco value every 0.5h afterwards after 55~65 DEG C are reacted 4h；
2), when the NCO of detection is 10 ± 0.5%, n-butanol and catalyst B are added, control temperature is at 55~60 DEG C；When
The NCO of detection adds polymerization inhibitor, antioxidant and diluted solvent at 7.5 ± 0.3%, stirs 0.5h, cools to 40 DEG C, sampling
Color (Fe-Co colorimetrics), solid content, viscosity, tolerance, nco value and free TDI value are determined, reaches the bag filter that discharges after requirement
Dress.
The TDI tripolymer light curing agent of low free monomer content produced by the present invention, technical target of the product are：Color
(Fe-Co)≤1, solid content be 50 ± 2%, nco value be 7.6 ± 0.3%, viscosity (apply -4 glasss) 25~35s, free TDI≤
0.5%th, toluene tolerance >=2, aromatic-free, there is environmental protection, scratch resistance is good, gloss is high, the transparency is good；With hydroxyl group
The polyurethane paint of assignment system has high glaze, high rigidity, high transparency, and paint film resistance to marring is good, levelability is good, richness height,
The features such as intermiscibility is wide, it is to be used for various bi-component polyester paints, polyurethane paint, decorative paint, plate paint, the bottoms such as woodenware, metal, plastics
The environment-friendlycuring curing agents such as paint.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1：
In synthesis reactor, based on formulation weight ratio, 18 parts of 210 polyethers, 40 parts of laruyl alcohol, butyl acetate 448 are sequentially added
Part, being warming up to 108 DEG C or so has backflow, and 2~3h of backflow is dehydrated, the cooling down if occurring in water knockout drum without the globule；When
When cooling to less than 40 DEG C, 465 parts of 2,4- toluene di-isocyanate(TDI)s are added, lead to N2 protections, are warming up to 75~80 DEG C, insulation 0.5
After~1h, 55 DEG C are cooled to, 1.6 parts of the catalyst A compounded by DMP-30, isooctyl acid potassium, butyl acetate is added, controls temperature
After 55~65 DEG C are reacted 4h, start to detect NCO, detect a nco value every 0.5h afterwards；When detection NCO 10 ±
When 0.5%, 0.4 part of 22 parts of n-butanol and isooctyl acid potassium catalyst are added, control temperature is at 55~60 DEG C；When the NCO of detection exists
When 7.5 ± 0.3%, stopping is passed through N2, adds 2.0 parts of chlorobenzoyl chloride, 3.0 parts of antioxidant BHEB and adds butyl acetate latting drown
To 50 ± 2% solid contents, 0.5h is stirred, 40 DEG C is cooled to, filters and packages.
Embodiment 2：
In synthesis reactor, based on formulation weight ratio, 15 parts of 220 polyethers, 42 parts of laruyl alcohol, butyl acetate 435 are sequentially added
Part, being warming up to 108 DEG C or so has backflow, and 2~3h of backflow is dehydrated, the cooling down if occurring in water knockout drum without the globule；When
When cooling to less than 40 DEG C, 476 parts of 2,4- toluene di-isocyanate(TDI)s are added, lead to N2 protections, are warming up to 75~80 DEG C, insulation 0.5
After~1h, 55 DEG C are cooled to, 1.8 parts of the catalyst A compounded by DMP-30, zinc naphthenate, butyl acetate is added, controls temperature
After 55~65 DEG C are reacted 4h, start to detect NCO, detect a nco value every 0.5h afterwards；When detection NCO 10 ±
When 0.5%, 0.6 part of 24 parts of n-butanol and zinc naphthenate catalyst are added, control temperature is at 55~60 DEG C when the NCO of detection exists
When 7.5 ± 0.3%, stopping is passed through N2, add 2.4 parts of phosphoric acid, 3.2 parts of antioxidant BHT and add butyl acetate latting drown to 50 ±
2% solid content, 0.5h is stirred, 40 DEG C is cooled to, filters and packages.
Embodiment 3：
In synthesis reactor, based on formulation weight ratio, 15 parts of 210 polyethers, 36 parts of 16 carbon alcohol, butyl acetate are sequentially added
434 parts, being warming up to 108 DEG C or so has backflow, and 2~3h of backflow is dehydrated, cooled but if occurring in water knockout drum without the globule；When
When cooling to less than 40 DEG C, 482 parts of 2,4- toluene di-isocyanate(TDI)s are added, lead to N2 protections, are warming up to 75~80 DEG C, insulation 0.5
After~1h, 55 DEG C are cooled to, adds 1.8 parts of the catalyst A compounded by PC-41, zinc Isoocatanoate, butyl acetate, control temperature exists
After 55~65 DEG C of reaction 4h, start to detect NCO, detect a nco value every 0.5h afterwards；When the NCO of detection is 10 ± 0.5%
When, 0.6 part of 25 parts of n-butanol and zinc Isoocatanoate catalyst are added, control temperature is at 55~60 DEG C；When detection NCO 7.5 ±
When 0.3%, stopping is passed through N, adds 2.6 parts of hypophosphorous acid, 3.0 parts of antioxidant 1010 and adds butyl acetate latting drown to 50 ± 2%
Solid content, 0.5h is stirred, 40 DEG C is cooled to, filters and packages.
Claims (2)
- A kind of 1. TDI tripolymer light curing agent of low free monomer content, it is characterised in that：By weight percentage, it is matched somebody with somebody Fang Zucheng is：2,4 toluene diisocyanate 46.0~52.0%, PPG 1.0~2.0%, long-chain alcohol 3.0~ 5.0%th, catalyst A0.1~0.3%, n-butanol 1.5~3.0%, catalyst B 0.05~0.1%, polymerization inhibitor 0.15~ 0.30%th, antioxidant 0.2~0.4%, solvent 40~52%；Described PPG is 210 polyethers, one kind of 220 polyethers； Described long-chain alcohol is one or more of combinations of laruyl alcohol, 16 carbon alcohol, octadecanol；Described catalyst A is DMP- 30th, one kind and isooctyl acid potassium, zinc Isoocatanoate, acetic acid of triazine (PC-41), double (dimethylaminoethyl) ethers or triethylenediamine A kind of composition of the and solvent of potassium or zinc naphthenate；Described catalyst B is isooctyl acid potassium, zinc Isoocatanoate, potassium acetate, cycloalkanes The one or more of combination of sour zinc；Described polymerization inhibitor is one kind of phosphoric acid, hypophosphorous acid or chlorobenzoyl chloride；Described antioxidant is BHT, BHEB, DBEP, 1331,1010,1098 or UV-P one or more of combinations；Described solvent alcohol or solvent is beforehand with Dewater treatment.
- 2. a kind of preparation method of the TDI tripolymer light curing agent of low free monomer content as claimed in claim 1, it is special Sign is：The preparation method, comprises the following steps：1) 2,4 toluene diisocyanate, PPG, long-chain alcohol, solvent, are put into reaction respectively by weight percentage In kettle, logical N 2 is protected, and is warming up to 75~80 DEG C, after being incubated 0.5~1h, cools to 55 DEG C, then adds the catalyst compounded A, control temperature start to detect NCO after reacting 4h at 55~65 DEG C, detect a nco value every 0.5h afterwards；2), when the NCO of detection is 10 ± 0.5%, n-butanol and catalyst B are added, control temperature is at 55~60 DEG C；Work as detection NCO at 7.6 ± 0.3%, add polymerization inhibitor, antioxidant and diluted solvent, stir 0.5h, cool to 40 DEG C, take measure face Color (Fe-Co colorimetrics), solid content, viscosity, tolerance, nco value and free TDI value, reach to discharge after requirement and filter and package.
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| CN201610852581.0A CN107868225A (en) | 2016-09-26 | 2016-09-26 | A kind of preparation method of the TDI tripolymer light curing agent of low free monomer content |
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