CN105131247A - High-flexibility low-free TDI trimer curing agent and preparation method thereof - Google Patents

High-flexibility low-free TDI trimer curing agent and preparation method thereof Download PDF

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Publication number
CN105131247A
CN105131247A CN201510429805.2A CN201510429805A CN105131247A CN 105131247 A CN105131247 A CN 105131247A CN 201510429805 A CN201510429805 A CN 201510429805A CN 105131247 A CN105131247 A CN 105131247A
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alcohol
curing agent
minutes
tdi
trimer curing
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曾晋
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SHUNDE HONGCHANG COATING CO Ltd FOSHAN CITY
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SHUNDE HONGCHANG COATING CO Ltd FOSHAN CITY
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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
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a high-flexibility low-free TDI trimer curing agent which is prepared from following components, by weight, 38-72% of TDI, 0.05-0.2% of an anti-oxidizing agent, 0.1-0.25% of a catalyst, 0.04-0.15% of a polymerization inhibitor, 1-4% of long-chain fatty alcohol and 25-60% of a solvent, wherein the TDI is composed by mixing 80% by weight of 2,4-toluene diisocyanate and 20% by weight of 2,6-toluene diisocyanate. The invention also discloses a preparation method of the TDI trimer curing agent. The TDI trimer curing agent is low in viscosity, is low in free TDI content, is high in flexibility, is easy to flat, is stable in storage, is high in tolerance degree of dimethylbenzene, is goon in compatibility with resin, can be cured rapidly at normal temperature and is good in paint film adhesive force.

Description

A kind of high-flexibility low-free TDI trimer curing agent and preparation method thereof
Technical field
The present invention relates to a kind of TDI trimer curing agent and preparation method thereof, specifically a kind of high-flexibility low-free TDI trimer curing agent and preparation method thereof.
Background technology
Polyurethane coating consumption in furniture and house decoration is large.Its component is allocated based on the hydroxyl materials such as Synolac, vibrin and acrylic resin, and another component is the material containing NCO group, also known as polyurethane curing agent.Polyurethane coating is very swift and violent in the development of China, is the maximum kind of solvent based coating, and occupies dominant position in coatings for furniture.The paint film of polyurethane coating has the advantages such as hardness is high, good toughness, chemical-resistant strong, fast drying.
The main component of polyurethane elastomer is polyurethane prepolymer, and prepolymer is reacted by polyether glycol and polyisocyanates and forms, and current polyisocyanates is tolylene diisocyanate (TDI) and diphenylmethanediisocyanate (MDI) mainly.In the polyurethane prepolymer structure of China, TDI type prepolymer accounting more than 90%.Containing a certain amount of unreacted TDI in finished prepolymer, these TDI can evaporate in air in follow-up operating process.
Because the vapour pressure (being 1.33Pa when 20 DEG C) of TDI monomer is higher, toxicity is larger, in highly volatile to environment, human body is damaged in process of production, therefore European Community's rules and regulations, when sticking on " poisonous " label containing during 1 ~ 7% free TDI on packaging vessel in TDI type prepolymer product; Free TDI content be 0.1 ~ 1% Product labelling on must put on " being harmful to " mark; TDI content lower than 0.1% then without the need to danger warning label.
Abroad from the sixties in last century just the research and development of this technology, and achieve remarkable effect.The domestic work starting this respect in the early 1990s, useful exploration has been carried out in small molecules reaction method, solvent extration and azeotropic distn etc., and achieve certain progress, but also only resting on laboratory stage, in home products, TDI content is still 2 ~ 7%.
TDI tripolymer generates six-membered ring structure by the TDI self-polymerization of three molecules, and compared with TDI monomer, TDI tripolymer has that volatility is little, functionality advantages of higher.The trimerical six-ring of TDI is a kind of stiffening ring, has higher polarity, and this just makes TDI tripolymer can only be dissolved in some intensive polar solvents, has higher selectivity when matching with hydroxy resin, and poor to the wettability of pigment; Therefore all there is the shortcomings such as poor compatibility in the existing numerous TDI tripolymer in market, affects the transparency of paint film and ornamental, seriously limit the use of TDI tripolymer in bicomponent polyurethane coating.
TDI trimer curing agent on the market, general solid content 50%, free TDI content≤1.5%, clear for supporting dumb light, paint film flexibility is at more than 5mm, impact≤10cm, mainly there is the problems such as free TDI content is higher, the feature of environmental protection is poor, and after solidifying agent participation film forming, paint film is more crisp, sticking power is low, easily causes and comes off.Therefore development & production high-flexibility low-free TDI trimer curing agent is significant.
Summary of the invention
The object of this invention is to provide the low free TDI trimer curing agent of a kind of high-flexibility.
Another object of the present invention is to provide the preparation method of this TDI trimer curing agent.
For achieving the above object, the present invention by the following technical solutions:
A kind of high-flexibility low-free TDI trimer curing agent, by weight percentage, by 38 ~ 72% TDI, 0.05 ~ 0.2% oxidation inhibitor, 0.1 ~ 0.25% catalyzer, the stopper of 0.04 ~ 0.15%, the long chain aliphatic alcohol of 1 ~ 4% and 25 ~ 60% solvent prepare and obtain.
Further, described TDI is mixed by the 2,4 toluene diisocyanate of 80wt% and 2, the 6-tolylene diisocyanates of 20wt%.
Further, described oxidation inhibitor is at least one in 2,6 ditertiary butyl p cresol, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester and four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Further, described catalyzer is at least one in trialkyl phosphine, N, N-dimethyl benzylamine, 2,4,6-tri-(dimethylamino methyl) phenol and triethylene diamine.
Further, described stopper is at least one in Benzoyl chloride, phosphoric acid, methyl-sulfate and methyl tosylate.
Further, described long chain aliphatic alcohol is at least one in the fatty alcohol of 12 ~ 18 carbon atoms.
Further, the fatty alcohol of described 12 ~ 18 carbon atoms is C 12~ C 14fatty alcohol, C 14~ C 16fatty alcohol or C 16~ C 18fatty alcohol.
Further, the fatty alcohol of described 12 ~ 18 carbon atoms is lauryl alcohol, 1-tridecyl alcohol, 1-tetradecanol, 1-pentadecylic alcohol, hexadecanol, cis-9-alkene n-Hexadecane-1-alcohol, 1-n-heptadecane alcohol, stearyl alcohol, isooctadecanol, anti-oleyl alcohol, oleyl alcohol, sub-oleyl alcohol, linolenyl alcohol or ricinoleyl alcohol.
Further, described solvent is at least one in N-BUTYL ACETATE, vinyl acetic monomer, propylene glycol monomethyl ether acetate, toluene, dimethylbenzene and methylcarbonate.
A kind of method preparing above-mentioned high-flexibility low-free TDI trimer curing agent, first drop into TDI, heat to 45 ~ 60 DEG C, add oxidation inhibitor and catalyzer, maintain the temperature at 55 ~ 70 DEG C of reactions 30 ~ 60 minutes, add the esters solvent of 5 ~ 15wt%, continue reaction adds 5 ~ 15wt% esters solvent after 30 ~ 60 minutes, continue reaction 30 ~ 60 minutes, add the esters solvent of 10 ~ 20wt%, be incubated 1 ~ 2 hour, sampling detection-nco value, stopper is added immediately when-NCO content is at 9 ~ 17wt%, within 20 ~ 30 minutes, long chain aliphatic alcohol is added again 55 ~ 68 DEG C of insulations, react 30 ~ 60 minutes, then the esters solvent of 5 ~ 10wt% is added, cool to 45 DEG C with bottom discharge.
The present invention has following beneficial effect:
The present invention adds long chain aliphatic alcohol in TDI trimer curing agent preparation process, and is added in batches by solvent, solves the defect that currently available products exists, one is make free TDI content reduction more, reduce volatilization, make product more environmental protection, be conducive to the healthy of the producer and user; Two is in trimerical structure, and after the product after polymerization and long chain aliphatic alcohol react, can reduce the cracking behavior of paint film, strengthen impact resistance, reduce fragility, snappiness improves; Three is that viscosity is low, and solve the lower but problem of the product package stability difference that viscosity is high again of free TDI content on the market, product of the present invention possesses low-free TDI content and low viscosity simultaneously, fine properties; Four is that product of the present invention and resin compatible are good, and dimethylbenzene tolerance is high, and film clarity is good, rapid solidification under normal temperature, and sticking power is good, easy delustring.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1
First drop into the TDI(of 49wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 45 DEG C, add the oxidation inhibitor (2 of 0.1wt%, 6-ditertbutylparacresol propionic acid] pentaerythritol ester) and the catalyzer (trialkyl phosphine) of 0.1wt%, maintain the temperature at 55 DEG C of reactions 30 minutes, add the N-BUTYL ACETATE of 10wt%, continue reaction adds 13wt% N-BUTYL ACETATE after 30 minutes, continue reaction 30 minutes, add the vinyl acetic monomer of 18wt%, be incubated 1 hour, sampling detection-nco value, the stopper (Benzoyl chloride) of 0.04wt% is added immediately when-NCO content is at 11.8wt%, the C of 3wt% within 20 minutes, is added again 55 DEG C of insulations 12~ C 14fatty alcohol, reacts 30 minutes, then adds the N-BUTYL ACETATE of 6.76wt%, cool to 45 DEG C with bottom discharge.
embodiment 2
First drop into the TDI(of 48wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 60 DEG C, add the oxidation inhibitor (three (2 of 0.15wt%, 4-di-tert-butyl-phenyl) phosphorous acid ester) and the catalyzer (N of 0.12wt%, N-dimethyl benzylamine), maintain the temperature at 70 DEG C of reactions 60 minutes, add the propylene glycol monomethyl ether acetate of 10wt%, continue reaction adds 15wt% vinyl acetic monomer after 60 minutes, continue reaction 60 minutes, add the toluene of 15wt%, be incubated 2 hours, sampling detection-nco value, the stopper (phosphoric acid) of 0.05wt% is added immediately when-NCO content is at 11.6wt%, the lauryl alcohol of 2wt% within 30 minutes, is added again 68 DEG C of insulations, react 60 minutes, then the vinyl acetic monomer of 9.68wt% is added, cool to 45 DEG C with bottom discharge.
embodiment 3
First drop into the TDI(of 49wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add oxidation inhibitor (four [β-(3 of 0.15wt%, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester) and the catalyzer (2 of 0.13wt%, 4, 6-tri-(dimethylamino methyl) phenol), maintain the temperature at 60 DEG C of reactions 40 minutes, add the N-BUTYL ACETATE of 12wt%, continue reaction adds 13wt% vinyl acetic monomer after 40 minutes, continue reaction 40 minutes, add the dimethylbenzene of 16wt%, be incubated 1.5 hours, sampling detection-nco value, the stopper (methyl-sulfate) of 0.055wt% is added immediately when-NCO content is at 11.7wt%, the C of 1wt% within 25 minutes, is added again 60 DEG C of insulations 16~ C 18fatty alcohol, reacts 45 minutes, then adds the propylene glycol monomethyl ether acetate of 8.665wt%, cool to 40 DEG C of dischargings.
embodiment 4
First drop into the TDI(of 46wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 55 DEG C, add the oxidation inhibitor (2 of 0.12wt%, 6-ditertbutylparacresol) and the catalyzer (triethylene diamine) of 0.11wt%, maintain the temperature at 65 DEG C of reactions 45 minutes, add the propylene glycol monomethyl ether acetate of 10wt%, continue reaction adds 10wt% vinyl acetic monomer after 45 minutes, continue reaction 50 minutes, add the N-BUTYL ACETATE of 20wt%, be incubated 1.8 hours, sampling detection-nco value, the stopper (methyl tosylate) of 0.045wt% is added immediately when-NCO content is at 11 ~ 12wt%, the 1-tetradecanol of 4wt% within 25 minutes, is added again 65 DEG C of insulations, react 50 minutes, then the dimethylbenzene of 9.725wt% is added, cool to 35 DEG C of dischargings.
embodiment 5
First drop into the TDI(of 47.5wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add the oxidation inhibitor (three (2 of 0.13wt%, 4-di-tert-butyl-phenyl) phosphorous acid ester) and the catalyzer (trialkyl phosphine) of 0.1wt%, maintain the temperature at 60 DEG C of reactions 35 minutes, add the N-BUTYL ACETATE of 10wt%, continue reaction adds 14wt% N-BUTYL ACETATE after 55 minutes, continue reaction 30 ~ 60 minutes, add the toluene of 18wt%, be incubated 1.2 hours, sampling detection-nco value, the stopper (Benzoyl chloride) of 0.06wt% is added immediately when-NCO content is at 11 ~ 12wt%, the 1-pentadecylic alcohol of 2.5wt% within 28 minutes, is added again 62 DEG C of insulations, react 55 minutes, then the N-BUTYL ACETATE of 7.71wt% is added, cool to 45 DEG C with bottom discharge.
embodiment 6
First drop into the TDI(of 38wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add oxidation inhibitor (four [β-(3 of 0.05wt%, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester) and the catalyzer (2 of 0.25wt%, 4, 6-tri-(dimethylamino methyl) phenol and N, the each 0.125wt% of N-dimethyl benzylamine), maintain the temperature at 60 DEG C of reactions 45 minutes, add the methylcarbonate of 15wt%, continue reaction adds 15wt% dimethylbenzene after 45 minutes, continue reaction 50 minutes, add the propylene glycol monomethyl ether acetate of 20wt%, be incubated 2 hours, sampling detection-nco value, the stopper (phosphoric acid) of 0.15wt% is added immediately when-NCO content is at 9wt%, the C of 1.55wt% within 25 minutes, is added again 62 DEG C of insulations 12~ C 14fatty alcohol, reacts 45 minutes, then adds the methylcarbonate of 10wt%, cool to 45 DEG C with bottom discharge.
embodiment 7
First drop into the TDI(of 72wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add the oxidation inhibitor (2 of 0.2wt%, 6-ditertbutylparacresol) and the catalyzer (N of 0.2wt%, N-dimethyl benzylamine), maintain the temperature at 60 DEG C of reactions 45 minutes, add the propylene glycol monomethyl ether acetate of 5wt%, continue reaction adds 5wt% methylcarbonate after 45 minutes, continue reaction 45 minutes, add the esters solvent toluene of 10wt%, be incubated 1.5 hours, sampling detection-nco value, the stopper (methyl-sulfate) of 0.1wt% is added immediately when-NCO content is at 17wt%, the stearyl alcohol of 2.5wt% within 25 minutes, is added again 60 DEG C of insulations, react 45 minutes, then the toluene of 5wt% is added, cool to 45 DEG C with bottom discharge.
embodiment 8
First drop into the TDI(of 60wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add the oxidation inhibitor (three (2 of 0.1wt%, 4-di-tert-butyl-phenyl) phosphorous acid ester) and the catalyzer (triethylene diamine) of 0.15wt%, maintain the temperature at 60 DEG C of reactions 45 minutes, add the vinyl acetic monomer of 8wt%, continue reaction adds 10wt% vinyl acetic monomer after 45 minutes, continue reaction 45 minutes, add the methylcarbonate of 10wt%, be incubated 1.5 hours, sampling detection-nco value, the stopper (methyl tosylate) of 0.15wt% is added immediately when-NCO content is at 14wt%, the oleyl alcohol of 1.6wt% within 25 minutes, is added again 60 DEG C of insulations, react 45 minutes, then the propylene glycol monomethyl ether acetate of 10wt% is added, cool to 45 DEG C with bottom discharge.
embodiment 9
First drop into the TDI(of 50wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add oxidation inhibitor (four [β-(3 of 0.05wt%, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester) and the catalyzer (trialkyl phosphine and each 0.1wt% of triethylene diamine) of 0.2wt%, maintain the temperature at 60 DEG C of reactions 45 minutes, add the N-BUTYL ACETATE of 10wt%, continue reaction adds 14wt% esters solvent dimethylbenzene after 45 minutes, continue reaction 45 minutes, add the propylene glycol monomethyl ether acetate of 16wt%, be incubated 1.5 hours, sampling detection-nco value, stopper (the Benzoyl chloride of 0.05wt% is added immediately when-NCO content is at 11 ~ 12wt%, phosphoric acid, methyl-sulfate and methyl tosylate), the C of 3.6wt% within 25 minutes, is added again 60 DEG C of insulations 14~ C 16fatty alcohol, reacts 45 minutes, then adds the methylcarbonate of 6wt%, cool to 45 DEG C with bottom discharge.
embodiment 10
First drop into the TDI(of 40wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate 20%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add the oxidation inhibitor (2 of 0.15wt%, 6-ditertbutylparacresol) and the catalyzer (N of 0.2wt%, N-dimethyl benzylamine), maintain the temperature at 60 DEG C of reactions 45 minutes, add the propylene glycol monomethyl ether acetate of 15wt%, continue reaction adds 14wt% methylcarbonate after 45 minutes, continue reaction 45 minutes, add the esters solvent vinyl acetic monomer of 20wt%, be incubated 1.5 hours, sampling detection-nco value, the stopper (methyl-sulfate) of 0.1wt% is added immediately when-NCO content is at 9.2wt%, the C of 2.55wt% within 25 minutes, is added again 60 DEG C of insulations 16~ C 18fatty alcohol, reacts 45 minutes, then adds the esters solvent dimethylbenzene of 8wt%, cool to 45 DEG C with bottom discharge.
comparative example 1
First drop into the TDI(of 46wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 55 DEG C, add the oxidation inhibitor (2 of 0.12wt%, 6-ditertbutylparacresol) and the catalyzer (triethylene diamine) of 0.11wt%, maintain the temperature at 65 DEG C of reactions 45 minutes, add the propylene glycol monomethyl ether acetate of 10wt%, the N-BUTYL ACETATE of 10wt% and the vinyl acetic monomer of 20wt%, be incubated 1.8 hours, sampling detection-nco value, the stopper (methyl tosylate) of 0.045wt% is added immediately when-NCO content is at 11 ~ 12wt%, the 1-tetradecanol of 4wt% within 25 minutes, is added again 65 DEG C of insulations, react 50 minutes, then the dimethylbenzene of 9.725wt% is added, cool to 35 DEG C of dischargings.
comparative example 2
First drop into the TDI(of 46.3wt% by 2 of 80wt%, 2 of 4-tolylene diisocyanate and 20wt%, 6-tolylene diisocyanate mixes), heat to 50 DEG C, add the oxidation inhibitor (three (2 of 0.13wt%, 4-di-tert-butyl-phenyl) phosphorous acid ester) and the catalyzer (trialkyl phosphine) of 0.1wt%, maintain the temperature at 60 DEG C of reactions 35 minutes, add the N-BUTYL ACETATE of 10wt%, continue reaction adds 14wt% N-BUTYL ACETATE after 55 minutes, continue reaction 30 ~ 60 minutes, add the toluene of 18wt%, be incubated 1.2 hours, sampling detection-nco value, the stopper (Benzoyl chloride) of 0.06wt% is added immediately when-NCO content is at 11 ~ 12wt%, the butanols of 2.5wt% within 28 minutes, is added again 62 DEG C of insulations, react 55 minutes, then the N-BUTYL ACETATE of 7.71wt% is added, cool to 45 DEG C with bottom discharge.
performance test
The TDI trimer curing agent of embodiment 1 ~ 5 and comparative example 1 ~ 2 is carried out performance test, and result is as shown in table 1:
The performance test results of table 1TDI trimer curing agent
As can be seen from Table 1, TDI trimer curing agent of the present invention-nco value is higher, solid content is high, and viscosity is low, free TDI content lower (≤0.7%), the tolerance of dimethylbenzene is higher (>=2.5), and in contrast product, solvent once adds by comparative example 1, comparative example 2 be micromolecular butanols but not long chain aliphatic alcohol, the free TDI content of products obtained therefrom is higher than the present invention product, and dimethylbenzene tolerance is also be not as good as product of the present invention.
Get the TDI trimer curing agent of the TDI trimer curing agent of 25wt% above-described embodiment 1 ~ 5 gained and comparative example 1 ~ 2, commercially available prod, the solidifying agent of 50% is mixed into respectively with affixture solidifying agent, carry out composite with half light clear finish, construction proportioning is main paint: solidifying agent: thinner=1:0.5:0.6 ~ 1, carry out performance test to gained paint film, result is as shown in table 2:
Table 2 paint film property test result
As can be seen from Table 2, the paint film property made with TDI trimer curing agent of the present invention is excellent, snappiness < 5mm(commercially available prod is 10mm), sticking power 0 grade (commercially available prod is 1 grade), hardness >=H(commercially available prod is HB), extinction is comparatively strong and stable, surface drying and do solid work time shorten (commercially available prod is 21min and 3.2h) under normal temperature, surface drying and the time of doing solid work of comparative example 1 product are longer than the present invention product, the snappiness of comparative example 2 product not as product of the present invention, and surface drying and the time of doing solid work longer than the present invention product.
In table 1,2 ,-NCO content detects with dibutylamine volumetry (HG/T2409-1992); Solidifying agent Free TDI adopts vapor-phase chromatography (GB/T18446-2009) to detect; The measuring method of dimethylbenzene tolerance is: the solidifying agent sample of precise 10.00g is in the beaker of drying, then in beaker, xylene solvent is dripped till occurring that white casse is no longer dissolved into transparence, record the quality of dimethylbenzene used, then the ratio of xylene mass and sample mass is the dimethylbenzene tolerance of solidifying agent, and its size can be used as the consistency size weighing solidifying agent and resin; Solids content is pressed GB/T1725-2007 and is detected, and sticking power is pressed GB/T9236-1998 and detected, and hardness is pressed GB/T6739-2006 and detected, and gloss is pressed GB/T9754-2007 and detected, and snappiness is pressed GB/T1731-93 and detected, and presses GB/T1728-1979 time of drying and detects.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly belongs to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.

Claims (10)

1. a high-flexibility low-free TDI trimer curing agent, it is characterized in that, by weight percentage, by 38 ~ 72% TDI, 0.05 ~ 0.2% oxidation inhibitor, 0.1 ~ 0.25% catalyzer, the stopper of 0.04 ~ 0.15%, the long chain aliphatic alcohol of 1 ~ 4% and 25 ~ 60% solvent prepare and obtain.
2. high-flexibility low-free TDI trimer curing agent according to claim 1, is characterized in that, described TDI is mixed by the 2,4 toluene diisocyanate of 80wt% and 2, the 6-tolylene diisocyanates of 20wt%.
3. high-flexibility low-free TDI trimer curing agent according to claim 1, it is characterized in that, described oxidation inhibitor is 2,6-ditertbutylparacresol, three (2,4-di-tert-butyl-phenyl) at least one in phosphorous acid ester and four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
4. high-flexibility low-free TDI trimer curing agent according to claim 1, is characterized in that, described catalyzer is at least one in trialkyl phosphine, N, N-dimethyl benzylamine, 2,4,6-tri-(dimethylamino methyl) phenol and triethylene diamine.
5. high-flexibility low-free TDI trimer curing agent according to claim 1, is characterized in that, described stopper is at least one in Benzoyl chloride, phosphoric acid, methyl-sulfate and methyl tosylate.
6. high-flexibility low-free TDI trimer curing agent according to claim 1, is characterized in that, described long chain aliphatic alcohol is at least one in the fatty alcohol of 12 ~ 18 carbon atoms.
7. high-flexibility low-free TDI trimer curing agent according to claim 6, is characterized in that, the fatty alcohol of described 12 ~ 18 carbon atoms is C 12~ C 14fatty alcohol, C 14~ C 16fatty alcohol or C 16~ C 18fatty alcohol.
8. high-flexibility low-free TDI trimer curing agent according to claim 6, it is characterized in that, the fatty alcohol of described 12 ~ 18 carbon atoms is lauryl alcohol, 1-tridecyl alcohol, 1-tetradecanol, 1-pentadecylic alcohol, hexadecanol, cis-9-alkene n-Hexadecane-1-alcohol, 1-n-heptadecane alcohol, stearyl alcohol, isooctadecanol, anti-oleyl alcohol, oleyl alcohol, sub-oleyl alcohol, linolenyl alcohol or ricinoleyl alcohol.
9. high-flexibility low-free TDI trimer curing agent according to claim 1, is characterized in that, described solvent is at least one in N-BUTYL ACETATE, vinyl acetic monomer, propylene glycol monomethyl ether acetate, toluene, dimethylbenzene and methylcarbonate.
10. prepare the method for high-flexibility low-free TDI trimer curing agent described in claim 1 for one kind, it is characterized in that, first drop into TDI, heat to 45 ~ 60 DEG C, add oxidation inhibitor and catalyzer, maintain the temperature at 55 ~ 70 DEG C of reactions 30 ~ 60 minutes, add the esters solvent of 5 ~ 15wt%, continue reaction adds 5 ~ 15wt% esters solvent after 30 ~ 60 minutes, continue reaction 30 ~ 60 minutes, add the esters solvent of 10 ~ 20wt%, be incubated 1 ~ 2 hour, sampling detection-nco value, stopper is added immediately when-NCO content is at 9 ~ 17wt%, within 20 ~ 30 minutes, long chain aliphatic alcohol is added again 55 ~ 68 DEG C of insulations, react 30 ~ 60 minutes, then the esters solvent of 5 ~ 10wt% is added, cool to 45 DEG C with bottom discharge.
CN201510429805.2A 2015-07-21 2015-07-21 High-flexibility low-free TDI trimer curing agent and preparation method thereof Pending CN105131247A (en)

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CN106084183A (en) * 2016-07-18 2016-11-09 华南理工大学 A kind of toluene diisocyanate trimer firming agent and preparation method thereof
CN107057034A (en) * 2017-03-17 2017-08-18 华南理工大学 A kind of low free light diisocyanate curing agent and preparation method thereof
CN109942783A (en) * 2019-02-22 2019-06-28 上海稻畑精细化工有限公司 A kind of high stability polyurethane curing agent and its preparation process
CN106084183B (en) * 2016-07-18 2019-07-16 华南理工大学 A kind of toluene diisocyanate trimer curing agent and preparation method thereof
CN110698628A (en) * 2019-09-29 2020-01-17 合肥科天水性科技有限责任公司 Novel solvent-free polyurethane resin and application thereof
CN110982045A (en) * 2019-11-21 2020-04-10 万华化学集团股份有限公司 Low-viscosity and low-color-number isocyanate curing agent, and preparation method and application thereof
CN116217888A (en) * 2023-02-24 2023-06-06 韶关东森合成材料有限公司 Trimer curing agent and preparation method thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084183A (en) * 2016-07-18 2016-11-09 华南理工大学 A kind of toluene diisocyanate trimer firming agent and preparation method thereof
CN106084183B (en) * 2016-07-18 2019-07-16 华南理工大学 A kind of toluene diisocyanate trimer curing agent and preparation method thereof
CN107057034A (en) * 2017-03-17 2017-08-18 华南理工大学 A kind of low free light diisocyanate curing agent and preparation method thereof
CN107057034B (en) * 2017-03-17 2020-02-18 华南理工大学 Low-free bright toluene diisocyanate curing agent and preparation method thereof
CN109942783A (en) * 2019-02-22 2019-06-28 上海稻畑精细化工有限公司 A kind of high stability polyurethane curing agent and its preparation process
CN110698628A (en) * 2019-09-29 2020-01-17 合肥科天水性科技有限责任公司 Novel solvent-free polyurethane resin and application thereof
CN110698628B (en) * 2019-09-29 2021-11-16 合肥科天水性科技有限责任公司 Solvent-free polyurethane resin and application thereof
CN110982045A (en) * 2019-11-21 2020-04-10 万华化学集团股份有限公司 Low-viscosity and low-color-number isocyanate curing agent, and preparation method and application thereof
CN110982045B (en) * 2019-11-21 2022-01-07 万华化学集团股份有限公司 Low-viscosity and low-color-number isocyanate curing agent, and preparation method and application thereof
CN116217888A (en) * 2023-02-24 2023-06-06 韶关东森合成材料有限公司 Trimer curing agent and preparation method thereof
CN116217888B (en) * 2023-02-24 2023-11-28 韶关东森合成材料有限公司 Trimer curing agent and preparation method thereof

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Application publication date: 20151209