CN1084192A - A kind of polyurethane powdered paint curing agent and preparation thereof - Google Patents
A kind of polyurethane powdered paint curing agent and preparation thereof Download PDFInfo
- Publication number
- CN1084192A CN1084192A CN 92110431 CN92110431A CN1084192A CN 1084192 A CN1084192 A CN 1084192A CN 92110431 CN92110431 CN 92110431 CN 92110431 A CN92110431 A CN 92110431A CN 1084192 A CN1084192 A CN 1084192A
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- CN
- China
- Prior art keywords
- tolylene diisocyanate
- trimerization
- curing agent
- paint curing
- obturator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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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
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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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8074—Lactams
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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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
Landscapes
- 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 present invention relates to a kind of polyurethane powdered paint curing agent production method.It is to be raw material with the tolylene diisocyanate, through the partial monosomy polymerization, is that encapsulant carries out capping and can make solidifying agent with caprolactam/polyvalent alcohol again.Solidifying agent production method provided by the invention, technology is simple, and raw material is easy to get, product technology economic target advanced person.
Description
The present invention relates to a kind of polyurethane powdered paint curing agent and preparation method thereof.
As far back as the sixties masked isocyanate just begin to be applied to the coating manufacturing, as water-borne coatings, electrocoating paint, urethane baking finish etc.At coating industry, in order to reduce pollution, economize on resources, powder coating is progressively replacing traditional solvent based coating.Powder coating is a kind of solventless coatings, development is very rapid both at home and abroad at present, in existing powder coating kind, be film forming matter with the oh type polyester resin, be the polyurethane series powder coating kind of solidifying agent has crucial status with the blocked isocyanate.As the exploitation of the blocked isocyanate of solidifying agent, be subjected to people day by day and pay attention to.Blocked isocyanate at high temperature it can take off blind end bear again (NCO) group and and polyester resin in hydroxyl (OH) generation crosslinking reaction and forming is filmed.Therefore, the quality of solidifying agent performance directly influences the quality of coating.The external at present blocked isocyanate curing agent preparation method who produces mainly contains three kinds:
(1), polyisocyanates directly seals method: it is that encapsulant direct reaction with polyisocyanates and equivalent makes; Encapsulant commonly used has caprolactam, Diacetylmonoxime, compounds such as imidazoles; Reaction process is:
The product softening temperature that makes is too low, is difficult to pulverize produce pulvis (seeing the clear 52-3200 of JP), finds afterwards that some vulcabond of directly sealing can crystallization, and available xln is made the solidifying agent of polyurethane powder coating.
(2), the sealing method of isocyanate trimerization body: it is isocyanic ester to be heated to certain temperature generation trimerization reaction generate isocyanuric acid ester under the effect of catalyzer:
Isocyanurate ring is still very stable under higher temperature, and resistance toheat is good, and the powder paint solidifying agent that it and encapsulant reaction make has higher chemical resistance, thermotolerance, weather resisteant.Shortcoming be softening temperature up to 120 ℃, the powder process difficulty.But use triethylamine/-hydroxyethyl methyl hydrogen amine oxide makes catalyzer, makes isophorone diisocyanate part trimerization rear enclosed, can improve processing characteristics (consulting US4252923).
(3), isocyanic ester and polyvalent alcohol affixture sealing method.It is by the NCO/OH=2-3(mol ratio with excessive polyisocyanates and polyvalent alcohol) react the affixture of formation, again with encapsulant with the end reaction-sealing of NCO base, also can isocyanic ester is earlier partially enclosed, again with polyvalent alcohol generation addition reaction.（US4125491，US3931117）
More than in three kinds of methods, the method for directly sealing is fairly simple, but product comminution ratio difficulty; Isocyanic ester/polyvalent alcohol affixture sealing method, the product mechanicalness, gloss is better, and it is convenient to pulverize, but thermotolerance is relatively poor; Isophorone diisocyanate part tripolymer sealing method, then product can improve thermotolerance, and coating quality is better, is raw material but only limit to isophorone diisocyanate at present, and raw material sources are limited.
The objective of the invention is to design a kind of new solidifying agent that is easy to pulverize, it and urethane resin powder formulated coating, filming has better heat-resisting, mechanicalness and glossiness preferably.
The present invention reacts the product that makes with tolylene diisocyanate and part tripolymer [three (the different perester radical of toluene) isocyanuric acid ester] thereof and hexanolactam encapsulant or hexanolactam/polyvalent alcohol compound closure agent.The present invention contains three (toluene diisocyanate base) isocyanuric acid ester obturator 60-80%, is preferably 70 ± 5%, and tolylene diisocyanate obturator 20-40% is preferably 30 ± 5%, hexanolactam/polyvalent alcohol=10/0-2.
The capping of three (toluene diisocyanate base) isocyanuric acid esters and hexanolactam:
Tolylene diisocyanate and hexanolactam capping:
Polyvalent alcohol can adopt propylene glycol, and 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, glycol ether is an example with the propylene glycol, and Blocking of Isocyanates is reacted:
The preparation method:
Take by weighing a certain amount of tolylene diisocyanate (TDI) and add in the reactor, start and stir, and material is warmed to 65-70 ℃, add the catalyzer of reaction solution total amount 0.1-0.2% then; Catalyzer can be selected three (dimethylamino methyl) phenol (DMP-30) or cobalt naphthenate for use, or triethylene diamine; Trimerization reaction is thermopositive reaction, should note controlled temperature in the reaction process at 70-75 ℃, isothermal reaction 2-4 hour; Termination reaction when material trimerization degree reaches 60-80% (this moment, solution still contained the tolylene diisocyanate monomer of 20-40%); Take by weighing a certain amount of caprolactam crystal and glycol ether (or propylene glycol then, 1,3-butyleneglycol) heats melting by in the given pace adding tripolymer mixed solution, heat up while feeding in raw material, when adding encapsulant, feed liquid will be raised to about 140-160 ℃, constant temperature 30-60 minute then, make capping complete.Cooling, the product that obtains is lurid solid.This solid phase prod contains free NCO group 0-3%, effective NCO group 13-15%, three (toluene diisocyanate base) isocyanuric acid ester closure 60-80% wherein, tolylene diisocyanate closure 20-40%.
Embodiment 1:
With 610g(3.5mol) tolylene diisocyanate adds in the jacket reactor.After being preheated to 65 ℃, add the toluene solution (concentration 200mg/ml) of 4.5mlDMP-30 catalyzer.Because the trimerization reaction heat release, temperature of charge rises to 70-75 ℃ very soon, descends subsequently, and the control temperature of charge reacted 3-4 hour about 70 ℃.When the NCO of reactant content drops to 29-30%, be warmed up to 120 ℃ and make catalyst deactivation, trimerization reaction stops.
With 436g(3.85mol) hexanolactam, after 18.6g(0.175mol) glycol ether places the feed hopper heat fused, in about 2.0-2.5 hour time, be added drop-wise in the reactor, make temperature of charge progressively bring up to 160 ℃ simultaneously.Dropwise, holding temperature reaction 0.5 hour obtains the light yellow solid product.Its free NCO content 0.90%, effectively NCO content 14.4%.
Embodiment 2:
By example 1 tolylene diisocyanate was carried out trimerization reaction 2-3 hour, when the NCO of reactant content drops to 31-32, add the 0.3g Benzoyl chloride trimerization reaction is stopped, be warmed up to 120 ℃ then.
With 436g(3.85mol) hexanolactam, after 37.1g(0.35mol) glycol ether places the feed hopper fusing, in 2-2.5 hour time, be added drop-wise in the reactor.Make temperature of reaction progressively bring up to 150 ℃ simultaneously, dropwise, holding temperature reaction 0.5 hour obtains its free NCO content 1.2% of light yellow solid product, effectively NCO content 14%
Embodiment 3-embodiment 5
Table 1 is listed three the batching composition and the results that prepare blocked isocyanate curing agent by said process
Table 1
The TDI CaL DEG catalyzer Benzoyl chloride effective NCO% of NCO% that dissociates
Embodiment 3 610 476-4.5 0.3 0.69 14.0
Embodiment 4 610 436 18.6 4.5 0.3 0.50 13.9
Embodiment 5 610 436 37.1 3.0-0.25 13.7
(TDI CAL DEG unit is a milliliter for gram catalyzer unit)
Claims (3)
1, a kind of polyurethane powdered paint curing agent is characterized in that containing three (toluene diisocyanate base) isocyanuric acid ester obturator 60-80%, tolylene diisocyanate obturator 20-40%.
2, according to the described solidifying agent of claim 1, it is characterized in that containing three (toluene diisocyanate base) isocyanuric acid ester closure 70 ± 5%, contain tolylene diisocyanate obturator 30 ± 5%.
3, a kind of polyurethane powdered paint curing agent preparation method comprises tolylene diisocyanate polymerization process and tolylene diisocyanate trimerization mixed solution closing step;
(a), polymerization process: the material tolylene diisocyanate is added reactor, and adds the catalyzer DMP-30 of material gross weight 0.1～0.2%, at 70～75 ℃ of following stoichiometric numbers hour, termination reaction when the trimerization degree reaches 60～80%;
(b), closing step: take by weighing encapsulant hexanolactam (or compound closure agent hexanolactam/polyvalent alcohol) adding tolylene diisocyanate trimerization mixed solution with tolylene diisocyanate trimerization mixed solution equivalent, reacted 30～60 minutes down at 140～160 ℃, be cooled to normal temperature then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110431 CN1084192A (en) | 1992-09-18 | 1992-09-18 | A kind of polyurethane powdered paint curing agent and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110431 CN1084192A (en) | 1992-09-18 | 1992-09-18 | A kind of polyurethane powdered paint curing agent and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1084192A true CN1084192A (en) | 1994-03-23 |
Family
ID=4944813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92110431 Pending CN1084192A (en) | 1992-09-18 | 1992-09-18 | A kind of polyurethane powdered paint curing agent and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1084192A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100572472C (en) * | 2008-01-04 | 2009-12-23 | 扬州三得利化工有限公司 | Polyester resin powder coating curing agent |
| US9637857B2 (en) | 2011-06-30 | 2017-05-02 | Electrolux Home Products Corporation N.V. | Laundry washing machine |
| CN114276520A (en) * | 2021-12-08 | 2022-04-05 | 万华化学集团股份有限公司 | Blocked polyisocyanate composition and preparation method and application thereof |
-
1992
- 1992-09-18 CN CN 92110431 patent/CN1084192A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100572472C (en) * | 2008-01-04 | 2009-12-23 | 扬州三得利化工有限公司 | Polyester resin powder coating curing agent |
| US9637857B2 (en) | 2011-06-30 | 2017-05-02 | Electrolux Home Products Corporation N.V. | Laundry washing machine |
| CN114276520A (en) * | 2021-12-08 | 2022-04-05 | 万华化学集团股份有限公司 | Blocked polyisocyanate composition and preparation method and application thereof |
| CN114276520B (en) * | 2021-12-08 | 2023-09-19 | 万华化学集团股份有限公司 | Blocked polyisocyanate composition and preparation method and application thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |