CN1424367A - Preparation of dissolvable curing agent for tripolymer of toluene diisocyanate - Google Patents
Preparation of dissolvable curing agent for tripolymer of toluene diisocyanate Download PDFInfo
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- CN1424367A CN1424367A CN 02149704 CN02149704A CN1424367A CN 1424367 A CN1424367 A CN 1424367A CN 02149704 CN02149704 CN 02149704 CN 02149704 A CN02149704 A CN 02149704A CN 1424367 A CN1424367 A CN 1424367A
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- toluene diisocyanate
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Abstract
A high-compatibility trimer as solidifying agent for paint is prepared from toluene diisocyanate or its mixture, ester-type solvent aliphatic alcohol and isocyanate trimer catalyst through reacting between first three under protection of N2 at 30-80 deg.C for 1-6 hr while stirring, adding the last one, reacting, cooling to 50-100 deg.C, continuous reacting until the Wt pecentage of NCO is 7.4-8.4, and polymerizing inhititor, and cooling to lower than 40 deg.C.
Description
Technical Field
The invention relates to a preparation method of a toluene diisocyanate trimer curing agent used in the paint decoration industry.
Background
At present, the quick-drying toluene diisocyanate tripolymer of the paint widely used in the market is realized by the following ways: taking 2, 4-toluene diisocyanate as an example, the structural formula of the trimer is as follows:
toluene diisocyanate trimer is used in matte paint for quick drying, but has the following two disadvantages in use:
1. the paint is only suitable for the coating matt paint, but is not suitable for the bright paint, so that the wide use of the paint is limited;
2. poor compatibility, low xylene dilution rate, high cost and the need of using a large amount of true solvent during paint preparation.
Disclosure of Invention
The invention aims to provide a preparation method of a toluene diisocyanate trimer curing agent with good solubility aiming at the defects of the existing toluene diisocyanate trimer curing agent, so that the prepared toluene diisocyanate trimer curing agent has good solubility, and can be used for matte paint and bright paint.
The purpose of the invention is realized as follows: the raw materials and the dosage are (A) one toluene diisocyanate or the mixture of two toluene diisocyanates, 40-66 parts, (B) ester solvent with boiling point less than or equal to 200 ℃, 25-55 parts, (C) aliphatic alcohol containing 1-2 hydroxyl groups and with molecular weight of 60-200, 3-10 parts, (D) isocyanate trimerization catalyst, 0.009-0.014 parts, the parts are all parts by weight;
the preparation method comprises putting raw material A, B, C into a reaction kettle, stirring, and introducing N2And (2) performing protection reaction, namely stirring and reacting for 1-6 hours, preferably 2-4 hours at the temperature of 30-80 ℃, preferably 40-60 ℃, then adding the raw material D to continue the reaction, cooling, keeping at the temperature of 50-100 ℃, preferably 60-90 ℃, detecting the weight percentage content of free NCO groups, namely free cyanate ester groups, once every 1 hour, immediately adding an isocyanate trimerization inhibitor when the relative solid content is 50 percent and the weight percentage content of NCO is 7.4-8.4 percent, and cooling to the temperature below 40 ℃ to discharge.
In the invention, the raw material A is selected from one of the following materials: 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate. Preferably: 2, 4-toluene diisocyanate and the mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, wherein the weight percentage of the 2, 4-toluene diisocyanate is more than 80 percent.
In the invention, the raw material B is selected from one of the following materials: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl acetate and butyl acetate. Preferably: ethyl acetate, butyl acetate, ethyl acetate and butyl acetate.
In the invention, the raw material C is selected from one of the following materials: 1-propanol, 2-propanol, 1-butanol, 2-butanol, n-pentanol, 1-methylbutanol, 1-ethyl-1-propanol, n-octanol, 2-ethyl-1-hexanol, neopentyl glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-ethyl-1, 3-hexanediol, diethyl glycol, triethyl glycol, dipropylene glycol, tripropylene glycol. Preferably one of the following: 1-butanol, 2-butanol, n-pentanol, n-octanol, 2-ethyl-1-hexanol, neopentyl glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol.
The isocyanate trimerisation catalyst of the present invention is selected from one of the following: tributyl phosphine, trialkyl phosphine, tertiary amine and phenyl glycidyl ether, lead naphthenate, alkaline potassium salt or sodium salt or lithium salt, lithium salicylate and stannous isooctanoate, lithium isooctanoate and stannous isooctanoate or zinc isooctanoate. Preferably: tri-n-butylphosphine, tertiary amine plus phenyl glycidyl ether, lithium salicylate plus stannous isooctanoate.
The isocyanate trimerization inhibitor in the invention is selected from one of the following acidic substances: anhydrous hydrogen chloride, sulfuric acid, bis (2-ethylhexyl) hydrogen phosphate, benzoyl chloride, phosphoric acid, etc., in an amount of 2 times the equivalent amount of the isocyanate trimerization catalyst.
Compared with the traditional method for generating the toluene diisocyanate trimer by directly adding the trimerization catalyst to polymerize the toluene diisocyanate, the method has the following differences: the invention removes the nail in the reactantIn addition to benzene diisocyanate, aliphatic alcohol is introduced and reacts with toluene diisocyanate to generate addition product which can increase the compatibility of trimer curing agent in the systemAnd (4) acting. The product of the invention is prepared by two steps of reactions, firstly, aliphatic alcohol reacts with partial toluene diisocyanate to generate an addition product, and then the addition product is polymerized under the action of a trimerization catalyst to generate the product of the invention: first step of Second step of
The toluene diisocyanate trimer curing agent produced by the invention has the following advantages:
1. the applicability is wide, and the paint can be used in matte paint and bright paint;
2. the advantage is obvious, is used in the flat lacquer, can reach quick-drying, can improve the matte degree again, saves the flat powder, is used in the bright lacquer, has solved the problem that the bright lacquer dries slowly winter, does not lose the gloss again, has solved the bright lacquer and has used the ordinary quick-drying curing agent to reach the quick-drying purpose and the problem that appears losing the gloss.
3. The compatibility is good, the dilution rate of xylene is high, and can completely meet the requirements of true solvent content in common diluent, and the common quick-drying curing agent requires that a large amount of or all true solvents are required in paint-preparing diluent, so that the paint-preparing range of the product is wide, and the paint-preparing cost is low.
The following table illustrates the distinct advantages of the tolylene diisocyanate trimer curing agent obtained in the present invention in xylene dissolution and applicability to gloss paints, respectively. In the table, the toluene diisocyanate trimer curing agent with good intermiscibility obtained by the invention is abbreviated as '50T'; the standard toluene diisocyanate trimer curing agent sold in the market is abbreviated as IL 50; the common toluene diisocyanate curing agent is abbreviated as 'universal curing agent GB 50'.
Table one: comparison of xylene tolerances:
table two: effect of 50T on gloss lacquer:
| bright paint | 50T content (other is GB50) | IL50 content (others are GB50) | |||||
| 5％ | 10％ | 15％ | 5％ | 10％ | 15％ | ||
| Acrylic acid account 50％ Synthesis of alkyd Is 50 percent | Exterior dryness, min | 20 | 16 | 14 | 16 | 14 | 12 |
| Hard dry, h | 8 | 7 | 6 | 6 | 5 | 4 | |
| Gloss (60% | 105 | 105 | 100 | 98 | 90 | 86 | |
| Hardness (Pencil) | 2H | 2H | 2H | 2H | 2H | 2H | |
| Scratch resistance | Good wine | Good wine | Good wine | Good wine | Good wine | Good wine | |
The present invention is further illustrated by the following examples.
Detailed Description
In the following examples, the abbreviations for the starting materials are as follows:
TDI: a mixture containing 80% 2, 4-toluene diisocyanate and 20% 2, 6-toluene diisocyanate.
TBI: a mixture containing 90% 2, 4-toluene diisocyanate and 10% 2, 6-toluene diisocyanate.
The first embodiment is as follows:
in a device equipped with a stirrer, a thermometer and a tube N2A1000 ml four-necked flask was charged with 450g of TDI and 50g of 1-butanol, and further 330g of ethyl acetate, and the mixture was stirred, heated, and reacted at 70 ℃ for 1 hour. Then 0.080g of lithium salicylate and 0.0032g of lithium salicylate were addedAnd (3) stannous isooctanoate, wherein the reaction starts to release heat, the reaction is carried out at 90 ℃, the weight percentage content of free NCO groups is detected every 1 hour, when the weight percentage content of NCO is 9.6 percent and the solid content is 60 percent, 0.6g of benzoyl chloride is immediately added, and the temperature is reduced to 40 ℃ for discharging.
Example two:
the experimental procedure was the same as in the first example. In a device equipped with a stirrer, a thermometer and a tube N2Adding 375g of TDI, 29g of 2-butanol and 494g of butyl acetate into a protected 1000ml four-neck flask, stirring, heating, reacting for 3 hours at 60 ℃, then heating to 80 ℃, adding 0.12g of lithium salicylate and 0.004g of stannous isooctanoate, reacting at 80 ℃, detecting the weight percentage content of free NCO groups once every 1 hour, immediately adding 0.42g of benzoyl chloride when the weight percentage content of NCO is 7.5 percent and the solid content is 50 percent, cooling to 40 ℃, and discharging.
Example three:
the experimental procedure was the same as in the first example. In a device equipped with a stirrer, a thermometer and a tube N2Into a protected 1000ml four-necked flask, 515g of TBI, 77g of n-pentanol, 100g of ethyl acetate, and 98g of vinegar were chargedButyl acetate is stirred, heated and heated, reacted for 3.5 hours at 70 ℃, added with 0.076g of lithium salicylate and 0.002g of stannous isooctanoate, reacted for releasing heat, and reacted at 85 ℃ with heat preservation, the weight percentage content of free NCO groups is detected every 1 hour, when the weight percentage content of NCO is 11 percent and the solid content thereof is 75 percent, immediately added with 0.52g of benzoyl chloride, cooled to 40 ℃ and discharged.
Example four:
the experimental procedure was the same as in the first example. In a device equipped with a stirrer, a thermometer and a tube N2Into a 1000ml four-necked flask with a cap, 425g of 2, 4-tolylene diisocyanate, 35g of 1-methylbutanol and 310g of ethyl acetate were charged, heated with stirring, reacted at 60 ℃ for 3 hours, and then raisedHeating to 70 ℃, adding 0.07g of lithium salicylate and 0.02g of stannous isooctanoate, carrying out reaction heat release, carrying out heat preservation reaction at 80 ℃, detecting the weight percentage content of free NCO groups once every 1 hour, immediately adding 0.50g of benzoyl chloride when the weight percentage content of NCO is 9.3 percent and the solid content is 60 percent, cooling to 40 ℃, and discharging.
In the above examples, the weight percent of free NCO groups was determined by dibutylamine titration.
The foregoing merely illustrates the specific manner in which the invention may be practiced and the spirit and scope of the present invention is not limited to the foregoing examples.
Claims (11)
1. A preparation method of a toluene diisocyanate trimer curing agent with good phase solubility is characterized in that: the raw materials and the dosage are (A) one toluene diisocyanate or the mixture of two toluene diisocyanates, 40-66 parts, (B) ester solvent with boiling point less than or equal to 200 ℃, 25-55 parts, (C) aliphatic alcohol containing 1-2 hydroxyl groups and with molecular weight of 60-200, 3-10 parts, (D) isocyanate trimerization catalyst, 0.009-0.014 parts, the parts are all parts by weight;
the preparation method comprises putting raw material A, B, C into a reaction kettle, stirring, and introducing N2Protecting reaction, stirring and reacting for 1-6 hours at 30-80 ℃, adding the raw material D for continuous reaction, cooling and keeping the temperature atReacting at 50-100 deg.C, detecting the weight percentage content of free NCO group every 1 hr, when the relative solid content is 50% and the weight percentage content of NCO is 7.4-8.4%, immediately adding isocyanate trimerization inhibitor, cooling to below 40 deg.C and discharging.
2. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 1, wherein: the raw material A is selected from one of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate according to any proportion.
3. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 2, characterized in that: the raw material A is preferably 2, 4-toluene diisocyanate and a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, wherein the weight percentage of the 2, 4-toluene diisocyanate is more than 80%.
4. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 1, wherein: the raw material B is selected from one of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl acetate and butyl acetate in any mixture ratio.
5. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 4, wherein: the raw material B is preferably a mixture of ethyl acetate, butyl acetate, ethyl acetate and butyl acetate in any proportion.
6. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 1, wherein: the raw material C is selected from one of 1-propanol, 2-propanol, 1-butanol, 2-butanol, n-pentanol, 1-methylbutanol, 1-ethyl-1-propanol, n-octanol, 2-ethyl-1-hexanol, neopentyl glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-ethyl-1, 3-hexanediol, diethyl glycol, triethyl glycol, dipropylene glycol and tripropylene glycol.
7. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 6, wherein: the raw material C is preferably one of 1-butanol, 2-butanol, n-pentanol, n-octanol, 2-ethyl-1-hexanol, neopentyl glycol, 1, 2-propanediol, 1, 4-butanediol, and 1, 3-butanediol.
8. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 1, wherein: the isocyanate trimerization catalyst is selected from one of tributyl phosphine, trialkyl phosphine, tertiary amine and phenyl glycidyl ether, lead naphthenate, alkaline potassium salt or sodium salt or lithium salt, lithium salicylate and stannous isooctanoate, lithium isooctanoate and stannous isooctanoate or zinc isooctanoate.
9. The method for preparing a tolylene diisocyanatetrimer curing agent with good compatibility according to claim 8, wherein: the isocyanate trimerization catalyst is preferably tri-n-butyl phosphine, tertiary amine and phenyl glycidyl ether, lithium salicylate and stannous isooctanoate.
10. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 1, wherein: the isocyanate trimerization inhibitor is one of the following acidic substances, namely anhydrous hydrogen chloride, sulfuric acid, bis (2-ethylhexyl) hydrogen phosphate, benzoyl chloride, phosphoric acid and the like, and the equivalent amount of the isocyanate trimerization inhibitor is 2 times of that of the isocyanate trimerization catalyst.
11. The method for preparing a tolylene diisocyanate trimer curing agent with good compatibility according to claim 1, wherein: in the step, the raw material A, B, C is preferably stirred to react at 40-60 deg.C for 2-4 hr, and then the raw material D is added to continue the reaction, preferably at 60-90 deg.C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02149704 CN1186405C (en) | 2002-12-20 | 2002-12-20 | Preparation of dissolvable curing agent for tripolymer of toluene diisocyanate |
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| CN 02149704 CN1186405C (en) | 2002-12-20 | 2002-12-20 | Preparation of dissolvable curing agent for tripolymer of toluene diisocyanate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100439414C (en) * | 2006-09-30 | 2008-12-03 | 北京展辰化工有限公司 | Production of low-free TDI polyurethane curing agent, curing agent therefrom and its products |
| CN102718724A (en) * | 2012-03-14 | 2012-10-10 | 江苏天竹化工科技有限公司 | Preparation method of environment-friendly and light resistant isocyanate trimer curing agent |
| CN102718944A (en) * | 2012-06-07 | 2012-10-10 | 华南理工大学 | Preparation method of polyurethane trimer curing agent of low free isocyanate monomer |
| WO2014146522A1 (en) * | 2013-03-19 | 2014-09-25 | 万华化学（北京）有限公司 | Method for preparing tdi isocyanurate |
| CN104403085A (en) * | 2014-11-26 | 2015-03-11 | 广东东旭化学工业制造有限公司 | European standard-reached low free matte trimer curing agent and preparation method thereof |
| CN104592483A (en) * | 2015-01-14 | 2015-05-06 | 嘉宝莉化工集团股份有限公司 | Environment-friendly polyurethane curing agent as well as preparation method and application of curing agent |
| CN105131249A (en) * | 2015-09-17 | 2015-12-09 | 广东聚盈化工有限公司 | High-tolerance low-free TDI tripolymer and preparation method thereof |
| CN105315433A (en) * | 2015-11-09 | 2016-02-10 | 华南理工大学 | Low-free high-compatibility toluene diisocyanate trimer curing agent and preparation method thereof |
| 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 |
| CN110092888A (en) * | 2019-04-26 | 2019-08-06 | 同济大学 | Fluorine-containing isocyanate curing agent and its preparation method and application |
| CN115850656A (en) * | 2022-12-31 | 2023-03-28 | 韶关东森合成材料有限公司 | High-compatibility low-free trimer and preparation method thereof |
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| CN100398525C (en) * | 2005-11-15 | 2008-07-02 | 中国科学院广州化学研究所 | Toluene diisocyanate trimer preparation method |
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- 2002-12-20 CN CN 02149704 patent/CN1186405C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100439414C (en) * | 2006-09-30 | 2008-12-03 | 北京展辰化工有限公司 | Production of low-free TDI polyurethane curing agent, curing agent therefrom and its products |
| CN102718724A (en) * | 2012-03-14 | 2012-10-10 | 江苏天竹化工科技有限公司 | Preparation method of environment-friendly and light resistant isocyanate trimer curing agent |
| CN102718944A (en) * | 2012-06-07 | 2012-10-10 | 华南理工大学 | Preparation method of polyurethane trimer curing agent of low free isocyanate monomer |
| CN102718944B (en) * | 2012-06-07 | 2014-04-02 | 华南理工大学 | Preparation method of polyurethane trimer curing agent of low free isocyanate monomer |
| US9593089B2 (en) | 2013-03-19 | 2017-03-14 | Wanhua Chemical (Beijing) Co., Ltd. | Process for preparing TDI isocyanurate |
| WO2014146522A1 (en) * | 2013-03-19 | 2014-09-25 | 万华化学（北京）有限公司 | Method for preparing tdi isocyanurate |
| CN104403085A (en) * | 2014-11-26 | 2015-03-11 | 广东东旭化学工业制造有限公司 | European standard-reached low free matte trimer curing agent and preparation method thereof |
| CN104592483A (en) * | 2015-01-14 | 2015-05-06 | 嘉宝莉化工集团股份有限公司 | Environment-friendly polyurethane curing agent as well as preparation method and application of curing agent |
| CN104592483B (en) * | 2015-01-14 | 2017-06-06 | 嘉宝莉化工集团股份有限公司 | Environment-protecting polyurethane curing agent and its preparation method and application |
| CN105131249A (en) * | 2015-09-17 | 2015-12-09 | 广东聚盈化工有限公司 | High-tolerance low-free TDI tripolymer and preparation method thereof |
| CN105315433A (en) * | 2015-11-09 | 2016-02-10 | 华南理工大学 | Low-free high-compatibility toluene diisocyanate trimer curing agent and preparation method thereof |
| CN105315433B (en) * | 2015-11-09 | 2018-06-29 | 华南理工大学 | Low-free toluene diisocyanate trimer with high compatibility curing agent and preparation method thereof |
| 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 |
| CN110092888A (en) * | 2019-04-26 | 2019-08-06 | 同济大学 | Fluorine-containing isocyanate curing agent and its preparation method and application |
| CN115850656A (en) * | 2022-12-31 | 2023-03-28 | 韶关东森合成材料有限公司 | High-compatibility low-free trimer and preparation method thereof |
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| CN1186405C (en) | 2005-01-26 |
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