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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- China
- Prior art keywords
- curing agent
- toluene diisocyanate
- raw material
- preparing
- good compatibility
- Prior art date
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Links
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000013638 trimer Substances 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005829 trimerization reaction Methods 0.000 claims description 13
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 11
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- PSBOOKLOXQFNPZ-UHFFFAOYSA-M lithium;2-hydroxybenzoate Chemical compound [Li+].OC1=CC=CC=C1C([O-])=O PSBOOKLOXQFNPZ-UHFFFAOYSA-M 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 6
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 4
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- MGBKJKDRMRAZKC-UHFFFAOYSA-N 3-aminobenzene-1,2-diol Chemical compound NC1=CC=CC(O)=C1O MGBKJKDRMRAZKC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 229940117969 neopentyl glycol Drugs 0.000 claims description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
- 125000005628 tolylene group Chemical group 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DNNXXFFLRWCPBC-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C1=CC=CC=C1 DNNXXFFLRWCPBC-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
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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| 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 |
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