CN102050935A - Water-soluble polyurethane curing agent and preparation method thereof - Google Patents
Water-soluble polyurethane curing agent and preparation method thereof Download PDFInfo
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- CN102050935A CN102050935A CN 201010579351 CN201010579351A CN102050935A CN 102050935 A CN102050935 A CN 102050935A CN 201010579351 CN201010579351 CN 201010579351 CN 201010579351 A CN201010579351 A CN 201010579351A CN 102050935 A CN102050935 A CN 102050935A
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Abstract
The invention discloses a water-soluble polyurethane curing agent and a preparation method thereof. The curing agent comprises toluene diisocyanate, trimethylolpropane, polyethylene glycol, polycarbonate diols, acetic ether and a catalyst. The preparation method comprises the following steps: adding 18-25% of toluene diisocyanate, 20.01-80% of acetic ether and 0.01-40% of polycarbonate diols, adding 1-5% of trimethylopropane for reaction in three batches, adding 0.01-40% of polyethylene glycol for reaction in two batches, and then keeping the temperature at 58-63 DEG C for 3 hours; and adding 0.1-0.5% of catalyst, reacting for 2.5-4 hours while the temperature is kept at 50-60 DEG C, cooling until the temperature is reduced to 20-30 DEG C, and discharging. According to the invention, the preparation method is simple, and the curing agent prepared by utilizing the method can react with water-soluble acrylic resins or water-soluble alkyd resins to form a film when being mixed with the water-soluble acrylic resins and water-soluble alkyd resins. Thus, the curing agent is not only applicable to curing at normal temperature but also applicable to preparation of high temperature curing paints.
Description
Technical field
The present invention relates to the interior solidifying agent of polyurethane coating and the preparation method of polyurethane coating curing agent.
Background technology
Polyurethane coating is with its outstanding performance, good protectiveness. and excellent low temperature resistant and easy construction.Be widely used in the decoration and the protection of military affairs, industry, work-at-home.In recent years, the position of polyurethane coating in coating industry is remarkable day by day.Particularly in woodwork coating, polyurethane coating has played irreplaceable effect, and the selection of its solidifying agent plays a part to close material, and its application and development receive much concern.Solidifying agent has another name called stiffening agent, ripening agent or set agent, is curing reaction is promoted or controlled to a class material or mixture.Resin solidification is through chemical reactions such as condensation, closed loop, addition or catalysis, makes thermosetting resin that irreversible change procedure take place, and curing is finished by adding solidifying agent.
Contain organic solvent dimethylbenzene, toluene, N-BUTYL ACETATE, cyclohexanone in the solidifying agent in the polyurethane coating at present, solvent is released in the air and pollutes greatly, and the cost height, and organic solvent is a hazardous chemical in storage, transportation and the use, inflammable and explosive, very dangerous.
Summary of the invention
The purpose of this invention is to provide a kind of aqueous polyurethane solidifying agent, the formed solidifying agent energy of the present invention and water-borne acrylic resin, aqueous alkide resin hybrid reaction form film, and can be used for the water-borne coatings preparation on the surfaces such as wooden, metal, plastics of ambient cure, also can be used to prepare the coating of hot setting.
Another object of the present invention provides a kind of preparation method of aqueous polyurethane solidifying agent, this method is simple, utilize solidifying agent energy and water-borne acrylic resin, the aqueous alkide resin hybrid reaction of this method preparation to form film, and can be used for the water-borne coatings preparation on the surfaces such as wooden, metal, plastics of ambient cure, also can be used to prepare the coating of hot setting.
For achieving the above object, the aqueous polyurethane solidifying agent comprises tolylene diisocyanate, TriMethylolPropane(TMP), polyoxyethylene glycol, polycarbonate diol, vinyl acetic monomer and catalyzer; The weight percent of each raw material is:
Tolylene diisocyanate 18-25%
TriMethylolPropane(TMP) 1-5%
Polyoxyethylene glycol 0.01-40%
Polycarbonate diol 0.01-40%
Vinyl acetic monomer 20.01-80%
Catalyzer 0.1-0.5%.
As improvement, substitute vinyl acetic monomer with acetone, the weight percent of other each raw materials and each raw material is constant.
As improvement, the aqueous polyurethane solidifying agent also comprises acetone, and wherein to account for the weight percent of whole material be 20-40% to vinyl acetic monomer, and the weight percent that acetone accounts for whole material is 0.01-40%, and the shared weight percent of other raw materials is constant.
As specializing, the weight percent of each raw material is:
Tolylene diisocyanate 20-23%
TriMethylolPropane(TMP) 2-3%
Polyoxyethylene glycol 11-30%
Polycarbonate diol 10-29%
Vinyl acetic monomer 25-34%
Acetone 12-31%
Catalyzer 0.2-0.3%.
As specializing, the weight percent of each raw material is:
Tolylene diisocyanate 22%
TriMethylolPropane(TMP) 2.5%
Polyoxyethylene glycol 14%
Polycarbonate diol 17.1%
Vinyl acetic monomer 33%
Acetone 11%
Catalyzer 0.4%.
Specialize as of the present invention, described catalyzer is three normal-butyl phosphorus and/or phosphoric acid.
For reaching another above-mentioned purpose, a kind of preparation method of aqueous polyurethane solidifying agent is characterized in that: the steps include: at one agitator, thermometer and logical N to be housed
2In the four-hole boiling flask of protection, adding weight percent is the tolylene diisocyanate of 18-25%, the acetic acid second vinegar that weight percent is 20.01-80%, heat to 40-50 ℃, then, is weight percent that the TriMethylolPropane(TMP) of 1-5% drops into reaction in three batches, then 70-80 ℃ of insulation 3-5 hour, detect the weight percentage of NCO, when containing admittedly for 55-65%, be cooled to 43-48 ℃, with weight percent is that the polyoxyethylene glycol of 0-40% drops into reaction in two batches, then 58-63 ℃ of insulation 3 hours; Add three normal-butyl phosphorus, between 50 ℃-60 ℃ insulation reaction 2.5-4 hour, add phosphoric acid, be cooled to 20-30 ℃, get final product discharging.
As preparation method's of the present invention improvement, substitute vinyl acetic monomer with acetone.
As preparation method's of the present invention improvement, add acetone, wherein to account for the weight percent of whole material be 20-40% to vinyl acetic monomer, and the weight percent that acetone accounts for whole material is 0.01-40%, and the shared weight percent of other raw materials is constant.
As specializing of preparation method of the present invention, the preparation method's of aqueous polyurethane solidifying agent step is: at one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add weight percent and be 22% tolylene diisocyanate, weight percent and be 33% acetic acid second vinegar and weight percent and be 11% acetone, heat to 45 ℃, then, is weight percent that 2.5% TriMethylolPropane(TMP) drops into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO, when containing admittedly when being 60%, be cooled to 45 ℃, with weight percent is that 14% polyoxyethylene glycol drops into reaction in two batches, then 60 ℃ of insulations 3 hours; The adding weight percent is 0.2% three normal-butyl phosphorus, and insulation reaction is 2.5 hours between 50 ℃, and the adding weight percent is 0.2% phosphoric acid, is cooled to 30 ℃, gets final product discharging.
Beneficial effect of the present invention is:
(1) because temperature of reaction of the present invention is not high, adopt hot cold water heating and cooling to get final product; React under normal pressure, therefore, reaction conditions is simple, is fit to industrial application.
(2) owing to the group of having introduced water-soluble in reaction process is a diol compound, the synthetic solidifying agent is miscible mutually in aqueous medium neutralized aqueous resin like this, and crosslinking reaction forms film.
(3) the formed waterborne curing agent of the present invention can be used for the water-borne coatings preparation on the surfaces such as wooden, metal, plastics of ambient cure, also can be used to prepare the coating of hot setting, and at high temperature reaction is more complete, crosslinked more abundant.
(4) the present invention is one of raw materials used is polycarbonate diol, is the further application that utilizes waste gas carbonic acid gas synthetic materials.
(5) after reacting, formed this structure of carbamate with solidifying agent raw material of the present invention, it has acid and alkali-resistance, water proof and wearable, good luster, hardness height, the characteristic that ground is had strong sticking power, therefore, the paint film of preparation also has acid and alkali-resistance, water proof and wearable, good luster, hardness height, ground is had the characteristic of strong sticking power.Film forming hardness, sticking power, water tolerance has all reached national standard.The film performance test is carried out according to GB: sticking power: GB/T 1720-79; Pencil hardness: GB/T 6739; Shock resistance: GB/T 1732-93; Water tolerance: GB/T 1733-93.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated.
Embodiment 1
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, the tolylene diisocyanate, 408.9 gram acetic acid second vinegar and the 400 gram polycarbonate diols that add 180 grams, heat to 40 ℃, then, 10 grams, three light methylpropanes are dropped into reaction in three batches, then 70 ℃ of insulations 3 hours, detect the weight percentage of NCO,, be cooled to 43 ℃ when containing admittedly when being 55%, 0.1 gram polyoxyethylene glycol is dropped into reaction in two batches, then 58 ℃ of insulations 3 hours; Add 0.2 gram, three normal-butyl phosphorus,, add 0.8 gram phosphoric acid, after stirring, be cooled to 20 ℃, get final product discharging 50 ℃ of insulation reaction 2.5 hours.
Embodiment 2
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 250 gram tolylene diisocyanates, 200.1 gram acetic acid second vinegar and 305.1 gram polycarbonate diols, heat to 50 ℃, then, 50 grams, three light methylpropanes are dropped into reaction in three batches, then 80 ℃ of insulations 5 hours, detect the weight percentage of NCO,, be cooled to 48 ℃ when containing admittedly when being 65%, 200 gram polyoxyethylene glycol are dropped into reaction in two batches, then 63 ℃ of insulations 3 hours; Add 1 gram, three normal-butyl phosphorus,, add 4 gram phosphoric acid, after stirring, be cooled to 30 ℃, get final product discharging 60 ℃ of insulation reaction 4 hours.
Embodiment 3
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 190 gram tolylene diisocyanates, 250 gram acetone and 128 gram polycarbonate diols, heat to 45 ℃, then, 30 grams, three light methylpropanes are dropped into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO,, be cooled to 45 ℃ when containing admittedly when being 60%, 400 gram polyoxyethylene glycol are dropped into reaction in two batches, then 60 ℃ of insulations 3 hours; Add 1 gram, three normal-butyl phosphorus,, add 1 gram phosphoric acid, after stirring, be cooled to 25 ℃, get final product discharging 55 ℃ of insulation reaction 3 hours.
Embodiment 4
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 180 gram tolylene diisocyanates, 800 gram acetone and 0.1 gram polycarbonate diol, heat to 45 ℃, then, 15 grams, three light methylpropanes are dropped into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO,, be cooled to 45 ℃ when containing admittedly when being 60%, 2.9 gram polyoxyethylene glycol are dropped into reaction in two batches, then 60 ℃ of insulations 3 hours; Add 0.5 gram, three normal-butyl phosphorus,, add 1.5 gram phosphoric acid, after stirring, be cooled to 25 ℃, get final product discharging 55 ℃ of insulation reaction 3 hours.
Embodiment 5
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 180 gram tolylene diisocyanates, 250 gram acetic acid second vinegar, 158.9 gram acetone and 400 gram polycarbonate diols, heat to 40 ℃, then, 10 grams, three light methylpropanes are dropped into reaction in three batches, then 70 ℃ of insulations 3 hours, detect the weight percentage of NCO,, be cooled to 43 ℃ when containing admittedly when being 55%, 0.1 gram polyoxyethylene glycol is dropped into reaction in two batches, then 58 ℃ of insulations 3 hours; Add 0.3 gram, three normal-butyl phosphorus,, add 0.7 gram phosphoric acid, after stirring, be cooled to 20 ℃, get final product discharging 50 ℃ of insulation reaction 2.5 hours.
Embodiment 6
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 250 gram tolylene diisocyanates, 200 gram acetic acid second vinegar, 0.1 gram acetone and 105.1 gram polycarbonate diols, heat to 42 ℃, then, 50 grams, three light methylpropanes are dropped into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO,, be cooled to 44 ℃ when containing admittedly when being 57%, 400 gram polyoxyethylene glycol are dropped into reaction in two batches, then 60 ℃ of insulations 3 hours; Add 2 grams, three normal-butyl phosphorus,, add 3 gram phosphoric acid, after stirring, be cooled to 25 ℃, get final product discharging 53 ℃ of insulation reaction 3 hours.
Embodiment 7
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 180 gram tolylene diisocyanates, 400 gram acetic acid second vinegar, 400 gram acetone and 0.1 gram polycarbonate diol, heat to 45 ℃, then, 13 grams, three light methylpropanes are dropped into reaction in three batches, then 77 ℃ of insulations 5 hours, detect the weight percentage of NCO,, be cooled to 48 ℃ when containing admittedly when being 60%, 4.9 gram polyoxyethylene glycol are dropped into reaction in two batches, then 63 ℃ of insulations 3 hours; Add 1 gram, three normal-butyl phosphorus,, add 2 gram phosphoric acid, after stirring, be cooled to 30 ℃, get final product discharging 60 ℃ of insulation reaction 2.5 hours.
Embodiment 8
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 200 gram tolylene diisocyanates, 340 gram acetic acid second vinegar, 120 gram acetone and 100 gram polycarbonate diols, heat to 50 ℃, then, 20 grams, three light methylpropanes are dropped into reaction in three batches, then 80 ℃ of insulations 3.3 hours, detect the weight percentage of NCO,, be cooled to 45 ℃ when containing admittedly when being 60%, 218 gram polyoxyethylene glycol are dropped into reaction in two batches, then 59 ℃ of insulations 3 hours; Add 0.8 gram, three normal-butyl phosphorus,, add 1.2 gram phosphoric acid, after stirring, be cooled to 25 ℃, get final product discharging 50 ℃ of insulation reaction 4 hours.Be cooled to 25 ℃, get final product discharging.
Embodiment 9
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 230 gram tolylene diisocyanates, 250 gram acetic acid second vinegar, 207 gram acetone and 170 gram polycarbonate diols, heat to 48 ℃, then, 30 grams, three light methylpropanes are dropped into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO,, be cooled to 46 ℃ when containing admittedly when being 60%, 110 gram polyoxyethylene glycol are dropped into reaction in two batches, then 60 ℃ of insulations 3 hours; Add 1 gram, three normal-butyl phosphorus,, add 2 gram phosphoric acid, after stirring, be cooled to 25 ℃, get final product discharging 55 ℃ of insulation reaction 3 hours.
Embodiment 10
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 200 gram tolylene diisocyanates, 253 gram acetic acid second vinegar, 120 gram acetone and 100 gram polycarbonate diols, heat to 42 ℃, then, 25 grams, three light methylpropanes are dropped into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO,, be cooled to 46 ℃ when containing admittedly when being 55%, 300 gram polyoxyethylene glycol are dropped into reaction in two batches, then 60 ℃ of insulations 3 hours; Add 1 gram, three normal-butyl phosphorus,, add 1 gram phosphoric acid, after stirring, be cooled to 30 ℃, get final product discharging 50 ℃ of insulation reaction 2.5 hours.
Embodiment 11
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 183 gram tolylene diisocyanates, 260 gram acetic acid second vinegar, 121.5 gram acetone and 290 gram polycarbonate diols, heat to 49 ℃, then, 23 grams, three light methylpropanes are dropped into reaction in three batches, then 74 ℃ of insulations 3.5 hours, detect the weight percentage of NCO,, be cooled to 45 ℃ when containing admittedly when being 65%, 120 gram polyoxyethylene glycol are dropped into reaction in two batches, then 63 ℃ of insulations 3 hours; Add 0.5 gram, three normal-butyl phosphorus,, add 2 gram phosphoric acid, after stirring, be cooled to 30 ℃, get final product discharging 50 ℃ of insulation reaction 2.5 hours.
Embodiment 12
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 22 gram tolylene diisocyanates, 250 gram acetic acid second vinegar, 310 gram acetone and 100 gram polycarbonate diols, heat to 49 ℃, then, 20 grams, three light methylpropanes are dropped into reaction in three batches, then 74 ℃ of insulations 3.5 hours, detect the weight percentage of NCO,, be cooled to 45 ℃ when containing admittedly when being 60%, 97.3 gram polyoxyethylene glycol are dropped into reaction in two batches, then 63 ℃ of insulations 3 hours; Add 0.7 gram, three normal-butyl phosphorus,, add 2 gram phosphoric acid, after stirring, be cooled to 30 ℃, get final product discharging 50 ℃ of insulation reaction 2.5 hours.
Embodiment 13
At one agitator, thermometer and logical N are housed
2In the four-hole boiling flask of protection, add 220 gram tolylene diisocyanates, 330 gram acetic acid second vinegar, 110 gram acetone and 171 gram polycarbonate diols, heat to 45 ℃, then, 25 grams, three light methylpropanes are dropped into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO,, be cooled to 45 ℃ when containing admittedly when being 60%, with weight percent is that 14% polyoxyethylene glycol drops into reaction in two batches, then 60 ℃ of insulations 3 hours; Add 2 grams, three normal-butyl phosphorus,, add 2 gram phosphoric acid, after stirring, be cooled to 30 ℃, get final product discharging 50 ℃ of insulation reaction 2.5 hours.
Solidifying agent performance such as following table that the foregoing description obtains after test:
Can draw paint film acid and alkali-resistance with solidifying agent of the present invention preparation, water-tolerant, wear-resisting, good luster, hardness height from above experimental result, ground is had strong sticking power.Film forming hardness, sticking power, water tolerance has all reached national standard.The film performance test is carried out according to GB: sticking power: GB/T 1720-79; Pencil hardness: GB/T 6739; Shock resistance: GB/T 1732-93; Water tolerance: GB/T 1733-93.In addition, because temperature of reaction of the present invention is not high, adopt hot cold water heating and cooling to get final product; React under normal pressure, therefore, reaction conditions is simple, is fit to industrial application.Because the group of having introduced water-soluble in reaction process is a diol compound, the synthetic solidifying agent is miscible mutually in aqueous medium neutralized aqueous resin like this, crosslinking reaction formation film, like this, pollute little, environmental protection.The formed waterborne curing agent of the present invention can be used for the water-borne coatings preparation on surfaces such as wooden, the metal, plastics of ambient cure, also can be used to prepare the coating of hot setting, and at high temperature reaction is more complete, crosslinked more abundant.Have, one of the present invention is raw materials used is polycarbonate diol, is the further application that utilizes waste gas carbonic acid gas synthetic materials again, and both environmental protection can rationally utilize resource again.
Claims (10)
1. aqueous polyurethane solidifying agent, it is characterized in that: this aqueous polyurethane solidifying agent comprises tolylene diisocyanate, TriMethylolPropane(TMP), polyoxyethylene glycol, polycarbonate diol, vinyl acetic monomer and catalyzer; The weight percent of each raw material is:
Tolylene diisocyanate 18-25%
TriMethylolPropane(TMP) 1-5%
Polyoxyethylene glycol 0.01-40%
Polycarbonate diol 0.01-40%
Vinyl acetic monomer 20.01-80%
Catalyzer 0.1-0.5%.
2. aqueous polyurethane solidifying agent according to claim 1 is characterized in that: substitute vinyl acetic monomer with acetone.
3. aqueous polyurethane solidifying agent according to claim 1, it is characterized in that: the aqueous polyurethane solidifying agent also comprises acetone, wherein to account for the weight percent of whole material be 20-40% to vinyl acetic monomer, the weight percent that acetone accounts for whole material is 0.01-40%, and the shared weight percent of other raw materials is constant.
4. aqueous polyurethane solidifying agent according to claim 3 is characterized in that: the weight percent of each raw material is:
Tolylene diisocyanate 20-23%
TriMethylolPropane(TMP) 2-3%
Polyoxyethylene glycol 11-30%
Polycarbonate diol 10-29%
Vinyl acetic monomer 25-34%
Acetone 12-31%
Catalyzer 0.2-0.3%.
5. aqueous polyurethane solidifying agent according to claim 4 is characterized in that: the weight percent of each raw material is:
Tolylene diisocyanate 22%
TriMethylolPropane(TMP) 2.5%
Polyoxyethylene glycol 14%
Polycarbonate diol 17.1%
Vinyl acetic monomer 33%
Acetone 11%
Catalyzer 0.4%.
6. according to each described aqueous polyurethane solidifying agent of claim 1-5, it is characterized in that: described catalyzer is three normal-butyl phosphorus and phosphoric acid.
7. the preparation method of an aqueous polyurethane solidifying agent is characterized in that: the steps include: at one agitator, thermometer and logical N to be housed
2In the four-hole boiling flask of protection, adding weight percent is the tolylene diisocyanate of 18-25%, weight percent is that acetic acid second vinegar and the weight percent of 20.01-80% is the polycarbonate diol of 0.01-40%, heat to 40-50 ℃, then, is weight percent that the TriMethylolPropane(TMP) of 1-5% drops into reaction in three batches, then 70-80 ℃ of insulation 3-5 hour, detect the weight percentage of NCO, when containing admittedly for 55-65%, be cooled to 43-48 ℃, with weight percent is that the polyoxyethylene glycol of 0-40% drops into reaction in two batches, then 58-63 ℃ of insulation 3 hours; Add three normal-butyl phosphorus, between 50 ℃-60 ℃ insulation reaction 2.5-4 hour, add phosphoric acid, be cooled to 20-30 ℃, get final product discharging.
8. the preparation method of aqueous polyurethane solidifying agent according to claim 7 is characterized in that: substitute vinyl acetic monomer with acetone.
9. the preparation method of aqueous polyurethane solidifying agent according to claim 7, it is characterized in that: add acetone, wherein to account for the weight percent of whole material be 20-40% to vinyl acetic monomer, the weight percent that acetone accounts for whole material is 0.01-40%, and the shared weight percent of other raw materials is constant.
10. the preparation method of aqueous polyurethane solidifying agent according to claim 9 is characterized in that: the steps include: at one agitator, thermometer and logical N to be housed
2In the four-hole boiling flask of protection, add weight percent and be 22% tolylene diisocyanate, weight percent and be 33% acetic acid second vinegar, weight percent and be 11% acetone and weight percent and be 17.1% polycarbonate diol, heat to 45 ℃, then, is weight percent that 2.5% TriMethylolPropane(TMP) drops into reaction in three batches, then 75 ℃ of insulations 4 hours, detect the weight percentage of NCO, when containing admittedly when being 60%, be cooled to 45 ℃, with weight percent is that 14% polyoxyethylene glycol drops into reaction in two batches, then 60 ℃ of insulations 3 hours; The adding weight percent is 0.2% three normal-butyl phosphorus, and insulation reaction is 2.5 hours between 50 ℃, and the adding weight percent is 0.2% phosphoric acid, is cooled to 30 ℃, gets final product discharging.
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| CN104341588A (en) * | 2013-08-09 | 2015-02-11 | 旭化成化学株式会社 | Copolymerized polycarbonate diol, thermoplastic polyurethane, coating composition and coating film |
| CN104761702A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Polyurethane curing agent |
| CN104804636A (en) * | 2015-04-24 | 2015-07-29 | 肇庆千江高新材料科技有限公司 | Air-drying automobile-used water-based finishing coat and water-based intermediate coat, as well as preparation method and use methods thereof |
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| CN111454414A (en) * | 2020-05-15 | 2020-07-28 | 万华化学集团股份有限公司 | Matte polyisocyanate curing agent and preparation method and application thereof |
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| CN103086991B (en) * | 2013-01-04 | 2016-01-06 | 甘肃银光聚银化工有限公司 | A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent |
| CN104341588A (en) * | 2013-08-09 | 2015-02-11 | 旭化成化学株式会社 | Copolymerized polycarbonate diol, thermoplastic polyurethane, coating composition and coating film |
| CN104761702A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Polyurethane curing agent |
| CN104804636A (en) * | 2015-04-24 | 2015-07-29 | 肇庆千江高新材料科技有限公司 | Air-drying automobile-used water-based finishing coat and water-based intermediate coat, as well as preparation method and use methods thereof |
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| CN106220826A (en) * | 2016-08-04 | 2016-12-14 | 中海油常州涂料化工研究院有限公司 | The preparation method of the water solublity isocyanate curing agent that a kind of Graphene is modified |
| CN106220826B (en) * | 2016-08-04 | 2019-10-11 | 中海油常州涂料化工研究院有限公司 | A kind of preparation method for the water-soluble isocyanate curing agent that graphene is modified |
| CN109468046A (en) * | 2018-11-23 | 2019-03-15 | 广东聚盈化工有限公司 | A kind of aqueous one-component acrylic acid modified polyurethane moisture solidification agent and preparation method |
| CN111454414A (en) * | 2020-05-15 | 2020-07-28 | 万华化学集团股份有限公司 | Matte polyisocyanate curing agent and preparation method and application thereof |
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