CN101440153B - Preparation of aqueous polyurethane fluid dispersion used with expansion type flame retardant - Google Patents
Preparation of aqueous polyurethane fluid dispersion used with expansion type flame retardant Download PDFInfo
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- CN101440153B CN101440153B CN200810204198XA CN200810204198A CN101440153B CN 101440153 B CN101440153 B CN 101440153B CN 200810204198X A CN200810204198X A CN 200810204198XA CN 200810204198 A CN200810204198 A CN 200810204198A CN 101440153 B CN101440153 B CN 101440153B
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- aqueous polyurethane
- flame retardant
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Abstract
The invention relates to a method for preparing waterborne polyurethane dispersion liquid used in matching with intumescent flame retardant. The method comprises the following steps: (1) 1mol to 2 mol of polyethylene glycol is added to a reaction vessel, decompressed, distilled and added with toluene-2,4-diisocyanate, and then the materials are cooled, diluted with acetone, so as to prepare prepolymer diluent; and (2) succinic acid is added to prepolymer; the succinic acid and the prepolymer react for 2 to 3 hours at a temperature between 60 and 80 DEG C; hydrophilic chain extender and the acetone are slowly added; the materials are thermally insulated, react at 40 DEG C, and are added with acetic acid for neutralization, stirred and simultaneously added with deionized water and uniformly dispersed; the pH value of a system is regulated to be between 6 and 7; and then a solvent in the system is decompressed and distilled. Waterborne polyurethane flame-retardant coating adhesive prepared from the polyurethane dispersion liquid of the invention has the advantages of non-combustible property, little pollution and low cost, has high adhesivity to fabric, good film-forming property and high strength, and can help the fabric to achieve durable flame retardance after film formation.
Description
Technical field
The invention belongs to the fire-retardant finish field, particularly relate to the matching used preparation of aqueous polyurethane fluid dispersion of a kind of expansion type flame retardant.
Background technology
The expansion type flame retardant system generally comprises three parts, it is carbon source (char-forming agent, it is the basis that forms the foam charring layer, mainly be high polyol of some carbon content and triazines etc., as tetramethylolmethane, hot amylalcohol, starch, hydroxyl organic resin etc.), acid source (dewatering agent, generally can be mineral acid or heat 100～250 ℃ of compounds that can generate mineral acid, as phosphoric acid, boric acid, various phosphoric acid salt, phosphoric acid ester etc.), source of the gas (foaming source, foaming source commonly used generally is a trimeric cyanamide, bis-phenol amine, nitrogenous compounds such as polyphosphoric acid).They form the charcoal layer by following interaction: 1. under lesser temps (about 150 ℃, actual temp depends on the character of acid source and other components), produce energy esterification polyol and the acid that can be used as dewatering agent by acid source; 2. discharge under the sour temperature a little higher than, acid is carried out esterification with polyol (carbon source), and the amine in the system then as the catalyzer of this esterification, carry out by accelerated reaction; 3. system melts before esterification or in the esterification reaction process; 4. the water vapour that produces in the reaction process and make the system that is in molten state expanded foamed by the non-flammable gases that source of the gas produces.Meanwhile, polyol and ester dehydration carbonization form inorganics and charcoal resistates, and system are further expanded foamed; When 5. reacting approaching finishing, system gel and curing form porous foam charcoal layer at last.Must be pointed out that above-mentioned each step reaction almost takes place simultaneously, but must be undertaken by the order of strictness.Promptly at first acid source decomposes generation acid, secondly must react with polyol, and nitrogenous compound quickens this reaction.Then the ester that generates must begin to be dehydrated into charcoal, and emits gas simultaneously, if wherein any one reaction can not be carried out just can not foaming in good time.Whole process as shown in Figure 2.
About becoming the charcoal reaction, mainly be to generate by the acid source decomposes to have high dehydrated phosphoric acid and tetra-sodium, they with carbon source in hydroxyl or amino generation dehydration or deamination reaction and generate phosphoric acid ester.The ester decomposes that generates generates unsaturated olefin, polymolecular cyclopolymerization reaction then takes place and generates stable poly aromatic structure charcoal layer.But not the alkyl branches in the aromatic structure then is fractured into small molecules and burns.
For different macromolecular materials, do not need several components simultaneously and deposit sometimes, only add wherein one or more, high polymer material itself also can serve as a certain component wherein sometimes.During burning, chemical reaction takes place between each component produce porous expansion charcoal layer, that this charcoal layer can play is heat insulation, oxygen barrier, press down cigarette and anti-molten drop effect, thereby reaches fire-retardant purpose.But expansion type flame retardant must with by the good flame retardant effect of fire-retardant polymer phase coupling competence exertion.
The expanded polystyrene veneer coating adhesive is present both at home and abroad most popular a kind of flame-retardant coatings glue, but easily anti-sticking, the easy binding dust of ubiquity poor heat resistance, high temperature.Easily become fragile shortcomings such as ventilation property difference during low temperature.For this reason, press for the expanded polystyrene veneer coating adhesive that exploitation can overcome above-mentioned shortcoming.
Summary of the invention
Technical problem to be solved by this invention provides the matching used preparation of aqueous polyurethane fluid dispersion of a kind of expansion type flame retardant, and the aqueous polyurethane flame-retardant coatings glue that uses polyurethane dispersing liquid of the present invention to make has and do not fire, pollutes advantage little and that cost is low.
The matching used preparation of aqueous polyurethane fluid dispersion of a kind of expansion type flame retardant of the present invention comprises:
(1) polyoxyethylene glycol (PEG) of adding 1mol-2mol in reaction vessel at 100 ℃-150 ℃ underpressure distillation (vacuum tightness 67mmHg post) 1h-2h, adds the Toluene-2,4-diisocyanate of 1.1mol～1.3mol, and 4-vulcabond (TDI) reacts 2-3h under nitrogen protection; Reduce temperature and add the acetone diluted that accounts for reaction system (30～50) volume % and make the prepolymer diluent;
(2) in prepolymer, add succsinic acid (2～6) volume %, at 60 ℃-80 ℃ reaction 2h-3h; Reduce below the temperature to 40 ℃, slowly add the hydrophilic chain extender of (7～9) volume % and account for reaction system (30-40) volume % acetone, maintain the temperature at 40 ℃ of reaction 30min-60min down, adding acetate neutralizes, under intensive stirs, slowly add then and account for whole system (50～70) weight % deionized water, and be uniformly dispersed fast, regulation system pH value is between 6-7; Then solvent is wherein removed through underpressure distillation, promptly get the stabilized aqueous polyurethane dispersing liquid.Building-up process as shown in Figure 1.
Described step (1) polyoxyethylene glycol is PEG800, PEG 1000 or PEG 2000.
Described step (2) hydrophilic chain extender is glycerine, TriMethylolPropane(TMP), N methyldiethanol amine or diethanolamine.
Described aqueous polyurethane dispersing liquid is used for being mixed with the aqueous polyurethane flame-retardant coatings glue with expansion type flame retardant.
The aqueous polyurethane flame-retardant coatings glue that uses polyurethane dispersing liquid of the present invention to make has and does not fire, pollutes advantage little and that cost is low, strong, the good film-forming property of the adhesivity to fabric simultaneously, and intensity is big, can give fabric competent flame retardant resistance after the film forming.
Description of drawings
Fig. 1 aqueous polyurethane dispersing liquid synthesizes synoptic diagram;
Fig. 2 porous charcoal layer formation process synoptic diagram.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The PEG800 that adds 1mol in reaction vessel at 100 ℃ of following underpressure distillation (vacuum tightness 67mmHg) 1h, adds the TDI (Toluene-2,4-diisocyanate, 4-vulcabond) of 1.1mol, reacts 2.5h under nitrogen protection; Reduce temperature and add the volume acetone diluted that accounts for reaction system 30% and make the prepolymer diluent; In performed polymer, go into succsinic acid 4%, react 2h down at 60 ℃; Reduce below the temperature to 40 ℃, slowly add a certain amount of hydrophilic chain extender N methyldiethanol amine 7% and (accounting for the volume of reaction system 30%) acetone, maintain the temperature at 40 ℃ of reaction 30min down; Add acetate and neutralize, account for whole system 50 weight % deionized waters slow the adding under intensive stirs then, and be uniformly dispersed fast, and regulation system pH value is between 6-7.Then solvent is wherein removed through underpressure distillation, promptly get the stabilized aqueous polyurethane dispersing liquid, be used for being mixed with the aqueous polyurethane flame-retardant coatings glue with expansion type flame retardant.
Embodiment 2
The PEG1000 that in reaction vessel, adds 1mol, at 100 ℃ of following underpressure distillation (vacuum tightness 67mmHg) 1h, the TDI (Toluene-2,4-diisocyanate, 4-vulcabond) that adds 1.2mol adds, and reacts 3h under nitrogen protection; Reduce temperature and add the volume acetone diluted that accounts for reaction system 40% and make the prepolymer diluent; In performed polymer, go into succsinic acid 5%, react 2h down at 60 ℃; Reduce below the temperature to 40 ℃, slowly add a certain amount of hydrophilic chain extender diethanolamine 7% and (accounting for the volume of reaction system 30%) acetone, maintain the temperature at 40 ℃ of reaction 30min down; Add acetate and neutralize, account for whole system 60 weight % deionized waters slow the adding under intensive stirs then, and be uniformly dispersed fast, and regulation system pH value is between 6-7.Then solvent is wherein removed through underpressure distillation, promptly get the stabilized aqueous polyurethane dispersing liquid, be used for being mixed with the aqueous polyurethane flame-retardant coatings glue with expansion type flame retardant.
Embodiment 3
The PEG 2000 that in reaction vessel, adds 1mol, at 100 ℃ of following underpressure distillation (vacuum tightness 67mmHg) 1h, the TDI (Toluene-2,4-diisocyanate, 4-vulcabond) that adds 1.3mol adds, and reacts 3h under nitrogen protection; Reduce temperature and add the volume acetone diluted that accounts for reaction system 50% and make the prepolymer diluent; In performed polymer, go into succsinic acid 6%, react 2h down at 60 ℃; Reduce below the temperature to 40 ℃, slowly add a certain amount of hydrophilic chain extender TriMethylolPropane(TMP) 9% and (accounting for the volume of reaction system 30%) acetone, maintain the temperature at 40 ℃ of reaction 30min down; Add acetate and neutralize, account for whole system 70 weight % deionized waters slow the adding under intensive stirs then, and be uniformly dispersed fast, and regulation system pH value is between 6-7.Then solvent is wherein removed through underpressure distillation, promptly get the stabilized aqueous polyurethane dispersing liquid, be used for being mixed with the aqueous polyurethane flame-retardant coatings glue with expansion type flame retardant.
Embodiment 4
The PEG800 that in reaction vessel, adds 1mol, at 100 ℃ of following underpressure distillation (vacuum tightness 67mmHg) 1h, the TDI (Toluene-2,4-diisocyanate, 4-vulcabond) that adds 1.2mol adds, and reacts 2.5h under nitrogen protection; Reduce temperature and add the volume acetone diluted that accounts for reaction system 40% and make the prepolymer diluent; In performed polymer, go into succsinic acid 4%, react 2h down at 60 ℃; Reduce below the temperature to 40 ℃, slowly add a certain amount of hydrophilic chain extender diethanolamine 7% and (accounting for the volume of reaction system 30%) acetone, maintain the temperature at 40 ℃ of reaction 30min down; Add acetate and neutralize, account for whole system 60 weight % deionized waters slow the adding under intensive stirs then, and be uniformly dispersed fast, and regulation system pH value is between 6-7.Then solvent is wherein removed through underpressure distillation, promptly get the stabilized aqueous polyurethane dispersing liquid, be used for being mixed with the aqueous polyurethane flame-retardant coatings glue with expansion type flame retardant.
Claims (4)
1. matching used preparation of aqueous polyurethane fluid dispersion of expansion type flame retardant comprises:
(1) the polyoxyethylene glycol PEG of adding 1mol-2mol in reaction vessel at 100 ℃ of-150 ℃ of underpressure distillation 1h-2h, adds the Toluene-2,4-diisocyanate of 1.1mol～1.3mol, and 4-vulcabond TDI reacts 2-3h under nitrogen protection; Reduce temperature and add that to account for the reaction system volume percent be that 30%～50% acetone diluted makes the prepolymer diluent;
(2) adding the succsinic acid volume percent in prepolymer is 2%～6%, at 60 ℃-80 ℃ reaction 2h-3h; Reduce below the temperature to 40 ℃, slowly the adding volume percent is that 7%～9% hydrophilic chain extender is a 30%-40% acetone with accounting for the reaction system volume percent, maintain the temperature at 40 ℃ of reaction 30min-60min down, adding acetate neutralizes, under stirring, intensive adds slowly then that to account for whole system weight per-cent be 50%～70% deionized water, and be uniformly dispersed fast, regulation system pH value is between 6-7; Then solvent is wherein removed through underpressure distillation, promptly.
2. the matching used preparation of aqueous polyurethane fluid dispersion of a kind of expansion type flame retardant according to claim 1 is characterized in that: described step (1) polyoxyethylene glycol is PEG800, PEG 1000 or PEG 2000.
3. the matching used preparation of aqueous polyurethane fluid dispersion of a kind of expansion type flame retardant according to claim 1 is characterized in that: described step (2) hydrophilic chain extender is glycerine, TriMethylolPropane(TMP), N methyldiethanol amine or diethanolamine.
4. the matching used preparation of aqueous polyurethane fluid dispersion of a kind of expansion type flame retardant according to claim 1 is characterized in that: described aqueous polyurethane dispersing liquid is used for being mixed with the aqueous polyurethane flame-retardant coatings glue with expansion type flame retardant.
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| CN101440153B true CN101440153B (en) | 2011-06-08 |
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| CN102418276A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of flame-retardant waterborne polyurethane |
| CN104004394B (en) * | 2014-06-14 | 2016-06-01 | 福州大学 | A kind of expandable flame retardant type double-component waterborne polyurethane wood lacquer |
| CN110885166A (en) * | 2018-09-07 | 2020-03-17 | 中国石油化工股份有限公司 | Treating agent for sulfur-containing oil sludge in high-sulfur-containing gas field and using method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101048477A (en) * | 2004-10-26 | 2007-10-03 | 诺誉有限公司 | Water-borne dispersions of oil modified urethane polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101048477A (en) * | 2004-10-26 | 2007-10-03 | 诺誉有限公司 | Water-borne dispersions of oil modified urethane polymers |
Non-Patent Citations (2)
| Title |
|---|
| 姜仲苏等.车用涤纶座椅面料阻燃整理.《印染》.2008,(第22期),6-9. * |
| 李莉等.阳离子水性聚氨酯乳液的合成方法及条件探讨.《中国涂料》.2007,第22卷(第6期),28-31. * |
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Granted publication date: 20110608 Termination date: 20131209 |