CN104672422A - Emulsifier applied to waterborne polyurethane synthesis as well as preparation method and application of emulsifier - Google Patents
Emulsifier applied to waterborne polyurethane synthesis as well as preparation method and application of emulsifier Download PDFInfo
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Abstract
The invention discloses an emulsifier applied to waterborne polyurethane synthesis as well as a preparation method and application of the emulsifier. According to the conventional patents, waterborne polyurethane emulsion is prepared by resin blending by using a prepolymer blending method, an exact structural design of the emulsifier is not provided, and the advantages of external emulsion cannot be fully exerted. According to the emulsifier disclosed by the invention, a polyurethane resin serves as a hydrophobic and lipophilic segment, carboxylic acid alcohol, sulfamate, amino acids or hydroxyl sulphonate are taken as hydrophilic terminal compounds, and the hydrophilic terminals are connected by virtue of the reaction with isocyanate bonds of the hydrophobic and lipophilic segment. The emulsifier disclosed by the invention has the hydrophobic segment of the polyurethane resin and can provide the compatibility superior to that of a common emulsifier and a polyurethane system, so that the provided stability of the emulsifier is superior to that of external emulsion method waterborne polyurethane emulsion prepared by the traditional emulsifier.
Description
Technical field
The present invention relates to aqueous polyurethane technical field, specifically a kind of emulsifying agent and its preparation method and application being applicable to aqueous polyurethane synthesis.
Background technology
Solvent borne polyurethane is widely used the field such as surfacecti proteon, tackiness agent, leatheroid in woodwork because of the performance of its excellence, but solvent borne polyurethane production, construction and solidification process in need to add a large amount of volatile organic solvents, health risk safety, to environment.
In recent years, countries in the world had all paid attention to the hazardness of volatile organic matter (VOC) in organic exhaust gas gradually, about controls VOC regulation day by day sternly, part western developed country is clear stipulaties organic discharge kind, quantity discharged.Be different from solvent borne polyurethane, aqueous polyurethane take water as medium, and water does not fire, not quick-fried, nontoxic, tasteless, do not pollute the environment, and execution conditions is good, produces and application safety, can not endanger the healthy of construction and operator; Meanwhile, water is cheap, is easy to get, therefore significantly can reduces the cost of product, because more and more causing the attention of people.
According to the synthesis technique of aqueous polyurethane, can be divided into internal emulsification method and outer emulsion process, emulsion solid content prepared by outer emulsion process is high, viscosity is rare but poor stability, and what therefore the production of current most of aqueous polyurethane adopted is internal emulsification technique.But common internal emulsification hydrophilic radical distributes uncontrollable thus inevitably there is certain thickness hydration layer, and the boundary of oil phase and aqueous phase is not very clear, causes hydration thickness, solid content is difficult to improve.How in the building-up process of aqueous polyurethane, to realize outer emulsification under the prerequisite ensureing stability, be the effective ways that the current internal emulsification aqueous polyurethane solid content of improvement is difficult to improve, viscosity is large, but for this partial content, research is all fewer both at home and abroad.US Patent No. 2004020847 and Chinese patent CN102093534A refer to and adopt the urethane resin of the coated not carboxylate-containing of urethane of carboxylate-containing to prepare aqueous polyurethane emulsion, and CN102181032A adopts response type super branched polyurethane coated base polyurethane prepolymer for use as preparation feedback type hyperbranched waterborne polyurethane film.But above-mentioned patent is all use prepolymer blend method, prepares aqueous polyurethane emulsion, does not propose definite emulsifying agent structure design, the advantage of outer emulsification can not be fully played by resin alloy.
Summary of the invention
Technical problem to be solved by this invention is the defect overcoming the existence of above-mentioned prior art, a kind of emulsifying agent being applicable to aqueous polyurethane synthesis is provided, it is good that it has with urethane resin consistency, be easy in the dispersion of urethane resin microparticle surfaces, and there is reactivity, do not affect the characteristic of final film forming physical property.
For this reason, the present invention is realized by the following technical programs: a kind of emulsifying agent being applicable to aqueous polyurethane synthesis, it is characterized in that, this emulsifying agent take urethane resin as hydrophobic oleophilic oil segment, with carboxylic acid alcohol, sulfamate, amino acid or hydroxy sulfonate for water-wet side compound, water-wet side is connected by reacting with the isocyanic acid ester bond of hydrophobic oleophilic oil segment, and the structural formula of this emulsifying agent hydrophobic oleophilic oil segment as shown in Equation 1
In formula 1,
X is encapsulant;
for polymer diatomic alcohol;
OCN-NCO is vulcabond.
The above-mentioned preparation method being applicable to the emulsifying agent of aqueous polyurethane synthesis, is characterized in that comprising following steps:
1) encapsulant of mol ratio 1:1 and vulcabond are stirred under nitrogen protection, at temperature 60 ~ 90 DEG C, react 1.5 ~ 3h, obtain compd A;
2) compd A of mol ratio 1:1 and polymer diatomic alcohol are stirred under nitrogen protection, 2.5 ~ 4h is reacted at temperature 60 ~ 90 DEG C, obtain compd B, add again and the vulcabond of compd B with mol ratio, stir under nitrogen protection, at temperature 60 ~ 90 DEG C, react 2.5 ~ 4h, obtain Compound C;
3) water-wet side compound and Compound C are pressed active function groups (as OH or NH
2) add with the mol ratio 1:1 of NCO, stir under nitrogen protection, at temperature 60 ~ 90 DEG C, react 2.5 ~ 4h, obtain the emulsifying agent being applicable to aqueous polyurethane synthesis.
Preparation method's process of the present invention is simple, can be applicable to the preparation that property requires aqueous polyurethane emulsion, high solid content aqueous polyurethane emulsion.
Further, described encapsulant is preferably methyl ethyl ketoxime, phenol, hexanolactam, 2-pyridol, 3-hydroxyquinoline, 3，5-dimethylpyrazole, 1,2,4-triazole, one or more in sodium bisulfite, Acetanilide, N-methylacetamide, diethyl ketone acryloyl amidoxime.
Further, described vulcabond is preferably tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), 2,4-ethylbenzene vulcabond (EDI), Methylcyclohexyl diisocyanate (HTDI), 2, one or more in 2,4-trimethylhexane diisocyanate (TMHDI).
Further, described polymer diatomic alcohol be selected from polyether Glycols, polyester diol one or more, be preferably in the asymmetrical polyether Glycols of hydroxyl activity, polyester diol one or more.
Further, described water-wet side compound be preferably in dimethylol propionic acid, dimethylolpropionic acid, amino acid, second diamino ethyl sulfonic acid sodium, second dihydroxyl ethyl sulfonic acid sodium, oxysuccinic acid, citric acid one or more.
Another object of the present invention is to provide the application of mentioned emulsifier, it is characterized in that, after by emulsifying agent, 1:2 ~ 3.5 mix in mass ratio with base polyurethane prepolymer for use as, abundant stirring 15 ~ 300 seconds, mixed performed polymer uniformly, add the neutralizing agent suitable with carboxylate radical mole number in emulsifying agent to neutralize, be then scattered in deionized water under the high-speed stirring of 800 ~ 2000r/min, obtain the aqueous polyurethane colostric fluid of high solid content; The rear chainextender being 0.01 ~ 0.8:1 by its active function groups (as OH or NH2) and NCO mol ratio in aqueous polyurethane colostric fluid is added drop-wise in aqueous polyurethane colostric fluid, stir 0.5 ~ 2h, reduce pressure the solvent sloughed in base polyurethane prepolymer for use as, obtains the aqueous polyurethane emulsion of high solid content.
Described rear chainextender is preferably quadrol, butanediamine, isophorone diamine, hexanediamine, pentamethylene diamine, piperazine, cyclohexanediamine, hydrazine, N, one or more in N '-dimethyl quadrol.
Described neutralizing agent be preferably in triethylamine, tri-n-butylamine, sodium hydroxide, diethanolamine, trolamine one or more.
Further, the aqueous polyurethane emulsion film forming of obtained high solid content, dry 2 ~ 10min for 130 ~ 150 DEG C, potential masked isocyanate functional group can react further with urethane resin, improves hardness and the intensity of film forming matter.
The preparation method of above-mentioned base polyurethane prepolymer for use as is as follows:
1) be that one or more in 500-4000 polymer diatomic alcohol or polymer polyatomic alcohol are warming up to 90-120 DEG C by the molecular weight of 50-80 mass parts, vacuum hydro-extraction 30-90min, the vulcabond of 10-50 mass parts is added after cooling to 55-75 DEG C, stir under nitrogen protection, churning time is 0.5-1h, then at least one is added in the dibutyl tin laurate of 0.01-0.2 mass parts, stannous octoate as catalyzer, at 60-90 DEG C, react 1-3h, obtain the reactant of clear;
2) with 2,2-dimethylol propionic acid (DMPA), 2, at least one in 2-dimethylolpropionic acid (DMBA), second diamino ethyl sulfonic acid sodium, second dihydroxyl ethyl sulfonic acid sodium is as hydrophilic chain extender, with 1,4-butyleneglycol, glycol ether, 2-methyl propanediol, 3-methyl pentanediol, neopentyl glycol, 1, at least one in 6-hexylene glycol, 2-methyl-2-ethyl glycol, TriMethylolPropane(TMP) is as small molecule chain extender, using at least one in acetone, butanone, DMF, N-Methyl pyrrolidone, N-ethyl pyrrolidone as solvent; The small molecule chain extender of the hydrophilic chain extender of 0.5-5 mass parts, 1-15 mass parts, the solvent of 0.1-50 mass parts are joined step 1) in the reactant that obtains, at 60-90 DEG C, react 1-3h; Cool to 45-70 DEG C, obtain the base polyurethane prepolymer for use as clarifying thickness.
Step 1) in, described vulcabond is preferably tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), 4,4 ' one methylene radical one dicyclohexyl vulcabond (H12MDI), xylylene diisocyanate (XDI), 2, one or more in 2,4-trimethylhexane diisocyanate (TMHDI).Described polymer diatomic alcohol be preferably in polyethylene glycol adipate glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, poly-hexanodioic acid glycol ether esterdiol, polyneopentyl glycol adipate glycol, polycaprolactone glycol, poly-carbonic acid hexylene glycol esterdiol, polyoxypropylene, PTMG one or more.
The advantage of emulsifying agent of the present invention is: the advantage that emulsifying agent possesses that consistency is good, good stability and later stage can react.Emulsifying agent possesses the hydrophobic segment of urethane resin, can provide that be better than common emulsifying agent with consistency that is polyurethane system, thus the outer emulsion process aqueous polyurethane emulsion providing stability to be better than conventional emulsifier to prepare.Emulsifying agent possesses potential blocked isocyanate functional group of reacting, and can cure in process be cross-linked further in application, eliminates the impact of small-molecule substance on the overall physical property of film forming.
Embodiment
Below by way of specific embodiment, the present invention is described, but the invention is not restricted to these examples.
Embodiment 1
1mol methyl ethyl ketoxime and 1mol tolylene diisocyanate are stirred under nitrogen protection, at temperature 90 DEG C, reacts 1.5h, obtain compd A; The polypropylene glycol of 1mol 2000 molecular weight is added under nitrogen protection and stirs, under temperature 60 C, reacts 4h, obtain compd B, add 1mol Methylcyclohexyl diisocyanate again, stir under nitrogen protection, under temperature 60 C, react 4h, obtain Compound C; 0.5mol dimethylol propionic acid is added, stirs under nitrogen protection, at temperature 90 DEG C, react 2.5h, obtain the emulsifying agent of applicable aqueous polyurethane synthesis.
By the polybutylene glyool adipate of 50g 500 molecular weight at 110 DEG C, vacuum hydro-extraction 1.5h, cools to 65 DEG C, adds 39g TDI, under nitrogen protection, stirs 0.5h, adds dibutyl tin laurate 0.015g, at 80 DEG C, and reaction 2h; Add 1g DMPA, 1g 1,4-butyleneglycol, 2g neopentyl glycol, 10g butanone, 5g N-Methyl pyrrolidone, at 80 DEG C, reaction 3h, cool to 50 DEG C, obtain the thickness performed polymer A of clear, 50g emulsifying agent and 100g performed polymer A are mixed, add and neutralize with the triethylamine of contained dimethylol propionic acid in emulsifying agent with mol ratio, be scattered under the high-speed stirring of 800 ~ 2000r/min in 150g deionized water, add chain extension after 3g quadrol, stir 1h, solvent is sloughed in decompression, obtains the aqueous polyurethane emulsion of high solid content.
Embodiment 2
1mol hexanolactam and 1mol tolylene diisocyanate are stirred under nitrogen protection, under temperature 60 C, reacts 3h, obtain compd A; The poly-DOPCP of 1mol 2000 molecular weight is added under nitrogen protection and stirs, at temperature 90 DEG C, reacts 2.5h, obtain compd B, add 1mol 2,4-ethylbenzene vulcabond again, stir under nitrogen protection, at temperature 90 DEG C, react 2.5h, obtain Compound C; 1mol oxysuccinic acid is added, stirs under nitrogen protection, under temperature 60 C, react 4h, obtain the emulsifying agent of applicable aqueous polyurethane synthesis.
By the polybutylene glyool adipate of 50g 500 molecular weight at 110 DEG C, vacuum hydro-extraction 1.5h, cools to 65 DEG C, adds 50g IPDI, under nitrogen protection, stirs 0.5h, adds stannous octoate 0.02g, at 80 DEG C, and reaction 2h; Add 2g second dihydroxyl ethyl sulfonic acid sodium, 3g 2-methyl propanediol, 2g 3-methyl pentanediol, 10g butanone, 5g N-Methyl pyrrolidone, at 80 DEG C, reaction 3h, cools to 50 DEG C, obtain the thickness performed polymer A of clear, 30g emulsifying agent and 100g performed polymer A are mixed, adds and neutralize with the triethylamine of contained oxysuccinic acid in emulsifying agent with mol ratio 2 times, be scattered in 100g deionized water under the high-speed stirring of 800 ~ 2000r/min, add chain extension after 2g hexanediamine, stir 1h, solvent is sloughed in decompression, obtains the aqueous polyurethane emulsion of high solid content.
Embodiment 3
1mol 3，5-dimethylpyrazole and 1mol isophorone diisocyanate are stirred under nitrogen protection, at temperature 90 DEG C, reacts 1.5h, obtain compd A; The polypropylene glycol of 1mol 1000 molecular weight is added under nitrogen protection and stirs, under temperature 60 C, reacts 4h, obtain compd B, add 1mol tolylene diisocyanate again, stir under nitrogen protection, under temperature 60 C, react 4h, obtain Compound C; 0.5mol dimethylolpropionic acid is added, stirs under nitrogen protection, at temperature 90 DEG C, react 2.5h, obtain the emulsifying agent of applicable aqueous polyurethane synthesis.
By the polypropylene glycol of 150g 2000 molecular weight, 50g polyether glycol N330 is at 110 DEG C, and vacuum hydro-extraction 1h, cools to 65 DEG C, adds 40g IPDI, 30gHDI, under nitrogen protection, stirs 0.5h, adds 0.15g stannous octoate, at 80 DEG C, and reaction 2h; Add 6g glycol ether, 2g TriMethylolPropane(TMP), 30g acetone, at 70 DEG C, reaction 3h, cools to 45 DEG C, obtain the thickness performed polymer A of clear, 50g emulsifying agent and 120g performed polymer A are mixed, adds and neutralize with the triethylamine of contained dimethylolpropionic acid in emulsifying agent with mol ratio, be scattered in 150g deionized water under the high-speed stirring of 800 ~ 2000r/min, add chain extension after 8g butanediamine, stir 1h, solvent is sloughed in decompression, obtains the aqueous polyurethane emulsion of high solid content.
Embodiment 4
1mol sodium bisulfite and 1mol tolylene diisocyanate are stirred under nitrogen protection, at temperature 90 DEG C, reacts 1.5h, obtain compd A; The polypropylene glycol of 1mol 2000 molecular weight is added under nitrogen protection and stirs, under temperature 60 C, reacts 4h, obtain compd B, add 1mol 2,2,4-trimethylhexane diisocyanate again, stir under nitrogen protection, under temperature 60 C, react 4h, obtain Compound C; 0.5mol dimethylol propionic acid is added, stirs under nitrogen protection, at temperature 90 DEG C, react 2.5h, obtain the emulsifying agent of applicable aqueous polyurethane synthesis.
By the polybutylene glyool adipate of 50g 500 molecular weight at 110 DEG C, vacuum hydro-extraction 1.5h, cools to 65 DEG C, adds 20g TDI, 18g TDHDI, under nitrogen protection, stirs 0.5h, adds dibutyl tin laurate 0.015g, at 80 DEG C, and reaction 2h; Add 0.5g DMBA, 5g 1,6-hexylene glycol, 10g butanone, 5g N-ethyl pyrrolidone, at 80 DEG C, reaction 3h, cools to 50 DEG C, obtain the thickness performed polymer A of clear, 50g emulsifying agent and 100g performed polymer A are mixed, adds and neutralize with the triethylamine of contained dimethylol propionic acid in emulsifying agent with mol ratio, be scattered in 150g deionized water under the high-speed stirring of 800 ~ 2000r/min, add chain extension after 3.5g cyclohexanediamine diamines, stir 1h, solvent is sloughed in decompression, obtains the aqueous polyurethane emulsion of high solid content.
Embodiment 5
1mol N-methylacetamide and 1mol isophorone diisocyanate are stirred under nitrogen protection, at temperature 90 DEG C, reacts 3.5h, obtain compd A; The polypropylene glycol of 1mol 2000 molecular weight is added under nitrogen protection and stirs, under temperature 60 C, reacts 4h, obtain compd B, add 1mol tolylene diisocyanate again, stir under nitrogen protection, under temperature 60 C, react 4h, obtain Compound C; 1mol citric acid is added, stirs under nitrogen protection, at temperature 90 DEG C, react 2.5h, obtain the emulsifying agent of applicable aqueous polyurethane synthesis.
By the PTMG of 200g 2000 molecular weight at 110 DEG C, vacuum hydro-extraction 1h, cools to 65 DEG C, adds 44.6g IPDI, under 15g H12MDI nitrogen protection, stirs 0.5h, adds 0.18g stannous octoate, at 80 DEG C, and reaction 2h; Add 1g BDO, 2g neopentyl glycol, 10g butanone, 5g DMF, at 80 DEG C, reaction 3h, cools to 50 DEG C, obtains the thickness performed polymer A of clear, 30g emulsifying agent and 100g performed polymer A are mixed, adds and neutralize with the triethylamine of contained citric acid 3 times of mol ratios in emulsifying agent, be scattered in 90g deionized water under the high-speed stirring of 800 ~ 2000r/min, add chain extension after 5g isophorone diamine, stir 1h, solvent is sloughed in decompression, obtains the aqueous polyurethane emulsion of high solid content.
Embodiment 6
0.5mol phenol, 0.5mol diethyl ketone acryloyl amidoxime and 1mol tolylene diisocyanate are stirred under nitrogen protection, at temperature 90 DEG C, reacts 2.5h, obtain compd A; The poly adipate succinic acid ester of 1mol 1000 molecular weight is added under nitrogen protection and stirs, under temperature 60 C, reacts 4h, obtain compd B, add 1mol isophorone diisocyanate again, stir under nitrogen protection, under temperature 60 C, react 4h, obtain Compound C; 0.5mol second diamino ethyl sulfonic acid sodium is added, stirs under nitrogen protection, at temperature 90 DEG C, react 2.5h, obtain the emulsifying agent of applicable aqueous polyurethane synthesis.
By the PTMG of 200g 2000 molecular weight at 110 DEG C, vacuum hydro-extraction 1h, cools to 65 DEG C, adds 43.5g XDI, under 29g MDI nitrogen protection, stirs 0.5h, adds 0.1g stannous octoate, at 80 DEG C, and reaction 2h; Add 1g 2-methyl-2-ethyl glycol, 2.5g 3-methyl pentanediol, 10g butanone, 5g N-Methyl pyrrolidone, at 80 DEG C, reaction 3h, cool to 50 DEG C, obtain the thickness performed polymer A of clear, 50g emulsifying agent and 100g performed polymer A are mixed, be scattered in 150g deionized water under the high-speed stirring of 800 ~ 2000r/min, add 1g pentamethylene diamine, 3g N, chain extension after N '-dimethyl quadrol, stir 1h, solvent is sloughed in decompression, obtains the aqueous polyurethane emulsion of high solid content.
Claims (10)
1. one kind is applicable to the emulsifying agent of aqueous polyurethane synthesis, it is characterized in that, this emulsifying agent take urethane resin as hydrophobic oleophilic oil segment, with carboxylic acid alcohol, sulfamate, amino acid or hydroxy sulfonate for water-wet side compound, water-wet side is connected by reacting with the isocyanic acid ester bond of hydrophobic oleophilic oil segment, the structural formula of this emulsifying agent hydrophobic oleophilic oil segment as shown in Equation 1
In formula 1,
X is encapsulant;
for polymer diatomic alcohol;
OCN-NCO is vulcabond.
2. the preparation method of emulsifying agent described in claim 1, it comprises following steps:
1) encapsulant of mol ratio 1:1 and vulcabond are stirred under nitrogen protection, at temperature 60 ~ 90 DEG C, react 1.5 ~ 3h, obtain compd A;
2) compd A of mol ratio 1:1 and polymer diatomic alcohol are stirred under nitrogen protection, 2.5 ~ 4h is reacted at temperature 60 ~ 90 DEG C, obtain compd B, add again and the vulcabond of compd B with mol ratio, stir under nitrogen protection, at temperature 60 ~ 90 DEG C, react 2.5 ~ 4h, obtain Compound C;
3) water-wet side compound and Compound C are added by the mol ratio 1:1 of active function groups and NCO, stir under nitrogen protection, at temperature 60 ~ 90 DEG C, react 2.5 ~ 4h, obtain the emulsifying agent being applicable to aqueous polyurethane synthesis.
3. preparation method according to claim 2, it is characterized in that, described encapsulant is methyl ethyl ketoxime, phenol, hexanolactam, 2-pyridol, 3-hydroxyquinoline, 3,5-dimethyl pyrazole, 1,2,4-triazole, one or more in sodium bisulfite, Acetanilide, N-methylacetamide, diethyl ketone acryloyl amidoxime.
4. preparation method according to claim 2, is characterized in that, described vulcabond is tolylene diisocyanate, isophorone diisocyanate, 2,4-ethylbenzene vulcabond, Methylcyclohexyl diisocyanate, 2, one or more in 2,4-trimethylhexane diisocyanate.
5. preparation method according to claim 2, is characterized in that, described polymer diatomic alcohol be selected from polyether Glycols, polyester diol one or more.
6. preparation method according to claim 5, is characterized in that, described polymer diatomic alcohol be selected from the asymmetrical polyether Glycols of hydroxyl activity, polyester diol one or more.
7. preparation method according to claim 2, it is characterized in that, described water-wet side compound is one or more in dimethylol propionic acid, dimethylolpropionic acid, amino acid, second diamino ethyl sulfonic acid sodium, second dihydroxyl ethyl sulfonic acid sodium, oxysuccinic acid, citric acid.
8. the application of emulsifying agent described in claim 1, it is characterized in that, after by emulsifying agent, 1:2 ~ 3.5 mix in mass ratio with base polyurethane prepolymer for use as, abundant stirring 15 ~ 300 seconds, mixed performed polymer uniformly, add the neutralizing agent suitable with carboxylate radical mole number in emulsifying agent to neutralize, be then scattered in deionized water under the high-speed stirring of 800 ~ 2000r/min, obtain the aqueous polyurethane colostric fluid of high solid content; The rear chainextender being 0.01 ~ 0.8:1 by NCO mol ratio in its active function groups and aqueous polyurethane colostric fluid is added drop-wise in aqueous polyurethane colostric fluid, stir 0.5 ~ 2h, reduce pressure the solvent sloughed in base polyurethane prepolymer for use as, obtains the aqueous polyurethane emulsion of high solid content.
9. application according to claim 8, is characterized in that, the aqueous polyurethane emulsion film forming of obtained high solid content, dries 2 ~ 10min for 130 ~ 150 DEG C.
10. application according to claim 8, is characterized in that, the preparation method of above-mentioned base polyurethane prepolymer for use as is as follows:
1) be that one or more in 500 ~ 4000 polymer diatomic alcohols or polymer polyatomic alcohol are warming up to 90 ~ 120 DEG C by the molecular weight of 50 ~ 80 mass parts, vacuum hydro-extraction 30 ~ 90min, the vulcabond of 10 ~ 50 mass parts is added after cooling to 55 ~ 75 DEG C, stir under nitrogen protection, churning time is 0.5 ~ 1h, then at least one is added in the dibutyl tin laurate of 0.01 ~ 0.2 mass parts, stannous octoate as catalyzer, at 60 ~ 90 DEG C, react 1 ~ 3h, obtain the reactant of clear;
2) with 2,2-dimethylol propionic acid (DMPA), 2, at least one in 2-dimethylolpropionic acid (DMBA), second diamino ethyl sulfonic acid sodium, second dihydroxyl ethyl sulfonic acid sodium is as hydrophilic chain extender, with 1,4-butyleneglycol, glycol ether, 2-methyl propanediol, 3-methyl pentanediol, neopentyl glycol, 1, at least one in 6-hexylene glycol, 2-methyl-2-ethyl glycol, TriMethylolPropane(TMP) is as small molecule chain extender, using at least one in acetone, butanone, DMF, N-Methyl pyrrolidone, N-ethyl pyrrolidone as solvent; The small molecule chain extender of the hydrophilic chain extender of 0.5 ~ 5 mass parts, 1 ~ 15 mass parts, the solvent of 0.1 ~ 50 mass parts are joined step 1) in the reactant that obtains, at 60 ~ 90 DEG C, react 1 ~ 3h; Cool to 45 ~ 70 DEG C, obtain the base polyurethane prepolymer for use as clarifying thickness.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543402A (en) * | 2016-10-21 | 2017-03-29 | 杭州传化精细化工有限公司 | A kind of preparation method of cross-linking block graft type high molecular polymer |
| CN108484862A (en) * | 2018-04-11 | 2018-09-04 | 肇庆市华莱特复合新型材料有限公司 | A kind of aqueous polyurethane dispersion and preparation method thereof |
| CN115403730A (en) * | 2022-10-13 | 2022-11-29 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
| CN115926105A (en) * | 2022-12-30 | 2023-04-07 | 佛山市精信汇明科技有限公司 | Reactive polyurethane anionic-nonionic emulsifier and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5189133A (en) * | 1991-02-27 | 1993-02-23 | Bayer Aktiengesellschaft | Hydrophylic, olefinically unsaturated polyurethanes and their use as reactive emulsifiers |
-
2015
- 2015-02-13 CN CN201510078433.3A patent/CN104672422B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5189133A (en) * | 1991-02-27 | 1993-02-23 | Bayer Aktiengesellschaft | Hydrophylic, olefinically unsaturated polyurethanes and their use as reactive emulsifiers |
Non-Patent Citations (4)
| Title |
|---|
| 代少俊等: "《涂料和粘合剂》", 31 August 2014, 江苏大学出版社 * |
| 任天斌等: "阴离子聚氨酯预聚体可聚合乳化剂的合成及性质研究", 《胶体与聚合物》 * |
| 张洪涛等: "聚氨酯预聚体—可聚合乳化剂用于MMA乳液聚合动力学及聚合稳定性研究", 《弹性体》 * |
| 耿耀宗: "《现代水性涂料工艺、配方、应用》", 30 April 2013, 中国石化出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543402A (en) * | 2016-10-21 | 2017-03-29 | 杭州传化精细化工有限公司 | A kind of preparation method of cross-linking block graft type high molecular polymer |
| CN108484862A (en) * | 2018-04-11 | 2018-09-04 | 肇庆市华莱特复合新型材料有限公司 | A kind of aqueous polyurethane dispersion and preparation method thereof |
| CN115403730A (en) * | 2022-10-13 | 2022-11-29 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
| CN115403730B (en) * | 2022-10-13 | 2023-06-27 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
| CN115926105A (en) * | 2022-12-30 | 2023-04-07 | 佛山市精信汇明科技有限公司 | Reactive polyurethane anionic-nonionic emulsifier and preparation method and application thereof |
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