CN104558497A - Preparation method of waterborne polyurethane emulsion modified by natural monosaccharide compound - Google Patents
Preparation method of waterborne polyurethane emulsion modified by natural monosaccharide compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a waterborne polyurethane emulsion modified by a natural monosaccharide compound. The preparation method comprises the following steps: firstly, adding polyglycol to a dry reaction bottle, heating to melt the polyglycol in the reaction bottle and vacuumizing to removal water for 1 hour at 120 DEG C; next, adding a hydrophilic reagent, a chain extender and diisocyanate to the reaction bottle to have a polymerization reaction, thereby obtaining a polyurethane prepolymer; next, adding the natural monosaccharide compound for reacting, cooling after a period of time, and adding an organic base to regulate the pH value of the reaction; and adding deionized water under high speed stirring for emulsifying, and removing the solvent by virtue of reduced pressure distillation, thereby obtaining the waterborne polyurethane emulsion modified by the natural monosaccharide compound. According to the preparation method, the waterborne polyurethane is modified by use of the natural monosaccharide, and the product has excellent overall properties, and also is environment-friendly, harmless, cheap and the like. The coating of the product can be just thermally decomposed at 300 DEG C; compared with the polyurethane before modification, the heat resistance of the modified polyurethane is obviously improved, and meanwhile, the water tolerance of the modified polyurethane is also greatly improved.
Description
Technical field
The invention belongs to field of macromolecular chemical material, specifically, relate to a kind of natural monosaccharide compound modified aqueous polyurethane emulsion preparation method.
Background technology
Urethane is a kind of multifunctional macromolecule material, and its raw material variety is various, and molecular structure is adjustable, is widely used in multiple fields such as porous plastics, elastomerics, sizing agent, coating.Polyurethane material has excellent snappiness, shock-resistance, solvent resistance, and its wear resistance, resistance to low temperature are excellent especially.Current polyurethane material has solvent-borne type and water-soluble two class.In general, solvent borne polyurethane is formed by solution polymerization for primary solvent with acetone, butanone, toluene etc., these solvents are all noxious solvents, therefore in production and use procedure contaminate environment, safety coefficient low, have very large harm to the healthy of people.Along with social progress and scientific and technical development, the environmental consciousness of people constantly strengthens, and development high quality, free of contamination environment-protecting polyurethane become development trend.
Aqueous polyurethane is using water to replace organic solvent as dispersion medium, has the advantages such as nontoxic, environmental protection, cheapness, is more and more subject to people's attention, is widely used in fields such as coating, sizing agent, leather finishes.But owing to needing to add hydrophilic reagent in water-base polyurethane material building-up process, introduce carboxyl or sodium group, some shortcomings such as viscosity is little, water tolerance, poor heat resistance that cause urethane to exist.The domestic research activities about synthesis aqueous polyurethane is very active at present.Little beautiful (CN101845133A) is such as relied to disclose a kind of preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion; Wang Xinbo (CN101429417A) discloses a kind of water-based polyurethane adhesive of the high adhesion adopting aliphatic isocyanates to synthesize; The people (CN1350016A) such as north Tian Man disclose a kind of aqueous binders containing polyurethane aqueous dispersion body, these aqueous polyurethanes have certain cementability, but the feature such as the thermomechanical property of all keeping away unavoidable glued membrane is not good and water-fast, solvent resistant, hardness are lower.
Summary of the invention
The present invention aims to provide the preparation method of a kind of cheapness, simple, the eco-friendly natural monosaccharide modified aqueous polyurethane emulsion of technique, and technical problem to be solved is under the prerequisite that can ensure polyaminoester emulsion mechanical property, improve water resistance and the resistance toheat of polyaminoester emulsion.
The present invention solves the technical scheme that its problem adopts:
A preparation method for natural monosaccharide modified aqueous polyurethane emulsion, comprises pre-polymerization, chain extension, neutralization and emulsifying step;
Polyglycol put into dry reactor in described pre-polymerization, after heating makes the polyglycol melting in reaction flask, at 120 DEG C, vacuumize the 1h that dewaters, be cooled to 70-80 DEG C subsequently and add hydrophilic reagent and stir, then vulcabond is joined in reactor carry out polyreaction.Wherein the ratio of the amount of substance of hydrophilic reagent and polyoxyethylene glycol is 3:100-5:100, and wherein vulcabond is 1.5:1-4:1 with the ratio of the amount of substance of polyoxyethylene glycol, and the reaction times is 1-5h;
Described chain extension joins in reaction flask by the DMF solution of chainextender BDO, natural monosaccharide compound, continues to react 1-4h at the temperature disclosed above, and wherein BDO is 0.5:1-1.5:1 with the ratio of the amount of substance of polyglycol; Wherein natural monosaccharide compound is 0.8:1-1.5:1 with the ratio of the amount of substance of polyglycol;
Described neutralization be by chain extension after reaction solution be cooled to 20 DEG C-30 DEG C and add organic bases neutralization reaction 30min; Wherein organic bases is 1:1-1.2:1 with the ratio of the amount of substance of hydrophilic reagent;
Described emulsification be by neutralization after reaction solution be cooled to 20 DEG C-30 DEG C after, add 0 DEG C of-10 DEG C of deionized water, make reaction solution emulsification under high-speed stirring, last underpressure distillation goes out desolventizing and obtains emulsion.
In above-mentioned preparation method, described polyglycol is polyester diol, and the relative molecular mass of polyester diol is 2000; Polyester diol is poly adipate succinic acid ester dibasic alcohol, one of PCDL or polycaprolactone diols or any two mixture.
In above-mentioned preparation method, described vulcabond is isophorone diisocyanate, tolylene diisocyanate, one of hexamethylene diisocyanate or diphenylmethanediisocyanate or any two mixture.
In above-mentioned preparation method, described hydrophilic reagent is carboxylic acid type: be one of dihydroxypropionic acid or dihydroxyl butyric acid.
In above-mentioned preparation method, described natural monosaccharide compound is fructose, one of glucose or semi-lactosi.
In preparation method described above, described organic bases be triethylamine, diethylamine, diisopropylamine or
n,None of-diisopropylethylamine.
Compared with prior art, the present invention has following beneficial effect:
1. preparation technology of the present invention is simple, and reaction conditions is gentle, and product characteristics is stablized, and production cost is low, is conducive to large-scale industrial production application, thus has broad application prospects.
2. the present invention synthesizes aqueous polyurethane and has the advantage such as simple economy, environmental protection, can not produce secondary pollution, thus have the social value theory of environmental protection.
3. the present invention utilizes natural monosaccharide compound to carry out modification to aqueous polyurethane, obtain the polyurethane material of excellent combination property, utilize natural monosaccharide to participate in reaction and hydroxyl is incorporated into polyurethane backbone, complicated structure can be formed, compare traditional waterborne polyurethane, water tolerance, thermotolerance, initial bonding strength are significantly improved.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of natural monosaccharide compound modified aqueous polyurethane.
Fig. 2 is the thermal multigraph of natural monosaccharide compound modified aqueous polyurethane, and X-coordinate is temperature T/ DEG C, and ordinate zou is rate of weight loss TG/%.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but protection scope of the present invention is not limited thereto.
Embodiment 1:
(1) PCDL is added in dry reactor; after heating makes the polyglycol melting in reaction flask; the 1h that dewaters is vacuumized at 120 DEG C; be cooled to 80 DEG C subsequently; dihydroxypropionic acid is added in reaction flask and stirs 10min; then isophorone diisocyanate is added in reaction flask, under 80 DEG C of nitrogen protections, react 4h.Wherein isophorone diisocyanate is 2:1 with the ratio of the amount of substance of PCDL, and dihydroxypropionic acid is 3:100 with the ratio of the amount of substance of PCDL;
(2) chainextender BDO is added reaction 1h, subsequently fructose (being dissolved in DMF) is added in reactor, 70 DEG C of reaction 3h, wherein BDO and PCDL are 0.5:1, and fructose is 1:1 with the ratio of the amount of substance of PCDL;
(3) reaction is cooled to 25 DEG C, adds triethylamine and regulate the pH value of reaction to be 7.5, add the deionized water that temperature is 25 DEG C under high shear agitation, namely obtain the aqueous polyurethane emulsion that natural monosaccharide is compound modified.
Embodiment 2:
(1) poly adipate succinic acid ester dibasic alcohol is joined in dry reactor, after heating makes the polyglycol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 70 DEG C subsequently, dihydroxypropionic acid is added in reaction flask and stirs 10min, then isophorone diisocyanate and hexamethylene diisocyanate is added, the lower 70 DEG C of reaction 4h of nitrogen protection, wherein dihydroxypropionic acid is 4:100 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol, vulcabond is 1.6:1 with the ratio of the amount of substance of poly adipate succinic acid ester, isophorone diisocyanate is 1:1 with the ratio of hexamethylene diisocyanate amount of substance,
(2) by chainextender 1,4-butyleneglycol adds reaction 0.5h, subsequently fructose (being dissolved in DMF) is added in reactor, 70 DEG C of reaction 3h, wherein 1,4-butyleneglycol and poly adipate succinic acid ester dibasic alcohol are 0.8:1, and fructose is 0.8:1 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol;
(3) reaction is cooled to 25 DEG C, adds triethylamine and regulate the pH value of reaction to be 7.5, add the deionized water that temperature is 10 DEG C under high shear agitation, namely obtain the aqueous polyurethane emulsion that natural monosaccharide is compound modified.Fig. 1 and Fig. 2 is shown in the test of its infrared detection, thermogravimetric.
Embodiment 3:
(1) poly adipate succinic acid ester dibasic alcohol is joined in dry reactor, after heating makes the polyglycol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 70 DEG C subsequently, dihydroxypropionic acid is added in reaction flask and stirs 10min, then isophorone diisocyanate and hexamethylene diisocyanate is added, the lower 70 DEG C of reaction 4h of nitrogen protection, wherein dihydroxypropionic acid is 3:100 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol, vulcabond is 2:1 with the ratio of the amount of substance of poly adipate succinic acid ester, isophorone diisocyanate is 1:1 with the ratio of hexamethylene diisocyanate amount of substance,
(2) by chainextender 1,4-butyleneglycol adds reaction 0.5h, subsequently fructose (being dissolved in DMF) is added in reactor, 70 DEG C of reaction 3h, wherein 1,4-butyleneglycol and poly adipate succinic acid ester dibasic alcohol are 0.8:1, and fructose is 0.8:1 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol;
(3) reaction is cooled to 25 DEG C, adds triethylamine and regulate the pH value of reaction to be 7.5, add the deionized water that temperature is 5 DEG C under high shear agitation, namely obtain the aqueous polyurethane emulsion that natural monosaccharide is compound modified.
Embodiment 4:
(1) polycaprolactone diols is joined in dry reactor, after heating makes the polyglycol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, dihydroxyl butyric acid is added in reaction flask and stirs 10min, then isophorone diisocyanate and hexamethylene diisocyanate is added, the lower 80 DEG C of reaction 5h of nitrogen protection, wherein dihydroxyl top butyric acid is 4:100 with the ratio of the amount of substance of polycaprolactone diols, vulcabond is 2:1 with the ratio of the amount of substance of poly adipate succinic acid ester, isophorone diisocyanate is 1:1 with the ratio of hexamethylene diisocyanate amount of substance,
(2) chainextender BDO is added reaction 0.5h, subsequently semi-lactosi (being dissolved in DMF) is added in reactor, 70 DEG C of reaction 3h, wherein BDO and polycaprolactone diols are 0.8:1, and fructose is 0.8:1 with the ratio of the amount of substance of polycaprolactone diols;
(3) reaction is cooled to 30 DEG C, adds
n,None of-diisopropylethylamine regulates the pH value of reaction to be 7.5, adds the deionized water that temperature is 5 DEG C, namely obtain the aqueous polyurethane emulsion that natural monosaccharide is compound modified under high shear agitation.
Embodiment 5:
(1) poly adipate succinic acid ester dibasic alcohol is joined in dry reactor, after heating makes the polyglycol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 70 DEG C subsequently, dihydroxypropionic acid is added in reaction flask and stirs 10min, then isophorone diisocyanate and hexamethylene diisocyanate is added, the lower 70 DEG C of reaction 4h of nitrogen protection, wherein dihydroxypropionic acid is 3:100 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol, vulcabond is 2:1 with the ratio of the amount of substance of poly adipate succinic acid ester, isophorone diisocyanate is 1:1 with the ratio of hexamethylene diisocyanate amount of substance,
(2) by chainextender 1,4-butyleneglycol adds reaction 0.5h, subsequently glucose (being dissolved in DMF) is added in reactor, 70 DEG C of reaction 3h, wherein 1,4-butyleneglycol and poly adipate succinic acid ester dibasic alcohol are 0.8:1, and glucose is 0.8:1 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol;
(3) reaction is cooled to 25 DEG C, add the viscosity that acetone reduces performed polymer, adding triethylamine subsequently regulates the pH value of reaction to be 7.5, add under high shear agitation temperature be the deionized water underpressure distillation of 5 DEG C except desolventizing, the aqueous polyurethane emulsion that natural monosaccharide is compound modified can be obtained.
Embodiment 6:
(1) PCDL is added in dry reactor, after heating makes the polyglycol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 75 DEG C subsequently, dihydroxypropionic acid is added in reaction flask and stirs 10min, then isophorone diisocyanate is added in reaction flask, 4h is reacted under 75 DEG C of nitrogen protections, wherein isophorone diisocyanate is 2:1 with the ratio of the amount of substance of PCDL, and dihydroxypropionic acid is 3:100 with the ratio of the amount of substance of PCDL;
(2) chainextender BDO is added reaction 1h, subsequently fructose (being dissolved in DMF) is added in reactor, 70 DEG C of reaction 3h, wherein BDO and PCDL are 0.5:1, and fructose is 1:1 with the ratio of the amount of substance of PCDL;
(3) reaction is cooled to 25 DEG C, add the viscosity that acetone reduces performed polymer, adding triethylamine subsequently regulates the pH value of reaction to be 7.5, add under high shear agitation temperature be the deionized water underpressure distillation of 25 DEG C except desolventizing, namely obtain the aqueous polyurethane emulsion that natural monosaccharide is compound modified.
Claims (6)
1. a preparation method for natural monosaccharide modified aqueous polyurethane emulsion, is characterized in that comprising pre-polymerization, chain extension, neutralization and emulsifying step; Polyglycol put into dry reactor in described pre-polymerization, after heating makes the polyglycol melting in reaction flask, at 120 DEG C, vacuumize the 1h that dewaters, be cooled to 70-80 DEG C subsequently and add hydrophilic reagent and stir, then vulcabond is joined in reactor carry out polyreaction; Wherein the ratio of the amount of substance of hydrophilic reagent and polyoxyethylene glycol is 3:100-5:100, and wherein vulcabond is 1.5:1-4:1 with the ratio of the amount of substance of polyoxyethylene glycol, and the reaction times is 1-5h;
Described chain extension joins in reaction flask by the DMF solution of chainextender BDO, natural monosaccharide compound, continues to react 1-4h at the temperature disclosed above, and wherein BDO is 0.5:1-1.5:1 with the ratio of the amount of substance of polyglycol; Wherein natural monosaccharide compound is 0.8:1-1.5:1 with the ratio of the amount of substance of polyglycol;
Described neutralization be by chain extension after reaction solution be cooled to 20 DEG C-30 DEG C and add organic bases neutralization reaction 30min; Wherein organic bases is 1:1-1.2:1 with the ratio of the amount of substance of hydrophilic reagent;
Described emulsification be by neutralization after reaction solution be cooled to 20 DEG C-30 DEG C after, add 0 DEG C of-10 DEG C of deionized water, make reaction solution emulsification under high-speed stirring, last underpressure distillation goes out desolventizing and obtains emulsion.
2. preparation method according to claim 1, is characterized in that: described polyglycol is polyester diol, and the relative molecular mass of polyester diol is 2000; Polyester diol is poly adipate succinic acid ester dibasic alcohol, one of PCDL or polycaprolactone diols or any two mixture.
3. preparation method according to claim 1, is characterized in that: described vulcabond is isophorone diisocyanate, tolylene diisocyanate, one of hexamethylene diisocyanate or diphenylmethanediisocyanate or any two mixture.
4. preparation method according to claim 1, is characterized in that: described hydrophilic reagent is carboxylic acid type, is one of dihydroxypropionic acid or dihydroxyl butyric acid.
5. preparation method according to claim 1, is characterized in that: described natural monosaccharide compound is fructose, one of glucose or semi-lactosi.
6. preparation method according to claim 1, is characterized in that: described organic bases be triethylamine, diethylamine, diisopropylamine or
n,None of-diisopropylethylamine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928427A (en) * | 2017-03-03 | 2017-07-07 | 中国科学院长春应用化学研究所 | Carbon dioxide-base cation aqueous polyurethane resin and its preparation method and application |
| CN108610942A (en) * | 2018-05-18 | 2018-10-02 | 安徽朗凯奇建材有限公司 | A kind of polymerization of acrylic modified polyurethane water-repellent paint and preparation method thereof |
| CN110092883A (en) * | 2019-04-25 | 2019-08-06 | 中科广化（重庆）新材料研究院有限公司 | Corrosion-resistant aqueous supermolecule polyurethane resin of one kind and the preparation method and application thereof |
| CN112341592A (en) * | 2020-09-22 | 2021-02-09 | 长春工业大学 | Preparation method of glucose and sulfonate modified degradable waterborne polyurethane |
-
2015
- 2015-02-09 CN CN201510065502.7A patent/CN104558497A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928427A (en) * | 2017-03-03 | 2017-07-07 | 中国科学院长春应用化学研究所 | Carbon dioxide-base cation aqueous polyurethane resin and its preparation method and application |
| CN108610942A (en) * | 2018-05-18 | 2018-10-02 | 安徽朗凯奇建材有限公司 | A kind of polymerization of acrylic modified polyurethane water-repellent paint and preparation method thereof |
| CN110092883A (en) * | 2019-04-25 | 2019-08-06 | 中科广化（重庆）新材料研究院有限公司 | Corrosion-resistant aqueous supermolecule polyurethane resin of one kind and the preparation method and application thereof |
| CN112341592A (en) * | 2020-09-22 | 2021-02-09 | 长春工业大学 | Preparation method of glucose and sulfonate modified degradable waterborne polyurethane |
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Application publication date: 20150429 |