CN105273153A - Degradable biological-based waterborne emulsion and preparation method thereof - Google Patents
Degradable biological-based waterborne emulsion and preparation method thereof Download PDFInfo
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- CN105273153A CN105273153A CN201410353483.3A CN201410353483A CN105273153A CN 105273153 A CN105273153 A CN 105273153A CN 201410353483 A CN201410353483 A CN 201410353483A CN 105273153 A CN105273153 A CN 105273153A
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Abstract
The invention discloses a degradable biological-based waterborne emulsion and a preparation method thereof. The preparation method comprises the following steps: carrying out a polymerization reaction on purified L-lactide, epsilon-caprolactone and polyol under the action of a catalyst, to obtain hydroxyl-terminated polyester polyol with the viscosity average molecular weight of 1000-10000; carrying out a reaction of hydroxyl-terminated polyester polyol, diisocyanate and a hydrophilic chain extender under the action of a catalyst, to obtain a prepolymer; and adding an emulsifier and water in the prepolymer, carrying out high-speed stirring emulsification, and carrying out a reaction with a crosslinking agent, to obtain the degradable waterborne emulsion. The degradable biological-based emulsion and the preparation method thereof are novel; the polylactide and caprolactone random copolymer which can be fully biodegradable is obtained, has relatively low glass transition temperature (Tg), has better emulsifying dispersion than polylactide, does not contain organic solvents, is biodegradable, can be widely applied in coatings, adhesives, fabric coating layers and other fields, is a quite good environmental-protection material, and has broad market prospects.
Description
Technical field
The invention belongs to biodegradable organic polymer technical field, be specifically related to a kind of degradable biological base water-based emulsion and preparation method thereof.
Background technology
In recent years, from the angle of environment protection, more active to investigation of materials biodegradable in physical environment.Particularly poly(lactic acid), polycaprolactone, PGA etc. its there is excellent biocompatibility and degradation property, and abundant raw material source, goods after discarded can in occurring in nature microorganism, water, the effect such as soda acid is lower decomposes, finally be decomposed into water and carbonic acid gas, any pollution can not be produced to environment, but these materials are generally that ring-opening polymerization obtains thermal plastic high polymer under catalyzer, and wetting ability is poor, be difficult to form water-based emulsion, limit its Application Areas, prepare degradable biological base water-based emulsion correlative study report at present seldom, the raw materials used abundance of the present invention is easy to get, the complete environmental protection of water-based emulsion of preparation, not containing organic solvent, and biological degradability is excellent, performance adjustability is interval wide.Patent CN200680005508.4 by PLA solution organic solvent toluene, then adds emulsifying agent and carries out emulsification, and after emulsification completes, underpressure distillation goes out organic solvent again, has finally prepared poly(lactic acid) emulsion.But use noxious solvent toluene in the method, this and poly(lactic acid) environmental protection concept are runed counter to; In addition, this poly(lactic acid) emulsion only can be used for coating film forming, and range of application is narrow.
Summary of the invention
For solving an above existing difficult problem, the invention discloses a kind of degradable biological base water-based emulsion and preparation method thereof, it comprises the following steps:
1, the L-rac-Lactide of purifying, 6-caprolactone, polyvalent alcohol are carried out polyreaction under catalyst action, obtain the hydroxyl telechelic polyester polyvalent alcohol of 1000-10000 viscosity-average molecular weight.
Wherein, the L-rac-Lactide optical purity after purifying is more than 99%, and moisture is at below 700ppm; 6-caprolactone purity is more than 99.5%; Catalyzer is stannous octoate or dibutyltin oxide, and consumption is the 0.05%-0.25% of L-rac-Lactide; Polyvalent alcohol is the initiator of polyreaction, is the one in ethylene glycol, tetramethylolmethane, glycerine or trimethylolethane; 6-caprolactone can carry out ring opening copolymer with L-rac-Lactide, can obtain polylactide and the caprolactone random copolymers of complete biodegradable, lower than the second-order transition temperature of pure polylactide (poly(lactic acid)), and emulsified dispersion easier in polylactide; Adopt nitrogen protection during polyreaction, reaction process takes gradient increased temperature, at 120-140 DEG C, react 4-8h, and raised temperature reacts 3-6h at 160-180 DEG C.
2, described hydroxyl telechelic polyester polyvalent alcohol, vulcabond and hydrophilic chain extender are reacted under catalyst action, obtain prepolymer.
Wherein, hydrophilic chain extender is the one in dihydroxypropionic acid, quadrol base ethyl sulfonic acid sodium, N methyldiethanol amine; Catalyzer is dibutyl tin laurate.
3, described prepolymer added emulsifying agent and water and after high-speed stirring emulsification, reacting with linking agent, obtain degradable aqueous emulsion.
Wherein, emulsifying agent is one or more in alkylphenol-polyethenoxy, fatty alcohol-polyoxyethylene ether, isomeric alcohol polyethenoxy ether, Sodium dodecylbenzene sulfonate, Soxylat A 25-7 sorbitan mono-laurate, Soxylat A 25-7 sorbitan monostearate or Soxylat A 25-7 sorbitan monooleate; Linking agent is TriMethylolPropane(TMP), trolamine or triethylamine.
Beneficial effect: degradable biological base emulsion of the present invention and preparation method's novelty, by bio-based L-rac-Lactide and 6-caprolactone are carried out ring opening copolymer, obtain polylactide and the caprolactone random copolymers of fully biodegradable, there is lower second-order transition temperature (Tg), than polylactide (poly(lactic acid)), there is better emulsifying dispersivity, domestic and international rarely seen relevant report and research, it is not only containing organic solvent, and there is biodegradable characteristics, the pressure to environment can be reduced, be a kind of very environmental protection material, there is wide market potential, coating can be widely used in later, sizing agent, the fields such as fabric coating, have broad application prospects and market potential.
Embodiment
By following examples, the present invention is described, but does not limit the present invention.
Embodiment 1
React front nitrogen flask is blown off.By the L-rac-Lactide after 70g purifying, 30g 6-caprolactone, 1.5g ethylene glycol joins in 500ml four-hole boiling flask, then 0.2g catalyst oxidation dibutyl tin is added, vacuumize and carry out nitrogen replacement, under nitrogen protection condition, increase the temperature to 130 DEG C, 6h is reacted under 130 DEG C of conditions, increase the temperature to 170 DEG C of reaction 5h, then room temperature is down to, in flask, add 25g isophorone diisocyanate (IPDI) again heat while stirring, under nitrogen protection, be warmed up to 85 DEG C to react, when NCO content reaches theoretical value 10%, dihydroxymethyl acid 5g is added again in reaction vessel, dibutyl tin laurate 0.1g, react 1 hour at 80 DEG C, then in flask, 5.0g alkylphenol polyoxyethylene OP-10 is added, 280g water, after high-speed stirring emulsification 30min, add 5g trolamine, be warming up to 50 DEG C, continue stirring after 20 minutes, be cooled to room temperature and obtain degradable biological base water-based emulsion.
Result shows: be white emulsion by the degradable biological base water-based emulsion obtained, and is placed in 60 DEG C of baking ovens and places 20 days without solid matter precipitation, and gel does not occur.
Embodiment 2
React front nitrogen flask is blown off.By the L-rac-Lactide after 80g purifying, 20g 6-caprolactone, 2g tetramethylolmethane joins in 500ml four-hole boiling flask, then the sub-tin of 0.15g octoate catalyst is added, vacuumize and carry out nitrogen replacement, under nitrogen protection condition, increase the temperature to 135 DEG C, 5h is reacted under 135 DEG C of conditions, increase the temperature to 175 DEG C of reaction 4h, then room temperature is down to, in flask, add 25gL-lysinediisocyanate (LDI) again heat while stirring, under nitrogen protection, be warmed up to 85 DEG C to react, when NCO content reaches theoretical value 10%, quadrol base ethyl sulfonic acid sodium 8g is added again in reaction vessel, dibutyl tin laurate 0.1g, react 1 hour at 80 DEG C, then in flask, 5.0g fatty alcohol-polyoxyethylene ether 0-15 is added, 280g water, after high-speed stirring emulsification 30min, add 5g triethylamine, be warming up to 50 DEG C, continue stirring after 20 minutes, be cooled to room temperature and obtain degradable biological base water-based emulsion.
Result shows: be white emulsion by the degradable biological base water-based emulsion obtained, and is placed in 60 DEG C of baking ovens and places 20 days without solid matter precipitation, and gel does not occur.
Embodiment 3
React front nitrogen flask is blown off.By the L-rac-Lactide after 75g purifying, 25g 6-caprolactone, 1.5g ethylene glycol joins in 500ml four-hole boiling flask, then 0.2g catalyst oxidation dibutyl tin is added, vacuumize and carry out nitrogen replacement, under nitrogen protection condition, increase the temperature to 130 DEG C, 6h is reacted under 130 DEG C of conditions, increase the temperature to 170 DEG C of reaction 5h, then room temperature is down to, in flask, add 25g isophorone diisocyanate (IPDI) again heat while stirring, under nitrogen protection, be warmed up to 85 DEG C to react, when NCO content reaches theoretical value 10%, N methyldiethanol amine 5g is added again in reaction vessel, dibutyl tin laurate 0.1g, react 1 hour at 80 DEG C, then in flask, 5.0g isomerous tridecanol polyoxyethylene ether is added, 280g water, after high-speed stirring emulsification 30min, add 5g trolamine, be warming up to 50 DEG C, continue stirring after 20 minutes, be cooled to room temperature and obtain degradable biological base water-based emulsion.
Result shows: be white emulsion by the degradable biological base water-based emulsion obtained, and is placed in 60 DEG C of baking ovens and places 20 days without solid matter precipitation, and gel does not occur.
Embodiment 4
React front nitrogen flask is blown off.By the L-rac-Lactide after 60g purifying, 40g 6-caprolactone, 1.0g ethylene glycol joins in 500ml four-hole boiling flask, then the sub-tin of 0.2g octoate catalyst is added, vacuumize and carry out nitrogen replacement, under nitrogen protection condition, increase the temperature to 140 DEG C, 4h is reacted under 140 DEG C of conditions, increase the temperature to 180 DEG C of reaction 4h, then room temperature is down to, in flask, add 20g hexamethylene diisocyanate (HDI) again heat while stirring, under nitrogen protection, be warmed up to 85 DEG C to react, when NCO content reaches theoretical value 10%, dihydroxymethyl acid 5g is added again in reaction vessel, dibutyl tin laurate 0.1g, react 1 hour at 80 DEG C, then in flask, add 5.0g Soxylat A 25-7 sorbitan monooleate Tween80, 280g water, after high-speed stirring emulsification 30min, add 5g TriMethylolPropane(TMP), be warming up to 50 DEG C, continue stirring after 20 minutes, be cooled to room temperature and obtain degradable biological base water-based emulsion.
Result shows: be white emulsion by the degradable biological base water-based emulsion obtained, and is placed in 60 DEG C of baking ovens and places 20 days without solid matter precipitation, and gel does not occur.
Claims (9)
1. degradable biological base water-based emulsion and preparation method thereof, it is characterized in that, comprise the following steps: the L-rac-Lactide of purifying, 6-caprolactone, polyvalent alcohol are carried out polyreaction under catalyst action, obtains the hydroxyl telechelic polyester polyvalent alcohol of 1000-10000 viscosity-average molecular weight; Described hydroxyl telechelic polyester polyvalent alcohol, vulcabond and hydrophilic chain extender are reacted under catalyst action, obtains prepolymer; Described prepolymer added emulsifying agent and water and after high-speed stirring emulsification, reacting with linking agent, obtain degradable aqueous emulsion.
2. according to claim 1, it is characterized in that, the optical purity after described L-rac-Lactide purifying is more than 99%, and moisture is at below 700ppm; 6-caprolactone purity is more than 99.5%.
3. according to claim 1, it is characterized in that, the catalyzer of described polyreaction is stannous octoate or dibutyltin oxide, and consumption is the 0.05%-0.25% of L-rac-Lactide.
4. according to claim 1, it is characterized in that, described polyvalent alcohol is the initiator of polyreaction, is the one in ethylene glycol, tetramethylolmethane, glycerine or trimethylolethane.
5. according to claim 1, it is characterized in that, adopt nitrogen protection during described polyreaction, reaction process takes gradient increased temperature, at 120-140 DEG C, react 4-8h, and raised temperature reacts 3-6h at 160-180 DEG C.
6. according to claim 1, it is characterized in that, described hydrophilic chain extender is the one in dihydroxypropionic acid, quadrol base ethyl sulfonic acid sodium, N methyldiethanol amine.
7. according to claim 1, it is characterized in that, during the reaction of described hydroxyl telechelic polyester polyvalent alcohol, vulcabond and hydrophilic chain extender, used catalyst is dibutyl tin laurate.
8. according to claim 1, it is characterized in that, described emulsifying agent is one or more in alkylphenol-polyethenoxy, fatty alcohol-polyoxyethylene ether, isomeric alcohol polyethenoxy ether, Sodium dodecylbenzene sulfonate, Soxylat A 25-7 sorbitan mono-laurate, Soxylat A 25-7 sorbitan monostearate or Soxylat A 25-7 sorbitan monooleate.
9. according to claim 1, it is characterized in that, described linking agent is TriMethylolPropane(TMP), trolamine or triethylamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793546A (en) * | 2017-11-13 | 2018-03-13 | 中海油常州涂料化工研究院有限公司 | A kind of cation nonionic phenotype aqueous polyurethane and its preparation method and application |
| CN110745929A (en) * | 2019-10-17 | 2020-02-04 | 邱振权 | Emulsion flocculant |
| CN111849000A (en) * | 2020-06-23 | 2020-10-30 | 吴晓金 | Surface enhancement method for prolonging service life of biodegradable plastic product |
| CN115785882A (en) * | 2022-12-14 | 2023-03-14 | 苏州高泰电子技术股份有限公司 | Aqueous adhesive composition and application thereof |
| CN116478653A (en) * | 2022-12-27 | 2023-07-25 | 烟台德邦科技股份有限公司 | Bio-based degradable moisture-curable polyurethane hot melt adhesive and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013015685A1 (en) * | 2011-07-22 | 2013-01-31 | Innocore Technologies B.V. | Biodegradable, semi-crystalline, phase separated, thermoplastic multi block copolymers for controlled release of biologically active compounds |
-
2014
- 2014-07-24 CN CN201410353483.3A patent/CN105273153A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013015685A1 (en) * | 2011-07-22 | 2013-01-31 | Innocore Technologies B.V. | Biodegradable, semi-crystalline, phase separated, thermoplastic multi block copolymers for controlled release of biologically active compounds |
Non-Patent Citations (2)
| Title |
|---|
| 田存等: ""PEG对生物可降解聚氨酯性能影响的研究"", 《化学推进剂与高分子材料》 * |
| 项尚林等: ""可生物降解水性聚氨酯乳液的合成"", 《包装工程》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793546A (en) * | 2017-11-13 | 2018-03-13 | 中海油常州涂料化工研究院有限公司 | A kind of cation nonionic phenotype aqueous polyurethane and its preparation method and application |
| CN110745929A (en) * | 2019-10-17 | 2020-02-04 | 邱振权 | Emulsion flocculant |
| CN111849000A (en) * | 2020-06-23 | 2020-10-30 | 吴晓金 | Surface enhancement method for prolonging service life of biodegradable plastic product |
| CN111849000B (en) * | 2020-06-23 | 2022-09-09 | 吴晓金 | Surface enhancement method for prolonging service life of biodegradable plastic product |
| CN115785882A (en) * | 2022-12-14 | 2023-03-14 | 苏州高泰电子技术股份有限公司 | Aqueous adhesive composition and application thereof |
| CN116478653A (en) * | 2022-12-27 | 2023-07-25 | 烟台德邦科技股份有限公司 | Bio-based degradable moisture-curable polyurethane hot melt adhesive and preparation method thereof |
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