CN101240056A - Method for preparing castor oil plasticizing polylactic acid type polyurethane - Google Patents
Method for preparing castor oil plasticizing polylactic acid type polyurethane Download PDFInfo
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- CN101240056A CN101240056A CNA2008100470321A CN200810047032A CN101240056A CN 101240056 A CN101240056 A CN 101240056A CN A2008100470321 A CNA2008100470321 A CN A2008100470321A CN 200810047032 A CN200810047032 A CN 200810047032A CN 101240056 A CN101240056 A CN 101240056A
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Abstract
The invention provides a castor oil toughened polyurethane of polylactide type and preparation thereof. Firstly, polycondensation is directly carried out by L lactci acid and 4-butanediol to prepare prepolymer of hydroxyl-terminated lactic acid, hexamethylene diisocyanate is used as chain extender, then chain extension in solution and polymerization are carried out by castor oil to obtain polyurethane of polylactide type. The invention uses green material prepared form absolute natural raw material, keeps biodegradability of polyurethane, modifies weak mechanical property of polyurethane by copolymerizaiton of castor oil and polyurethane. The obtained polyurethane of polylactide type not only keeps degradability of polyurethane, but also increases toughness and elongation at break of castor oil.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of manufacture method of castor oil plasticizing polylactic acid type polyurethane.
Background technology
Along with petroleum-based energy imbalance between supply and demand day is becoming tight, oil price sharp rises, come from all types of plastic goods of oil production and be difficult to degraded again after discarded, severe contamination the ecotope that goes from bad to worse, directly threaten human existence, healthy with develop; Developing biodegradable " biological plastics " (being ecological friendly plastics) to replace, is trend of the times, is plastics industry developing direction from now on.
By the typical case's representative as natural materials of the poly(lactic acid) (PLA) that is polymerized, produce the 20%-50% that power consumption only is equivalent to traditional petrochemicals by biosynthetic lactic acid, the carbon dioxide of generation is corresponding 50% only then.Because of its good processing properties, have biocompatibility and hypotoxicity simultaneously, become one of most active ecomaterial of Recent study.But the fragility of poly-lactic acid material is big, poor toughness and defect of high cost, has limited its widespread use.Along with the price increase of petroleum products, poly(lactic acid) will be occupied the more market share.Further improve the polymerization technique of lactic acid, the over-all properties that improves poly(lactic acid) is the focus of research.Therefore, it is good to develop over-all properties energetically, and the poly-lactic acid material that has biological degradability and lower cost again concurrently is brought benefit to the mankind, and has its own strategic significance and application prospect.
There are many researchs that poly(lactic acid) has been carried out modification at present both at home and abroad, for example 1) applying date 2005.4.30, application number 200510016771.0, Granted publication day 2007.8.8, the Chinese patent application file of patent No. ZL200510016771.0 " preparation method of surface lactic acid graft modified starch and aliphatic polyester graft copolymer " adopts the synthetic method of ring opening copolymer to obtain the mixture with good plasticity-and workability, but its complex process, cost is higher; 2) applying date 2005.11.10, the Chinese patent file of application number 200510110181.4 " a kind of preparation method of composite material of poly lacltic acid enhanced by ramie fiber " adopts the matrix material of higher molecular weight poly(lactic acid) preparation to have excellent interface performance, but it fails to improve preferably the mechanical property of material; 3) applying date 2005.12.28, the Chinese patent application file of application number 200510119120.4 " preparation method of complete biological degradation high flexible polyalctic material " carries out the crosslinked poly-lactic acid material that obtains having higher toughness with the poly-lactic acid material after the moulding under the irradiation of electron beam, but this class methods cost is higher, is difficult for industrial realization.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of castor oil plasticizing polylactic acid type polyurethane, the polylactic acid type polyurethane material of this method preparation had both kept the degradation property of poly(lactic acid), increased the toughness of Viscotrol C again, and cost was low, easily industrial realization.
Technical scheme of the present invention is:
(1) with L lactic acid and 1,4-butyleneglycol dehydration reaction 1～2 hour under 130～160 ℃ of temperature, condition of normal pressure, reduce pressure-0.08 again～-0.09MPa dehydration reaction 1～2 hour, reduce pressure-0.095 at last～-the 0.1MPa dehydration reaction obtained oligopolymer in 3～5 hours, described 1,4-butyleneglycol and L lactic acid mass ratio are 1: 50～400;
(2) add catalyzer in oligopolymer, described catalyzer and oligopolymer quality ratio are 1: 50～200,170～190 ℃ of temperature ,-0.095～-react under the 0.1MPa condition and obtained polyester glycol in 5～10 hours;
(3) in polyester glycol, add Viscotrol C, described Viscotrol C is 1～4: 1 with polyester glycol molar weight ratio, and its vacuum-drying was added chainextender after 1～2 hour, feeds rare gas element again, under 60～105 ℃ of temperature condition, reacted 1～2 hour, obtain castor oil plasticizing polylactic acid type polyurethane.
Described catalyzer is the binary mixture of tin compound or tin compound and protonic acid, and tin compound content is 0.4～1% of described oligopolymer quality, and protonic acid is 0.32～0.8% of a described oligopolymer quality.
Described chainextender is a kind of in tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), the diphenylmethanediisocyanate (MDI), and the amount of vulcabond is-NCO/-OH=0.8～1.2.
The performance that the present invention utilizes the premium properties of Viscotrol C to improve poly(lactic acid) lacks property, carries out copolyreaction by adding vulcabond with Viscotrol C and poly lactic acid type polyester glycol, obtains to have the thermoplasticity castor oil plasticizing polylactic acid type polyurethane of premium properties.Raw material of the present invention is from natural product, equipment is simple, operational path is short, and working method is easy, and cost is low, and can access polylactic acid type polyurethane copolymeric material with premium properties, this material can be degraded fully, environment is not produced and pollutes, and has both kept the degradation property of poly(lactic acid), increased the toughness and the elongation at break of Viscotrol C again, made that the range of application of polylactic acid-based material is more extensive.
Embodiment
Specific embodiment 1:
A. with 112 gram L lactic acid (88% aqueous solution) and 0.25 gram 1, the 4-butyleneglycol is added in the 250mL four-hole boiling flask, under 130～150 ℃ of normal pressures, stir dehydration 1～2 hour earlier, reduce pressure-0.08 again～-0.09MPa dehydration reaction 1～2 hour, obtain oligopolymer after under-0.1MPa, reacting 5～10 hours again, be about 70 grams; With 0.35 gram stannous chloride dihydrate, 0.28 gram tosic acid is added in the reaction system then, then 160～190 ℃ ,-reacted 5～15 hours under the 0.1MPa, obtain polyester glycol.
B. the Viscotrol C that takes by weighing the top synthetic polyester glycol of 10 grams and 2 times (mole numbers) is added in the 250mL four-hole bottle, earlier 110～120 ℃ of following vacuum-dryings 1～2 hour, adding 100mL toluene then in reactant dissolves reactant fully, then under agitation feed argon gas and be warmed up to 60～105 ℃, add the chainextender hexamethylene diisocyanate again (NCO/-OH=1.1), stirring reaction 2 hours, obtaining tensile strength is 3.15～6.34MPa, Young's modulus is 87.2～142.5MPa, and elongation at break is 25.6～32.5% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 2: the difference of present embodiment and specific embodiment 1 is that the content of Viscotrol C is 1 times of polyester glycol, other synthesis step is identical with specific embodiment 1 with processing condition, finally obtaining tensile strength is 0.42～0.77MPa, Young's modulus is 10.1～18.6MPa, and elongation at break is 6.5～32.2% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 3: when the difference of present embodiment and specific embodiment 1 is prepolymerization 1, the content of 4-butyleneglycol is 0.5% of lactic acid, other synthesis step is identical with specific embodiment 1 with processing condition, finally obtaining tensile strength is 18.3～35.2MPa, Young's modulus is 652～1235MPa, and elongation at break is 3.74～8.62% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 4: the content of Viscotrol C was 4 times of polyester glycol when the difference of present embodiment and specific embodiment 1 was chain extending reaction, other synthesis step is identical with specific embodiment 4 with processing condition, finally obtaining tensile strength is 15.5～31.3MPa, Young's modulus is 541～1045MPa, and elongation at break is 4.6～8.8% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 5: when the difference of present embodiment and specific embodiment 1 is prepolymerization 1, the content of 4-butyleneglycol is 0.75% of lactic acid, Viscotrol C is 4 times of polyester glycol during chain extending reaction, other synthesis steps are identical with specific embodiment 1 with technology, finally obtaining tensile strength is 0.87～1.82MPa, Young's modulus is 8.2～14.7MPa, and elongation at break is 7.6～21.3% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 6: when the difference of present embodiment and specific embodiment 1 is prepolymerization 1, the content of 4-butyleneglycol is 2% of lactic acid, Viscotrol C is 2 times (mole numbers) of polyester glycol, the amount of HDI is pressed-the NCO/-OH=1.0 adding, other synthesis steps are identical with specific embodiment 1 with technology, finally obtaining tensile strength is 1.06MPa, and Young's modulus is 19.7MPa, and elongation at break is 98.2～243.7% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 7: when the difference of present embodiment and specific embodiment 1 is prepolymerization 1, the content of 4-butyleneglycol is 0.5% of lactic acid, Viscotrol C is 2 times (mole numbers) of polyester glycol, chainextender is tolylene diisocyanate (TDI), other synthesis steps are identical with specific embodiment 1 with technology, finally obtaining tensile strength is 0.38～0.92MPa, and Young's modulus is 16.8～53.2MPa, and elongation at break is 15.2～32.4% castor oil plasticizing polylactic acid type polyurethane.
Specific embodiment 8: when the difference of present embodiment and specific embodiment 1 is prepolymerization 1, the content of 4-butyleneglycol is 0.5% of lactic acid, Viscotrol C is 2 times (mole numbers) of polyester glycol, chainextender is '-diphenylmethane diisocyanate (MDI), other synthesis steps are identical with specific embodiment 1 with technology, finally obtaining tensile strength is 0.82～3.92MPa, and Young's modulus is 25.8～102.8MPa, and elongation at break is 18.4～24.5% castor oil plasticizing polylactic acid type polyurethane.
Claims (7)
1, a kind of preparation method of castor oil plasticizing polylactic acid type polyurethane, carry out according to following steps:
(1) with L lactic acid and 1,4-butyleneglycol dehydration reaction 1～2 hour under 130～160 ℃ of temperature, condition of normal pressure, reduce pressure-0.08 again～-0.09MPa dehydration reaction 1～2 hour, reduce pressure-0.095 at last～-the 0.1MPa dehydration reaction obtained oligopolymer in 3～5 hours, described 1,4-butyleneglycol and L lactic acid mass ratio are 1: 50～400;
(2) add catalyzer in oligopolymer, described catalyzer and oligopolymer quality ratio are 1: 50～200,170～190 ℃ of temperature ,-0.095～-react under the 0.1MPa condition and obtained polyester glycol in 5～10 hours;
(3) in polyester glycol, add Viscotrol C, described Viscotrol C is 1～4: 1 with polyester glycol molar weight ratio, and its vacuum-drying was added chainextender after 1～2 hour, feeds rare gas element again, under 60～105 ℃ of temperature condition, reacted 1～2 hour, obtain castor oil plasticizing polylactic acid type polyurethane.
2, the preparation method of castor oil plasticizing polylactic acid type polyurethane according to claim 1 is characterized in that, described catalyzer is a tin compound.
3, the preparation method of castor oil plasticizing polylactic acid type polyurethane according to claim 1 is characterized in that, described catalyzer is the binary mixture of tin compound and protonic acid.
4, the preparation method of castor oil plasticizing polylactic acid type polyurethane according to claim 3 is characterized in that, described tin compound content is 0.4～1% of described oligopolymer quality, and described protonic acid is 0.32～0.8% of a described oligopolymer quality.
5, the preparation method of castor oil plasticizing polylactic acid type polyurethane according to claim 4 is characterized in that described tin compound is a stannous chloride dihydrate, and protonic acid is a tosic acid.
6, the preparation method of castor oil plasticizing polylactic acid type polyurethane according to claim 1, it is characterized in that described chainextender is a kind of in tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), the diphenylmethanediisocyanate (MDI).
7, the preparation method of castor oil plasticizing polylactic acid type polyurethane according to claim 5 is characterized in that, the amount of described vulcabond is-NCO/-OH=0.8～1.2.
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| CNA2008100470321A CN101240056A (en) | 2008-03-07 | 2008-03-07 | Method for preparing castor oil plasticizing polylactic acid type polyurethane |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102741311A (en) * | 2010-04-22 | 2012-10-17 | Dic株式会社 | Two-component curable foam polyurethane resin composition, molded body formed from the same, and shoe sole |
| CN102977319A (en) * | 2012-12-17 | 2013-03-20 | 中国科学院长春应用化学研究所 | Degradable polylactic acid diblock copolymer, preparation method and application to modified polylactic acid |
| CN104640896A (en) * | 2012-09-25 | 2015-05-20 | 拜耳材料科技股份有限公司 | Polyisocyanate-polyaddition products |
| CN104640897A (en) * | 2012-09-25 | 2015-05-20 | 拜耳材料科技股份有限公司 | Polyisocyanate-polyaddition products |
| CN105693987A (en) * | 2014-11-25 | 2016-06-22 | 江苏华信新材料股份有限公司 | Degradable waterborne polyurethane, and preparation method and applications thereof |
| CN106336496A (en) * | 2016-08-25 | 2017-01-18 | 中国电子科技集团公司第四十六研究所 | Modified polylactic acid material for 3D printing, and preparation method thereof |
| CN109563448A (en) * | 2016-07-27 | 2019-04-02 | 弗门尼舍有限公司 | The method for preparing microcapsules |
| CN113527611A (en) * | 2021-07-29 | 2021-10-22 | 华南理工大学 | Polyurethane dispersion liquid and preparation method and application thereof |
| WO2021237405A1 (en) * | 2020-05-25 | 2021-12-02 | 厦门双瑞船舶涂料有限公司 | Solvent-free marine antifouling coating and preparation method therefor |
| CN114085356A (en) * | 2021-11-19 | 2022-02-25 | 合肥安利聚氨酯新材料有限公司 | Chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and preparation method thereof |
| CN115505348A (en) * | 2022-10-25 | 2022-12-23 | 苏州世华新材料科技股份有限公司 | Impact-resistant degradable foam and preparation method thereof |
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2008
- 2008-03-07 CN CNA2008100470321A patent/CN101240056A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102741311B (en) * | 2010-04-22 | 2014-09-03 | Dic株式会社 | Two-component curable foam polyurethane resin composition, molded body formed from the same, and shoe sole |
| CN102741311A (en) * | 2010-04-22 | 2012-10-17 | Dic株式会社 | Two-component curable foam polyurethane resin composition, molded body formed from the same, and shoe sole |
| CN104640897B (en) * | 2012-09-25 | 2018-02-23 | 科思创德国股份有限公司 | Polyisocyanate polyaddition products |
| CN104640896A (en) * | 2012-09-25 | 2015-05-20 | 拜耳材料科技股份有限公司 | Polyisocyanate-polyaddition products |
| CN104640897A (en) * | 2012-09-25 | 2015-05-20 | 拜耳材料科技股份有限公司 | Polyisocyanate-polyaddition products |
| CN102977319A (en) * | 2012-12-17 | 2013-03-20 | 中国科学院长春应用化学研究所 | Degradable polylactic acid diblock copolymer, preparation method and application to modified polylactic acid |
| CN102977319B (en) * | 2012-12-17 | 2014-09-03 | 中国科学院长春应用化学研究所 | Degradable polylactic acid diblock copolymer, preparation method and application to modified polylactic acid |
| CN105693987B (en) * | 2014-11-25 | 2019-03-05 | 江苏华信新材料股份有限公司 | Degradable aqueous polyurethane and its preparation method and application |
| CN105693987A (en) * | 2014-11-25 | 2016-06-22 | 江苏华信新材料股份有限公司 | Degradable waterborne polyurethane, and preparation method and applications thereof |
| CN109563448A (en) * | 2016-07-27 | 2019-04-02 | 弗门尼舍有限公司 | The method for preparing microcapsules |
| CN106336496A (en) * | 2016-08-25 | 2017-01-18 | 中国电子科技集团公司第四十六研究所 | Modified polylactic acid material for 3D printing, and preparation method thereof |
| WO2021237405A1 (en) * | 2020-05-25 | 2021-12-02 | 厦门双瑞船舶涂料有限公司 | Solvent-free marine antifouling coating and preparation method therefor |
| CN113527611A (en) * | 2021-07-29 | 2021-10-22 | 华南理工大学 | Polyurethane dispersion liquid and preparation method and application thereof |
| CN113527611B (en) * | 2021-07-29 | 2023-03-21 | 华南理工大学 | Polyurethane dispersion liquid and preparation method and application thereof |
| CN114085356A (en) * | 2021-11-19 | 2022-02-25 | 合肥安利聚氨酯新材料有限公司 | Chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and preparation method thereof |
| CN115505348A (en) * | 2022-10-25 | 2022-12-23 | 苏州世华新材料科技股份有限公司 | Impact-resistant degradable foam and preparation method thereof |
| CN115505348B (en) * | 2022-10-25 | 2023-08-15 | 苏州世华新材料科技股份有限公司 | Impact-resistant degradable foam and preparation method thereof |
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