CN101597368B - Bio-degradable plastic and preparation method thereof - Google Patents
Bio-degradable plastic and preparation method thereof Download PDFInfo
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- CN101597368B CN101597368B CN2009100632975A CN200910063297A CN101597368B CN 101597368 B CN101597368 B CN 101597368B CN 2009100632975 A CN2009100632975 A CN 2009100632975A CN 200910063297 A CN200910063297 A CN 200910063297A CN 101597368 B CN101597368 B CN 101597368B
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- rapeseed cake
- polypropylene glycol
- diisocyanate
- toluene
- vulcabond
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Abstract
The invention relates to a bio-degradable plastic and a preparation method thereof; the raw materials of the plastic consists of rapeseed cake, toluene-2,4-diisocyanate, polypropylene glycol, 1,2-dichloroethane, glycerol and China wood oil; wherein, the molar ratio of the toluene-2,4-diisocyanate and the polypropylene glycol is 2:1; the mass ratio of the total mass of the toluene-2,4-diisocyanate and the polypropylene glycol and rapeseed cake is 2:3-3:2, the dosages of the 1,2-dichloroethane, the glycerol and the China wood oil are respectively 3%, 0.6%-3% and 0.9-3% of the total mass of the rapeseed cake, the toluene-2,4-diisocyanate and the polypropylene glycol. The bio-degradable plastic of the invention has good tensile strength (8MPa-10MPa), low water absorption (0.5w/w%-1.2w/w%), better soil landfill biodegradability (the degradation rate is between 45% - 51% after 90 days). The rapeseed cake used as the main raw material of the bio-degradable plastic has rich resource, low cost, and degradability, thus the cost performance is high.
Description
Technical field
The present invention relates to the plastics field, relate in particular to a kind of biodegradable plastic and preparation method thereof.
Background technology
The use of nondegradable polyvalent alcohol raw material causes very big pollution to environment in the plastic raw materials.The degradable polyurethane plastics become the focus of research owing to its biological degradability.
The synthetic method of degradable polyurethane mainly is divided into two big classes: 1, utilize the polyvalent alcohol in the natural polymer; 2, utilize degradable synthesis of polymer polyalcohol, used polyvalent alcohol raw material when partly or entirely replacing non-degradable urethane synthetic, thereby synthesized degradable type polyurethane.Biodegradable plastic is divided into several big classes of natural biological degradative plastics, micro-biological degradable plastic and chemosynthetic organism degradative plastics, and wherein, the natural biological degradable material is present research tendency, mainly comprises natural polymer and various derivative and mixture.At present, the research field of biodegradable material mainly concentrates on thermoplastic starch, regenerated cellulose class, protein-based etc.But the above-mentioned raw materials price is higher, and the source is extensive inadequately.
Summary of the invention
Problem to be solved by this invention is utilized degradable synthetic polyvalent alcohol and cheap exactly, used polyvalent alcohol raw material when the rapeseed cake dregs of wide material sources replaces the non-degradable plastics synthetic, make biodegradable plastics, and a kind of biodegradable plastic and preparation method thereof is provided.
The technical scheme that realizes the object of the invention is: a kind of biodegradable plastic is characterized in that the raw material of these plastics consists of: rapeseed cake dregs, Toluene-2,4-diisocyanate, 4-vulcabond, polypropylene glycol, 1,2-ethylene dichloride, glycerine and tung oil; Wherein, described Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and polypropylene glycol is 2: 1; Toluene-2,4-diisocyanate, the quality total amount of 4-vulcabond and polypropylene glycol and rapeseed cake dregs mass ratio are 2: 3～3: 2; Described 1, the consumption of 2-ethylene dichloride, glycerine and tung oil is respectively rapeseed cake dregs, Toluene-2,4-diisocyanate, 3%, 0.6%～3% and 0.9%～3% of 4-vulcabond and three kinds of material total masses of polypropylene glycol.The molecular weight of above-mentioned polypropylene glycol is 1000～2000, functionality is 2.
The tensile strength of above-mentioned prepared degradative plastics is 8MPa～10MPa, and water-intake rate is 0.5w/w%～1.2w/w%, and soil landfill biological degradability is: degradation rate is between 45wt%～51wt% after 90 days.
The above-mentioned rapeseed cake dregs of stating is the purebred double-low rapeseed seedcake dregs of rice.
The preparation method of above-mentioned plastics is characterized in that, comprises the steps:
1) with Toluene-2,4-diisocyanate, 4-vulcabond and polypropylene glycol distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2) Toluene-2,4-diisocyanate of weighing distillation back proportional quantity, 4-vulcabond and polypropylene glycol are put into reaction vessel;
3) reaction system is heated to 80 ℃ while stirring, constant temperature 0.5～2h;
4) add the rapeseed cake dregs of proportional quantity, and splash into and account for rapeseed cake dregs, Toluene-2,4-diisocyanate, 4-vulcabond and three kinds of material total masses of polypropylene glycol 3% 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5) splash in the reaction process and account for rapeseed cake dregs, Toluene-2,4-diisocyanate, 0.6%～3% glycerine of 4-vulcabond and three kinds of material total masses of polypropylene glycol, also splash into simultaneously and account for rapeseed cake dregs, Toluene-2,4-diisocyanate, 0.9%～3% tung oil of 4-vulcabond and three kinds of material total masses of polypropylene glycol;
6) continue reaction 0.5h, pour reaction system into mould; Then mould is put into oven drying; Take out behind the 24h, promptly get biodegradable plastic.
The preparation method of above-mentioned biodegradable plastic, its order of addition(of ingredients) also can change, and promptly also can add the Toluene-2,4-diisocyanate of proportional quantity earlier, and 4-vulcabond and rapeseed cake dregs are treated to add polypropylene glycol again after its reaction for some time.
The present invention utilizes rich in protein contained in the rapeseed cake, with Toluene-2,4-diisocyanate, and 4-vulcabond (TDI), polypropylene glycol (PPG) reaction generates the degradable type polyurethane.In the tolylene diisocyanate (TDI)-in NCO group and the polypropylene glycol-OH, rapeseed cake dregs protein be contained-NH
2,-COOH reacts and generates the rapeseed cake dregs degradative plastics.
The outstanding feature of the plastics of the present invention's preparation:
1. utilize the polyvalent alcohol in the degradable natural polymer, substitute non-degradable type polyurethane used polyvalent alcohol raw material when synthetic, thus the synthesized degradable type polyurethane.
2. the present invention breaks through the restriction that rapeseed cake dregs only is used for the feed aspect, introduces rapeseed cake dregs raw material preparing biodegradable plastic, low, the degradable of cost.
3. this abundant, cheap, degradable in biodegradable plastic main raw material rapeseed cake dregs source, thereby cost performance height.
4. these plastics preparation technology is simpler, and processing parameter is more easy to control.
Embodiment
1) with Toluene-2,4-diisocyanate, 4-vulcabond distillation purifying, polypropylene glycol decompression dewaters, and 1, the 2-ethylene dichloride drying that dewaters (adds excessive anhydrous CaCl
2Dewater), rapeseed cake dregs drying in baking oven dewaters;
2) 2: 1 Toluene-2,4-diisocyanate of weighing distillation back mol ratio, 4-vulcabond and polypropylene glycol are put into reaction vessel;
3) reaction system is heated to 80 ℃ while stirring, constant temperature 0.5～2h;
4) adding and Toluene-2,4-diisocyanate, the mass ratio of the quality total amount of 4-vulcabond and polypropylene glycol is 2: 3～3: 2.Rapeseed cake dregs, and splash into rapeseed cake dregs, Toluene-2,4-diisocyanate, 4-vulcabond and three kinds of material total masses of polypropylene glycol 3% 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5) splash into rapeseed cake dregs, Toluene-2,4-diisocyanate in the reaction process, 0.6%～3% glycerine of 4-vulcabond and three kinds of material total masses of polypropylene glycol, also splash into simultaneously rapeseed cake dregs, Toluene-2,4-diisocyanate, 0.9%～3% tung oil of 4-vulcabond and three kinds of material total masses of polypropylene glycol;
6) behind the above-mentioned system reaction 0.5h, pour reaction system into mould.Then mould is put into oven drying, take out behind the 24h, promptly get biodegradable plastic.
The Toluene-2,4-diisocyanate that also can add formula ratio when reinforced earlier, 4-vulcabond and rapeseed cake dregs, treat its reaction for some time after, add polypropylene glycol again and continue reaction.
Plastics to the present invention's preparation carry out performance test:
Mechanical property: 8MPa～10MPa; Water-intake rate: 0.5w/w%～1.2w/w%; Soil landfill biological degradability: degradation rate is between 45%～51% after 90 days.
Below in conjunction with embodiment, further illustrate the present invention, but only be the present invention is described and never limit the present invention.
Embodiment 1
1. reaction sequence: add Toluene-2,4-diisocyanate earlier, 4-vulcabond (TDI) and polypropylene glycol (PPG), back adding rapeseed cake dregs; 2. reaction raw materials proportioning: TDI is 2: 1 with PPG amount of substance ratio, is 1: 1 with the rapeseed cake dregs mass ratio (TDI+PPG); 3. reaction times: 2.5h.
Concrete experimental procedure is as follows:
1. TDI and PPG distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2. weighing 1.29gTDI, 3.71g PPG puts into the single port bottle;
3. reaction system is heated at heat collecting type thermostatically heating magnetic stirring apparatus, temperature is made as 80 ℃;
4. add the 5g rapeseed cake dregs behind the 2h, and splash into 3g 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5. splash into 0.30g glycerine, 0.30g tung oil in the reaction process;
6. pour mould into behind the above-mentioned system reaction 0.5h;
7. mould is put into oven drying;
8. take out behind the 24h, place at the drying place.
The plastics mechanical property for preparing under this condition is: 8.9MPa; Water-intake rate: 0.9w/w%; Soil landfill biological degradability: degradation rate is 48% after 90 days.
Embodiment 2
1. reaction sequence: add Toluene-2,4-diisocyanate earlier, 4-vulcabond (TDI) and polypropylene glycol (PPG), back adding rapeseed cake dregs; 2. reaction raw materials proportioning: TDI is 2: 1 with PPG amount of substance ratio, is 3: 2 with the rapeseed cake dregs mass ratio (TDI+PPG); 3. reaction times: 2h.
Concrete experimental procedure is as follows:
1. TDI and PPG distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2. weighing 1.55gTDI, 4.45g PPG puts into the single port bottle;
3. reaction system is heated at heat collecting type thermostatically heating magnetic stirring apparatus, temperature is made as 80 ℃;
4. add the 4g rapeseed cake dregs behind the 1.5h, and splash into 3g 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5. splash into 0.21g glycerine, 0.30g tung oil in the reaction process;
6. pour mould into behind the above-mentioned system reaction 0.5h;
7. mould is put into oven drying;
8. take out behind the 24h, place at the drying place.
The plastics mechanical property for preparing under this condition is: 9.7MPa; Water-intake rate: 0.5w/w%; Soil landfill biological degradability: degradation rate is 43% after 90 days.
Embodiment 3
1. reaction sequence: add Toluene-2,4-diisocyanate earlier, 4-vulcabond (TDI) and rapeseed cake dregs, the back adds polypropylene glycol (PPG); 2. reaction raw materials proportioning: TDI is 2: 1 with PPG amount of substance ratio, is 1: 1 with the rapeseed cake dregs mass ratio (TDI+PPG); 3. reaction times: 1h.
Concrete experimental procedure is as follows:
1. TDI and PPG distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2. weighing 1.29g TDI, the 5g rapeseed cake is put into the single port bottle;
3. reaction system is heated at heat collecting type thermostatically heating magnetic stirring apparatus, temperature is made as 80 ℃;
4. add 3.71g PPG behind the 0.5h, and splash into 3g 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5. splash into 0.12g glycerine, 0.24g tung oil in the reaction process;
6. pour mould into behind the above-mentioned system reaction 0.5h;
7. mould is put into oven drying;
8. take out behind the 24h, place at the drying place.
The plastics mechanical property for preparing under this condition is: 9.1MPa; Water-intake rate: 0.8w/w%; Soil landfill biological degradability: degradation rate is 46.5% after 90 days.
Embodiment 4
1. reaction sequence: add Toluene-2,4-diisocyanate earlier, 4-vulcabond (TDI) and rapeseed cake dregs, the back adds polypropylene glycol (PPG); 2. reaction raw materials proportioning: TDI is 2: 1 with PPG amount of substance ratio, is 3: 2 with the rapeseed cake dregs mass ratio (TDI+PPG); 3. reaction times: 1.5h.
Concrete experimental procedure is as follows:
1. TDI and PPG distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2. weighing 1.55g TDI, the 5g rapeseed cake dregs is put into the single port bottle;
3. reaction system is heated at heat collecting type thermostatically heating magnetic stirring apparatus, temperature is made as 80 ℃;
4. add 4.45g PPG behind the 1h, and splash into 3g 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5. splash into 0.30g glycerine, 0.09g tung oil in the reaction process;
6. pour mould into behind the above-mentioned system reaction 0.5h;
7. mould is put into oven drying;
8. take out behind the 24h, place at the drying place.
The plastics mechanical property for preparing under this condition is: 8.1MPa; Water-intake rate: 1.2w/w%; Soil landfill biological degradability: degradation rate is 51% after 90 days.
Embodiment 5
1. reaction sequence: add Toluene-2,4-diisocyanate earlier, 4-vulcabond (TDI) and rapeseed cake dregs, the back adds polypropylene glycol (PPG); 2. reaction raw materials proportioning: TDI is 2: 1 with PPG amount of substance ratio, is 1: 1 with the rapeseed cake dregs mass ratio (TDI+PPG); 3. reaction times: 1h.
Concrete experimental procedure is as follows:
1. TDI and PPG distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2. weighing 1.29g TDI, the 5g rapeseed cake dregs is put into the single port bottle;
3. reaction system is heated at heat collecting type thermostatically heating magnetic stirring apparatus, temperature is made as 80 ℃;
4. add 3.71g PPG behind the 0.5h, and splash into 3g 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5. splash into 0.06g glycerine, 0.30g tung oil in the reaction process;
6. pour mould into behind the above-mentioned system reaction 0.5h;
7. mould is put into oven drying;
8. take out behind the 24h, place at the drying place.
The plastics mechanical property for preparing under this condition is: 8.8MPa; Water-intake rate: 0.89w/w%; Soil landfill biological degradability: degradation rate is 49.5% after 90 days.
Claims (5)
1. a biodegradable plastic is characterized in that, the raw material of these plastics consists of: rapeseed cake dregs, Toluene-2,4-diisocyanate, 4-vulcabond, polypropylene glycol, 1,2-ethylene dichloride, glycerine and tung oil; Wherein, described Toluene-2,4-diisocyanate, the mol ratio of 4-vulcabond and polypropylene glycol is 2: 1; Described Toluene-2,4-diisocyanate, the quality total amount of 4-vulcabond and polypropylene glycol and rapeseed cake dregs mass ratio are 2: 3～3: 2; Described 1, the consumption of 2-ethylene dichloride, glycerine and tung oil is respectively rapeseed cake dregs, Toluene-2,4-diisocyanate, 3%, 0.6%～3% and 0.9%～3% of 4-vulcabond and three kinds of material total masses of polypropylene glycol.
2. biodegradable plastic according to claim 1 is characterized in that, the molecular weight of described polypropylene glycol is 1000～2000, functionality is 2.
3. biodegradable plastic according to claim 1 and 2, it is characterized in that, the tensile strength of prepared degradative plastics is 8MPa～10MPa, and water-intake rate is 0.5w/w%～1.2w/w%, and soil landfill biological degradability is: degradation rate is between 45wt%～51wt% after 90 days.
4. biodegradable plastic according to claim 1 and 2 is characterized in that, described rapeseed cake dregs is the purebred double-low rapeseed seedcake dregs of rice.
5. the preparation method as one of claim 1-3 described biodegradable plastic is characterized in that, comprises the steps:
1) with Toluene-2,4-diisocyanate, 4-vulcabond and polypropylene glycol distillation purifying; 1, the 2-ethylene dichloride drying that dewaters, rapeseed cake dregs drying in baking oven dewaters;
2) Toluene-2,4-diisocyanate of weighing proportional quantity, reaction vessel is put in 4-vulcabond and polypropylene glycol distillation;
3) reaction system is heated to 80 ℃ while stirring, constant temperature 0.5-2h;
4) add the rapeseed cake dregs of proportional quantity, and splash into and account for rapeseed cake dregs, Toluene-2,4-diisocyanate, 4-vulcabond and three kinds of material total masses of polypropylene glycol 3% 1, the 2-ethylene dichloride can be immersed in the polymkeric substance to rapeseed cake dregs, continues reaction;
5) splash in the reaction process and account for rapeseed cake dregs, Toluene-2,4-diisocyanate, 0.6%～3% glycerine of 4-vulcabond and three kinds of material total masses of polypropylene glycol, also drip simultaneously and account for rapeseed cake dregs, Toluene-2,4-diisocyanate, 0.9%～3% tung oil of 4-vulcabond and three kinds of material total masses of polypropylene glycol;
6) pour in the mould behind the above-mentioned system reaction 0.5h, then mould is put into oven drying; Take out behind the 24h, promptly get biodegradable plastic.
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| CN2009100632975A CN101597368B (en) | 2009-07-24 | 2009-07-24 | Bio-degradable plastic and preparation method thereof |
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| CN2009100632975A CN101597368B (en) | 2009-07-24 | 2009-07-24 | Bio-degradable plastic and preparation method thereof |
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| CN101597368B true CN101597368B (en) | 2011-05-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451027A (en) * | 2000-01-11 | 2003-10-22 | E·喀硕吉工业有限公司 | Thermoplastic starch compositions in corporating a particulate filler component |
| WO2006116456A1 (en) * | 2005-04-25 | 2006-11-02 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
| CN1974627A (en) * | 2006-12-28 | 2007-06-06 | 李剑飞 | Polyurethane material and its prepn |
| CN101348553A (en) * | 2008-07-23 | 2009-01-21 | 福建省新达保温材料有限公司 | Plant polyatomic alcohol polyurethane rigid foam material |
-
2009
- 2009-07-24 CN CN2009100632975A patent/CN101597368B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451027A (en) * | 2000-01-11 | 2003-10-22 | E·喀硕吉工业有限公司 | Thermoplastic starch compositions in corporating a particulate filler component |
| WO2006116456A1 (en) * | 2005-04-25 | 2006-11-02 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
| CN1974627A (en) * | 2006-12-28 | 2007-06-06 | 李剑飞 | Polyurethane material and its prepn |
| CN101348553A (en) * | 2008-07-23 | 2009-01-21 | 福建省新达保温材料有限公司 | Plant polyatomic alcohol polyurethane rigid foam material |
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