CN101538359B - Method for preparing high molecular weight branched polylactic acid by molten polymerization - Google Patents
Method for preparing high molecular weight branched polylactic acid by molten polymerization Download PDFInfo
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Abstract
The invention relates to a method for preparing high molecular weight branched polylactic acid by molten polymerization, which uses polyolefin containing multi-epoxy groups or fatty acid containing epoxy group for copolymerization with lactic acid to obtain the high molecular weight branched polylactic acid. The polylactic acid prepared by the method has simple process, short reaction period, low side reaction, higher yield, lower cost and better quality of the obtained polylactic acid, and can be applied in a plurality of fields as an environment-friendly general-purpose plastic.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of method of preparing high molecular weight branched polylactic acid by molten polymerization.
Background technology
Plastics develop into a kind of material that is widely used in every field gradually, yet, because the non-degradable of plastics, thereby the right ecosystem has caused serious threat.In addition, plastics are mainly derived from the petroleum-type Nonrenewable resources, and a large amount of uses of plastics certainly will cause the serious energy and human survival crisis.Therefore, supply with at global petroleum resources day be becoming tight, be under the environmental issue that synthetic plastics caused of the raw material situation about becoming increasingly conspicuous with the oil, formed the upsurge of one research biodegradable plastic in the world wide.In numerous biodegradable polymers, poly(lactic acid) is a dark horse, and with its excellent mechanical property, wide application field has won attracting attention and favoring of people.Poly(lactic acid) is most typical a kind of biodegradable plastic in the aliphatics, can thoroughly resolve into water and carbonic acid gas under the occurring in nature action of microorganisms, thereby environment is safe from harm, and has overcome the maximum disadvantage of chemical plastic.In addition, poly(lactic acid) derives from renewable resources (for example starch, Mierocrystalline cellulose etc.), thus can reduce the consumption of Nonrenewable resources, and then alleviate the human resource crisis.
Synthesizing polylactic acid has two kinds of approach, the one, make by rac-Lactide (lactic acid cyclic dimer) ring-opening polymerization, synthetic polylactic acid molecule amount height, dispersion coefficient are little by this method, has good physicals, but rac-Lactide complicated process of preparation and the purity that requires when polymerization are higher, thereby make production cost high, therefore present this method synthetic poly(lactic acid) can't be used widely as common plastics.Poly(lactic acid) also can make by lactic acid direct condensation method, but since in lactic acid direct condensation process in the presence of column balancing:
Therefore, the polylactic acid molecule amount that direct polymerization obtains is on the low side,
For improving the molecular weight of lactic acid direct polymerization product, at present mainly by following several approach: patent CN1563138 mentions, earlier synthetic lower molecular weight lactic acid polycondensation product, use chain extensions such as polyprotonic acid, polyvalent alcohol, polyisocyanates then, but, because lactic acid direct condensation synthetic polycondensate complicated component, contain small molecules oligopolymer and lactic acid and lactide monomer etc., in the chain extension process, at first small molecules product reaction of chainextender, desire improves product bulk molecule amount, will certainly increase the chainextender consumption.Among the patent CN1616515; prepare poly-lactic acid in high molecular weight with melt phase polycondensation-solid phase method polymerization, this method only is suitable for L-type lactic acid, and owing to need performed polymer in the process by crystallization-powder essence-solid state polymerization processes; be unfavorable for the large-scale production requirement of serialization, and reaction time is longer.Utilize the polymerization of organic solvent azeotropic dehydrating solution to prepare poly(lactic acid) among the patent US5310865,, increased producting process difficulty and production cost owing to use a large amount of organic solvents.The key of direct polymerization method is effectively to get rid of the water that generates in the reaction, and polymer cracking generates the side reaction of rac-Lactide when reducing high temperature, high vacuum polymerization.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing high molecular weight branched polylactic acid by molten polymerization, overcome low, the inferior defective of molecular weight that exists when having the scorification synthesizing polylactic acid now.
The preparation method of the high molecular weight branched polylactic acid that the present invention proposes, concrete grammar may further comprise the steps:
1, material acid dehydration:
Under 70～100 ℃ of temperature, under the vacuum condition of 5～30KPa pressure, mechanical stirring is removed the moisture in the lactic acid; Described lactic acid is D, L-lactic acid or L-lactic acid;
2, pre-polymerization
Add branching agent 0.1～3.0wt% by mass percentage in the lactic acid after the dehydration, behind the mixing, be warmed up to polymerization 4-5h under 140～160 ℃, 5～10Kp pressure, obtaining the polymerization degree is 8 performed polymers about lactic acid molecules;
3, add catalyzer, melt polymerization
The catalyzer that in performed polymer, adds performed polymer weight 0.3～1.0wt%, at 160～180 ℃, 5～10Kpa, polymerization 10～20h under the pressure vacuum state directly obtains weight-average molecular weight in 15～200,000 poly(lactic acid); Perhaps further add performed polymer weight 0.1～3.0wt% branching agent again, continue reaction 1～5h, carry out chain extension and obtain poly-lactic acid in high molecular weight;
Described catalyzer is a kind of or its mixture in stannous octoate, tin protochloride, tosic acid, antimonous oxide, butyl (tetra) titanate, the lanthanum titanium complex catalyst;
Said branching agent is the lipid acid that contains epoxide group, the low-molecular-weight polyolefin that contains epoxy group(ing), comprises the ADR-4368 of BASF AG, ADR-4370, epoxidised soybean oil etc.
By above-mentioned disclosed technical scheme as seen, the technology that the present invention prepares poly(lactic acid) is simple, reaction time is short, side reaction is low, yield is higher, cost is lower, and the poly(lactic acid) quality that obtains is better, can be applicable to a plurality of fields as a kind of eco-friendly general-purpose plastics.
Embodiment
Embodiment 1
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, add 0.25wt%ADR-4370 (BASF Aktiengesellschaft's product) then, behind the stirring and evenly mixing, temperature is raised to 140 ℃, continued to take off condensation water 5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.The stannous octoate that adds 0.5wt% then is raised to 180 ℃ with temperature, and pressure is under the vacuum condition of 5KPa, and reaction 20h obtains the 50g weight-average molecular weight and be 63,280 poly(lactic acid).
Embodiment 2
Take by weighing 100g D, L-lactic acid (lactic acid content is greater than 85%) is in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, add the 0.5wt%ADR-4370 mixing then, temperature is raised to 140 ℃, continued to take off condensation water 5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add 0.4wt% tin protochloride and etc. the tosic acid of amount, temperature is raised to 180 ℃, pressure is under the vacuum condition of 5KPa, reaction 20h obtains the 56g weight-average molecular weight and is 113,500 poly(lactic acid).
Embodiment 3
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, add the 0.75wt%ADR-4370 stirring and evenly mixing then, temperature is raised to 140 ℃, continued to take off condensation water 4～5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add the stannous octoate of 0.5wt%, temperature is raised to 180 ℃, pressure is under the vacuum condition of 5KPa, and reaction 15h obtains the 55g weight-average molecular weight and be 179,700 poly(lactic acid).
Embodiment 4
Take by weighing 100g D, L-lactic acid (lactic acid content is greater than 85%) is in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, add the 1.0wt%ADR-4368 stirring and evenly mixing then, temperature is raised to 140 ℃, continued to take off condensation water 4 hours, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add 0.4wt% tin protochloride and etc. the tosic acid of amount, temperature is raised to 180 ℃, pressure is under the vacuum condition of 5KPa, reaction 15h obtains the 52g weight-average molecular weight and is 165,300 poly(lactic acid).
Embodiment 5
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, add the 1.0wt% epoxidised soybean oil then, temperature is raised to 140 ℃, continued to take off condensation water 5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add the stannous octoate of 0.5wt%, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, reaction 20h obtains the 57g weight-average molecular weight and is 145,800 poly(lactic acid).
Embodiment 6
Take by weighing 100g D, L-lactic acid (lactic acid content is greater than 85%) is in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, add the 1.0wt% epoxidised soybean oil then, temperature is raised to 140 ℃, continued to take off condensation water 4h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add 0.4wt% tin protochloride and etc. the tosic acid of amount, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, reaction 20h obtains the 53g weight-average molecular weight and is 152,300 poly(lactic acid).
Embodiment 7
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, the ADR-4370 that adds 0.3wt% then, temperature is raised to 140 ℃, continued to take off condensation water 5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add 0.4wt% tin protochloride and etc. the tosic acid of amount, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, reaction 20h, and then in reaction system, add the ADR-4370 of 0.4wt%, and continuing at 180 ℃, the vacuum condition of 5KPa is reaction 2h down.Obtain the 55g weight-average molecular weight and be 234.500 ten thousand branched polylactic acid.
Embodiment 8
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, the epoxy soybean oil that adds 1.0wt% then, temperature is raised to 140 ℃, continued to take off condensation water 5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add the antimonous oxide of 0.5wt%, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, react 20h, and then add the epoxy soybean oil of 1.0wt% in reaction system, continue at 180 ℃, the vacuum condition of 5KPa is reaction 3h down.Obtain the 56g weight-average molecular weight and be 213.200 ten thousand branched polylactic acid.
Embodiment 9
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, the epoxidised soybean oil that adds 1.0wt% then, temperature is raised to 140 ℃, continued to take off condensation water 5h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add 0.4wt% tin protochloride and etc. the tosic acid of amount, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, reaction 20h, and then in reaction system, add the epoxy soybean oil of 1.0wt%, and continuing at 180 ℃, the vacuum condition of 5KPa is reaction 3h down.Obtain the 53g weight-average molecular weight and be 122.100 branched polylactic acid.
Embodiment 10
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 70 ℃ of temperature, the epoxy soybean oil that adds 0.8wt% then, temperature is raised to 140 ℃, continued to take off condensation water 4h hour, obtaining mean polymerisation degree is 8 lactic acid molecules left and right sides prepolymers.Add the butyl (tetra) titanate of 0.5wt%, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, react 25h, and then add the epoxy soybean oil of 1.0wt% in reaction system, continue at 180 ℃, the vacuum condition of 5KPa is reaction 5h down.Obtain the 54g weight-average molecular weight and be 143.800 ten thousand branched polylactic acid.
The contrast experiment 1
Take by weighing 100g L-lactic acid (lactic acid content is greater than 85%) in the three-necked bottle of 250ml, remove the moisture in the lactic acid under 15KPa, the 80 ℃ of temperature, temperature is raised to 140 ℃ afterwards, continues to take off condensation water 5h hour, obtains the prepolymer that mean polymerisation degree is 8 lactic acid molecules.Add 0.4wt% tin protochloride and etc. the tosic acid of amount, temperature is raised to 180 ℃, under the vacuum condition of pressure 5KPa, reaction 20h obtains the 42g weight-average molecular weight and is 34,500 poly(lactic acid).
Can find by the contrast experiment, under the identical situation of experiment condition, add the molecular weight that branching agent can significantly improve poly(lactic acid), and yield increase.
Claims (1)
1. the method for a preparing high molecular weight branched polylactic acid by molten polymerization is characterized in that, may further comprise the steps:
(1) material acid dehydration:
Under 70～100 ℃ of temperature, under the vacuum condition of 5～30KPa pressure, mechanical stirring is removed the moisture in the lactic acid; Described lactic acid is D, L-lactic acid or L-lactic acid;
(2) pre-polymerization
Add branching agent 0.1～3.0wt% by mass percentage in the lactic acid after the dehydration, behind the mixing, be warmed up to polymerization 4-5h under 140～160 ℃, 5～10Kp pressure, obtaining the polymerization degree is the performed polymer of 8 lactic acid molecules;
(3) add catalyzer, melt polymerization
The catalyzer that in performed polymer, adds performed polymer weight 0.3～1.0wt%, at 160～180 ℃, 5～10Kpa, polymerization 10～20h under the pressure vacuum state directly obtains weight-average molecular weight in 15～200,000 poly(lactic acid);
The branching agent that adopts in the described step (2) is the ADR-4368 of BASF AG, ADR-4370 or epoxidised soybean oil;
Described catalyzer is a kind of in stannous octoate, tin protochloride, tosic acid, antimonous oxide, the butyl (tetra) titanate or their mixture.
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| CN117384649A (en) * | 2023-12-13 | 2024-01-12 | 中国矿业大学(北京) | Soil conditioner and preparation method and application thereof |
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