CN105418900B - The preparation method of poly butylene succinate and polylactic-acid block copolymer - Google Patents
The preparation method of poly butylene succinate and polylactic-acid block copolymer Download PDFInfo
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- CN105418900B CN105418900B CN201610018019.8A CN201610018019A CN105418900B CN 105418900 B CN105418900 B CN 105418900B CN 201610018019 A CN201610018019 A CN 201610018019A CN 105418900 B CN105418900 B CN 105418900B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Abstract
The invention provides a kind of preparation method of poly butylene succinate, including:Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly butylene succinate is obtained.Present invention also provides a kind of preparation method of polylactic-acid block copolymer, comprise the following steps：Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly butylene succinate is obtained；Ring-opening copolymerization reaction is carried out after the poly butylene succinate is mixed with lactide, polylactic-acid block copolymer is obtained.During polylactic-acid block copolymer is prepared, benzoic acid stannous once added as catalyst can be catalyzed succinic acid and butanediol esterification, may then continue to be catalyzed the ring-opening copolymerization of lactide and poly butylene succinate；Secondary addition catalyst is avoided in whole course of reaction, catalyst amount is reduced, cost is reduced, production efficiency is improved.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of poly butylene succinate and a kind of PLA
The preparation method of block copolymer.
Background technology
General-purpose plastics has excellent mechanical property, and density ratio steel is small, its can be processed into various everyday articles or
Shopping bag etc. is packed, the life given people is brought convenience, can be with substituted metal product in many application fields.Current general-purpose plastics
Yield and consumption it is huge, every year in terms of several hundred million tons.The life that although general-purpose plastics gives people is brought fast, but it needs
The time of many decades could degrade.Non-degradable plastics carry out huge harm to natural zone, and it is remained in soil for a long time, influence
The growth of plant, endangers the existence of animal.Therefore, the friendly degradation plastic of development environment substitutes traditional non-degradable plastics,
White pollution is solved, the direction developed as current macromolecule industrial field.
PLA (PLA) derives from renewable plant resources, is current cost performance highest and realizes industrialization in batches at first
Sustainable development degradation plastic.PLA has good biocompatibility and biodegradability, and it is in such as power
Performance and polypropylene and polystyrene in terms of intensity, anti-permeability, glossiness, light transmittance and processability is close.PLA is
A kind of new polyester material, raw material sources are in plant resourceses such as starch, sugar and celluloses, and biodegradability is good, makes
Can be degradable in nature after, carbon dioxide and water are ultimately generated, it is free from environmental pollution.PLA collection economy and " green "
It is integrated, is a degradation plastic product with potential great market.
But the flexibility of polylactic acid molecule chain is poor, causes its toughness poor, lacks certain flexible and elasticity, tearing strength
It is low, it is difficult to be processed as packing film product, disadvantages mentioned above limits the application field of PLA.Utilize flexible degradable macromolecule
The PLA block prepared as polymeric monomer initiator can improve the pliability of PLA, such as poly butylene succinate
(PBS) trigger lactide ring-opening copolymerization, prepare lactic acid poly butylene succinate block copolymer (PLLA-PBS-PLLA),
Improve the mechanical property and processing characteristics of PLA.It is currently reported, by the introducing of PBS soft segments, poly- breast can be made
Acid obtains preferable pliability, and elongation at break equally may be used up to more than 200%, in addition PLLA-PBS-PLLA block copolymers
Degradable property.Publication No. CN101935390A Chinese patent discloses a kind of polylactic acid toughening modifier and its preparation side
Method, PBS and lactide are dissolved in solvent by it, and the ring-opening copolymerization for triggering lactide using stannous octoate is prepared for PLLA-
PBS-PLLA, reaction uses the pure copolymer processed of solvent deposition after terminating；This method can be carried out under lower temperature and normal pressure, still
Substantial amounts of organic solvent is consumed, increases production cost, is unfavorable for environmental protection.Publication No. CN102786672A Chinese patents are disclosed
A kind of preparation method of polylactic-acid block copolymer, it uses two-step method to synthesize PLLA-PBS-PLLA, first with the fourth of metatitanic acid four
Ester catalysis succinic acid reacts with butanediol, esterification dehydration generation PBS；After esterification terminates, stannous octoate catalysis is added to PBS
With in lactide mixed material, lactide ring-opening copolymerization obtains block copolymer；The patent uses two step body frit reactions,
Solvent is not used, production process is more environmentally friendly, but esterification dehydration is both needed to add catalyst with ring-opening copolymerization, multistep addition is different
Catalyst, increase complex process degree and production cost.
The content of the invention
Present invention solves the technical problem that being to provide a kind of preparation technology the preparation of simple polylactic-acid block copolymer
Method.
In view of this, this application provides a kind of preparation method of poly butylene succinate, including:
Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly-succinic is obtained
Butanediol ester.
Present invention also provides a kind of preparation method of polylactic-acid block copolymer, comprise the following steps：
Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly-succinic is obtained
Butanediol ester；
Ring-opening copolymerization reaction is carried out after the poly butylene succinate is mixed with lactide, PLA block is obtained
Copolymer.
It is preferred that, the ratio of the benzoic acid stannous quality and the succinic acid source and the butanediol gross mass is
(0.01~1)：100.
It is preferred that, one or more of the succinic acid source in succinic acid and butanedioic acid derivative；The succinic acid
One or more of the derivative in succinic anhydride, succinate monoester and succinate；The succinate is selected from fourth
One kind or many in acid dimethyl, diethyl succinate, dipropyl succinate, dibutyl succinate and diamyl succinate
Kind, the succinate monoester is selected from monomethyl succinate, single-ethyl succinate, succinic acid list propyl ester, succinic acid mono-n-butylester and fourth
One or more in diacid list pentyl ester.
It is preferred that, the temperature of the esterification is 130~250 DEG C, and the time of the esterification is 6~48h.
It is preferred that, the poly butylene succinate is molten state.
It is preferred that, the mass ratio of the lactide and the poly butylene succinate is (1~90)：10.
It is preferred that, the preparation process of the polylactic-acid block copolymer is specially：
Under inert gas shielding, mix, be total to after heating with lactide again after poly butylene succinate is cooled down
Polymerisation.
It is preferred that, the temperature of the cooling is 120~180 DEG C.
It is preferred that, the speed of the heating is 1~50 DEG C/h, and the temperature of the copolymerization is 180~200 DEG C.
This application provides a kind of preparation method of polylactic-acid block copolymer, it makees in benzoic acid stannous catalysis first
Under, esterification is occurred into for succinic acid source and butanediol, poly butylene succinate is obtained, then by poly-succinic acid-butanediol
Ester is mixed with lactide, and poly butylene succinate directly triggers lactide ring-opening copolymerization, obtains polylactic-acid block copolymer.
The application is during polylactic-acid block copolymer is prepared, and benzoic acid stannous catalysis succinic acid source first and butanediol esterification are de-
Water, it is benzoic acid stannous that still there is catalytic activity after esterification dehydration terminates, lactide ring-opening copolymerization can be directly catalyzed,
Polylactic-acid block copolymer is obtained, said process, which only need to once add catalyst, can prepare polylactic-acid block copolymer, simplified
Preparation technology；In addition, poly butylene succinate prepared by the application is molten condition, it directly triggers lactide open loop to be total to
Polymerization, it is to avoid use solvent, is produced more environmentally friendly.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of poly butylene succinate, including:
Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly-succinic is obtained
Butanediol ester.
The application is made succinic acid source occur esterification with butanediol, obtained using benzoic acid stannous as catalyst
The poly butylene succinate of molten condition.
During poly butylene succinate is prepared, the succinic acid source is preferably succinic acid and butanedioic acid derivative
In one or more；One kind in succinic anhydride, succinate monoester and succinate of the butanedioic acid derivative or
It is a variety of, the succinate monoester be selected from monomethyl succinate, single-ethyl succinate, succinic acid list propyl ester, succinic acid mono-n-butylester and
One or more in succinic acid list pentyl ester, the succinate is selected from dimethyl succinate, diethyl succinate, succinic acid
One or more in dipropyl, dibutyl succinate and diamyl succinate.
The process that the application prepares poly butylene succinate is specially：
Under -0.06MPa~-0.02MPa rough vacuums, succinic acid source is mixed with butanediol, after esterification
Water byproduct is heated to be changed into vapor and distillates, and contracting is dehydrated using vacuum decompression to -0.1MPa after being distillated to condenser pipe dripless
It is poly-, obtain poly butylene succinate.
In above process, the mol ratio of the succinic acid source and the butanediol is preferably 1：(1~2), more preferably
1：(1.0~1.3).The temperature of the esterification is preferably 110~200 DEG C, in embodiment, the temperature of the esterification
More preferably 130~180 DEG C, the time of the reaction is preferably 3~10h, in embodiment, more preferably 4~6h.It is above-mentioned extremely
Condenser pipe dripless is distillated, and the product now obtained in reaction system is the oligomer of succinic acid butanediol.The dehydrating polycondensation
Reaction temperature be 200~250 DEG C, in embodiment, the reaction temperature of the dehydrating polycondensation is preferably 200~230 DEG C, described
The reaction time of dehydrating polycondensation is preferably 2~24h, more preferably 8~12h.
Based on the poly butylene succinate of above-mentioned preparation, polylactic-acid block copolymer is then prepared for.Thus, originally
Application additionally provides a kind of preparation method of polylactic-acid block copolymer, comprises the following steps：
Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly-succinic is obtained
Butanediol ester；
Ring-opening copolymerization reaction is carried out after the poly butylene succinate is mixed with lactide, PLA block is obtained
Copolymer.
The characteristics of the application is persistently kept using benzoic acid stannous catalytic activity, uses it for catalysis succinic acid source, fourth two
Alcohol esterification dehydration production poly butylene succinate (PBS)；Retaining in melting PBS benzoic acid stannous can directly be catalyzed the third friendship
The ring-opening copolymerization of ester, is prepared for polylactic acid and polyethylene butanediol succinate block copolymer, need not add in copolymerization process
Plus new polymerization catalyst, production cost is reduced, simplifies production operation, production efficiency is higher.
According to the present invention, the process and such scheme for preparing poly butylene succinate prepare poly butylene succinate
Process is identical, is no longer repeated herein.
After poly butylene succinate is obtained, then the preparation of polylactic-acid block copolymer is carried out.It is herein described poly-
Succinic acid-butanediol ester is molten condition.Herein described lactide is selected from levorotatory lactide, dextrorotation lactide and meso
One or more in lactide, in embodiment, the lactide is preferably levorotatory lactide.The lactide gathers with described
The mass ratio of succinic acid-butanediol ester is preferably (1~90)：10, in embodiment, the lactide and the poly-succinic fourth
The mass ratio of diol ester is more preferably (5~40):10.
During polylactic-acid block copolymer is prepared, also there is catalytic activity due to benzoic acid stannous, can be catalyzed
The ring-opening copolymerization of lactide, therefore in the step of preparing polylactic-acid block copolymer, can no longer add catalyst.The system
It is specially for the process of polylactic-acid block copolymer：
Under inert gas shielding, mixed after poly butylene succinate is cooled down with lactide, be gradually heating to open loop
Combined polymerization is completed, and obtains polylactic-acid block copolymer.
In above process, the poly butylene succinate is preferably cooled to 120~180 DEG C, in embodiment, more excellent
Elect 130 DEG C~160 DEG C as.The speed of the heating is preferably 1~50 DEG C/h, preferably 5~20 DEG C/h.The ring-opening copolymerization
The temperature of end is preferably 160~220 DEG C, preferably 180~200 DEG C.
The invention provides benzoic acid stannous as catalyst preparation poly butylene succinate and its lactic acid poly-succinic
The method of butanediol ester copolymer catalyst, during polylactic-acid block copolymer is prepared, adds benzoic acid stannous first
It is added to succinic acid and in butanediol, catalytic esterification dehydration obtains melting PBS；After further reaction to be drained off terminates, without addition
Any polymerization catalyst, the melting PBS for being cooled to certain temperature directly triggers lactide ring-opening copolymerization.The present invention is using melting
Polymerisation in bulk, directly triggers lactide ring-opening copolymerization, it is to avoid use solvent, whole production process with poly butylene succinate
It is more environmentally friendly, it is good in economic efficiency.It is benzoic acid stannous to be catalyzed succinic acid, butanediol esterification dehydration, simultaneously because benzoic acid stannous
Still there is catalytic activity after esterification dehydration terminates, therefore it can also be catalyzed the open loop homopolymerization of lactide, with showing
There is body to melt copolymerization process to compare, without adding polymerization catalyst in copolymerization process, reduce production cost, simplify production exercise
Make, production efficiency is higher.
For a further understanding of the present invention, the system of the poly butylene succinate provided with reference to embodiment the present invention
The preparation method of Preparation Method and polylactic-acid block copolymer is described in detail, and protection scope of the present invention is not by following examples
Limitation.
The reagent raw material used in following case study on implementation is market products；Lactide is left-handed in following examples
Lactide.
In following case study on implementation, the conversion ratio of lactide is determined using weight reduction, and specific method of testing is：In combined polymerization knot
Shu Hou, weighs a certain amount of polylactic-acid block copolymer, places and is heated to removing not under 120 DEG C, vacuum condition in vacuum drying oven
The monomer of reaction, the weight according to pure copolymer processed calculates conversion ratio.PLA block copolymerization is tested at 25 DEG C using GPC method
The molecular weight of thing, wherein CHCl3It is used as mobile phase.
Embodiment 1
Succinic acid 118g, butanediol 94.5g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser,
Reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting what side reaction was produced
Water；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 205 DEG C are progressively warming up to,
Reacted 12 hours at 205 DEG C, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 140 DEG C, the mixing of 250g lactides, temperature of charge after mixing is then added
For 120 DEG C, risen to 10 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 95.07g to weigh after above-mentioned polylactic-acid block copolymer 100g, vacuum volatilization, calculates turning for lactide
Rate is 93%, and the number-average molecular weight of polylactic-acid block copolymer is 8.5 × 104G/mol, the polydispersity coefficient of block copolymer
For 1.8.
Embodiment 2
Succinic acid 118g, butanediol 94.5g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser,
Reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting what side reaction was produced
Water；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 205 DEG C are progressively warming up to,
Reacted 12 hours at 205 DEG C, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 140 DEG C, the mixing of 100g lactides, temperature of charge after mixing is then added
For 120 DEG C, risen to 10 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 97.0g to weigh after above-mentioned polylactic-acid block copolymer 100g, vacuum volatilization, calculates the conversion of lactide
Rate is 94%, and the number-average molecular weight of polylactic-acid block copolymer is 6.1 × 104G/mol, the polydispersity coefficient of block copolymer is
1.9。
Embodiment 3
Succinic acid 118g, butanediol 94.5g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser,
Reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting what side reaction was produced
Water；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 220 DEG C are progressively warming up to,
Reacted 12 hours at 220 DEG C, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 170 DEG C, the mixing of 250g lactides, temperature of charge after mixing is then added
For 150 DEG C, risen to 5 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 94.28g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, the conversion ratio for calculating lactide is
92%, the number-average molecular weight of polylactic-acid block copolymer is 9.1 × 104G/mol, the polydispersity coefficient of block copolymer is 1.9.
Embodiment 4
Succinic acid 118g, butanediol 94.5g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser,
Reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting what side reaction was produced
Water；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 220 DEG C are progressively warming up to,
Reacted 8 hours at 220 DEG C, the poly butylene succinate melted；
The PBS of the above-mentioned meltings of 100g is cooled to 170 DEG C, the mixing of 100g lactides, temperature of charge after mixing is then added
For 160 DEG C, risen to 5 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 96.25g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
92.5%, the number-average molecular weight 7.5 × 10 of polylactic-acid block copolymer4G/mol, the polydispersity coefficient of block copolymer is 1.8.
Embodiment 5
Succinic acid 118g, butanediol 94.5g, benzoic acid stannous 0.6g are directly added into band condenser 1L reactors, reaction
Kettle uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 110 DEG C, while collecting the water that side reaction is produced；Extremely
No liquid is distillated in condenser, is opened vavuum pump and is vacuumized progress depth polycondensation, while 230 DEG C are progressively warming up to, at 230 DEG C
Reaction 6 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 170 DEG C, the mixing of 250g lactides, temperature of charge after mixing is then added
For 150 DEG C, risen to 5 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 95.07g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, calculates the conversion ratio of lactide
93.1%, the number-average molecular weight of polylactic-acid block copolymer is 9.5 × 104G/mol, the polydispersity coefficient of block copolymer is
2.1。
Embodiment 6
Succinic acid 118g, butanediol 94.5g, benzoic acid stannous 0.6g are directly added into the 1L reactors with condenser,
Reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 110 DEG C, while collecting what side reaction was produced
Water；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 230 DEG C are progressively warming up to,
Reacted 10 hours at 230 DEG C, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 150 DEG C, the mixing of 200g lactides, temperature of charge after mixing is then added
For 130 DEG C, risen to 5 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 96.67g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
95%, the number-average molecular weight of polylactic-acid block copolymer is 9.5 × 104G/mol, the polydispersity coefficient of block copolymer is 2.1.
Embodiment 7
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.6g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 210 DEG C are progressively warming up to, at 210 DEG C
Lower reaction 12 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 140 DEG C, the mixing of 150g lactides, temperature of charge after mixing is then added
For 120 DEG C, risen to 10 DEG C/h after 190 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 96.1g to weigh after block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
93.5%, the number-average molecular weight of polylactic-acid block copolymer is 8.3 × 104G/mol, the polydispersity coefficient of block copolymer is
2.1。
Embodiment 8
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 205 DEG C are progressively warming up to, at 205 DEG C
Lower reaction 12 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 140 DEG C, the mixing of 250g lactides, temperature of charge after mixing is then added
For 120 DEG C, risen to 10 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 95.36g to weigh after block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
93.5%, the number-average molecular weight of polylactic-acid block copolymer is 10.5 × 104G/mol, the polydispersity coefficient of block copolymer is
1.93。
Embodiment 9
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 205 DEG C are progressively warming up to, at 205 DEG C
Lower reaction 12 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 140 DEG C, the mixing of 100g lactides, temperature of charge after mixing is then added
For 120 DEG C, risen to 5 DEG C/h after 180 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 97g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
94%, the number-average molecular weight 7.1 × 10 of polylactic-acid block copolymer4G/mol, the polydispersity coefficient of block copolymer is 1.9.
Embodiment 10
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 220 DEG C are progressively warming up to, at 220 DEG C
Lower reaction 12 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 170 DEG C, the mixing of 250g lactides, temperature of charge after mixing is then added
For 160 DEG C, risen to 5 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 94.78g to weigh after block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
92.7%, the number-average molecular weight of polylactic-acid block copolymer is 9.7 × 104G/mol, the polydispersity coefficient of block copolymer is
2.0。
Embodiment 11
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 220 DEG C are progressively warming up to, at 220 DEG C
Lower reaction 8 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 170 DEG C, the mixing of 100g lactides, temperature of charge after mixing is then added
For 160 DEG C, risen to 5 DEG C/h after 200 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 96.75g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
93.5%, the number-average molecular weight of polylactic-acid block copolymer is 7.5 × 104G/mol, the polydispersity coefficient of block copolymer is
1.7。
Embodiment 12
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.6g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 110 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 230 DEG C are progressively warming up to, at 230 DEG C
Lower reaction 6 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 170 DEG C, the mixing of 250g lactides, temperature of charge after mixing is then added
For 150 DEG C, risen to 5 DEG C/h after 190 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 94.3g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
92%, the number-average molecular weight of polylactic-acid block copolymer is 8.7 × 104G/mol, the polydispersity coefficient of block copolymer is 2.1.
Embodiment 13
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.6g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 110 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 230 DEG C are progressively warming up to, at 230 DEG C
Lower reaction 10 hours, the poly butylene succinate melted (PBS)；
The PBS of the above-mentioned meltings of 100g is cooled to 150 DEG C, the mixing of 200g lactides, temperature of charge after mixing is then added
For 130 DEG C, risen to 5 DEG C/h after 190 DEG C and stop reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 96.66g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
95%, the number-average molecular weight of polylactic-acid block copolymer is 8.9 × 104G/mol, the polydispersity coefficient of block copolymer is 2.1.
Embodiment 14
Succinic acid 118g, butanediol 91g, benzoic acid stannous 0.6g are directly added into the 1L reactors with condenser, instead
Kettle is answered to use heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 170 DEG C, while collecting the water that side reaction is produced；
Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 215 DEG C are progressively warming up to, at 215 DEG C
Lower reaction 10 hours, the poly butylene succinate melted (PBS)；
The above-mentioned PBS melted of 100g are cooled to 150 DEG C, the mixing of 200g lactides, material after mixing is then added
Temperature is 130 DEG C, is risen to 5 DEG C/h after 180 DEG C and stops reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 96.8g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
95.2%, the number-average molecular weight of polylactic-acid block copolymer is 7.7 × 104G/mol, the polydispersity coefficient of block copolymer is
2.1。
Embodiment 15
Monomethyl succinate 131g, butanediol 92g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser
In, reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, is produced while collecting side reaction
Liquid；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 215 DEG C are progressively warming up to,
Reacted 10 hours at 215 DEG C, the poly butylene succinate melted (PBS)；
The above-mentioned PBS melted of 100g are cooled to 150 DEG C, the mixing of 200g lactides, material after mixing is then added
Temperature is 130 DEG C, is risen to 5 DEG C/h after 180 DEG C and stops reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 97.0g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
95.5%, the number-average molecular weight of polylactic-acid block copolymer is 7.2 × 104G/mol, the polydispersity coefficient of block copolymer is
1.9。
Embodiment 16
Monomethyl succinate 146g, butanediol 92g, benzoic acid stannous 0.3g are directly added into the 1L reactors with condenser
In, reactor uses heat-conducting oil heating；Mechanical agitation is opened after temperature in the kettle rises to 140 DEG C, is produced while collecting side reaction
Liquid；Into condenser, no liquid is distillated, and is opened vavuum pump and is vacuumized progress depth polycondensation, while 215 DEG C are progressively warming up to,
Reacted 10 hours at 215 DEG C, the poly butylene succinate melted (PBS)；
The above-mentioned PBS melted of 100g are cooled to 150 DEG C, the mixing of 200g lactides, material after mixing is then added
Temperature is 130 DEG C, is risen to 5 DEG C/h after 180 DEG C and stops reacting, extruding pelletization obtains polylactic-acid block copolymer.
It is that weight is 97.2g to weigh after above-mentioned block copolymer 100g, vacuum volatilization, and the conversion ratio for calculating lactide is
95.8%, the number-average molecular weight of polylactic-acid block copolymer is 7.0 × 104G/mol, the polydispersity coefficient of block copolymer is
1.9。
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (9)
1. a kind of preparation method of polylactic-acid block copolymer, comprises the following steps：
Under benzoic acid stannous catalytic action, succinic acid source and butanediol are subjected to esterification, poly-succinic fourth two is obtained
Alcohol ester；
Ring-opening copolymerization reaction is carried out after the poly butylene succinate is mixed with lactide, PLA block copolymerization is obtained
Thing.
2. preparation method according to claim 1, it is characterised in that the benzoic acid stannous quality and the succinic acid
The ratio of source and the butanediol gross mass is (0.01~1): 100.
3. preparation method according to claim 1, it is characterised in that the succinic acid source is selected from succinic acid and succinic acid derivatives
One or more in biology；The butanedioic acid derivative in succinic anhydride, succinate monoester and succinate one
Plant or a variety of；The succinate is selected from dimethyl succinate, diethyl succinate, dipropyl succinate, the fourth of succinic acid two
One or more in ester and diamyl succinate, the succinate monoester is selected from monomethyl succinate, single-ethyl succinate, fourth
One or more in diacid list propyl ester, succinic acid mono-n-butylester and succinic acid list pentyl ester.
4. preparation method according to claim 1, it is characterised in that the temperature of the esterification is 130~250 DEG C,
The time of the esterification is 6~48h.
5. preparation method according to claim 1, it is characterised in that the poly butylene succinate is molten state.
6. preparation method according to claim 1, it is characterised in that the lactide and the poly butylene succinate
Mass ratio be (1~90): 10.
7. preparation method according to claim 1, it is characterised in that the preparation process tool of the polylactic-acid block copolymer
Body is：
Under inert gas shielding, mixed again with lactide after poly butylene succinate is cooled down, combined polymerization is carried out after heating
Reaction.
8. preparation method according to claim 7, it is characterised in that the temperature of the cooling is 120~180 DEG C.
9. preparation method according to claim 7, it is characterised in that the speed of the heating is 1~50 DEG C/h, described common
The temperature of polymerisation is 180~200 DEG C.
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