CN107033563A - A kind of activeness and quietness poly-lactic acid material and preparation method thereof - Google Patents
A kind of activeness and quietness poly-lactic acid material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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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Abstract
The present invention provides a kind of activeness and quietness poly-lactic acid material and preparation method thereof, is related to polymeric material field.The preparation method includes：Reactant is obtained after layer dihydroxy metal oxide, ε caprolactones are mixed, ring-opening polymerization obtains Polycaprolactone modified thing.Polycaprolactone modified thing and diisocyanate are subjected to sudden reaction and obtain performed polymer.Performed polymer and chain extender reaction are obtained into polyurethane-modified thing.Polyurethane-modified thing and PLA melt blending are obtained into activeness and quietness poly-lactic acid material.Soft segment in polyurethane-modified thing improves the elasticity and compliance of material, and its rigid chain segment contained improves the intensity and heat resistance of material, final to improve material overall mechanical properties.The layer dihydroxy metal oxide dispersion of lamellar structure in the substrate, improves the bending strength and tensile strength of material, and its " Anchoring Effect " for having can avoid the incidental modifying agent compatibility of simple physical blending and migration problem.
Description
Technical field
The present invention relates to polymeric material field, and more particularly to a kind of activeness and quietness poly-lactic acid material and its preparation side
Method.
Background technology
PLA (PLA) material is as a kind of aliphatic polyester of totally biodegradable, with excellent bio-compatible
Property and rigidity.Starch of this linear thermoplastic's biodegradable aliphatic polyester to be extracted in the plants such as corn, wheat, cassava
For initial raw material, decomposed by enzyme and obtain glucose, then become lactic acid after lactobacillus-fermented, be then chemically synthesized
Obtain high-purity PLA.PLA material has good mechanical strength, thermoplasticity, fibre forming property and transparency etc., it is adaptable to many
Plant processing method, it is considered to be the alternative materials of optimal petroleum-based plastics.The PLA prepared by lactic acid can be in natural ring
Through microbial degradation it is carbon dioxide and water in border, environmentally safe, in fields such as medical, agricultural and general-purpose plastics, application is wide
It is general.There is also some more obvious shortcomings for PLA simultaneously：(1) PLA is due to the polarity of ester backbone and the position of pending methyl group
Resistance, causes segment rigidly larger, shock resistance is poor；(2) PLA has crystalline rate slowly, the problems such as crystal defect is more,
Its mechanical property etc. is further degrading, extensive use of the PLA material in general-purpose plastics field is limited.
Copolymerization, blending and the method for modifying such as compound can be generally carried out with other flexible high molecular materials to improve PLA materials
The toughness of material, but PLA material and the compatibility of most of high polymer material are poor, to the property of PLA material under the conditions of physical blending
It can change limited.And some modifying agent, such as polyethylene glycol, there is good plasticization effect to PLA, can effectively improve PLA's
Toughness.But the molecular weight of modifying agent is low, and heat endurance is poor, can slowly move to material surface in use, and easily with
Phase separation, which occurs, for PLA causes toughness of material to decline, it is impossible to play long-acting plasticization effect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of activeness and quietness poly-lactic acid material, the operation letter of this preparation method
It is single, easily realize, it is adaptable to industrialization large-scale production.
Another object of the present invention is to provide a kind of activeness and quietness poly-lactic acid material, the material have good toughness and
Intensity, and shock resistance and stretch capability are strong, the performance of material is stable, and overall mechanical properties are excellent.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of preparation method of activeness and quietness poly-lactic acid material, and it comprises the following steps：
Reactant is obtained after layer dihydroxy metal oxide, 6-caprolactone are mixed, 100~140 DEG C are then heated to,
Ring-opening polymerization is carried out in the presence of catalyst and obtains Polycaprolactone modified thing.
Polycaprolactone modified thing and diisocyanate are subjected to sudden reaction and obtain performed polymer, performed polymer is anti-with chain extender
Polyurethane-modified thing should be obtained.
Polyurethane-modified thing and PLA melt blending are obtained into activeness and quietness poly-lactic acid material.
The present invention proposes a kind of activeness and quietness poly-lactic acid material, and it is prepared according to above-mentioned preparation method.
The beneficial effect of the activeness and quietness poly-lactic acid material and preparation method thereof of the present invention is：
Layer dihydroxy metal oxide (LDHs) is a kind of inorganic laminated nano-particle, with size is small, surface area big,
The features such as being also easy to produce skin effect, it is possible to increase the toughness of material, improves the compatibility of material, and can improve the size of material
Stability and processing fluidity etc..
Trigger 6-caprolactone ring-opening polymerisation in situ using LDHs surfaces polyhydroxy, realize the firm PCL claddings of chemical bonding
The booklike particle of nano inorganic containing LDHs so that LDHs reaches more preferable dispersion effect.After a large amount of PCL of LDHs surface graftings, obtain
Polycaprolactone modified thing (LDHs-g-PCL).LDHs-g-PCL occurs sudden reaction with diisocyanate again and prepares performed polymer,
And then the polyurethane-modified thing (LDHs-g-PU) of secondary function is obtained with chain extender reaction.The flexibility included in LDHs-g-PU
Segment improves the elasticity and compliance of material, and rigid chain segment improves the intensity and heat resistance of material, finally improves its whole
Mechanics performance.Meanwhile, the LDHs of lamellar structure is uniform in the scattered impact and drawing for further resisting the external world in the substrate
Stretch, improve the bending strength and tensile strength of material.Inorganic nano-particle LDHs is fixed on PLA base material as " ship anchor "
In, the migration of material is further limit, effect of getting twice the result with half the effort is reached.
Compared with other high polymer materials, polyurethane (PU) material has the regulatable spy of the easy design and performance of molecular structure
Point, can meet the different performance requirement of poly-lactic acid material.Soft and hard segments ratio can be changed in LDHs-g-PU to adjust PLA
The performance of material.With reference to stratiform LDHs " Anchoring Effect ", incidental low point of simple physical blending can not only be avoided
The problems such as son amount plasticization modifier migration or incompatible modifying agent, additionally it is possible to effectively improve toughness of poly-lactic acid material etc., protect
Having demonstrate,proved material has excellent mechanical property and long-term stability.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be attached to what is used required in embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the sem test figure of the material brittle failure provided in comparative example 1 of the present invention；
Fig. 2 is the sem test figure of the material brittle failure provided in the embodiment of the present invention 1.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
Below to activeness and quietness poly-lactic acid material of the embodiment of the present invention and preparation method thereof, using being specifically described.
The embodiment of the present invention provides a kind of preparation method of activeness and quietness poly-lactic acid material.
First, reactant is obtained after layer dihydroxy metal oxide (LDHs), 6-caprolactone being mixed, is then heated to
100~140 DEG C, progress ring-opening polymerization obtains Polycaprolactone modified thing (LDHs-g-PCL) in the presence of catalyst.It is excellent
Selection of land, carries out being mixed to get reactant so that material quickly, can be mixed equably using 30~50min of ultrasound to material.
LDHs is the important novel inorganic functional material of a class, can be multiple as inorganic-inorganic, inorganic-organic nanocomposite is prepared
The parent of condensation material.Inorganic laminated nano-particle LDHs sizes are small, surface atom Numerous, and Atomic coordinate is not enough and surface area
Greatly, surface can be high, is also easy to produce skin effect, can improve compatibility, the size of material while toughness of material is improved
Stability and processing fluidity etc..LDHs special construction and chemical composition becomes a kind of efficient heat stabilizer, its
Body structure is stable, and non-volatile with good photostability, do not distil migration, and solvent resistance is strong, greatly improves the performance of material
And service life.In addition, inorganic laminated nano-particle LDHs can also improve the elongation at break of poly-lactic acid material and impact strong
Spend and improve the performance of poly-lactic acid material.
Further, in present pre-ferred embodiments, LDHs is selected from MgAl-CO3LDHs、MgAlZn-CO3LDHs and
CaAl-CO3It is one or more in LDHs.LDHs can be commercially commercially available, and can also be made by oneself and be obtained, for example with high temperature
Hydro-thermal method prepares LDHs.LDHs special constructions, which make its laminate constitute metal, has changeability, divalence and trivalent metal ion
Carry out after efficient combination, the LDHs materials of binary, ternary or quaternary can be formed.Preferably, from commercially available MgAl-
CO3LDHs、MgAlZn-CO3LDHs and CaAl-CO3One or more are as raw material in LDHs, and raw material sources are convenient, and cost is low,
Best in quality, condition is controllable.
Further, in present pre-ferred embodiments, the catalyst during ring-opening polymerization is selected from dibutyl tin
Or stannous octoate.The high catalytic efficiency of above-mentioned catalyst, ensure that ring-opening polymerization is efficiently carried out.
Further, in present pre-ferred embodiments, the ring-opening polymerization process for preparing LDHs-g-PCL is：Reaction
Thing obtains polymer after reacting 20~30h under inert gas shielding, dissolves the polymer in chlorinated solvents, is obtained after removal of impurities
LDHs-g-PCL.Specifically, reactant is in N2Thick polymer is obtained after 20~30h of the lower reaction of protection.Then will polymerization
Thing is dissolved in dichloromethane, is removed impurity after filtering, washing, is precipitated in ice hexane, and washing removes the complete monomer of unreacted,
20~30h is dried in vacuo at 35~45 DEG C and obtains LDHs-g-PCL.
6-caprolactone monomer is a very useful chemical intermediate, and in synthesis compound, it can be provided to synthetic
Many excellent chemical properties, can provide excellent pliability, impact resistance, solvent resistant and water resistance for poly-lactic acid material
Deng.The PCL that ring-opening polymerization is obtained has excellent biodegradability, biocompatibility and permeability.LDHs surfaces
Polyhydroxy triggers 6-caprolactone ring-opening polymerisation in situ, realizes firm PCL cladding nano inorganics containing the LDHs stratiform grain of chemical bonding
Son so that LDHs reaches more preferable dispersion effect.In addition, a large amount of PCL of LDHs surface graftings, compared to small molecule plasticizer, table
Reveal more preferable resistance to migration.
Further, in present pre-ferred embodiments, during ring-opening polymerization, layer dihydroxy metal oxide
Mass fraction in reactant is 1~30%.Under the ratio, it is ensured that LDHs surface graftings enough PCL, obtained LDHs-
To the modified effect of material more preferably, the activeness and quietness of material is better by g-PCL.
Secondly, LDHs-g-PCL said process prepared carries out sudden reaction with diisocyanate and obtains pre-polymerization
Body, polyurethane-modified thing (LDHs-g-PU) is obtained by performed polymer and chain extender reaction.
Polyurethane (PU) full name is polyurethanes, is containing the macromolecular for repeating carbamate groups on main chain
The general designation of compound.Usual polyurethane backbone is the soft segment and glass transition temperature for being less than room temperature by glass transition temperature
Rigid chain segment block higher than room temperature is formed., can be by selecting different block and regulation in the building-up process of polyurethane
The ratio of soft and hard segments is designed to polyurethane, constructs the polyurethane for adapting to different demands.
Compared with other high polymer materials, polyurethane material has the regulatable feature of the easy design and performance of molecular structure.
By macromolecule dihydric alcohol, diisocyanate and the small molecule chain extender from variety classes and different molecular weight, adjust soft or hard
Section ratio and control the methods such as its relative molecular mass, the performance of polyurethane material can be in a relatively wide scope
Regulated and controled, such as intensity, hardness, elasticity, wearability, anti-flexibility, hydrophilic and hydrophobic etc..Therefore change by polyurethane advantage
Property PLA is with preferable feasibility application prospect.
The embodiment of the present invention carries out sudden reaction with diisocyanate using LDHs-g-PCL and prepares isocyanic acid performed polymer,
And then the LDHs-g-PU of secondary function is obtained with small molecule dihydric alcohol or diamine chain stretching agent reaction.LDHs-g-PU is as poly-
Propylhomoserin is modified LDHs, wherein the soft segment included improves the elasticity of material, and rigid chain segment improves the intensity of material and resistance to
It is hot, so as to improve material overall mechanical properties.
Further, in present pre-ferred embodiments, diisocyanate is selected from hydrogenated toluene diisocyanate, hydrogenation two
In methylenebis phenyl isocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI) and methyl diphenylene diisocyanate
It is one or more.
Further, in present pre-ferred embodiments, chain extender is selected from BDO, ethylene glycol, a contracting diethyl two
Alcohol, 1,6-HD, 1,2- propane diols, 1,3- propane diols, diethanol amine, triethanolamine, methyl diethanolamine, diethyltoluene
One or more in diamines and 3,5- dimethythiotoluene diamines.
Further, in present pre-ferred embodiments, diisocyanate and LDHs-g-PCL mol ratio are 2.3~5:
1。
Further, in present pre-ferred embodiments, the mol ratio of chain extender and diisocyanate is 0.14~0.75:
1。
Under aforementioned proportion, Reasonable Regulation And Control LDHs-g-PU soft and hard segments ratio and the size of its molecular weight, PU materials
The polar group of tensile strength, elongation at break and modulus of elasticity and polymer, firm, the flexible and crystallization of segment has
Close.By adjusting the proportioning between LDHs-g-PCL, diisocyanate and chain extender, it is ensured that obtained LDHs-g-PU has
Preferable molecular weight distribution, and soft and hard segments ratio reaches most preferably, it is ensured that material toughening effect is excellent, the bending strength of raising material
And tensile strength.
Further, in present pre-ferred embodiments, the sudden reaction process for preparing performed polymer is：By LDHs-g-PCL
It is dissolved in organic solvent, adds diisocyanate and catalyst, reacting 1~2h in atmosphere of inert gases obtains performed polymer.Tool
After body, LDHs-g-PCL and organic solvent mixing, inert gas is passed through, using oil bath heating.Oil bath temperature is warming up to 60
~70 DEG C, and with mechanical agitation etc. raw material is completely dissolved.Then diisocyanate and catalyst are added to reaction system
In, react 1~2h in atmosphere of inert gases and obtain performed polymer.It is understood that in embodiments of the present invention, inert gas can
To be nitrogen, argon gas etc., but it is not limited to this.
Further, in present pre-ferred embodiments, obtain after performed polymer, performed polymer is with chain extender in 70~80 DEG C of bars
1~3h is reacted under part, question response product is cooled to room temperature, that is, obtains the LDHs-g-PU of secondary function.
Finally, polyurethane-modified thing (LDHs-g-PU) and PLA melt blending are obtained into activeness and quietness poly-lactic acid material.
LDHs-g-PU because of its special structure and performance, PLA is modified obtain product show it is better
Activeness and quietness effect, its compatibility with PLA is high, and modified PLA has higher toughness.LDHs-g-PU has
Higher molecular weight, it is to avoid the problem of it moves out from PLA matrix, modified PLA has long-term stability.This
Outside, LDHs-g-PCL and LDHs-g-PU molecular weight made from diisocyanate, chain extender reaction are higher, with reference to stratiform LDHs pictures
" ship anchor " is equally fixed in PLA base material, limits LDHs-g-PU migration, not only avoid simple physical blending and occurs
Low molecule amount plasticization modifier migration or modifying agent it is incompatible the problems such as, also ensure toughness reinforcing after poly-lactic acid material keep
Higher modulus and intensity.And without addition plasticizer, stabilizer, bulking agent etc. in addition, preparation method is more simple, cost
It is more cheap, environmental protection and economy.
Further, in present pre-ferred embodiments, PLA and LDHs-g-PU mass ratio are 1~19:1.It is preferred that
Ground, PLA and LDHs-g-PU mass ratio are 1~5:1, it is further preferable that PLA and LDHs-g-PU mass ratio are 2:
1.Under said ratio, the activeness and quietness effect of PLA reaches that most preferably overall performance is the most superior, and material stability reaches
To optimal.
Further, in present pre-ferred embodiments, the detailed process of LDHs-g-PU and PLA melt blending is：
By PLA and LDHs-g-PU, melt blending 10-30min obtains activeness and quietness poly-lactic acid material, torque in torque rheometer
Rheometer temperature setting is 160-190 DEG C, and rotating speed is 40-70rpm.
It is made after activeness and quietness poly-lactic acid material, the thick sheet materials of 1-5mm, vulcanizing press is hot pressed on vulcanizing press
Temperature setting is 180-200 DEG C, and pressure is 8-15MPa.
The embodiment of the present invention provides a kind of activeness and quietness poly-lactic acid material, is prepared according to above-mentioned preparation method.The material
Material has good intensity and toughness, and shock resistance and stretch capability are strong, and the performance of material is stable, and overall mechanical properties are excellent.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
(1) ε-CL for weighing 8g LDHs and 35g are added in there-necked flask, and ultrasonic 30min is warming up to 110 DEG C, adds catalysis
Agent stannous octoate, N2The lower reaction 24h of protection, after reaction terminates, thick polymer is dissolved in dichloromethane, filtering,
Impurity is removed after washing, is precipitated in ice hexane, washing removes vacuum drying 24h at the complete monomer of unreacted, 40 DEG C and obtained
LDHs-g-PCL。
(2) 3g LDHs-g-PCL and organic solvent are added in the three-necked flask for being provided with mechanical agitator, are passed through
Nitrogen, 70 DEG C are warming up to by oil bath temperature, after raw material is completely dissolved, and add the 2.2126g isocyanide of hydrogenated diphenyl methane two
Acid esters adds catalyst into reaction system, and 2h is reacted in nitrogen atmosphere, then by temperature adjustment to 75 DEG C, addition 0.8g Isosorbide-5-Nitraes-
After butanediol, continue to react 1.5h, reaction question response product is cooled to room temperature, obtains the LDHs-g-PU of secondary function.
(3) 10g LDHs-g-PU and 20g PLAs melt blending 15min in torque rheometer are obtained into activeness and quietness
Poly-lactic acid material, it is 185 DEG C to set torque rheometer temperature, and rotating speed is 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) are obtained is hot pressed into the thick sheet materials of 4mm, flat board on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, and pressure is 12MPa.
Embodiment 2
(1) ε-CL for weighing 8g LDHs and 45g are added in there-necked flask, and ultrasonic 40min is warming up to 100 DEG C, adds catalysis
Agent stannous octoate, N2The lower reaction 20h of protection, after reaction terminates, thick polymer is dissolved in dichloromethane, filtering,
Impurity is removed after washing, is precipitated in ice hexane, washing removes vacuum drying 30h at the complete monomer of unreacted, 35 DEG C and obtained
LDHs-g-PCL。
(2) 3g LDHs-g-PCL and organic solvent are added in the three-necked flask for being provided with mechanical agitator, are passed through
Nitrogen, 60 DEG C are warming up to by oil bath temperature, after raw material is completely dissolved, and the mol ratio by LDHs-g-PCL and diisocyanate is
1:2.3 add methyl diphenylene diisocyanates into reaction system, add catalyst, 1h is reacted in nitrogen atmosphere, then by temperature
Degree regulation, to 70 DEG C, is 0.14 by the mol ratio of diisocyanate and chain extender:1 adds after ethylene glycol, continues to react 1h, reaction
Question response product is cooled to room temperature, obtains the LDHs-g-PU of secondary function.
(3) 10g LDHs-g-PU and 10g PLAs melt blending 30min in torque rheometer are obtained into activeness and quietness
Poly-lactic acid material, it is 160 DEG C to set torque rheometer temperature, and rotating speed is 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) are obtained is hot pressed into the thick sheet materials of 4mm, flat board on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, and pressure is 12MPa.
Embodiment 3
(1) ε-CL for weighing 8g LDHs and 19g are added in there-necked flask, and ultrasonic 50min is warming up to 120 DEG C, adds catalysis
Agent dibutyl tin, N2The lower reaction 30h of protection, after reaction terminates, thick polymer is dissolved in dichloromethane, filtering,
Impurity is removed after washing, is precipitated in ice hexane, washing removes vacuum drying 20h at the complete monomer of unreacted, 45 DEG C and obtained
LDHs-g-PCL。
(2) 3g LDHs-g-PCL and organic solvent are added in the three-necked flask for being provided with mechanical agitator, are passed through
Nitrogen, 70 DEG C are warming up to by oil bath temperature, after raw material is completely dissolved, and the mol ratio by LDHs-g-PCL and diisocyanate is
1:5 add 1, and hexamethylene-diisocyanate and toluene di-isocyanate(TDI) add catalyst into reaction system, in nitrogen atmosphere reaction
2h, then be 0.75 by the mol ratio of diisocyanate and chain extender by temperature adjustment to 80 DEG C:1 adds after 1,2-PD, after
Continuous reaction 3h, reaction question response product is cooled to room temperature, obtains the LDHs-g-PU of secondary function.
(3) by 4g LDHs-g-PU and 20g PLAs, melt blending 15min obtains activeness and quietness and gathered in torque rheometer
Lactate material, it is 190 DEG C to set torque rheometer temperature, and rotating speed is 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) are obtained is hot pressed into the thick sheet materials of 4mm, flat board on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, and pressure is 12MPa.
Embodiment 4
(1) ε-CL for weighing 1g LDHs and 99g are added in there-necked flask, and ultrasonic 50min is warming up to 140 DEG C, adds catalysis
Agent stannous octoate, N2The lower reaction 26h of protection, after reaction terminates, thick polymer is dissolved in dichloromethane, filtering,
Impurity is removed after washing, is precipitated in ice hexane, washing removes vacuum drying 30h at the complete monomer of unreacted, 40 DEG C and obtained
LDHs-g-PCL。
(2) 3g LDHs-g-PCL and organic solvent are added in the three-necked flask for being provided with mechanical agitator, are passed through
Nitrogen, 65 DEG C are warming up to by oil bath temperature, after raw material is completely dissolved, and the mol ratio by LDHs-g-PCL and diisocyanate is
1:4 add hydrogenated toluene diisocyanates into reaction system, add catalyst, 1.5h is reacted in nitrogen atmosphere, then by temperature
Regulation, to 75 DEG C, is 0.5 by the mol ratio of diisocyanate and chain extender:1 adds methyl diethanolamine and diethyltoluene two
After amine, continue to react 2.5h, reaction question response product is cooled to room temperature, obtains the LDHs-g-PU of secondary function.
(3) by 1g LDHs-g-PU and 19g PLAs, melt blending 20min obtains activeness and quietness and gathered in torque rheometer
Lactate material, it is 180 DEG C to set torque rheometer temperature, and rotating speed is 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) are obtained is hot pressed into the thick sheet materials of 4mm, flat board on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, and pressure is 12MPa.
Comparative example 1
Pure PLA is hot pressed into the thick sheet materials of 4mm on vulcanizing press, and vulcanizing press temperature setting is 200 DEG C,
Pressure is 12MPa.
Test example 1
The material provided using scanning electron microscope analysis comparative example 1 and embodiment 1, as a result as depicted in figs. 1 and 2.Wherein, scheme
1 is the brittle failure face for the material that comparative example 1 is provided, and as seen from Figure 1, the brittle failure face of the material is smooth straight, visually observes phase section
It is body color, belongs to typical brittle fracture.Fig. 2 is the brittle failure face for the material that embodiment 1 is provided, from Figure 2 it can be seen that brittle failure
There is rough surface in face, substantial amounts of depression and projection occurs, and the breaking property of activeness and quietness poly-lactic acid material belongs to significant tough
Property fracture.
Test example 2
Determine the tensile strength of the sheet material that comparative example 1 and embodiment 1 are provided, elongation at break, notch impact strength and
Bending strength, as a result as shown in table 1.
Table 1
From table 1 it can be seen that, compared to the pure PLA in comparative example 1, the activeness and quietness PLA material in embodiment 1
130% and 275% has been respectively increased in the elongation at break and notch impact strength of material, and tensile strength and bending strength are respectively increased
37% and 17%.From experimental result it can be seen that, toughening modifying crosses poly-lactic acid material, and not only toughness significantly improves, draw
Stretch intensity and bending strength and also obtain a certain degree of improvement, overall mechanical properties are significantly improved.
In summary, the activeness and quietness poly-lactic acid material of the embodiment of the present invention is without addition bulking agent, plasticizer etc. in addition
Composition, activeness and quietness poly-lactic acid material is obtained using the LDHs-g-PU and PLA melt blending of secondary function.With LDHs layers
Hydroxyl on plate triggers ε-CL cyclopolymerizations to obtain LDHs-g-PCL, then LDHs-g-PCL and diisocyanate into sudden reaction occur
Performed polymer is prepared, and then obtains with chain extender reaction the polyurethane-modified LDHs, i.e. LDHs-g-PU of secondary function.LDHs-
G-PU not only increases the elasticity and compliance of material, also improves the intensity and heat resistance of material, finally improves its body force
Learn performance.Meanwhile, the LDHs of lamellar structure is uniform in the scattered impact and stretching for further resisting the external world in the substrate, carries
The bending strength and tensile strength of high material.Polyurethane material is modified " Anchoring Effect " for combining stratiform LDHs, can not only keep away
The problems such as having exempted from the incidental low molecule amount plasticization modifier migration of simple physical blending or incompatible modifying agent, moreover it is possible to
Enough effectively improve toughness of poly-lactic acid material etc., it is ensured that material has excellent mechanical property and long-term stability.Except this it
Outside, its preparation method is simple, easy to operate, and reaction is gentle, easily realizes, it is adaptable to industrialization large-scale production, with great
Development and application prospect.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of activeness and quietness poly-lactic acid material, it is characterised in that comprise the following steps：
Reactant is obtained after layer dihydroxy metal oxide, 6-caprolactone are mixed, 100~140 DEG C is then heated to, is urging
Ring-opening polymerization is carried out in the presence of agent and obtains Polycaprolactone modified thing；
The Polycaprolactone modified thing and diisocyanate are subjected to sudden reaction and obtain performed polymer, by the performed polymer and chain extension
Agent reaction obtains polyurethane-modified thing；
The polyurethane-modified thing and PLA melt blending are obtained into the activeness and quietness poly-lactic acid material.
2. preparation method according to claim 1, it is characterised in that layered pair of hydroxy metal oxide is selected from
MgAl-CO3 LDHs、MgAlZn-CO3LDHs and CaAl-CO3It is one or more in LDHs.
3. preparation method according to claim 1, it is characterised in that layered pair of hydroxy metal oxide is described anti-
It is 1~30% to answer the mass fraction in thing.
4. preparation method according to claim 1, it is characterised in that the chain extender be selected from BDO, ethylene glycol,
Diglycol, 1,6-HD, 1,2- propane diols, 1,3- propane diols, diethanol amine, triethanolamine, methyl diethanolamine,
One or more in diethyl toluene diamine and 3,5- dimethythiotoluene diamines.
5. preparation method according to claim 1, it is characterised in that the diisocyanate with it is described Polycaprolactone modified
The mol ratio of thing is 2.3~5:1.
6. preparation method according to claim 1, it is characterised in that mole of the chain extender and the diisocyanate
Than for 0.14~0.75:1.
7. preparation method according to claim 1, it is characterised in that the matter of the PLA and the polyurethane-modified thing
Amount is than being 1~19:1.
8. preparation method according to claim 1, it is characterised in that the sudden reaction process for preparing the performed polymer is：
The Polycaprolactone modified thing is dissolved in organic solvent, the diisocyanate and catalyst are added, in inert gas atmosphere
Enclose 1~2h of reaction and obtain the performed polymer.
9. preparation method according to claim 1, it is characterised in that during the performed polymer and chain extender reaction, instead
It is 70~80 DEG C to answer temperature, and the reaction time is 1~3h.
10. a kind of activeness and quietness poly-lactic acid material, it is characterised in that the preparation side according to claim 1~9 any one
Method is prepared.
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| CN110903452A (en) * | 2019-11-22 | 2020-03-24 | 广州睿特新材料科技有限公司 | Preparation method of lactic acid copolymer with high relative molecular mass |
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| CN111961188A (en) * | 2020-08-31 | 2020-11-20 | 重庆文理学院 | Flame-retardant toughening bifunctional ionomer auxiliary agent and preparation method and application thereof |
| CN113930065A (en) * | 2021-11-20 | 2022-01-14 | 郑州市彦峰塑料包装有限公司 | High-strength degradable packaging bag and preparation method thereof |
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| CN114230992A (en) * | 2022-01-20 | 2022-03-25 | 江南大学 | Preparation method and application of high-strength high-toughness biodegradable plastic |
| CN114230992B (en) * | 2022-01-20 | 2022-09-06 | 江南大学 | Preparation method and application of high-strength high-toughness biodegradable plastic |
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