CN107033563B - 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
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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: to obtain reactant after mixing layer dihydroxy metal oxide, 6-caprolactone, and ring-opening polymerization obtains Polycaprolactone modified object.Polycaprolactone modified object and diisocyanate are subjected to sudden reaction and obtain performed polymer.Performed polymer and chain extender reaction are obtained into polyurethane-modified object.Polyurethane-modified object and polylactic acid melt blending are obtained into activeness and quietness poly-lactic acid material.Soft segment in polyurethane-modified object improves the elasticity and flexibility 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 be to avoid the incidental modifying agent compatibility of simple physical blending and migration problem.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of activeness and quietness poly-lactic acid material and its preparation side
Method.
Background technique
A kind of aliphatic polyester of polylactic acid (PLA) material as totally biodegradable has 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
It for initial raw material, decomposes to obtain glucose by enzyme, using lactic acid is become after lactobacillus-fermented, then be chemically synthesized
Obtain high-purity polylactic acid.PLA material has good mechanical strength, thermoplasticity, fibre forming property and transparency etc., is suitable for more
Kind processing method, it is considered to be the alternative materials of optimal petroleum-based plastics.It can be in natural ring by polylactic acid prepared by lactic acid
It through microbial degradation is carbon dioxide and water in border, no pollution to the environment, in fields such as medical, agricultural and general-purpose plastics, application is wide
It is general.There is also some more obvious disadvantages for polylactic acid simultaneously: (1) polylactic acid 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) the problems such as that there is crystalline rates is slow for polylactic acid, and crystal defect is more,
It is further degrading its mechanical property etc., limits PLA material in the extensive use in general-purpose plastics field.
It can be usually copolymerized, be blended and the method for modifying such as compound improve PLA material with other flexible high molecular materials
The toughness of material, but PLA material and the compatibility of most of high molecular 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 thermal stability is poor, will be slow move to material surface in use, and be easy with
Mutually separation, which occurs, for PLA causes toughness of material to decline, and cannot play long-acting plasticization effect.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of activeness and quietness poly-lactic acid material, the operation letters of this preparation method
It is single, it is easy to accomplish, it is suitable for 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 stablized, and overall mechanical properties are excellent.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method of activeness and quietness poly-lactic acid material comprising following steps:
Reactant is obtained after layer dihydroxy metal oxide, 6-caprolactone are mixed, then heats to 100~140 DEG C,
Ring-opening polymerization is carried out under the effect of the catalyst obtains Polycaprolactone modified object.
Polycaprolactone modified object and diisocyanate are subjected to sudden reaction and obtain performed polymer, performed polymer is anti-with chain extender
It should obtain polyurethane-modified object.
Polyurethane-modified object and polylactic acid 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, is prepared according to above-mentioned preparation method.
The beneficial effect of activeness and quietness poly-lactic acid material of the invention and preparation method thereof is:
Layer dihydroxy metal oxide (LDHs) is a kind of inorganic laminated nanoparticle, have size is small, surface area is big,
The features such as being also easy to produce skin effect can be improved the toughness of material, improve the compatibility of material, and can be improved the size of material
Stability and processing fluidity etc..
Cause the ring-opening polymerisation of 6-caprolactone original position using the surface LDHs polyhydroxy, realizes and be chemically bonded firm PCL cladding
The booklike particle of nano inorganic containing LDHs, so that LDHs reaches better dispersion effect.After a large amount of PCL of LDHs surface grafting, obtain
Polycaprolactone modified object (LDHs-g-PCL).LDHs-g-PCL occurs sudden reaction with diisocyanate again and prepares performed polymer,
And then the polyurethane-modified object (LDHs-g-PU) of secondary function is obtained with chain extender reaction.The flexibility for including in LDHs-g-PU
Segment improves the elasticity and flexibility of material, and rigid chain segment improves the intensity and heat resistance of material, it is whole to finally improve its
Mechanics performance.Meanwhile the LDHs of lamellar structure uniformly is dispersing further to resist extraneous impact and drawing in the substrate
It stretches, improves the bending strength and tensile strength of material.Inorganic nano-particle LDHs is fixed on polylactic acid substrate as " ship anchor "
In, the migration of material is further limited, effect of getting twice the result with half the effort is reached.
Compared with other high molecular materials, polyurethane (PU) material has the regulatable spy of the easy design and performance of molecular structure
Point can satisfy the different performance requirement of poly-lactic acid material.Soft and hard segments ratio be can change in LDHs-g-PU to adjust polylactic acid
The performance of material.In conjunction with " Anchoring Effect " of stratiform LDHs, 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 the toughness etc. of poly-lactic acid material, protect
Material has been demonstrate,proved with excellent mechanical property and long-term stability.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached 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.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is 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.
Firstly, obtaining reactant after layer dihydroxy metal oxide (LDHs), 6-caprolactone are mixed, then heat to
100~140 DEG C, ring-opening polymerization is carried out under the effect of the catalyst and obtains Polycaprolactone modified object (LDHs-g-PCL).It is excellent
Selection of land carries out material to be mixed to get reactant, material quickly, is equably mixed using 30~50min of ultrasound.
LDHs is a kind of important novel inorganic functional material, can be used as that prepare inorganic-inorganic, inorganic-organic nanocomposite multiple
The parent of condensation material.Inorganic laminated nanoparticle LDHs size is small, surface atom Numerous, and Atomic coordinate is insufficient and surface area
Greatly, surface can be high, is also easy to produce skin effect, can improve compatibility, the size of material while improving toughness of material
Stability and processing fluidity etc..The special construction and chemical composition of LDHs becomes a kind of efficient heat stabilizer,
Body structure is stablized, and has good photostability, and non-volatile, do not distil migration, and solvent resistance is strong, greatly improves the performance of material
And service life.In addition, inorganic laminated nanoparticle LDHs can also improve the elongation at break of poly-lactic acid material and impact strong
Spend and improve the service performance of poly-lactic acid material.
Further, in a preferred embodiment of the present invention, LDHs is selected from MgAl-CO3LDHs、MgAlZn-CO3LDHs and
CaAl-CO3It is one or more in LDHs.LDHs can be commercially available on the market, can also make by oneself to obtain, for example, by using high temperature
LDHs is prepared in hydro-thermal method.LDHs special construction makes its laminate composition metal have changeability, divalent and trivalent metal ion
After carrying out efficient combination, the LDHs material of binary, ternary or quaternary can be formed.Preferably, commercially available MgAl- is selected
CO3LDHs、MgAlZn-CO3LDHs and CaAl-CO3One or more in LDHs to be used as raw material, raw material sources are convenient, at low cost,
Best in quality, condition is controllable.
Further, in a preferred embodiment of the present invention, the catalyst during ring-opening polymerization is selected from dibutyl tin
Or stannous octoate.The high catalytic efficiency of above-mentioned catalyst can guarantee that ring-opening polymerization efficiently carries out.
Further, in a preferred embodiment of the present invention, the ring-opening polymerization process of LDHs-g-PCL is prepared are as follows: reaction
Object obtains polymer after reacting 20~30h under inert gas protection, dissolves the polymer in chlorinated solvents, obtains after removal of impurities
LDHs-g-PCL.Specifically, reactant is in N2Thick polymer is obtained after 20~30h of the lower reaction of protection.It then will polymerization
Object is dissolved in methylene chloride, removes impurity after being filtered, washed, and is precipitated in ice hexane, and washing removes the complete monomer of unreacted,
It is dried in vacuo 20~30h 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 flexibility, impact resistance, solvent resistant and water resistance for poly-lactic acid material
Deng.The PCL that ring-opening polymerization obtains has excellent biodegradability, biocompatibility and permeability.The surface LDHs
Polyhydroxy causes the ring-opening polymerisation of 6-caprolactone original position, realizes that being chemically bonded firm PCL coats the stratiform of nano inorganic containing LDHs grain
Son, so that LDHs reaches better dispersion effect.In addition, a large amount of PCL of LDHs surface grafting, compared to small molecule plasticizer, table
Reveal better resistance to migration.
Further, in a preferred embodiment of the present invention, during ring-opening polymerization, layer dihydroxy metal oxide
Mass fraction in reactant is 1~30%.Under the ratio, guarantee LDHs surface grafting enough PCL, obtained LDHs-
G-PCL to the modified effect of material more preferably, the activeness and quietness better effect of material.
Secondly, LDHs-g-PCL and diisocyanate that the above process is prepared, which are carried out sudden reaction, obtains pre-polymerization
Performed polymer and chain extender reaction are obtained polyurethane-modified object (LDHs-g-PU) by body.
Polyurethane (PU) full name is polyurethanes, is on main chain containing the macromolecular for repeating carbamate groups
Close the general designation of object.Usual polyurethane backbone is the soft segment and glass transition temperature for being lower than room temperature by glass transition temperature
Rigid chain segment block higher than room temperature forms.It, can be by selecting different block and adjusting in the synthesis process of polyurethane
The ratio of soft and hard segments is designed polyurethane, constructs the polyurethane for adapting to different demands.
Compared with other high molecular materials, polyurethane material has the characteristics that the easy design and performance of molecular structure is regulatable.
By selecting macromolecule dihydric alcohol, diisocyanate and the small molecule chain extender of variety classes and different molecular weight, adjust soft or hard
The ratio of section and the methods of control its relative molecular mass, the performance of polyurethane material can be in a relatively wide range
Regulated and controled, such as intensity, hardness, elasticity, wearability, anti-flexibility, hydrophilic and hydrophobic etc..Therefore change by polyurethane advantage
Property polylactic acid is that have preferable feasibility application prospect.
The embodiment of the present invention carries out sudden reaction using LDHs-g-PCL and diisocyanate and prepares isocyanic acid performed polymer,
And then it reacts to obtain the LDHs-g-PU of secondary function with small molecule dihydric alcohol or diamine chain stretching agent.LDHs-g-PU is as poly-
Propylhomoserin is modified LDHs, and soft segment wherein included improves the elasticity of material, and rigid chain segment improves the intensity of material and resistance to
It is hot, to improve material overall mechanical properties.
Further, in a preferred embodiment of the present invention, 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 a preferred embodiment of the present invention, chain extender is selected from 1,4-butanediol, ethylene glycol, a contracting diethyl two
Alcohol, 1,6-HD, 1,2- propylene glycol, 1,3- propylene glycol, diethanol amine, triethanolamine, methyl diethanolamine, diethyltoluene
One of diamines and 3,5- dimethythiotoluene diamine are a variety of.
Further, in a preferred embodiment of the present invention, the molar ratio of diisocyanate and LDHs-g-PCL are 2.3~5:
1。
Further, in a preferred embodiment of the present invention, the molar ratio of chain extender and diisocyanate is 0.14~0.75:
1。
Under aforementioned proportion, the soft and hard segments ratio of Reasonable Regulation And Control LDHs-g-PU and the size of its molecular weight, PU material
Rigid, the flexible and crystallization of the polar group of tensile strength, elongation at break and elasticity modulus and polymer, segment has
It closes.By adjusting the proportion between LDHs-g-PCL, diisocyanate and chain extender, the LDHs-g-PU guaranteed has
Preferable molecular weight distribution, and soft and hard segments ratio reaches most preferably, guarantees that material toughening effect is excellent, improves the bending strength of material
And tensile strength.
Further, in a preferred embodiment of the present invention, the sudden reaction process of performed polymer is prepared are as follows: by LDHs-g-PCL
It is dissolved in organic solvent, diisocyanate and catalyst is added, react 1~2h in atmosphere of inert gases and obtain performed polymer.Tool
After body, LDHs-g-PCL and organic solvent mixing, it is passed through inert gas, using oil bath heating.Oil bath temperature is warming up to 60
~70 DEG C, and with mechanical stirring etc. raw material is completely dissolved.Then diisocyanate and catalyst is added to reaction system
In, 1~2h, which is reacted, in atmosphere of inert gases obtains performed polymer.It is understood that in embodiments of the present invention, inert gas can
To be nitrogen, argon gas etc., but not limited to this.
Further, in a preferred embodiment of the present invention, after obtaining performed polymer, performed polymer and chain extender are in 70~80 DEG C of items
1~3h is reacted under part, is cooled to room temperature to reaction product to get the LDHs-g-PU of secondary function is arrived.
Finally, polyurethane-modified object (LDHs-g-PU) and polylactic acid melt blending are obtained activeness and quietness poly-lactic acid material.
LDHs-g-PU because of its special structure and performance, to polylactic acid be modified to obtain product show it is more good
Activeness and quietness effect, high with the compatibility of polylactic acid, modified polylactic acid has higher toughness.LDHs-g-PU has
Higher molecular weight, avoids the problem of it moves out from polylactic acid matrix, and modified polylactic acid has long-term stability.This
Outside, LDHs-g-PCL and LDHs-g-PU molecular weight made from diisocyanate, chain extender reaction are higher, in conjunction with stratiform LDHs picture
" ship anchor " is equally fixed in polylactic acid substrate, limits the migration of LDHs-g-PU, is not only avoided simple physical blending and is occurred
Low molecular weight plasticization modifier migration or modifying agent it is incompatible the problems such as, also after guaranteeing toughening poly-lactic acid material holding
Higher modulus and intensity.And without in addition addition plasticizer, stabilizer, expanding material etc., preparation method is more simple, cost
It is more cheap, environmental protection and economy.
Further, in a preferred embodiment of the present invention, the mass ratio of polylactic acid and LDHs-g-PU are 1~19:1.It is preferred that
The mass ratio of ground, polylactic acid and LDHs-g-PU are 1~5:1, it is further preferable that the mass ratio of polylactic acid and LDHs-g-PU are 2:
1.Under said ratio, the activeness and quietness effect of polylactic acid reaches most preferably, and overall performance is the most superior, and material stability reaches
To best.
Further, in a preferred embodiment of the present invention, the detailed process of LDHs-g-PU and polylactic acid melt blending are as follows:
By polylactic acid 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, revolving speed 40-70rpm.
After activeness and quietness poly-lactic acid material is made, the plate of 1-5mm thickness, vulcanizing press are hot pressed on vulcanizing press
Temperature setting is 180-200 DEG C, pressure 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 stablized, and overall mechanical properties are excellent.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
(1) ε-CL for weighing the LDHs and 35g of 8g is added in there-necked flask, and ultrasonic 30min is warming up to 110 DEG C, and catalysis is added
Agent stannous octoate, N2For 24 hours, after reaction, thick polymer is dissolved in methylene chloride for the lower reaction of protection, filtering,
Impurity is removed after washing, is precipitated in ice hexane, and washing removes the complete monomer of unreacted, is dried in vacuo at 40 DEG C and obtains for 24 hours
LDHs-g-PCL。
(2) LDHs-g-PCL of 3g and organic solvent are added in the three-necked flask for being equipped with mechanical agitator, are passed through
Oil bath temperature is warming up to 70 DEG C by nitrogen, and after raw material is completely dissolved, two isocyanide of hydrogenated diphenyl methane of 2.2126g is added
Catalyst is added into reaction system in acid esters, reacts 2h in nitrogen atmosphere, then the temperature was then adjusted to 75 DEG C, 0.8g Isosorbide-5-Nitrae-is added
After butanediol, the reaction was continued 1.5h, reaction is cooled to room temperature to reaction product, obtains the LDHs-g-PU of secondary function.
(3) 10g LDHs-g-PU and 20g polylactic acid melt blending 15min in torque rheometer are obtained into activeness and quietness
Poly-lactic acid material, setting torque rheometer temperature are 185 DEG C, revolving speed 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) obtain is hot pressed into the plate of 4mm thickness, plate on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, pressure 12MPa.
Embodiment 2
(1) ε-CL for weighing the LDHs and 45g of 8g is added in there-necked flask, and ultrasonic 40min is warming up to 100 DEG C, and catalysis is added
Agent stannous octoate, N2Thick polymer is dissolved in methylene chloride by the lower reaction 20h of protection after reaction, filtering,
Impurity is removed after washing, is precipitated in ice hexane, and washing removes the complete monomer of unreacted, and vacuum drying 30h is obtained at 35 DEG C
LDHs-g-PCL。
(2) LDHs-g-PCL of 3g and organic solvent are added in the three-necked flask for being equipped with mechanical agitator, are passed through
Oil bath temperature is warming up to 60 DEG C by nitrogen, and after raw material is completely dissolved, the molar ratio by LDHs-g-PCL and diisocyanate is
Methyl diphenylene diisocyanate is added into reaction system in 1:2.3, and catalyst is added, and reacts 1h in nitrogen atmosphere, then will be warm
Degree is adjusted to 70 DEG C, is the reaction was continued 1h, reaction after 0.14:1 addition ethylene glycol by the molar ratio of diisocyanate and chain extender
It is cooled to room temperature to reaction product, obtains the LDHs-g-PU of secondary function.
(3) 10g LDHs-g-PU and 10g polylactic acid melt blending 30min in torque rheometer are obtained into activeness and quietness
Poly-lactic acid material, setting torque rheometer temperature are 160 DEG C, revolving speed 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) obtain is hot pressed into the plate of 4mm thickness, plate on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, pressure 12MPa.
Embodiment 3
(1) ε-CL for weighing the LDHs and 19g of 8g is added in there-necked flask, and ultrasonic 50min is warming up to 120 DEG C, and catalysis is added
Agent dibutyl tin, N2Thick polymer is dissolved in methylene chloride by the lower reaction 30h of protection after reaction, filtering,
Impurity is removed after washing, is precipitated in ice hexane, and washing removes the complete monomer of unreacted, and vacuum drying 20h is obtained at 45 DEG C
LDHs-g-PCL。
(2) LDHs-g-PCL of 3g and organic solvent are added in the three-necked flask for being equipped with mechanical agitator, are passed through
Oil bath temperature is warming up to 70 DEG C by nitrogen, and after raw material is completely dissolved, the molar ratio by LDHs-g-PCL and diisocyanate is
1:5 is added 1, and catalyst is added into reaction system in hexamethylene-diisocyanate and toluene di-isocyanate(TDI), reacts in nitrogen atmosphere
2h, then the temperature was then adjusted to 80 DEG C, after 1,2-PD is added for 0.75:1 by the molar ratio of diisocyanate and chain extender, after
Continuous reaction 3h, reaction are cooled to room temperature to reaction product, obtain the LDHs-g-PU of secondary function.
(3) by 4g LDHs-g-PU and 20g polylactic acid, melt blending 15min obtains activeness and quietness and gathers in torque rheometer
Lactate material, setting torque rheometer temperature are 190 DEG C, revolving speed 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) obtain is hot pressed into the plate of 4mm thickness, plate on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, pressure 12MPa.
Embodiment 4
(1) ε-CL for weighing the LDHs and 99g of 1g is added in there-necked flask, and ultrasonic 50min is warming up to 140 DEG C, and catalysis is added
Agent stannous octoate, N2Thick polymer is dissolved in methylene chloride by the lower reaction 26h of protection after reaction, filtering,
Impurity is removed after washing, is precipitated in ice hexane, and washing removes the complete monomer of unreacted, and vacuum drying 30h is obtained at 40 DEG C
LDHs-g-PCL。
(2) LDHs-g-PCL of 3g and organic solvent are added in the three-necked flask for being equipped with mechanical agitator, are passed through
Oil bath temperature is warming up to 65 DEG C by nitrogen, and after raw material is completely dissolved, the molar ratio by LDHs-g-PCL and diisocyanate is
Hydrogenated toluene diisocyanate is added into reaction system in 1:4, and catalyst is added, and reacts 1.5h in nitrogen atmosphere, then by temperature
75 DEG C are adjusted to, is that methyl diethanolamine and diethyltoluene two is added in 0.5:1 by the molar ratio of diisocyanate and chain extender
After amine, the reaction was continued 2.5h, reaction is cooled to room temperature to reaction product, obtains the LDHs-g-PU of secondary function.
(3) by 1g LDHs-g-PU and 19g polylactic acid, melt blending 20min obtains activeness and quietness and gathers in torque rheometer
Lactate material, setting torque rheometer temperature are 180 DEG C, revolving speed 40-70rpm.
(4) the activeness and quietness poly-lactic acid material that (3) obtain is hot pressed into the plate of 4mm thickness, plate on vulcanizing press
Vulcanizer temperature setting is 200 DEG C, pressure 12MPa.
Comparative example 1
Pure polylactic acid is hot pressed into the plate of 4mm thickness 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
The brittle failure face of 1 material provided for comparative example 1, 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 provides, from Figure 2 it can be seen that brittle failure
There is rough surface in face, a large amount of recess and protrusion occurs, and the breaking property of activeness and quietness poly-lactic acid material belongs to significant tough
Property fracture.
Test example 2
Measure the tensile strength of the plate that comparative example 1 and embodiment 1 provide, elongation at break, notch impact strength and
Bending strength, the results are shown in Table 1.
Table 1
From table 1 it can be seen that, the activeness and quietness polylactic acid material compared to the pure polylactic acid in comparative example 1, 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, and draws
It stretches intensity and bending strength and also obtains a degree of improvement, overall mechanical properties are significantly improved.
In conclusion the activeness and quietness poly-lactic acid material of the embodiment of the present invention is without in addition addition expanding material, plasticizer etc.
Ingredient obtains activeness and quietness poly-lactic acid material using the LDHs-g-PU and polylactic acid melt blending of secondary function.With LDHs layers
Hydroxyl on plate causes ε-CL cyclopolymerization and obtains LDHs-g-PCL, then sudden reaction is occurred for LDHs-g-PCL and diisocyanate
Performed polymer is prepared, and then obtains the polyurethane-modified LDHs of secondary function, i.e. LDHs-g-PU with chain extender reaction.LDHs-
G-PU not only increases the elasticity and flexibility of material, also improves the intensity and heat resistance of material, finally improves its body force
Learn performance.Meanwhile the LDHs of lamellar structure uniformly is dispersing further to resist extraneous impact and stretching in the substrate, mention
The bending strength and tensile strength of high material.Modified " Anchoring Effect " for combining stratiform LDHs of polyurethane material, can not only keep away
The problems such as having exempted from the incidental low molecular weight plasticization modifier migration of simple physical blending or incompatible modifying agent, moreover it is possible to
The toughness etc. for enough effectively improving poly-lactic acid material ensure that material has excellent mechanical property and long-term stability.Except this it
Outside, preparation method is simple, easy to operate, and reaction is mild, easy to accomplish, is suitable for industrialization large-scale production, has great
Development and application prospect.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of toughening modified polylactic acid material, which comprises 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 under the action of agent obtains modified layered double hydroxy metal oxides, modified layered double hydroxyl gold
The structure for belonging to oxide LDHs-g-PCL is that PCL coats the booklike particle of nano inorganic containing LDHs；
In atmosphere of inert gases, make modified layered double hydroxy metal oxides and the polylactic acid in 165~205 DEG C of conditions
After lower melting completely, isocyanates is added, after atmosphere of inert gases reacts 1~2h, the LDHs-g-PCL is connected to described
In polylactic acid hard section, crystallisation by cooling obtains the toughening modified polylactic acid material；
Mass fraction of the layered double hydroxy metal oxides in the reactant is 10~15%；
The mass ratio of the polylactic acid and modified layered double hydroxy metal oxides is 2~5:1；
The total moles ratio of isocyanates, modified layered double hydroxy metal oxides and polylactic acid is 1.05:1-1.15:1.
2. preparation method according to claim 1, which is characterized in that layered double hydroxy metal oxides are selected from
MgAl-CO3 LDHs、MgAlZn-CO3LDHs and CaAl-CO3It is one or more in LDHs.
3. preparation method according to claim 1, which is characterized in that the isocyanates is selected from hydrogenated toluene diisocyanate
Ester, hydrogenated diphenyl methane diisocyanate, two isocyanide of hexamethylene diisocyanate, toluene di-isocyanate(TDI) and diphenyl methane
One of acid esters is a variety of.
4. preparation method according to claim 1, which is characterized in that prepare modified layered double hydroxy metal oxides
Ring-opening polymerization process are as follows: the reactant obtains polymer after reacting 20~30h under inert gas protection, will be described
Polymer is dissolved in chlorinated solvents, and modified layered double hydroxy metal oxides are obtained after removal of impurities.
5. preparation method according to claim 1, which is characterized in that the catalyst is stannous octoate, stannous chloride, two
Butyl tin or stannous oxide.
6. a kind of toughening modified polylactic acid material, which is characterized in that preparation side described in any one according to claim 1~5
Method is prepared.
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| CN110423443B (en) * | 2019-08-20 | 2021-06-29 | 湖南工业大学 | Biomass-based high-toughness flame-retardant plate |
| 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 |
| CN111748309B (en) * | 2020-07-09 | 2021-11-26 | 漳州市锐普化工有限公司 | High-temperature-and-humidity-resistant environment-friendly adhesive and preparation method thereof |
| CN111961188B (en) * | 2020-08-31 | 2022-03-18 | 重庆文理学院 | Flame-retardant toughening bifunctional ionomer auxiliary agent and preparation method and application thereof |
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