CN107163194A - A kind of high-ductility lactic acid composite material and preparation method thereof - Google Patents
A kind of high-ductility lactic acid composite material and preparation method thereof Download PDFInfo
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- CN107163194A CN107163194A CN201710297903.4A CN201710297903A CN107163194A CN 107163194 A CN107163194 A CN 107163194A CN 201710297903 A CN201710297903 A CN 201710297903A CN 107163194 A CN107163194 A CN 107163194A
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- pla
- lactic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a kind of high-ductility poly-lactic acid material and preparation method thereof, toughener, increase-volume solvent and PLA are specifically included.Using the monomer or low polymer of difunctional as toughener, the monomer containing difunctional includes one kind or combination in lauryl acrylate or hydroxy-ethyl acrylate or trimethylol-propane trimethacrylate or 1,6 hexanediyl esters；Low polymer containing difunctional includes polyethylene ethyl acrylate GMA or one kind in ethylene butyl acrylate-GMA or esters of acrylic acid or combination；Increase-volume solvent includes methyl methacrylate or maleic anhydride or one kind in acrylic acid or butyl acrylate or its combination.Toughener, increase-volume solvent and PLA prepare the high-ductility poly-lactic acid material by melt blending, significantly improve the toughness of PLA, expand application of the PLA in fields such as packaging, film and sheet materials.
Description
Technical field
The present invention relates to a kind of poly-lactic acid material and preparation method thereof, more particularly to a kind of high-ductility lactic acid composite material,
Belong to technical field of polymer materials.
Background technology
Plastic products have light weight, and satisfactory mechanical property, chemical property is stable, and good appearance, manufacturing cost is low, wide
General to be applied to every profession and trade, the daily life that plastic products give people brings facility.But plastic products have preferable chemistry
Stability, is difficult degraded in nature, with the growth of application and quantity, plastic products cause the serious dirt of environment
Dye, such as " white pollution " pollutes water source and soil, white elephant is brought to earth environment.With expanding economy,
Environmental problem is increasingly paid close attention to by society, especially payes attention to the research and development of degradable high polymer material, is given up with reducing solid
Gurry, improves sustainable development.The application of PLA is relatively broad in degradation material, and combination property is more excellent.PLA（PLA）
It is thermoplastic aliphatic's polyester resin, PLA is prepared by raw material of lactic acid, comes from reproducible starch and carbohydrate fermentation.
PLA has preferable physics, chemistry and processing characteristics, and with degradable characteristic, CO is degraded in the Nature2And H2O,
It is a kind of green material.In recent years, PLA is widely used as packaging material, agricultural film and sheet material etc..The vitrifying temperature of PLA
Spend for 50-60 DEG C, high-crystallinity, the notch impact strength of purer PLA is 2.56kJ/m2, elongation at break is 10.7%,
Under tensile strength is 61.2MPa, normal temperature, PLA is hard and crisp, poor toughness, significantly limit its application.Existing polydactyl acid
Technology on the one hand change the degradability of poly-lactic acid material, on the other hand modified means are single, do not consider
Synergy between each modifying agent, these problems limit application of the PLA in fields such as packaging, film and sheet materials.The present invention
There is provided a kind of lactic acid composite material of high tenacity and preparation method thereof, using the method polydactyl acid of blending, operation side
Method is simple, and blending and modifying agent uses the monomer or oligomer of double-functional group, at high temperature melt blending, while it is molten to add increase-volume
Progress continuation reaction under agent, the condition of high temperature, and not exclusively physical blending.The monomer or oligomer of wherein blending double-functional group draw
Enter flexible heterochain, so as to reduce the crystallinity of PLA, the glass transition temperature of PLA, the PLA for preparing high tenacity is combined
Material.
The content of the invention
It is an object of the invention to provide a kind of lactic acid composite material of high tenacity and preparation method thereof, polydactyl acid
The problem of hard and crisp, poor toughness.Toughener, increase-volume solvent and PLA are specifically included, with the monomer containing difunctional or oligomeric
Compound is prepared as toughener with PLA by melt blending.Blend is reacted under the melting condition of high temperature, and not only
It is physical blending.Flexible heterochain is introduced by the monomer or oligomer of melt blending double-functional group, so as to reduce the knot of PLA
The glass transition temperature of brilliant degree, PLA, prepares the lactic acid composite material of high tenacity.
Technical scheme is mainly included the following steps that：
Step（1）, the PLA of certain mass and increase-volume solvent are blended in torque rheometer, blending temperature is 100-200
DEG C, rotating speed is 60-80r/min, and the time is that 5-15min obtains blend A；
Step（2）, the monomer containing difunctional or low polymer are added into step（1）Middle A blends continue that 10-30min is blended,
Obtain blend B；
Step（3）, by step（2）In blend tabletting in vulcanizing press, operation temperature is 160-230 DEG C, and pressure is
4-15MPa, is compressed to thin slice.
The mass parts of described reactant are：PLA：100 parts；Monomer or low polymer containing difunctional：10-60
Part；Increase-volume solvent：2-15 parts.
The described monomer containing difunctional can include hydroxy-ethyl acrylate, trimethylolpropane for lauryl acrylate
One or more in trimethyl acrylic ester or 1,6 hexanediol diacrylate.Functional group can be that carboxyl can be ester group
Can be that hydroxyl can be one or more in amide groups.
The described low polymer containing difunctional includes any or several in hydroxyl or carboxyl or ester group or amide groups
The oligomer of the monomer for the difunctional planted, including polyethylene-propylene acetoacetic ester-GMA, ethene-the third
One or more in olefin(e) acid butyl ester-GMA or esters of acrylic acid.
The notch impact strength of purer PLA is 2.56kJ/m2, elongation at break is 10.7%, and tensile strength is
61.2MPa, pure PLA mechanical property parameters show that pure PLA is crisp and hard, poor toughness.This is primarily due to PLA glass
It is 50-60 DEG C, high-crystallinity to change temperature.Introduce flexible miscellaneous by the way that the monomer or oligomer of double-functional group are blended in PLA
Chain, so as to reduce the crystallinity of PLA, the glass transition temperature of PLA, prepares the lactic acid composite material of high tenacity, changes
The defect of kind PLA, expands application of the PLA in fields such as packaging, film and sheet materials.
Described increase-volume solvent can be that methyl methacrylate can be maleic anhydride or acrylic acid can be acrylic acid
Butyl ester.On the other hand on the one hand increase-volume solvent will can participate in polymerisation with increase-volume PLA, and contained functional group is beneficial to change
The problem of hard and crisp poor toughness of kind PLA.
The advantage of the invention is that：
（1）Obtained lactic acid composite material is still degradable, does not destroy the degradable characteristic of PLA matrix, belongs to green
Material；
（2）Toughener and PLA are reacted under high-temperature blending, toughening effect is substantially, simple to operate, under the conditions of high-temperature blending,
PLA is effective to improve molecule chain flexibility by reacting introducing hetero-atoms strand with the agent of double-functional group blending and modifying, together
When reduce PLA crystallinity, finally prepare the poly-lactic acid material of high-ductility；
（3）On the one hand addition feature increase-volume solvent can improve compatibilization effect, and another aspect increase-volume solvent participates in reaction and improved
The toughness of PLA.
Brief description of the drawings
Nothing.
Embodiment
Embodiment 1
Take 100g PLA（3051D）It is blended with 10g increase-volume solvent butyl acrylates in torque rheometer, blending temperature is
160 DEG C, rotating speed is 60r/min, and the time is that 5min obtains blend；20g dodecyl acrylates are added to continue that 20min is blended.Will
Blend tabletting in vulcanizing press, operation temperature is 180 DEG C, and pressure is 6MPa, is compressed to thin slice, prepares PLA and answers
Condensation material 1.
The mechanical property of composite is tested impact by GB1843 and drawn on omnipotent shock machine and electronic tensile machine
Stretch performance.
The notch impact strength of lactic acid composite material 1 is 10.1kJ/m2, and elongation at break is 145.3%, tensile strength
For 50.1MPa；The notch impact strength of purer PLA is 2.56kJ/m2, and elongation at break is 10.7%, and tensile strength is
61.2MPa；Mechanical property contrast with pure PLA is clear that the stretching of modified lactic acid composite material 1 is strong
Degree reduction, elongation at break and notch impact strength substantially increase, and have prepared the lactic acid composite material of high tenacity.High temperature is total to
Under the conditions of mixed, PLA with double-functional group blending and modifying agent dodecyl acrylate, the reaction of increase-volume solvent butyl acrylate by existing
Introducing hetero-atoms strand in the strand of PLA, effectively raises the flexibility of polylactic acid molecule chain, while the poly- breast of reduction
The crystallinity of acid, finally prepares the lactic acid composite material of high-ductility.
Embodiment 2
Take 100g PLA（3051D）It is blended with 10g increase-volume solvent butyl acrylates in torque rheometer, blending temperature is
160 DEG C, rotating speed is 60r/min, and the time is that 5min obtains blend；Add 15g three block elastomeric polymer polyethylene acrylic acids
Ethyl ester-GMA（AX8900）Continue that 20min is blended.The tabletting in vulcanizing press by blend, behaviour
Make temperature for 180 DEG C, pressure is 6MPa, is compressed to thin slice, prepares lactic acid composite material 2.
The notch impact strength of lactic acid composite material 2 is 12.2kJ/m2, elongation at break is 170.2%, tensile strength
For 45.1MPa；The notch impact strength of purer PLA is 2.56kJ/m2, elongation at break is 10.7%, and tensile strength is
61.2MPa；Mechanical property contrast with pure PLA is clear that the stretching of modified lactic acid composite material 1 is strong
Degree reduction, elongation at break and notch impact strength substantially increase, and have prepared the lactic acid composite material of high tenacity.High temperature is total to
Under the conditions of mixed, PLA by with double-functional group blending and modifying agent three block elastomeric polymer polyethylene-propylene acetoacetic ester-methyl
Glycidyl acrylate（AX8900）, increase-volume solvent butyl acrylate reaction introducing hetero-atoms point in the strand of PLA
Subchain, effectively raises the flexibility of polylactic acid molecule chain, while reducing the crystallinity of PLA, finally prepares the poly- of high-ductility
Lactic acid composite.
It is described above, only it is presently preferred embodiments of the present invention, but the invention is not restricted to above-described embodiment, can also be according to this
The purpose of the innovation and creation of invention makes a variety of changes, and that is done under all Spirit Essences and principle according to technical solution of the present invention changes
Become, modify, substitute, combine or simplify, should be equivalent substitute mode, belong to protection scope of the present invention.
Claims (6)
1. a kind of high-ductility lactic acid composite material, including toughener and PLA, it is characterised in that with the monomer containing difunctional
Or low polymer is used as toughener and PLA melt blending.
2. the preparation method of a kind of high-ductility lactic acid composite material according to claim 1, it is characterised in that including following
Preparation process：
Step（1）, the PLA of certain mass and increase-volume solvent are blended in torque rheometer, blending temperature is 100-200
DEG C, rotating speed is 60-80r/min, and the time is that 5-15min obtains blend A；
Step（2）, the monomer containing difunctional or low polymer are added into step（1）Middle A blends continue that 10-30min is blended,
Obtain blend B；
Step（3）, by step（2）In blend tabletting in vulcanizing press, operation temperature is 160-230 DEG C, and pressure is
4-15MPa, is compressed to thin slice.
3. the preparation method of a kind of high-ductility lactic acid composite material according to claim 1, it is characterised in that reactant
Mass parts are：
PLA：100 parts；
Monomer or low polymer containing difunctional：10-60 parts；
Increase-volume solvent：2-15 parts.
4. the preparation method of a kind of high-ductility lactic acid composite material according to claim 1, it is characterised in that described contains
The monomer of difunctional includes lauryl acrylate or hydroxy-ethyl acrylate or trimethylol-propane trimethacrylate or 1,
One kind or its combination in 6- hexanediyl esters.
5. the preparation method of a kind of high-ductility lactic acid composite material according to claim 1, it is characterised in that described contains
The low polymer of difunctional includes polyethylene-propylene acetoacetic ester-GMA or ethylene-acrylic acid fourth
One kind or its combination in ester-GMA or esters of acrylic acid.
6. a kind of preparation method of high-ductility lactic acid composite material according to claim 2, it is characterised in that step（1）
Described in increase-volume solvent include methyl methacrylate or maleic anhydride or one kind in acrylic acid or butyl acrylate or its
With reference to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710297903.4A CN107163194A (en) | 2017-04-29 | 2017-04-29 | A kind of high-ductility lactic acid composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710297903.4A CN107163194A (en) | 2017-04-29 | 2017-04-29 | A kind of high-ductility lactic acid composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535673A (en) * | 2018-10-22 | 2019-03-29 | 诺思贝瑞新材料科技（苏州）有限公司 | A kind of heat-proof impact-resistant high transparency lactic acid composite material and preparation method thereof |
| CN111393860A (en) * | 2020-04-30 | 2020-07-10 | 安徽宏飞钓具有限公司 | Quickly degradable bionic bait for sea fishing and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906193A (en) * | 2010-05-17 | 2013-01-30 | 梅塔玻利克斯公司 | Toughening polylactic acid with polyhydroxyalkanoates |
| CN105440608A (en) * | 2015-04-16 | 2016-03-30 | 湖南工业大学 | High-toughness high-strength polylactic acid composite material and preparation process therefor |
| CN105566617A (en) * | 2016-02-01 | 2016-05-11 | 中山大学 | Unsaturated polyester toughening agent and preparation method and polyactic acid composition thereof |
| CN105694401A (en) * | 2016-03-15 | 2016-06-22 | 江苏永盛三维打印新材料有限公司 | Toughened polylactic acid capable of being used for rapid forming and preparation method thereof |
-
2017
- 2017-04-29 CN CN201710297903.4A patent/CN107163194A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906193A (en) * | 2010-05-17 | 2013-01-30 | 梅塔玻利克斯公司 | Toughening polylactic acid with polyhydroxyalkanoates |
| CN105440608A (en) * | 2015-04-16 | 2016-03-30 | 湖南工业大学 | High-toughness high-strength polylactic acid composite material and preparation process therefor |
| CN105566617A (en) * | 2016-02-01 | 2016-05-11 | 中山大学 | Unsaturated polyester toughening agent and preparation method and polyactic acid composition thereof |
| CN105694401A (en) * | 2016-03-15 | 2016-06-22 | 江苏永盛三维打印新材料有限公司 | Toughened polylactic acid capable of being used for rapid forming and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535673A (en) * | 2018-10-22 | 2019-03-29 | 诺思贝瑞新材料科技（苏州）有限公司 | A kind of heat-proof impact-resistant high transparency lactic acid composite material and preparation method thereof |
| CN111393860A (en) * | 2020-04-30 | 2020-07-10 | 安徽宏飞钓具有限公司 | Quickly degradable bionic bait for sea fishing and production process thereof |
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Application publication date: 20170915 |