CN108359087A - Low melting point branched polylactic acid and preparation method thereof - Google Patents
Low melting point branched polylactic acid and preparation method thereof Download PDFInfo
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- CN108359087A CN108359087A CN201810144439.XA CN201810144439A CN108359087A CN 108359087 A CN108359087 A CN 108359087A CN 201810144439 A CN201810144439 A CN 201810144439A CN 108359087 A CN108359087 A CN 108359087A
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- polylactic acid
- melting point
- low melting
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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Abstract
The invention discloses a kind of low melting point branched polylactic acids and preparation method thereof.Its reaction system is made of polylactic acid, lewis acid and three-functionality-degree acrylic ester monomer, the above material is carried out in screw extruder or mixer to melt blending reaction after mixing, the synergy of lewis acid and three-functionality-degree acrylic ester monomer can make polylactic acid reduce crystallinity, generate branched and degrade, and prepare the branched polylactic acid of lower molecular weight, low-crystallinity.Due to being greatly reduced of crystallinity, molecular weight and molecular weight and destroying the branched structure of strand regularity can make polydactyl acid have preferable mobility at 130 DEG C, can be used for the melting cladding of chemical fertilizer, achieve the purpose that sustained release.
Description
Technical field
The present invention relates to field of high-polymer material science, specially a kind of low melting point branched polylactic acid and its preparation side
Method.
Background technology
Polylactic acid is polymerized by amylaceous fermented lactic acid, and source is renewable, and it is that one kind can be complete that polylactic acid, which belongs to,
The final product of the high molecular material of degradation, degradation is carbon dioxide and water, and any pollution is had no to environment.Therefore use polylactic acid
Covering material as slow-release fertilizer is best one of selection, but polylactic acid fusing point is higher, can have at 180 DEG C or more good
Good mobility, and the chemical fertilizer such as urea, ammonium phosphate will be decomposed at 140 DEG C or more, therefore melt cladding and be difficult to realize.State at present
It is inside and outside that polylactic acid is mainly dissolved in solvent by polylactic acid for slow-release fertilizer, then the mode of spraying is taken to be coated on polylactic acid
Chemical fertilizer granule surface, the disadvantages of this method are that the solvent processing after spraying is complex, and environment friendly is poor.
To realize melting cladding, needs the fusing point of polylactic acid being greatly reduced, make it that will have at 130 DEG C or less well
Mobility, and have good film forming.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of low melting point branched polylactic acid and preparation method thereof, it makes
Polylactic acid has good mobility at 130 DEG C or less, can be used for the melting cladding on chemical fertilizer granule surface, to overcome existing skill
The deficiency of art.
In order to achieve the above object, the present invention is achieved by the following technical programs：Low melting point branched polylactic acid, by quality
Number calculates, including 0.5~5 part of 100 parts of polylactic acid, 0.5~6 part of lewis acid and three-functionality-degree acrylic ester monomer are system
Standby raw material.
The lewis acid is magnesium chloride, iron chloride, calcium chloride, aluminium chloride, lithium chloride or zinc chloride.
The three-functionality-degree acrylic ester monomer is trimethylolpropane trimethacrylate, ethoxyquin trihydroxy methyl third
Alkane triacrylate, glycerol propoxylate triacrylate or pentaerythritol triacrylate.
A kind of low melting point branched polylactic acid and preparation method thereof, takes each component by above-mentioned parts by weight, all components is filled
Divide and be uniformly mixed, melt blending reacts in screw extruder or mixer；190~250 DEG C of extruder temperature, time rotating speed 50
~300r/min；180~250 DEG C of mixer temperature, 5~30min of time, 30~100r/min of rotating speed.
The principle of the present invention is：Coordination occurs for the ketonic oxygen of lewis acidic metal ion and strand in polylactic acid
(lone pair electrons of oxygen enter the unoccupied orbital of metal ion), electronics arrives the combination that effect reduces the adjacent C-O keys of carbonyl again,
First cause the chain rupture of C-O keys under the action of residual water that macromolecules degradation, molecular weight and molecular weight is made to form smaller point of terminal hydroxy group
Son amount polylactic acid；Subsequent hydroxyl-terminated polylactic acid strand with the ester group generation transesterification of three-functionality-degree acrylic ester monomer is anti-
It answers, the electron attraction of Lewis Acid metal ion improves the efficiency of ester exchange reaction, by three-functionality-degree acrylic monomer
Be introduced into polylactic acid macromolecular, due to three-functionality-degree acrylic monomer there are three can reactive group, formed with three officials
The lower branched polylactic acid of molecular weight is consequently formed in star structure centered on energy degree acrylic ester monomer.Macromolecular is regular
The reduction of degree makes being greatly reduced of crystallinity, molecular weight and molecular weight and destroys the branched structure of strand regularity that modified poly- breast can be made
Acid has good mobility at 130 DEG C.
Advantageous effect
Compared with prior art, the present invention is by the polylactic acid fast degradation of linear higher molecular weight, and generates branched structure,
Polylactic acid crystal degree is reduced, polylactic acid is made to have good mobility at 130 DEG C or less, can be used for the molten of chemical fertilizer granule surface
Melt cladding, achievees the purpose that sustained release.The present invention is simple and practicable, and of low cost, using effect is good.
Specific implementation mode
The embodiment of the present invention 1：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (2003D,
NATUREWORKS companies of the U.S.), aluminium chloride (AlCl3), the addition of trimethylolpropane trimethacrylate (TMPTA) difference
It it is 100 parts, 6 parts, 3 parts, it is respectively 250 that the above material is added to 1L mixers with temperature, time, rotating speed after mixing
DEG C, carry out degradation branching reaction under 5min, 100r/min low melting point branched polylactic acid be made.
The embodiment of the present invention 2：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (2003D,
NATUREWORKS companies of the U.S.), lithium chloride (LiCl), glycerol propoxylate triacrylate (GPTA) by addition be respectively 100
Part, 0.5 part, 0.5 part to be added to 1L mixers after mixing with temperature, time, rotating speed be respectively 190 DEG C, 30min, 50r/
Degradation branching reaction is carried out under min, and low melting point branched polylactic acid is made.
The embodiment of the present invention 3：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (2003D,
NATUREWORKS companies of the U.S.), calcium chloride (CaCl2), ethoxyquin trimethylolpropane trimethacrylate (TMP3EOTA) by plus
Enter amount and be respectively 100 parts, 3 parts, 5 parts to be added to 1L mixers after mixing, with temperature, time, rotating speed be respectively 200 DEG C,
Degradation branching reaction is carried out under 20min, 80r/min, and low melting point branched polylactic acid is made.
The embodiment of the present invention 4：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (6204D,
NATUREWORKS companies of the U.S.), iron chloride (FeCl3), trimethylolpropane trimethacrylate (TMPTA) by addition distinguish
Be added to 1L mixers after mixing for 100 parts, 2 parts, 3 parts, with temperature, time, rotating speed be respectively 200 DEG C, 20min,
Degradation branching reaction is carried out under 100r/min, and low melting point branched polylactic acid is made.
The embodiment of the present invention 5：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (2003D,
NATUREWORKS companies of the U.S.), zinc chloride (ZnCl2), pentaerythritol triacrylate (PETA) by addition be respectively 100
Part, 5 parts, 3 parts be added to 1L mixers after mixing, be respectively 230 DEG C, 10min, 100r/min with temperature, time, rotating speed
Under carry out degradation branching reaction low melting point branched polylactic acid be made.
The embodiment of the present invention 6：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (2003D,
NATUREWORKS companies of the U.S.), aluminium chloride (AlCl3), trimethylolpropane trimethacrylate (TMPTA) by addition distinguish
It is added to 45 double screw extruders of Φ after mixing for 100 parts, 5 parts, 3 parts, is respectively 250 DEG C, 300r/ in temperature, rotating speed
Degradation branching reaction is carried out under min, and low melting point branched polylactic acid is made.
The embodiment of the present invention 7：The preparation of low melting point branched polylactic acid, is calculated according to the mass fraction, by polylactic acid (6204D,
NATUREWORKS companies of the U.S.), iron chloride (FeCl3), trimethylol-propane trimethacrylate (TMPTA) press addition
Respectively 100 parts, 2 parts, 3 parts are added to 60 single screw extrusion machines of Φ after mixing, be respectively 190 DEG C with temperature, rotating speed,
Degradation branching reaction is carried out under 50r/min, and low melting point branched polylactic acid is made.
Test result
Test result such as following table：
| Serial number | Melt index (g/10min) |
| Embodiment 1 | 8.5 |
| Embodiment 2 | 10.8 |
| Embodiment 3 | 15.2 |
| Embodiment 4 | 4.3 |
| Embodiment 5 | 10.6 |
| Embodiment 6 | 9.2 |
| Embodiment 7 | 5.0 |
Note:Melt index determination condition is 130 DEG C, 2.16kg
Show that embodiment 1-7 has a preferable mobility at 130 DEG C, and pure polylactic acid (2003D, the U.S.
NATUREWORKS companies) melt index is 10.8g/10min at 190 DEG C.Illustrate polylactic acid and lewis acid, trifunctional
It spends acrylic monomer compounding and carries out melt blending, can make polydactyl acid that there is preferable mobility at 130 DEG C.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (4)
1. a kind of low melting point branched polylactic acid, it is characterised in that：It calculates according to the mass fraction, including 100 parts of polylactic acid, lewis acid
0.5~6 part and 0.5~5 part of three-functionality-degree acrylic ester monomer is prepare raw material.
2. low melting point branched polylactic acid according to claim 1, it is characterised in that：The lewis acid be magnesium chloride,
Iron chloride, calcium chloride, aluminium chloride, lithium chloride or zinc chloride.
3. low melting point branched polylactic acid according to claim 1, it is characterised in that：The three-functionality-degree esters of acrylic acid
Monomer is trimethylolpropane trimethacrylate, ethoxyquin trimethylolpropane trimethacrylate, three acrylic acid of glycerol propoxylate
Ester or pentaerythritol triacrylate.
4. a kind of preparation method of low melting point branched polylactic acid as described in claim 1, it is characterised in that：By above-mentioned parts by weight
Number takes each component, and all components are sufficiently mixed uniformly, and melt blending reacts in screw extruder or mixer；Extruder temperature
Spend 190~250 DEG C, time 50~300r/min of rotating speed；180~250 DEG C of mixer temperature, 5~30min of time, rotating speed 30~
100r/min。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608690A (en) * | 2018-12-12 | 2019-04-12 | 贵州大学 | The method of fast degradation polylactic acid |
| CN111303600A (en) * | 2020-04-24 | 2020-06-19 | 中国科学技术大学 | Polylactic acid/Zn+Heat-resistant composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608690A (en) * | 2018-12-12 | 2019-04-12 | 贵州大学 | The method of fast degradation polylactic acid |
| CN111303600A (en) * | 2020-04-24 | 2020-06-19 | 中国科学技术大学 | Polylactic acid/Zn+Heat-resistant composite material and preparation method thereof |
| CN111303600B (en) * | 2020-04-24 | 2021-07-06 | 中国科学技术大学 | Polylactic acid/Zn2+Heat-resistant composite material and preparation method thereof |
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| CN108359087B (en) | 2021-04-13 |
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