CN102558795B - Polylactic acid-starch blended material and preparation method thereof - Google Patents
Polylactic acid-starch blended material and preparation method thereof Download PDFInfo
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- CN102558795B CN102558795B CN201010594708.6A CN201010594708A CN102558795B CN 102558795 B CN102558795 B CN 102558795B CN 201010594708 A CN201010594708 A CN 201010594708A CN 102558795 B CN102558795 B CN 102558795B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract
The invention belongs to the field of modification of high polymer blended plastics, and discloses a polylactic acid-starch blended material and a preparation method thereof. The polylactic acid-starch blended material disclosed by the invention comprises the following components in parts by weight: 448-8207 parts of polylactic acid, 1000 parts of starch, 10-114 parts of grafting agent, 36-286 parts of plasticizer, 2-29 parts of coupling agent and 3-97 parts of antioxidant. The preparation method comprises the following steps: (1) adding 1000 parts of pretreated starch, 10-114 parts of grafting agent, 36-286 parts of plasticizer and 2-29 parts of coupling agent into a high-speed mixer, and mixing at normal temperature for 10-50 minutes; and (2) granulating 1053-1429 parts of the mixture obtained in the step (1) by a double screw extruder, mixing with 448-8207 parts of polylactic acid and 3-97 parts of antioxidant and granulating, or directly mixing the mixture obtained in the step (1) with 448-8207 parts of polylactic acid and 3-97 parts of antioxidant and granulating by the double screw extruder. The product disclosed by the invention has the advantages of favorable mechanical properties and low cost.
Description
Technical field
The invention belongs to polymer blended modifying plastics field, relate to a kind of polylactic acid-starch blended material and preparation method thereof.
Background technology
Poly(lactic acid) (PLA, claim again polylactide) be a kind of polymer crystallization compound that comes from biological and degradable thermoplastic polyester class, compare as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) with petroleum base polyester, there is completely renewable, degradable advantage.Starch source is extensive, is plastified as filler and adds in resin, can accelerate plastics in natural physical decomposition process.The polylactic acid-starch blended material extensive concern that caused in the field of business, but its machine-shaping and goods there are the following problems: starch and poly(lactic acid) consistency are poor, and product surface is coarse; Mechanical property is on the low side; Starch easily absorbs water, and intermingling material goods poor water resistance, has accelerated degradation with aging process.
Conventionally there are two kinds of methods to address the above problem: one, to add the plasticizing that the 3rd component promotes starch, as glycerine, Sorbitol Powder, methane amide, butyleneglycol, polyoxyethylene glycol etc., contain the compound of the functional groups such as hydroxyl, amide group or ester group; Two, the compound that the MALEIC ANHYDRIDE that interpolation can react with starch, poly(lactic acid), epoxy silane, isocyanate-based silane etc. contain the functional groups such as acid anhydrides, epoxy, isocyanato is done graft polymerization preformer to starch and is processed, or jointly adds the 3rd component when extruding pelletization.Patent 200610042002.2 is by adding the softening agent such as polyvalent alcohol, dibutyl phthalate and along the grafting agents such as Succinic anhydried, methacrylic acid and initiator, starch being processed and made starch master batch, and method is novel.
In fact, except above-mentioned two kinds of processing modes, also has a kind of plastics processing mode to starch.Bibliographical information (reference: the ultra-high voltage gelatinization research of wheat starch, < < Food science > > 10 phases in 1997; The impact of high pressure on corn starch pasting characteristic, < < starch industry > > 7 phases in 2007), starch structure (> 400MPa) under ultra-high voltage can change, the gelatinization of starch improves, and crystallization degree declines.This is not only conducive to the follow-up reactions such as chemical graft, also helps the consistency improving with matrix resin.
Summary of the invention
Strong for polylactic acid-starch blended material water-absorbent, the shortcoming such as interface compatibility is poor, mechanical strength, the object of this invention is to provide that a kind of to have consistency good, the polylactic acid-starch blended material that mechanical property is high.
Another object of the present invention is to provide a kind of preparation method of above-mentioned polylactic acid-starch blended material.
Technical scheme of the present invention is as follows:
The invention provides a kind of polylactic acid-starch blended material, this polylactic acid-starch blended material comprises following component and weight part: 448～8207 parts of poly(lactic acid), 1000 parts of starch, 10～114 parts of grafting agents, 36～286 parts, softening agent, 2～29 parts of coupling agents, 3～97 parts, oxidation inhibitor.
Described poly(lactic acid) is selected from extrusion grade poly (l-lactic acid) (PLLA) or poly-D-ALPHA-Hydroxypropionic acid (PDLA).
Described starch is selected from one or more the mixture in conventional corn starch, yam starch or wheat starch.
Described grafting agent is selected from the compound that contains epoxy group(ing), isocyanato or amide group isoreactivity group, is preferably selected from one or more the mixture in MALEIC ANHYDRIDE, diphenylmethane diisocyanate or methane amide.
Described softening agent is usual auxiliaries, is preferably selected from one or more the mixture in dibutyl phthalate, glycerine, polyoxyethylene glycol, polypropylene glycol or tributyl citrate.
Described coupling agent is usual auxiliaries; be selected from one or more the mixture in silane coupling agent or titanate coupling agent, the mixture of one or more in preferred vinyl Trimethoxy silane, isopropyl triisostearoyl titanate, isopropyl tri (dioctylpyrophosphato)titanate or vinyl three (beta-methoxy-oxyethyl group) silane.
Described oxidation inhibitor is Hinered phenols antioxidant, preferably a kind of in antioxidant 1076 or antioxidant 1010.
The present invention also provides a kind of preparation method of above-mentioned polylactic acid-starch blended material, and the method comprises the following steps:
(1) add high speed mixing smelting machine stirring normal temperature to mix with the grafting agent of 10～114 parts, the softening agent of 36～286 parts and the coupling agent of 2～29 parts 1000 parts of pretreated starch, mixing time 10-50 minute;
(2) 1053～1429 parts, the mixture that step (1) obtained is through twin screw extruder granulation, mix granulation again with the poly(lactic acid) of 448～8207 parts and the oxidation inhibitor of 3～97 parts, or the mixture that step (1) is obtained directly mixes through twin screw extruder granulation with the poly(lactic acid) of 448～8207 parts and the oxidation inhibitor of 3～97 parts.
Described pretreated starch treatment step is: starch is distributed in distilled water, make the starch suspension of concentration 5-10%, pour into and in ultrahigh pressure vessel, carry out 500-1000MPa uhp treatment 10-20h, then normal temperature dewatering is dried to water content < 0.5%, obtains pretreated starch.
Described twin screw extruder length-to-diameter ratio is 25: 1-40: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
The present invention compared with the existing technology, has the following advantages and beneficial effect:
(1) the inventive method, owing to adopting ultra-high voltage to do pre-treatment to starch, declines the crystallization degree of starch, and gelatinization degree is higher, and hydrophobicity strengthens, dispersed better, and it is better to be combined with poly(lactic acid) in starch interface.
(2) the inventive method is owing to adopting the uhp treatment technology can more effective destruction starch particle surface, there is efficient graft reaction with grafting agent, thereby improve the consistency with poly(lactic acid), effectively improved the mechanical strength of intermingling material, reduce the use of reinforcing aids, reduced production cost.
(3) raw materials of the present invention is all renewable, degradable environment-friendly material, and products obtained therefrom mechanical property is good, with low cost, compares and has great advantage with traditional poly(lactic acid) starch plastic.
Embodiment
Below in conjunction with illustrated embodiment, the present invention is further illustrated.
Mechanical test and thermodynamics test bars and testing method are pressed ASTM standard formulation.
Embodiment 1
(1), by pretreated starch 1000g and MALEIC ANHYDRIDE 11g, dibutyl phthalate 98g, silane coupling agent vinyl Trimethoxy silane 2.2g, add high speed mixing smelting machine to stir normal temperature and mix, mixing time 10 minutes;
(2) the mixture 1111g that step (1) obtained directly and extrusion grade poly(lactic acid) PLLA2075g, antioxidant 1076 97g mixes through twin screw extruder granulation, twin screw extruder length-to-diameter ratio is 40: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
Described pretreated starch treatment step is: W-Gum 1000g is distributed in 19L distilled water, make the starch suspension of concentration 5%, pour into and in ultrahigh pressure vessel, carry out 500MPa uhp treatment 10h, then the dry water content < 0.5% of normal temperature dewatering, obtains pretreated starch.
The pellet that above-described embodiment is obtained is thoroughly dried 3-5 hour in 90-110 ℃ of convection oven, then by drying particulate sample preparation on 80T injection moulding machine, mould temperature maintains room temperature (20-40 ℃), and the dwell time is set as 5 seconds.Mechanics Performance Testing is in Table 1.
Embodiment 2
(1) pretreated starch 1000g and diphenylmethane diisocyanate 62.5g, dibutyl phthalate 162.5g, titanate coupling agent isopropyl triisostearoyl titanate 25g are added high speed mixing smelting machine stir normal temperature and mix, mixing time 30 minutes;
(2) mixture 1250g step (1) being obtained, through twin screw extruder granulation, mixes granulation again with extrusion grade poly(lactic acid) PDLA 7179g, antioxidant 1010 16.9g.Twin screw extruder length-to-diameter ratio is 40: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
Described pretreated starch treatment step is: yam starch 1000g is distributed in distilled water 9L, make the starch suspension of concentration 10%, pour into and in ultrahigh pressure vessel, carry out 700MPa uhp treatment 15h, then the dry water content < 0.5% of normal temperature dewatering, obtains pretreated starch.
The pellet that above-described embodiment is obtained is thoroughly dried 3-5 hour in 90-110 ℃ of convection oven, then by drying particulate sample preparation on 80T injection moulding machine, mould temperature maintains room temperature (20-40 ℃), and the dwell time is set as 5 seconds.Mechanics Performance Testing is in Table 1.
Embodiment 3
(1), by pretreated starch 1000g and methane amide 114g, polyoxyethylene glycol 286g, titanate coupling agent isopropyl tri (dioctylpyrophosphato)titanate 28.6g, add high speed mixing smelting machine to stir normal temperature and mix, mixing time 40 minutes;
(2) mixture 1428g step (1) being obtained, through twin screw extruder granulation, mixes granulation again with extrusion grade poly(lactic acid) PLLA 608g, antioxidant 1076 4g by proportioning.Twin screw extruder length-to-diameter ratio is 30: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
Described pretreated starch treatment step is: wheat starch 1000g is distributed in distilled water 11.5L, make the starch suspension of concentration 8%, pour into and in ultrahigh pressure vessel, carry out 800MPa uhp treatment 20h, then the dry water content < 0.5% of normal temperature dewatering, obtains pretreated starch.
The pellet that above-described embodiment is obtained is thoroughly dried 3-5 hour in 90-110 ℃ of convection oven, then by drying particulate sample preparation on 80T injection moulding machine, mould temperature maintains room temperature (20-40 ℃), and the dwell time is set as 5 seconds.Mechanics Performance Testing is in Table 1.
Embodiment 4
(1), by pretreated starch 1000g and diphenylmethane diisocyanate 10.5g, glycerine 36.8g, silane coupling agent vinyl three (beta-methoxy-oxyethyl group) silane 5.3g, add high speed mixing smelting machine to stir normal temperature and mix, mixing time 50 minutes;
(2) directly and extrusion grade poly(lactic acid) PDLA 1552g, antioxidant 1010 26.3g mixes through twin screw extruder granulation for the mixture 1052g that step (1) obtained.Twin screw extruder length-to-diameter ratio is 25: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
Described pretreated starch treatment step is: W-Gum 1000g is distributed in distilled water 11.5L, make the starch suspension of concentration 8%, pour into and in ultrahigh pressure vessel, carry out 900MPa uhp treatment 15h, then the dry water content < 0.5% of normal temperature dewatering, obtains pretreated starch.
The pellet that above-described embodiment is obtained is thoroughly dried 3-5 hour in 90-110 ℃ of convection oven, then by drying particulate sample preparation on 80T injection moulding machine, mould temperature maintains room temperature (20-40 ℃), and the dwell time is set as 5 seconds.Mechanics Performance Testing is in Table 1.
Embodiment 5
(1), by pretreated starch 1000g and MALEIC ANHYDRIDE 22g, dibutyl phthalate 78g, titanate coupling agent isopropyl triisostearoyl titanate 11g, add high speed mixing smelting machine to stir normal temperature and mix, mixing time 50 minutes;
(2) mixture 1111g step (1) being obtained directly mixes through twin screw extruder granulation with extrusion grade poly(lactic acid) PLLA2555g, antioxidant 1010 37g.Twin screw extruder length-to-diameter ratio is 40: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
Described pretreated starch treatment step is: yam starch 1000g is distributed in distilled water 9L, make the starch suspension of concentration 10%, pour into and in ultrahigh pressure vessel, carry out 1000MPa uhp treatment 20h, then the dry water content < 0.5% of normal temperature dewatering, obtains pretreated starch.
The pellet that above-described embodiment is obtained is thoroughly dried 3-5 hour in 90-110 ℃ of convection oven, then by drying particulate sample preparation on 80T injection moulding machine, mould temperature maintains room temperature (20-40 ℃), and the dwell time is set as 5 seconds.Mechanics Performance Testing is in Table 1.
Comparative example
(1) by common dried corn starch 1000g and MALEIC ANHYDRIDE 22g, dibutyl phthalate 78g, silane coupling agent vinyl Trimethoxy silane 11g, add high speed mixing smelting machine to stir normal temperature and mix, mixing time 50 minutes;
(2) directly and extrusion grade poly(lactic acid) PLLA2555g, antioxidant 1076 37g mixes through twin screw extruder granulation for the mixture 1111g that step (1) obtained.Twin screw extruder length-to-diameter ratio is 40: 1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
The pellet that above-described embodiment is obtained is thoroughly dried 3-5 hour in 90-110 ℃ of convection oven, then by drying particulate sample preparation on 80T injection moulding machine, mould temperature maintains room temperature left and right (20-40 ℃), and the dwell time is set as 5 seconds.
Table 1
By table 1, found out, after the starch of ultra-high voltage special processing and polylactic acid blend are extruded, its mechanical property is higher, and embodiment 5 and the comparative example of contrast identical weight proportioning can find out, embodiment 5 has very large performance advantage.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and one application of principle described herein in other embodiment and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (8)
1. a polylactic acid-starch blended material, is characterized in that: this polylactic acid-starch blended material comprises following component and weight part, 448～8207 parts of poly(lactic acid), 1000 parts of starch, 10～114 parts of grafting agents, 36～286 parts, softening agent, 2～29 parts of coupling agents, 3～97 parts, oxidation inhibitor;
The preparation method of described polylactic acid-starch blended material comprises the following steps:
(1) add high speed mixing smelting machine stirring normal temperature to mix with the grafting agent of 10～114 parts, the softening agent of 36～286 parts and the coupling agent of 2～29 parts 1000 parts of pretreated starch, mixing time 10-50 minute;
(2) 1053～1429 parts, the mixture that step (1) obtained is through twin screw extruder granulation, mix granulation again with the poly(lactic acid) of 448～8207 parts and the oxidation inhibitor of 3～97 parts, or the mixture that step (1) is obtained directly mixes through twin screw extruder granulation with the poly(lactic acid) of 448～8207 parts and the oxidation inhibitor of 3～97 parts;
Described pretreated starch treatment step is, starch is distributed in distilled water, makes the starch suspension of concentration 5-10%, pour into and in ultrahigh pressure vessel, carry out 500-1000MPa uhp treatment 10-20h, then normal temperature dewatering is dried to water content <0.5%, obtains pretreated starch;
Described grafting agent is selected from the compound that contains epoxy group(ing), isocyanato or amide group active group.
2. polylactic acid-starch blended material according to claim 1, is characterized in that: described poly(lactic acid) is selected from poly (l-lactic acid) or poly-D-ALPHA-Hydroxypropionic acid.
3. polylactic acid-starch blended material according to claim 1, is characterized in that: described starch is selected from one or more the mixture in conventional corn starch, yam starch or wheat starch.
4. polylactic acid-starch blended material according to claim 1, is characterized in that: described softening agent is selected from one or more the mixture in dibutyl phthalate, glycerine, polyoxyethylene glycol, polypropylene glycol or tributyl citrate.
5. polylactic acid-starch blended material according to claim 1, is characterized in that: described coupling agent is selected from one or more the mixture in silane coupling agent or titanate coupling agent.
6. polylactic acid-starch blended material according to claim 1, is characterized in that: described oxidation inhibitor is Hinered phenols antioxidant.
7. the preparation method of the arbitrary described polylactic acid-starch blended material of claim 1 to 6, is characterized in that: the method comprises the following steps,
(1) add high speed mixing smelting machine stirring normal temperature to mix with the grafting agent of 10～114 parts, the softening agent of 36～286 parts and the coupling agent of 2～29 parts 1000 parts of pretreated starch, mixing time 10-50 minute;
(2) 1053～1429 parts, the mixture that step (1) obtained is through twin screw extruder granulation, mix granulation again with the poly(lactic acid) of 448～8207 parts and the oxidation inhibitor of 3～97 parts, or the mixture that step (1) is obtained directly mixes through twin screw extruder granulation with the poly(lactic acid) of 448～8207 parts and the oxidation inhibitor of 3～97 parts;
Described pretreated starch treatment step is, starch is distributed in distilled water, makes the starch suspension of concentration 5-10%, pour into and in ultrahigh pressure vessel, carry out 500-1000MPa uhp treatment 10-20h, then normal temperature dewatering is dried to water content <0.5%, obtains pretreated starch.
8. the preparation method of polylactic acid-starch blended material according to claim 7, is characterized in that: described twin screw extruder length-to-diameter ratio is 25:1-40:1, and it is 120,155,175,180,180,175 ℃ that each district's temperature is controlled.
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| CN106366587A (en) * | 2016-08-26 | 2017-02-01 | 江苏允友成生物环保材料有限公司 | Preparation method of biodegradable polylactic acid/starch composite |
| CN109096711A (en) * | 2018-07-04 | 2018-12-28 | 汕头卜高通美实业有限公司 | A kind of rice meal modified polylactic acid composite material and preparation method |
| CN109233773A (en) * | 2018-11-06 | 2019-01-18 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | The non-linear self-degradation diverting agent of more cluster fracturing reforms and preparation method in a kind of section |
| CN110845830B (en) * | 2019-11-13 | 2022-04-26 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
| CN113021676A (en) * | 2021-03-12 | 2021-06-25 | 南通瑞诚高分子材料有限公司 | Preparation process of environment-friendly plastic particles filled and modified by starch |
| CN113185817A (en) * | 2021-04-08 | 2021-07-30 | 孚莱孚(上海)新材料有限公司 | Polylactic acid plastic containing composite flame retardant and preparation method thereof |
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| CN1712435A (en) * | 2005-07-21 | 2005-12-28 | 同济大学 | Green degradable resin and production thereof |
| CN101343406A (en) * | 2008-08-18 | 2009-01-14 | 丹阳市华东工程塑料有限公司 | Heat-proof polylactic acid-starch alloy system full-biodegradation material and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1712435A (en) * | 2005-07-21 | 2005-12-28 | 同济大学 | Green degradable resin and production thereof |
| CN101343406A (en) * | 2008-08-18 | 2009-01-14 | 丹阳市华东工程塑料有限公司 | Heat-proof polylactic acid-starch alloy system full-biodegradation material and preparation thereof |
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