CN107778799A - Cross-linking modified lactic acid composite material and its products formed - Google Patents
Cross-linking modified lactic acid composite material and its products formed Download PDFInfo
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- CN107778799A CN107778799A CN201610768199.1A CN201610768199A CN107778799A CN 107778799 A CN107778799 A CN 107778799A CN 201610768199 A CN201610768199 A CN 201610768199A CN 107778799 A CN107778799 A CN 107778799A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The present invention discloses a kind of cross-linking modified lactic acid composite material and its products formed, and the composite represents to include in parts by weight：80 99 parts of polylactic resin；0.1 5 parts of crosslinking agent；0.1 10 parts of lubricant；0.1 10 parts of antioxidant；0.1 10 parts of flow ability modifying agent.The PLA products formed, it is made up of described cross-linking modified lactic acid composite material.The cross-linking modified PLA products formed uses electron beam or gamma-ray irradiation, and irradiation dose is 20 60kGy.To make product have better performance, product is transparent or semitransparent state, and thin-wall product is more easy to operate.The cross-linking modified lactic acid composite material of the present invention, is cross-linking by successive process radiation, improves the heat resistance of cross-linking modified PLA products formed.
Description
【Technical field】
The present invention relates to technical field of polymer materials, be specifically related to a kind of cross-linking modified lactic acid composite material and
Its products formed.
【Background technology】
PLA (PLA) is a kind of environment amenable green decomposable asymmetric choice net material, has good mechanical performance, physical
Energy, processing characteristics.Therefore, PLA has a extensive future, and has the potentiality of substitution conventional petroleum based polyalcohol.
Due to the characteristics of PLA heat endurance is poor, poor mechanical property, its use in heat-resisting field is limited.In order to improve
Above-mentioned performance, currently used polylactic acid modified means have synthesizing polylactic acid stereoscopic composite, annealing, are blended, are made again
Condensation material, crosslinking and a variety of modified method dual-purposes etc..PLA degraded after crosslinking is slowed by, but still can be degraded.
Conventional crosslinking gimmick has crosslinking with radiation and chemical induction crosslinking.However, after using conventional crosslinking gimmick crosslinking
PLA poor fluidity, processing difficulties.
In view of this, it is necessary to develop a kind of cross-linking modified lactic acid composite material and its products formed in fact, with solution
State problem.
【The content of the invention】
It is therefore an object of the present invention to a kind of cross-linking modified lactic acid composite material and its products formed are provided, the poly- breast
The products formed crosslinking with radiation that sour composite is obtained by rear processing procedure, improves heat resistance.
In order to achieve the above object, cross-linking modified lactic acid composite material of the invention, represent to include in parts by weight：
Optionally, the cross-linking modified lactic acid composite material, represent to include in parts by weight：
Optionally, the cross-linking modified lactic acid composite material, represent to include in parts by weight：
Optionally, the polylactic resin is L-type PLA, melt index (MI) be 3-30g/10min (210 DEG C of national standard/
2.16KG)。
Optionally, the crosslinking agent is selected from Triallyl isocyanurate (TAIC), front three for allyl iso cyanurate
(TMAIC), trimethylolpropane trimethacrylate (TMPTA), trimethylol-propane trimethacrylate (TMPTMA), three contractings
Water glyceryl isocyanuric acid ester (TGIC) at least one.
Optionally, the lubricant is selected from ester type flow ability modifying agent, vinyl bis-stearamides, low molecular weight polyethylene
One or more in wax, erucyl amide, stearic acid.
Optionally, the antioxidant is pentaerythritol ester, 4.4 ' two (α, α dimethyl benzyl diphenylamines)；N- phenyl-N '-
Isopropyl-p-phenylenediamine；Hydrogenated quinoline mixture；N, N '-two (Isosorbide-5-Nitrae-dimethyl amyl group)-p-phenylenediamine；N- phenyl-N '-
At least one of (ptoluene-sulfonyl)-p-phenylenediamine, three (bis--uncles of 2,6- are to butyl phenyl) phosphite esters.
Optionally, the flow ability modifying agent is ester type flow ability modifying agent, vinyl bis-stearamides, fatty acid monoglyceride
Ester, stearic acid, phthalate, fatty acid ester, phosphoric acid ester, epoxy ester series, trimellitic acid esters, polyol ester
At least one of class, alkyl sulfonic acid vinegar class.
In addition, the present invention also provides a kind of cross-linking modified PLA products formed, it is by described cross-linking modified poly- breast
Sour composite is formed.
Optionally, the cross-linking modified PLA products formed uses electron beam or gamma-ray irradiation, irradiation dose 20-
60kGy.To make product have better performance, product is transparent or semitransparent state, and thin-wall product is more easy to operate.
Compared to prior art, cross-linking modified lactic acid composite material of the invention, radiated by successive process
Crosslinking, the heat resistance of cross-linking modified PLA products formed is improved, available for apparatus such as transparent water cup, bucket, washbowls.
【Embodiment】
The cross-linking modified lactic acid composite material of the present invention, represent to include in parts by weight：
Polylactic resin 80-99 parts, the polylactic resin are L-type PLA, and melt index (MI) is 3-30g/10min
(210 DEG C/2.16KG of national standard).
Crosslinking agent 0.1-5 parts, the crosslinking agent are selected from Triallyl isocyanurate (TAIC), three methylallyl isocyanides
Acid esters (TMAIC), trimethylolpropane trimethacrylate (TMPTA), trimethylol-propane trimethacrylate (TMPTMA),
Triglycidyl group isocyanuric acid ester (TGIC) at least one.
Lubricant 0.1-10 parts, the lubricant are selected from ester type flow ability modifying agent, vinyl bis-stearamides, low molecule amount
One or more in Tissuemat E, erucyl amide, stearic acid, the lubricant are carried out by most main body of ester type flow ability modifying agent
Compound is arranged in pairs or groups, and mobility and physical property can reach optimum efficiency.
Antioxidant 0.1-10 parts, the antioxidant are pentaerythritol ester, 4.4 ' two (α, α dimethyl benzyl diphenylamines)；N-
Phenyl-N '-isopropyl-p-phenylenediamine；Hydrogenated quinoline mixture；N, N '-two (Isosorbide-5-Nitrae-dimethyl amyl group)-p-phenylenediamine；N-
At least one of phenyl-N '-(ptoluene-sulfonyl)-p-phenylenediamine, three (bis--uncles of 2,6- are to butyl phenyl) phosphite esters.
Flow ability modifying agent 0.1-10 parts, the flow ability modifying agent are ester type flow ability modifying agent, vinyl bis-stearamides, fat
Fat acid monoglyceride, stearic acid, phthalate, fatty acid ester, phosphoric acid ester, epoxy ester series, trimellitate
At least one of class, polyalcohol esters, alkyl sulfonic acid vinegar class.This flow ability modifying agent carries on the premise of material property is not reduced
High material flowability, makes the mobility of system increase 3-5 times, shortens molding cycle, the especially application in thin-wall part field.
The present invention also provides a kind of cross-linking modified PLA products formed, and it is compound by described cross-linking modified PLA
Material is formed.
Optionally, the cross-linking modified PLA products formed uses electron beam or gamma-ray irradiation, irradiation dose 20-
60kGy (preferably 40).To make product have better performance, product is transparent or semitransparent state, and thin-wall product is more easy to operate.
In order to have further understanding to the purpose of the present invention, effect and technological means, illustrate in conjunction with specific embodiment
It is as follows.
Embodiment 1
99 parts of polylactic resin；
0.5 part of crosslinking agent；
0.3 part of lubricant；
0.1 part of antioxidant；
0.1 part of flow ability modifying agent.
Crosslinking agent, lubricant, antioxidant and flow ability modifying agent are weighed in proportion and stir pretreatment, is subsequently placed at a high speed
Mixed at high speed is done in mixer, is taken out standby；Mixed powder, polylactic resin are processed in double screw extruder and take out grain
Son；By particle under conditions of 80 DEG C, dried 4 hours in heated-air circulation oven；After being molded into standard batten, in 40kGy spokes
Penetrate 5 minutes；Tensile strength, bending strength, Chalpy impact, the test of load heat distortion temperature are carried out according to national standard.
Comparative example 1
Crosslinking agent, lubricant, antioxidant and flow ability modifying agent are weighed in proportion and stir pretreatment, is subsequently placed at a high speed
Mixed at high speed is done in mixer, is taken out standby；Mixed powder, polylactic resin are processed in double screw extruder and take out grain
Son；By particle under conditions of 80 DEG C, dried 4 hours in heated-air circulation oven；Tensile strength, bending are carried out according to national standard by force
Degree, Chalpy impact, the test of load heat distortion temperature.
Embodiment 2
Crosslinking agent, lubricant, antioxidant and flow ability modifying agent are weighed in proportion and stir pretreatment, is subsequently placed at a high speed
Mixed at high speed is done in mixer, is taken out standby；Mixed powder, polylactic resin are processed in double screw extruder and take out grain
Son；By particle under conditions of 80 DEG C, dried 4 hours in heated-air circulation oven；After being molded into standard batten, in 40kGy spokes
Penetrate 5 minutes；Tensile strength, bending strength, Chalpy impact, the test of load heat distortion temperature are carried out according to national standard.
Comparative example 2
Crosslinking agent, lubricant, antioxidant and flow ability modifying agent are weighed in proportion and stir pretreatment, is subsequently placed at a high speed
Mixed at high speed is done in mixer, is taken out standby；Mixed powder, polylactic resin are processed in double screw extruder and take out grain
Son；By particle under conditions of 80 DEG C, dried 4 hours in heated-air circulation oven；Tensile strength, bending are carried out according to national standard by force
Degree, Chalpy impact, the test of load heat distortion temperature.
Above example 1,2 and comparative example 1 are tested, test result is as shown in table 1：
Table 1：Embodiment and comparative example test result
It can be learnt by table 1：Embodiment 1,2 is made comparisons with comparative example 1,2 respectively, as a result of suitable radiation
After intensity, tensile strength, impact strength, bending strength meter bending modulus all increase, and heat distortion temperature has also carried
It is high；Embodiment 2 is made comparisons with embodiment 1, is crosslinked the increase of agent dose, tensile strength, impact strength, the bending of bending strength meter
Modulus all increases, and heat distortion temperature also increases.It can be seen that cross-linking modified lactic acid composite material of the invention
Mechanical performance and heat resistance all lifted.
Claims (10)
1. a kind of lactic acid composite material of modification, it is characterised in that represent to include in parts by weight：
2. cross-linking modified lactic acid composite material according to claim 1, it is characterised in that the cross-linking modified poly- breast
Sour composite, represent to include in parts by weight：
3. cross-linking modified lactic acid composite material according to claim 1, it is characterised in that the cross-linking modified poly- breast
Sour composite, represent to include in parts by weight：
4. the cross-linking modified lactic acid composite material according to any one of claim 1-3, it is characterised in that described poly-
Lactic acid resin is L-type PLA, melt index 3-30g/10min.
5. the cross-linking modified lactic acid composite material according to any one of claim 1-3, it is characterised in that the friendship
Join agent and be selected from Triallyl isocyanurate, front three for allyl iso cyanurate, trimethylolpropane trimethacrylate, three hydroxyl first
Base propane trimethyl acrylic ester, triglycidyl group isocyanuric acid ester at least one.
6. the cross-linking modified lactic acid composite material according to any one of claim 1-3, it is characterised in that the profit
Lubrication prescription is in ester type flow ability modifying agent, vinyl bis-stearamides, low molecular weight polyethylene wax, erucyl amide, stearic acid
It is one or more.
7. the cross-linking modified lactic acid composite material according to any one of claim 1-3, it is characterised in that described anti-
Oxygen agent is pentaerythritol ester, 4.4 ' two (α, α dimethyl benzyl diphenylamines)；N- phenyl-N '-isopropyl-p-phenylenediamine；Hydrogenation
Quinoline mixture；N, N '-two (Isosorbide-5-Nitrae-dimethyl amyl group)-p-phenylenediamine；N- phenyl-N '-(ptoluene-sulfonyl)-to benzene two
At least one of amine, three (bis--uncles of 2,6- are to butyl phenyl) phosphite esters.
8. the cross-linking modified lactic acid composite material according to any one of claim 1-3, it is characterised in that the stream
Dynamic modifying agent is ester type flow ability modifying agent, vinyl bis-stearamides, glycerine monofatty ester, stearic acid, phthalic acid
In esters, fatty acid ester, phosphoric acid ester, epoxy ester series, trimellitic acid esters, polyalcohol esters, alkyl sulfonic acid vinegar class at least
It is a kind of.
9. a kind of cross-linking modified PLA products formed, it is characterised in that cross-linking modified PLA products formed is by claim
Cross-linking modified lactic acid composite material any one of 1-8 is formed.
10. cross-linking modified PLA products formed according to claim 9, it is characterised in that the cross-linking modified poly- breast
Sour products formed uses electron beam or gamma-ray irradiation, irradiation dose 20-60kGy.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610768199.1A CN107778799A (en) | 2016-08-30 | 2016-08-30 | Cross-linking modified lactic acid composite material and its products formed |
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| CN201610768199.1A CN107778799A (en) | 2016-08-30 | 2016-08-30 | Cross-linking modified lactic acid composite material and its products formed |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109706785A (en) * | 2019-01-14 | 2019-05-03 | 温州信环生物材料科技有限公司 | A kind of biodegradable lamination paper board material and the method using its manufacture hot-fill food containers |
| CN111978695A (en) * | 2020-08-14 | 2020-11-24 | 郑州大学 | Degradable full-bio-based high-toughness polylactic acid composite material and preparation method thereof |
| CN115012058A (en) * | 2022-07-14 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Preparation method and application of heat-resistant high-fluidity polylactic acid |
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