CN102492273A - Reinforced heat-resistant polylactic-acid-based composite material and preparation method thereof - Google Patents
Reinforced heat-resistant polylactic-acid-based composite material and preparation method thereof Download PDFInfo
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- CN102492273A CN102492273A CN2011103997954A CN201110399795A CN102492273A CN 102492273 A CN102492273 A CN 102492273A CN 2011103997954 A CN2011103997954 A CN 2011103997954A CN 201110399795 A CN201110399795 A CN 201110399795A CN 102492273 A CN102492273 A CN 102492273A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000011068 loading method Methods 0.000 claims description 5
- MAMMVUWCKMOLSG-UHFFFAOYSA-N Cyclohexyl propionate Chemical compound CCC(=O)OC1CCCCC1 MAMMVUWCKMOLSG-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- YTXCAJNHPVBVDJ-UHFFFAOYSA-N octadecyl propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC YTXCAJNHPVBVDJ-UHFFFAOYSA-N 0.000 claims description 4
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
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- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
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- TWDJIKFUVRYBJF-UHFFFAOYSA-N Cyanthoate Chemical compound CCOP(=O)(OCC)SCC(=O)NC(C)(C)C#N TWDJIKFUVRYBJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a reinforced heat-resistant polylactic-acid-based composite material and a preparation method thereof. The composite material comprises the following components: 58-95 parts by weight of polylactic acid, 5-20 parts by weight of ultramicro phenolic fiber, 5-20 parts by weight of fiberglass, 0.1-1 part by weight of antioxidant and 0.1-1 part by weight of stabilizer. According to the invention, the defects of high frangibility and poor high-temperature resistance of the traditional polylactic-acid-based composite material are overcome; and the prepared reinforced heat-resistant polylactic-acid-based composite material has biodegradability and good mechanical and thermal properties.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of modified polylactic acid composite material and preparation method thereof.
Background technology
Serious day by day, renewable, the biodegradable POLYACTIC ACID of environmental pollution (PLA) that causes along with the exhaustion day by day and the petroleum base goods of fossil resource becomes the research focus of field of materials gradually.
POLYACTIC ACID is to be the biopolymer that fermenting raw materials makes with starch of natural reproducible etc.; It has certain mechanical property and good thermoplastic, compostability; Easy to process, be successfully applied to fields such as automotive trim, weaving, mechanical fitting, medical science at present.But POLYACTIC ACID second-order transition temperature low (about 60 ℃) causes the general polylactic acid based product softening transform easily that is heated more than 50 ℃, and poor dimensional stability can not satisfy the requirement of use usually.Therefore, developing the polylactic acid-base composite material with good heat resistance ability, mechanical property and degradation property is that correlated performance is required harsh field of materials problem demanding prompt solution.
One Chinese patent application number: 200610037894.7 disclose the patent that name is called " POLYACTIC ACID/natural-fiber composite material and working method thereof ", adopt the coupling agent treatment natural fiber after, melt extrude granulation with POLYACTIC ACID, oxidation inhibitor, nucleator, lubricant.The advantage of this method is that coupling agent has improved the interface compatibility of natural fiber and POLYACTIC ACID; Has forming process property preferably; The material fully biodegradable that obtains; But it is not good that the composite modified mechanical property to POLYACTIC ACID of natural fiber is improved, and composite material toughness improves not obvious, even can reduce shock strength.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art; A kind of enhancing heat resistant polylactic acid-base composite material and preparation method thereof is provided; Make polylactic acid-base composite material keep strengthening mechanical property such as tensile strength and flexural strength on original degradable characteristic basis; And improved heat resisting temperature, the polylactic acid-base composite material range of application is enlarged.
Solving the technical scheme that technical problem of the present invention adopted is POLYACTIC ACID, the ultra micro phenolic fibre of 5-20 weight part, the spun glass of 5-20 weight part, the oxidation inhibitor of 0.1-1 weight part and the stablizer of 0.1-1 weight part that this enhancing heat resistant polylactic acid-base composite material comprises the 58-95 weight part.Adopting the ultra micro phenolic fibre that POLYACTIC ACID is carried out modification, still is main raw material with the POLYACTIC ACID in the matrix material, and the content of POLYACTIC ACID is less than 50wt% if this is, the effect that then alleviates carrying capacity of environment becomes insufficient easily.
Phenolic fibre is the made cross filament of thermosetting resin, has excellent specific properties such as heat-resisting, fire-retardant, anti-molten, resistance to chemical attack, and the life-time service temperature is 150-180 ℃.Thereby can be used as the skeleton structure of polylactic acid-base composite material, improve the softening transform temperature of matrix material.The ultra micro phenolic fibre is compared short more and thin with common phenolic fibre, more easy and uniform is dispersed in the composite system, helps the compound of phenolic fibre and POLYACTIC ACID and spun glass.
Can improve the mechanical property of polylactic acid-base composite material with the spun glass blend.Through the cooperation of spun glass, the fastness of matrix material is increased, and the temperature of deflection under load of matrix material is risen.While is not flammable owing to spun glass, thereby can effectively improve the flame retardant properties of matrix material again, has widened the range of application of POLYACTIC ACID greatly.
The adding of oxidation inhibitor and stablizer is improved the matrix material ageing-resistant performance, can keep good performance for a long time, and nondiscoloration in appearance.
Preferably, said polylactic acid molecule amount is 20-30 ten thousand, and said ultra micro phenolic fibre length is 50-100 μ m.
Spun glass main rising in matrix material carried and enhancement; For carrying and the enhancement of giving full play to spun glass; The difference that reduces spun glass and POLYACTIC ACID matrix is to Influence on Composite Interface; Be necessary the surface of spun glass is handled, improve the over-all properties of matrix material.
Preferably, said spun glass was handled 1-5 hour with 0.1-1wt% silane coupling agent aqueous solution soaking, and preferred 3 hours, and glass fibre length is 3-5mm.Handle spun glass with silane coupling agent; Can improve the interface performance of spun glass and synthetic resins POLYACTIC ACID and ultra micro phenolic fibre; Help spun glass and in matrix material, disperse, and combine closely, the intensity of matrix material and cohesive force are significantly improved with POLYACTIC ACID and resol.
Preferably; Said silane coupling agent is vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy Trimethoxy silane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, a kind of in N-(beta-aminoethyl)-γ TSL 8330, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-methyl mercapto propyl trimethoxy silicane or the γ-r-chloropropyl trimethoxyl silane.
Further preferably, said silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.Its main amine functional group can be had an effect with a series of thermosetting resins, thermoplastics and tartan, is widely used in the enhancing of spun glass.In spun glass enhanced thermoset and thermoplastics, use.When under dried hygrometric state situation, using this silane, spun glass enhanced thermoplastics all rose with later flexural strength and tensile strength before immersion.
Preferably; Said oxidation inhibitor is four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester; A kind of in β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate or the Tyox B.
Preferably, said stablizer is maleic acid anhydrides or epoxy soybean oil.
The present invention also provides the method for the above-mentioned enhancing heat resistant polylactic acid-base composite material of preparation, may further comprise the steps:
(1) handle spun glass: with spun glass with silane coupling agent aqueous solution soaking processing 1-5 hour of 0.1-1wt% concentration and in air dry oven, dry the spun glass after obtaining handling;
(2) drying treatment: with POLYACTIC ACID, ultra micro phenolic fibre, oxidation inhibitor vacuum drying;
(3) batch mixing: mixed is even by weight for each dried component that step (2) is obtained and stablizer, and what obtain mixing extrudes starting material;
(4) mixing, granulation: extrude in the loading hopper that starting material join twin screw extruder with what step (3) obtained; The spun glass of the corresponding weight part after simultaneously step (1) being handled adopts side position feeding manner to add in the twin screw extruder, through mixing, melt extrude, granulation, oven dry are enhanced heat resistant polylactic acid-base composite material.
Preferably, the twin screw extruder rotating speed is 25-180rpm in the said step (4), and twin screw extruder internal heating temperature is 160-200 ℃.
Preferably, the method that each component mixes in the said step (3) is to put into stirrer to stir 1-3 minute.
Preferably, drying condition is 60-80 ℃ of baking 5-8 hour in the said step (1); The vacuum drying condition is for being under the 0.02-0.08MPa dry 3-8 hour at 50-80 ℃, vacuum tightness in the step (2); Drying condition described in the step (4) is for being that 50-80 ℃, vacuum tightness are under the 0.02-0.08MPa dry 3-8 hour in temperature.
The invention has the beneficial effects as follows: prepare a kind of biodegradable polylactic acid-base composite material; This composite materials property is good: tensile strength reaches 55.32-71.56MPa; Flexural strength reaches 71.82-111.87MPa, and heat resisting temperature reaches 70.52-105.63 ℃.
Description of drawings
Fig. 1 is the electron microscope photo scanning of ultra micro phenolic fibre in specific embodiment of the present invention.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with embodiment.
The used stirrer of the embodiment of the invention is that Bel's machinery ltd produces, and model is SHR-10A; Used twin screw extruder is that Nanjing machinery ltd of sincere alliance produces, and model is SHJ-35.
Embodiment one
Present embodiment adopts the following steps preparation to strengthen heat resistant polylactic acid-base composite material:
(1) handle spun glass: with spun glass handled 1 hour with the silane coupling agent vinyl trichlorosilane aqueous solution soaking of 0.5wt% concentration and in air dry oven 80 ℃ dry by the fire 4 hours dryings, the spun glass after obtaining handling;
(2) drying treatment: is under the 0.02MPa dry 8 hours with POLYACTIC ACID (molecular weight 20W), ultra micro phenolic fibre (staple length 50-100 μ m), oxidation inhibitor four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester at 50 ℃, vacuum tightness;
(3) batch mixing: each dried component that step (2) is obtained and stablizer maleic acid anhydrides be ratio 95: 5: 0.1 by weight: 0.1 takes by weighing 95kg POLYACTIC ACID, 5kg ultra micro phenolic fibre, 0.1kg oxidation inhibitor four (β-(3 respectively; 5 di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester and 0.1kg stablizer maleic acid anhydrides are put into stirrer stirring 3 minutes; It is mixed, and what obtain mixing extrudes starting material;
(4) mixing, granulation: extrude in the loading hopper that starting material join twin screw extruder with what step (3) obtained; 5kg spun glass after simultaneously step (1) being handled adopts side position feeding manner to add in the twin screw extruder; Screw speed is 180rpm; Extrusion temperature is 175 ℃, through mixing, melt extrude, granulation, oven dry are enhanced heat resistant polylactic acid-base composite material.
Through test, this enhancing heat resistant polylactic acid-base composite material tensile strength is 55.32MPa, and flexural strength is 71.82MPa, and vicat softening temperature is 70.52 ℃.
Embodiment two
Present embodiment adopts the following steps preparation to strengthen heat resistant polylactic acid-base composite material:
(1) handle spun glass: with spun glass handled 5 hours with the silane coupling agent γ-An Bingjisanyiyangjiguiwan aqueous solution soaking of 0.1wt% concentration and in air dry oven 80 ℃ dry by the fire 3 hours dryings, the spun glass after obtaining handling;
(2) drying treatment: is under the 0.03MPa dry 5 hours with POLYACTIC ACID (molecular weight 30W), ultra micro phenolic fibre (staple length 50-100 μ m), oxidation inhibitor (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester at 60 ℃, vacuum tightness;
(3) batch mixing: each dried component that step (2) is obtained and stablizer maleic acid anhydrides be ratio 79: 10: 0.5 by weight: 0.5 takes by weighing 79kg POLYACTIC ACID, 10kg ultra micro phenolic fibre, 0.5kg oxidation inhibitor (3 respectively; The 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and 0.5kg stablizer maleic acid anhydrides are put into stirrer stirring 3 minutes; It is mixed, and what obtain mixing extrudes starting material;
(4) mixing, granulation: extrude in the loading hopper that starting material join twin screw extruder with what step (3) obtained; The spun glass of 10kg after simultaneously step (1) being handled adopts side position feeding manner to add in the twin screw extruder; Screw speed is 100rpm; Extrusion temperature is 185 ℃, through mixing, melt extrude, granulation, oven dry are enhanced heat resistant polylactic acid-base composite material.
Ultra micro phenolic fibre electromicroscopic photograph used in the present embodiment is as shown in Figure 1: as can be seen from Figure 1 the ultra micro phenolic fibre is the network structure of IPN; The network structure mechanical strength is big; In matrix material, play the effect of skeleton, insert mechanical property and resistance toheat that strongthener such as spun glass can further improve matrix material in the inner microporosity of ultra micro phenolic fibre.
Through test, this enhancing heat resistant polylactic acid-base composite material tensile strength is 66.73MPa, and flexural strength is 90.79MPa, and vicat softening temperature is 91.23 ℃.
Embodiment three
Present embodiment adopts the following steps preparation to strengthen heat resistant polylactic acid-base composite material:
(1) handle spun glass: with spun glass handled 3 hours with the silane coupling agent vinyl trichlorosilane aqueous solution soaking of 1wt% concentration and in air dry oven 80 ℃ dry by the fire 3 hours dryings, the spun glass after obtaining handling;
(2) drying treatment: is under the 0.08MPa dry 3 hours with POLYACTIC ACID (molecular weight 25W), ultra micro phenolic fibre (staple length 50-100 μ m), oxidation inhibitor β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate at 80 ℃, vacuum tightness;
(3) batch mixing: each dried component that step (2) is obtained and stablizer maleic acid anhydrides be ratio 58: 20: 1 by weight: 1 takes by weighing 58kg POLYACTIC ACID, 20kg ultra micro phenolic fibre, 1kg oxidation inhibitor β-(3 respectively; The 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate and 1kg stablizer epoxy soybean oil are put into stirrer stirring 3 minutes; It is mixed, and what obtain mixing extrudes starting material;
(4) mixing, granulation: extrude in the loading hopper that starting material join twin screw extruder with what step (3) obtained; 20kg spun glass after simultaneously step (1) being handled adopts side position feeding manner to add in the twin screw extruder; Screw speed is 25rpm; Extrusion temperature is 190 ℃, through mixing, melt extrude, granulation, oven dry are enhanced heat resistant polylactic acid-base composite material.
Through test, this enhancing heat resistant polylactic acid-base composite material tensile strength is 71.56MPa, and flexural strength is 111.87MPa, and vicat softening temperature is 105.63 ℃.
The resulting enhancing heat resistant polylactic acid-base composite material of the foregoing description is compared with pure poly-lactic acid material; Performance has had remarkable lifting, and (tensile strength of pure poly-lactic acid material is 48MPa; Flexural strength is 70MPa; Vicat softening temperature is 50 ℃), can be applicable to aspects such as household appliances shell, automotive upholstery.
By above detailed description to the embodiment of the invention, can understand the problem that the invention solves general polylactic acid based material mechanical performance difference, improved the heat resisting temperature of polylactic acid based material simultaneously, enlarged the range of application of conventional polylactic acid based material.
It is understandable that above embodiment only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (10)
1. one kind strengthens heat resistant polylactic acid-base composite material, it is characterized in that component comprises: the oxidation inhibitor of the ultra micro phenolic fibre of the POLYACTIC ACID of 58-95 weight part, 5-20 weight part, the spun glass of 5-20 weight part, 0.1-1 weight part and the stablizer of 0.1-1 weight part.
2. matrix material according to claim 1 is characterized in that said polylactic acid molecule amount is 20-30 ten thousand, and said ultra micro phenolic fibre length is 50-100 μ m.
3. matrix material according to claim 2 it is characterized in that said spun glass with 0.1-1wt% silane coupling agent aqueous solution soaking processing 1-5 hour, and glass fibre length is 3-5mm.
4. matrix material according to claim 3; It is characterized in that at said silane coupling agent be vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy Trimethoxy silane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, a kind of in N-(beta-aminoethyl)-γ TSL 8330, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-methyl mercapto propyl trimethoxy silicane or the γ-r-chloropropyl trimethoxyl silane.
5. matrix material according to claim 4 is characterized in that said silane coupling agent is preferably γ-An Bingjisanyiyangjiguiwan.
6. matrix material according to claim 1; It is characterized in that said oxidation inhibitor is four (β-(3; 5 di-tert-butyl-hydroxy phenyls) pentaerythritol ester, (3 propionic acid); The 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, a kind of in β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate or the Tyox B.
7. matrix material according to claim 1 is characterized in that said stablizer is maleic acid anhydrides or epoxy soybean oil.
8. method for preparing the arbitrary described enhancing heat resistant polylactic acid-base composite material of claim 1-7 is characterized in that may further comprise the steps:
(1) handle spun glass: with spun glass with silane coupling agent aqueous solution soaking processing 1-5 hour of 0.1-1wt% concentration and in air dry oven, dry the spun glass after obtaining handling;
(2) drying treatment: with POLYACTIC ACID, ultra micro phenolic fibre, oxidation inhibitor vacuum drying;
(3) batch mixing: mixed is even by weight for each dried component that step (2) is obtained and stablizer, and what obtain mixing extrudes starting material;
(4) mixing, granulation: extrude in the loading hopper that starting material join twin screw extruder with what step (3) obtained; The spun glass of the corresponding weight part after simultaneously step (1) being handled adopts side position feeding manner to add in the twin screw extruder, through mixing, melt extrude, granulation, oven dry are enhanced heat resistant polylactic acid-base composite material.
9. preparation method according to claim 8 is characterized in that the twin screw extruder rotating speed is 25-180rpm described in the step (4), and twin screw extruder internal heating temperature is 160-200 ℃.
10. preparation method according to claim 8 is characterized in that drying condition is 60-80 ℃ of baking 5-8 hour in the step (1); The vacuum drying condition is for being under the 0.02-0.08MPa dry 3-8 hour at 50-80 ℃, vacuum tightness in the step (2); Drying condition described in the step (4) is for being that 50-80 ℃, vacuum tightness are under the 0.02-0.08MPa dry 3-8 hour in temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110399795.4A CN102492273B (en) | 2011-11-30 | 2011-11-30 | Reinforced heat-resistant polylactic-acid-based composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110399795.4A CN102492273B (en) | 2011-11-30 | 2011-11-30 | Reinforced heat-resistant polylactic-acid-based composite material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102492273A true CN102492273A (en) | 2012-06-13 |
| CN102492273B CN102492273B (en) | 2014-03-12 |
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| CN201110399795.4A Active CN102492273B (en) | 2011-11-30 | 2011-11-30 | Reinforced heat-resistant polylactic-acid-based composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175779A (en) * | 2014-10-16 | 2015-12-23 | 中国林业科学研究院林产化学工业研究所 | Silicon-containing flame retardation plasticizer and preparation method thereof |
| CN108624016A (en) * | 2018-04-24 | 2018-10-09 | 上海交通大学 | Aramid fiber modified carbon fiber enhances polylactic acid thermoplastic composite and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508832A (en) * | 2008-12-17 | 2009-08-19 | 深圳市科聚新材料有限公司 | Reinforced polylactic acid composite material and method for producing the same |
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Patent Citations (1)
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| CN101508832A (en) * | 2008-12-17 | 2009-08-19 | 深圳市科聚新材料有限公司 | Reinforced polylactic acid composite material and method for producing the same |
Non-Patent Citations (1)
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| 郭金海等: "酚醛纤维的研究进展及应用", 《合成纤维工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175779A (en) * | 2014-10-16 | 2015-12-23 | 中国林业科学研究院林产化学工业研究所 | Silicon-containing flame retardation plasticizer and preparation method thereof |
| CN108624016A (en) * | 2018-04-24 | 2018-10-09 | 上海交通大学 | Aramid fiber modified carbon fiber enhances polylactic acid thermoplastic composite and preparation method |
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| CN102492273B (en) | 2014-03-12 |
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