CN101020781A - Heat resistant polylactic acid-base composite material and its prepn process - Google Patents

Heat resistant polylactic acid-base composite material and its prepn process Download PDF

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Publication number
CN101020781A
CN101020781A CNA2007100554750A CN200710055475A CN101020781A CN 101020781 A CN101020781 A CN 101020781A CN A2007100554750 A CNA2007100554750 A CN A2007100554750A CN 200710055475 A CN200710055475 A CN 200710055475A CN 101020781 A CN101020781 A CN 101020781A
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Prior art keywords
polylactic acid
composite material
base composite
heat
fiber
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CNA2007100554750A
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CN100532454C (en
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邓鹏飏
刘南安
柳美华
董丽松
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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
    • B29C48/04—Particle-shaped
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Abstract

The present invention relates to one kind of heat resistant polylactic acid-base composite material and its preparation process. The polylactic acid-base composite material is prepared with polylactic acid 100 weight portions, fiber 5-50 weight portions, antioxidant 0.5-3 weight portions, heat stabilizer 0.5-3 weight portions and vinyl radical polyfunctional monomer 1-10 weight portions, and through mixing, pelletizing in a double screw extruder, drying, injection molding and irradiation cross-linking with a Co-60 source or an electronic accelerator. It has the Vicat softening point raised from 55-80 deg.c to 150 deg.c.

Description

A kind of heat resistant polylactic acid-base composite material and preparation method thereof
Technical field
The present invention relates to a kind of heat resistant polylactic acid-base composite material and preparation method thereof.
Background technology
Along with the exhausted day by day of disposable fossil resource (as oil, coal) and because the white pollution that a large amount of use caused of petroleum base goods is serious day by day, it is found that to have only and utilize reproducible natural resources production can satisfy the goods of people's needs, and after using, be degraded to CO 2And water, realize the nature resources circulation utilization, be only the only way that human society is realized Sustainable development.Consider from resource and environment two aspects that just focus, especially poly(lactic acid) (PLA) that the Biodegradable polyester material becomes people's concern gradually especially are subjected to people's attention.Poly(lactic acid) is to be raw material with starch, the macromolecular material that has good processing properties and physical and mechanical properties by a series of biochemical industry synthetic.Therefore be it is believed that it is the macromolecular material that has development potentiality in 21 century most.But it has a significant disadvantages, is exactly that high temperature dimensional stability is poor.When storage, transportation or the use temperature of its goods surpass 60 ℃,, goods lose its functions of use thereby will being out of shape.Therefore, the high temperature dimensional stability of raising PLA goods just becomes an important factor of PLA energy widespread use.
The traditional method that improves the high temperature dimensional stability of goods mainly contains: 1 and fiber composite; 2, improve second-order transition temperature; 3 improve degree of crystallinity.People such as M.Huda in 2006 point out (Composites Science andTechnology at the article that composite science and technology are delivered, 2006,66,1813-1824), because the interface compatibility between PLA matrix and fibrous packing is poor, therefore can not improve the resistance toheat of PLA by simple fiber composite method.(the Chinese invention patent application number: 200510017296.9) by strengthening the second-order transition temperature that the radiation crosslinking means improve PLA, still the amplitude that improves is limited, and therefore this method can not be independently solved the weakness of PLA resistance toheat difference for people such as Deng Peng Yang.People (Journal of Applied PolymerScierce on the using polymer magazine such as S.Serizawa in 2006,2006,100,618-624) point out, improve the crystallization degree of PLA/ fibre composite by anneal, can effectively improve the resistance toheat of this matrix material, but therefore this method can not be directly used in industrialized production because production efficiency is low.Also do not have at present a kind ofly can satisfy large-scale industrialization production application requirement, can effectively improve the stable on heating method of PLA again.
Summary of the invention
Purpose of the present invention is exactly at present above-mentioned difficult point, utilize to strengthen the synergistic effect of radiation crosslinking and fiber composite, the heat-drawn wire of PLA is significantly brought up to about 150 ℃ from 55 ℃, thereby widened its use range.
One of purpose of the present invention provides a kind of heat resistant polylactic acid-base composite material; Two of purpose of the present invention provides a kind of preparation method of heat resistant polylactic acid-base composite material, specially refers to by strengthening radiation crosslinking and fiber composite to strengthen the synergy method.
The weight ratio that the starting material of a kind of heat resistant polylactic acid-base composite material of the present invention are formed is as follows: poly(lactic acid): 100; Fiber: 5-50; Oxidation inhibitor: 0.5-3; Thermo-stabilizer: 0.5-3; Vinyl polyfunctional monomer: 1-10;
The weight-average molecular weight of described poly(lactic acid) is 4-30 ten thousand, and optimum molecular weight is 6-20 ten thousand;
Described fiber is glass fibre, cotton fibre, xylon, flaxen fiber, straw fiber, bagasse or wood powder;
The optimum weight percent of fiber is 20-50 in the described matrix material;
Described oxidation inhibitor is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid;
Described thermo-stabilizer is a triphenyl phosphite;
Described vinyl polyfunctional monomer is a triallyl isocyanurate.
A kind of preparation method of heat-stable polylactic acid-base composite material, its preparation is undertaken by following step: it is even to put into stirrer for mixing by weight load weighted various raw materials, and the material that mixes adds in the twin screw extruder, melt extrudes in 100-170 ℃, 160 ℃ of die head temperatures, the masterbatch that obtains making after the masterbatch vacuum-drying of making, is used injector injection molding again, injecting forming temperature is 120-170 ℃, nozzle temperature is 170 ℃, after the injection member cooling, takes out injection member at N 2Cross-linking radiation under protection or the vacuum condition, irradiation dose is at 1-10Mrad, and best dosage is 2-5Mrad, obtains a kind of heat resistant polylactic acid-base composite material.
The effect of oxidation inhibitor of the present invention and thermo-stabilizer is to guarantee that polyester material can not produce thermal destruction in hot procedure, and its consumption can not exert an influence to next step radiation crosslinking again simultaneously; The effect of vinyl polyfunctional monomer is the room temperature radiation crosslinking that promotes polyester material, improves its gel content.It is generally acknowledged that the vinyl polyfunctional monomer promotes that the crosslinked mechanism of action was divided into for two steps, the first step is the graft reaction that the vinyl polyfunctional monomer takes place on the free polymer readical that irradiation causes, second step was to react the generation cross-link bond between two keys remaining between the polyfunctional monomer that connects.In the irradiation process, the freeradical yield of polymkeric substance can not increase owing to the adding of polyfunctional monomer, therefore the effect of polyfunctional monomer just can not be carried out crosslinking reaction with those and make its resurrection from disappearing from the free radical graft reaction that goes out, and it is just passable to add a spot of polyfunctional monomer.
A kind of heat-stable polylactic acid-base composite material of the present invention utilizes the synergistic effect of strengthening radiation crosslinking and fiber composite, and the heat-drawn wire of PLA is significantly brought up to about 150 ℃ from 55 ℃.
Embodiment
Embodiment 1-9
Equal weighing molecular weight is 8.3 ten thousand PLA5000g among the embodiment 1-9, vinyl-functional monomer triallyl isocyanurate 250g, thermo-stabilizer triphenyl phosphite 50g, oxidation inhibitor 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 100g, xylon is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g, 2500g; Will be in proportion load weighted various raw material to put into stirrer for mixing even, the material that mixes adds in the twin screw extruder, the corresponding embodiment 1-9 of extrusion temperature is respectively 100 ℃ of temperature ins, 105 ℃, 110 ℃, 105 ℃, 115 ℃, 115 ℃, 115 ℃, 120 ℃, 120 ℃, high processing temperature is respectively 150 ℃, 155 ℃, 160 ℃, 160 ℃, 165 ℃, 165 ℃, 165 ℃, 170 ℃, between 170 ℃, 160 ℃ of die head temperatures after the masterbatch vacuum-drying of making, are used injector injection molding, and the corresponding embodiment 1-9 of injecting forming temperature is respectively 120 ℃ of temperature ins, 125 ℃, 125 ℃, 125 ℃, 130 ℃, 135 ℃, 135 ℃, 140 ℃, 140 ℃, high processing temperature is respectively 150 ℃, 150 ℃, 155 ℃, 155 ℃, 160 ℃, 160 ℃, 165 ℃, 165 ℃, between 170 ℃, nozzle temperature is 170 ℃.After to be injected the abundant cooling, take out injection member at N 2Cross-linking radiation under protection or the vacuum condition.Irradiation dose is 2 or 3Mrad, obtains a kind of heat resistant polylactic acid-base composite material.
Obtain a kind of heat resistant polylactic acid-base composite material, press GB/T1633-20 method test heat-drawn wire, the result shows that its product heat-drawn wire increases substantially 155 ℃ by original 55-75 ℃.See table 1 for details.
Table 1: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
1 ?53 ?80
2 ?55 ?93
3 ?57 ?93
4 ?62 ?105
5 ?65 ?120
6 ?67 ?145
7 ?69 ?150
8 ?71 ?150
9 ?75 ?155
Embodiment 10-18
Equal weighing molecular weight is 120,000 PLA500g among the embodiment 10-18, vinyl-functional monomer triallyl isocyanurate 150g, thermo-stabilizer triphenyl phosphite 150g, oxidation inhibitor β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecyl ester 150g of propionic acid, the paper fibre content is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g and 2500g.Preparation technology such as embodiment 1-9.Irradiation dose is 1Mrad, obtains a kind of heat resistant polylactic acid-base composite material.The heat-drawn wire of this heat resistant polylactic acid-base composite material changes as table 2.
Table 2: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
?10 ?55 ?67
?11 ?57 ?75
?12 ?58 ?97
?13 ?61 ?125
?14 ?67 ?135
?15 ?71 ?135
?16 ?75 ?141
?17 ?80 ?147
?18 ?83 ?152
Embodiment 19-27
Equal weighing molecular weight is 300,000 PLA5000g among the embodiment 19-27, vinyl-functional monomer triallyl isocyanurate 350g, thermo-stabilizer triphenyl phosphite 250g, oxidation inhibitor 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 50g, glass fibre is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g and 2500g; Preparation technology such as embodiment 1-9, irradiation dose is 5Mrad, obtains a kind of heat resistant polylactic acid-base composite material.The heat-drawn wire of this heat resistant polylactic acid-base composite material changes as table 3.
Table 3: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
?19 ?55 ?85
?20 ?58 ?97
?21 ?59 ?105
?22 ?61 ?127
?23 ?66 ?133
?24 ?70 ?137
?25 ?75 ?147
?26 ?80 ?150
?27 ?83 ?150
Embodiment 28-36
The equal weighing molecular weight of embodiment 18-36 is 200,000 PLA5000g, vinyl-functional monomer triallyl isocyanurate 200g, thermo-stabilizer triphenyl phosphite 200g, oxidation inhibitor β-positive octadecyl ester the 150g of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, cotton fibre is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g, 2500g.Preparation technology such as embodiment 1-9.Irradiation dose is 7Mrad, obtains a kind of heat resistant polylactic acid-base composite material.The heat-drawn wire of this heat resistant polylactic acid-base composite material changes as table 4.
Table 4: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
?28 ?55 ?73
?29 ?57 ?87
?30 ?58 ?95
?31 ?59 ?103
?32 ?65 ?125
?33 ?70 ?137
?34 ?75 ?140
?35 ?78 ?149
?36 ?80 ?152
Embodiment 37-45
The equal weighing molecular weight of embodiment 37-45 is 40,000 PLA5000g, and vinyl-functional monomer triallyl isocyanurate is 300g, thermo-stabilizer triphenyl phosphite 100g, oxidation inhibitor β-positive the octadecyl ester 3 of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 200g, bamboo fibers is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g, 2500g.Preparation technology such as embodiment 1-9.Irradiation dose is 10Mrad.Obtain a kind of heat resistant polylactic acid-base composite material.The heat-drawn wire of this heat resistant polylactic acid-base composite material changes as table 5.
Table 5: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
?37 ?55 ?82
?38 ?57 ?97
?39 ?58 ?102
?40 ?61 ?115
?41 ?67 ?127
?42 ?70 ?136
?43 ?75 ?141
?44 ?80 ?141
?45 ?84 ?153
Embodiment 46-54
The equal weighing molecular weight of embodiment 46-54 is 110,000 PLA5000g, and vinyl-functional monomer triallyl isocyanurate is 500g, thermo-stabilizer triphenyl phosphite 100g, oxidation inhibitor β-positive octadecyl ester the 100g of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, bagasse is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g, 2500g; Preparation technology such as embodiment 1-9, irradiation dose are 2Mrad.Obtain a kind of heat resistant polylactic acid-base composite material.The heat-drawn wire of this heat resistant polylactic acid-base composite material changes as table 6.
Table 6: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
?46 ?55 ?80
?47 ?57 ?95
?48 ?59 ?103
?49 ?61 ?115
?50 ?65 ?128
?51 ?70 ?136
?52 ?75 ?142
?53 ?80 ?142
?54 ?85 ?152
Embodiment 55-63
The equal weighing molecular weight of embodiment 55-63 is 60,000 PLA5000g, vinyl-functional monomer triallyl isocyanurate 250g, thermo-stabilizer triphenyl phosphite 150g, oxidation inhibitor 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 70g, wood powder content is followed successively by 250g, 300g, 500g, 700g, 1000g, 1300g, 1500g, 2000g and 2500g.Preparation technology such as embodiment 1-9, irradiation dose are 4Mrad.Obtain a kind of heat resistant polylactic acid-base composite material.The heat-drawn wire of this heat resistant polylactic acid-base composite material changes as table 7.
Table 7: before and after the cross-linking radiation, the variation of PLA thermal denaturation temperature
Embodiment The pre-irradiation heat-drawn wire Heat-drawn wire behind the irradiation
?55 ?56 ?80
?56 ?58 ?93
?57 ?59 ?93
?58 ?61 ?105
?59 ?66 ?122
?60 ?72 ?145
?61 ?75 ?150
?62 ?80 ?150
?63 ?84 ?152

Claims (6)

1, a kind of heat-stable polylactic acid-base composite material is characterized in that the weight ratio of its starting material composition is as follows: poly(lactic acid): 100; Fiber: 5-50; Oxidation inhibitor: 0.5-3; Thermo-stabilizer: 0.5-3; Vinyl polyfunctional monomer: 1-10;
The weight-average molecular weight of described poly(lactic acid) is 4-30 ten thousand;
Described fiber is glass fibre, cotton fibre, xylon, flaxen fiber, straw fiber, bagasse or wood powder;
Described oxidation inhibitor is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid;
Described thermo-stabilizer is a triphenyl phosphite;
Described vinyl polyfunctional monomer is a triallyl isocyanurate.
2, a kind of heat-stable polylactic acid-base composite material as claimed in claim 1 is characterized in that its weight-average molecular weight of described poly(lactic acid) is 6-20 ten thousand.
3, a kind of heat-stable polylactic acid-base composite material as claimed in claim 1, the weight ratio that it is characterized in that fiber in the described matrix material is 20-50.
4, a kind of heat-stable polylactic acid-base composite material as claimed in claim 1 is characterized in that described fiber is glass fibre, cotton fibre, xylon, flaxen fiber, straw fiber, bagasse or wood powder.
5, a kind of preparation method of heat-stable polylactic acid-base composite material, it is characterized in that step and condition are as follows: it is even to put into stirrer for mixing by weight load weighted various raw materials, the material that mixes adds in the twin screw extruder, melt extrude in 100-170 ℃, 160 ℃ of die head temperatures, the masterbatch that obtains making, after the masterbatch vacuum-drying of making, use injector injection molding again, injecting forming temperature is 120-170 ℃, nozzle temperature is 170 ℃, after the injection member cooling, takes out injection member at N 2Cross-linking radiation under protection or the vacuum condition, irradiation dose is 1-10Mrad, obtains a kind of heat resistant polylactic acid-base composite material.
6, the preparation method of a kind of heat-stable polylactic acid-base composite material as claimed in claim 5 is characterized in that described irradiation dose is 2-5Mrad.
CNB2007100554750A 2007-04-02 2007-04-02 Heat resistant polylactic acid-base composite material and its preparation process Expired - Fee Related CN100532454C (en)

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CN101962468A (en) * 2010-09-21 2011-02-02 上海大学 High strength and high heat resistance polylactic acid composite material and preparation method thereof
CN101962483A (en) * 2010-09-01 2011-02-02 孟庆雄 Composition material formed by natural cellulose and synthetic resin or polylactic acid
CN101284934B (en) * 2008-04-15 2011-03-30 中国科学院长春应用化学研究所 Preparation method of heat resisting polylactic acid based resin
CN102702704A (en) * 2012-06-19 2012-10-03 张家港柴能生物科技有限公司 Degradable polylactic acid (PLA) composite material and preparation method thereof
CN103819884A (en) * 2012-11-16 2014-05-28 上海载和实业投资有限公司 Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof
CN104017340A (en) * 2014-06-25 2014-09-03 广州甘蔗糖业研究所 Bagasse/cassava starch polylactic acid biodegradable material, and preparation method and application thereof
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CN101284934B (en) * 2008-04-15 2011-03-30 中国科学院长春应用化学研究所 Preparation method of heat resisting polylactic acid based resin
CN101962483A (en) * 2010-09-01 2011-02-02 孟庆雄 Composition material formed by natural cellulose and synthetic resin or polylactic acid
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JP2015514139A (en) * 2012-03-29 2015-05-18 エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． Board using cross-linked polylactic acid and method for producing the same
CN104245260B (en) * 2012-03-29 2017-04-12 乐金华奥斯有限公司 Board using crosslinked polylactic acid and method for preparing same
CN104169055A (en) * 2012-03-29 2014-11-26 乐金华奥斯有限公司 Board using crosslinked polylactic acid and method for preparing same
CN104245260A (en) * 2012-03-29 2014-12-24 乐金华奥斯有限公司 Board using crosslinked polylactic acid and method for preparing same
CN102702704A (en) * 2012-06-19 2012-10-03 张家港柴能生物科技有限公司 Degradable polylactic acid (PLA) composite material and preparation method thereof
CN103819884A (en) * 2012-11-16 2014-05-28 上海载和实业投资有限公司 Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof
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CN104448154A (en) * 2014-11-26 2015-03-25 北京市射线应用研究中心 Radiation grafting long-chain branch polylactic acid and preparation method thereof
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CN107868417A (en) * 2017-10-31 2018-04-03 南方医科大学 A kind of bagasse PLA composites suitable for 3D printing and its preparation method and application
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CN114410090B (en) * 2022-01-25 2023-08-15 佛山市顺德区建德包装实业有限公司 Preparation method of packaging film

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