CN101157793B - Heat-proof polylactic acid blend and preparation method thereof - Google Patents
Heat-proof polylactic acid blend and preparation method thereof Download PDFInfo
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- CN101157793B CN101157793B CN2007100713598A CN200710071359A CN101157793B CN 101157793 B CN101157793 B CN 101157793B CN 2007100713598 A CN2007100713598 A CN 2007100713598A CN 200710071359 A CN200710071359 A CN 200710071359A CN 101157793 B CN101157793 B CN 101157793B
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Abstract
The invention provides a heat-resistant polylactic acid blend and a preparation method thereof, pertaining to the polymer materials technique field, solving the problems of bad heat-resistant performance, weak mechanical performance and being not to be biodegraded, etc. The heat-resistant polylactic acid blend consists of the following components according to weight proportion: 100 parts of polylactic acid, 5 parts to 100 parts of heat-resistant polymer materials which can be biodegraded, 0 to 100 parts of fillers; the preparation method is that: A. blending; B. banburying; C. hot pressing forming; D. isothermal crystallization. The heat-resistant polylactic acid blend of the invention uses the polylactic acid which has a synergistic effect between crystallization and heat-resistant components, and therefore the invention has good heat-resistant performance. The invention adopts various components matching use, so the blend can not only be biodegraded, but also has good mechanical performance; the whole preparation method has simple technical process, good processing performance, low cost and can realize large-scale and industrialized production.
Description
Technical field
The present invention relates to a kind of polyester composite and preparation method thereof, relate in particular to a kind of heat-proof polylactic acid blend and preparation method thereof; Belong to technical field of polymer materials.
Background technology
The waste of macromolecular material has caused people's extensive concern day by day to the negative impact that environment brings, and solving serious day by day " white pollution " problem becomes people's question of common concern.Therefore, the development work of degradative plastics now both at home and abroad is very active, and existing part begun suitability for industrialized production, develops quite rapid.Biodegradable plastic had both had the premium properties of performance plastics when using itself, and did not bring pollution to environment again when discarding with the back, can be by the rapid feature of decomposing of various biologies (enzyme).Therefore develop and promote biodegradable polymer energetically, be only the method for taking stopgap measures and effecting a permanent cure, also meet the trend of current macromolecular material greenization.
The initial raw material of synthesizing polylactic acid is a starch, and starch is converted into lactic acid through biological fermentation process, and lactic acid is through polycondensation or ring-opening polymerization obtains poly(lactic acid) through rac-Lactide again.This shows that it is the plant resources that it has utilized recyclability that poly(lactic acid) is different from one of essence of other general-purpose plastics.Can effectively alleviate exhausted day by day Nonrenewable resources like this.And poly(lactic acid) has and the identical performance of general-purpose plastics, as mechanical property and workability.Particularly large-scale at present production makes the cost of polylactic resin descend, and becoming with respect to other biodegradated polymer materal is dirt cheap.Had as U.S. Jia Ji (Cargill) company and to have produced 140000 tons poly(lactic acid) throughput per year, the positive group in sea, domestic Zhejiang builds up and produces 5000 tons poly(lactic acid) demonstration plant per year.Therefore, in the last few years, poly(lactic acid) is the concern of the academic boundary of polymer and industrial community extremely, became 21 century hot research object.
But, because the crystallization rate of poly(lactic acid) is very slow, almost is amorphous polymer after the processing, like this after temperature is higher than second-order transition temperature (about 60 ℃), the dimensional stability of goods is very poor, and relatively poor resistance toheat has limited the widespread use of poly(lactic acid) to a great extent.Therefore, there are a lot of research work reports to improve the resistance toheat of poly(lactic acid).Comprise that Chinese patent application (CN02813024.3) is by adding the degree of crystallinity of nucleator raising poly(lactic acid); Improving its degree of crystallinity is to add nucleators such as metal organophosphate, benzal base glucitol derivative in poly(lactic acid), and polymer crystallization is speeded up, and improves degree of crystallinity, and spherulite size is evenly fine and closely woven, makes polymkeric substance thermal characteristics, mechanical property be improved.Chinese patent application (CN03149911.2) is by dosing the thermotolerance that mineral filler strengthens poly(lactic acid); Dosing mineral filler is to add synusia shape micro mists such as mica powder, talcum powder, polynite in poly(lactic acid), and laminal filler has better thermal characteristics and mechanical property than particulate filler.Chinese patent application (CN99119441) improves its thermotolerance and other mechanical property by the copolyreaction between poly(lactic acid) and aliphatics and/or the aliphatic polyester carbonate ester; Although above-mentioned technology can realize the improvement of poly(lactic acid) resistance toheat, the amplitude that improves is limited, can't satisfy the goods that some resistance toheats are had relatively high expectations; As tableware of in hot food and drink, using etc.
Blending and modifying is a polymkeric substance modified method commonly used, can realize mutual supplement with each other's advantages between the different components by blend, satisfies the not available performance of one-component; Chinese patent application (CN200510119118.7) discloses uses higher polymkeric substance styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer or polycarbonate and the poly(lactic acid) of resistance toheat to carry out blend to improve the resistance toheat of poly(lactic acid).But the blend heat resistant type polymkeric substance styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer or the polycarbonate that use in this technology are cannot be biodegradable, after use is discarded, still can pollute environment, in addition, poly(lactic acid) after this technology blend is unformed poly(lactic acid), so resistance toheat improves limited.
Summary of the invention
The present invention is directed to existing in prior technology the problems referred to above, provide that a kind of resistance toheat is good, mechanical property is strong, biodegradable heat-proof polylactic acid blend and preparation method thereof.
Above-mentioned technical problem of the present invention can be implemented by the following technical programs: a kind of heat-proof polylactic acid blend, and this material is grouped into by the one-tenth of following weight part:
100 parts of poly(lactic acid); Biodegradable heat-proof macromolecule material: 5～100 parts; Filler: 0～100 part.
The poly(lactic acid) that heat-proof polylactic acid blend of the present invention adopts because the crystallization of himself and and heat-proof macromolecule material between synergistic effect, not only have the better heat-resisting performance; And the employing various components matching is used, compatibility is reasonable, has biodegradable and excellent mechanical property.
In above-mentioned a kind of heat-proof polylactic acid blend, the optimization weight part of this composition is: 100 parts of poly(lactic acid); Biodegradable heat-proof macromolecule material: 30～100 parts; Filler: 10～100 parts.
In above-mentioned a kind of heat-proof polylactic acid blend, the number-average molecular weight of described poly(lactic acid) is 5～200,000 dalton, and degree of crystallinity is 5～50%.If the number-average molecular weight of poly(lactic acid) is less than 50,000 dalton, the mechanical property of material can not satisfy practical application, and number-average molecular weight is greater than 200,000 dalton, and processing characteristics is relatively poor, can't process on existing equipment.If its degree of crystallinity is too little, the thermotolerance of poly(lactic acid) can't be improved.
In above-mentioned a kind of heat-proof polylactic acid blend, described biodegradable heat-proof macromolecule material is one or more mixing in poly butylene succinate, poly butyric ester, 3-butyric ester-4-hydroxyl pentanoate copolymer, the Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer.After carrying out blend, can effectively improve the heat resisting temperature of poly(lactic acid) with these blends.
In above-mentioned a kind of heat-proof polylactic acid blend, described filler is one or both mixing in lime carbonate, the starch.
The present invention also provides a kind of preparation method as heat-proof polylactic acid blend in addition, and this method may further comprise the steps:
A, blend: the composition of getting above-mentioned weight part mixes, and stirs after the mixing;
B, banburying: the composition of above-mentioned blend is put into the Banbury mixer banburying, and wherein banburying temperature is 150 ℃～190 ℃, and the banburying time is 5～20 minutes;
C, hot-forming: is 150 ℃～200 ℃ with the resin after the above-mentioned banburying in temperature, and pressure is hot-forming under the condition of 8～15MPa;
D, isothermal crystal: be that isothermal crystal obtained heat-proof polylactic acid blend after 5～120 minutes under 60 ℃～120 ℃ the condition with above-mentioned sheet material after hot-forming in temperature.
In above-mentioned preparation method, as preferably, the banburying temperature described in the step B is 170 ℃, and the banburying time is 10 minutes; Temperature during hot-forming described in the step C is 180 ℃, and pressure is 10Mpa; Temperature during isothermal crystal described in the step D is 80 ℃～100 ℃, and crystallization time is 5～90 minutes.
Indulge the above, the present invention has the following advantages:
1, the poly(lactic acid) that adopts of heat-proof polylactic acid blend of the present invention because the crystallization of himself and and heat-resisting component between synergistic effect, have the better heat-resisting performance, its vicat softening temperature can reach 80-130 ℃; Can satisfy the tableware requirement of using in the hot food and drink fully.
2, heat-proof polylactic acid blend of the present invention adopts various components matching to use, and compatibility is reasonable, and is not only biodegradable; And has an excellent mechanical property; Wherein tensile strength can reach 15-45MPa, and elongation at break can reach 10-50%.
3, the preparation method of heat-proof polylactic acid blend of the present invention, technical process is simple, and processing characteristics is strong, and cost is low can realize large-scale industrial production; The blend that obtains can be used for extrusion board, sheet material, and the preparation of corresponding Blister product.Also be applicable to the production technique of injection molding product.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
Table 1: the component of heat-proof polylactic acid blend of the present invention (by weight)
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 1 is 50,000 dalton; Degree of crystallinity is 5%; Described biodegradable heat-proof macromolecule material is a poly butylene succinate; Described filler is a lime carbonate.
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 2 is 200,000 dalton; Degree of crystallinity is 50%; Described biodegradable heat-proof macromolecule material is a poly butyric ester.
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 3 is 150,000 dalton; Degree of crystallinity is 10%; Described biodegradable heat-proof macromolecule material is 3-butyric ester-4-hydroxyl pentanoate copolymer; Described filler is a lime carbonate.
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 4 is 80,000 dalton; Degree of crystallinity is 40%; Described biodegradable heat-proof macromolecule material is Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer; Described filler is a lime carbonate.
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 5 is 80,000 dalton; Degree of crystallinity is 20%; Described biodegradable heat-proof macromolecule material is poly butylene succinate and polyhydroxybutyrate ester mixture, and both weight ratios are 3: 1; Described filler is starch and lime carbonate, and both weight ratios are 4: 1.
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 6 is 100,000 dalton; Degree of crystallinity is 30%; Described biodegradable heat-proof macromolecule material is the mixture of 3-butyric ester-4-hydroxyl pentanoate copolymer and Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer, and both weight ratios are 5: 1; Described filler is a starch.
Wherein the number-average molecular weight of the poly(lactic acid) described in the embodiment 7 is 150,000 dalton; Degree of crystallinity is 20%; Described biodegradable heat-proof macromolecule material is the mixture of poly butylene succinate, poly butyric ester and Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer, and three's weight ratio is 5: 3: 1; Described filler is a starch.
Embodiment 1
A, mixing: the composition according to the weight part of embodiment in the table 11 mixes, and puts into homogenizer after the mixing and stirs;
B, banburying: the composition of above-mentioned blend is put into the Banbury mixer banburying, and wherein banburying temperature is 150 ℃, and the banburying time is 20 minutes;
C, hot-forming: is 150 ℃ with the resin after the above-mentioned banburying in temperature, and pressure is the hot-forming thick sheet material of 1.0mm that obtains under the condition of 15MPa;
D, isothermal crystal: be that isothermal crystal obtained heat-proof polylactic acid blend after 5 minutes under 60 ℃ the condition in temperature with above-mentioned sheet material after hot-forming, it is as shown in table 2 to form different measured mechanical property and resistance toheats according to sample.
Embodiment 2
A, mixing: the composition according to the weight part of embodiment in the table 12 mixes, and puts into homogenizer after the mixing and stirs;
B, banburying: the composition of above-mentioned blend is put into the Banbury mixer banburying, and wherein banburying temperature is 170 ℃, and the banburying time is 10 minutes;
C, hot-forming: is 180 ℃ with the resin after the above-mentioned banburying in temperature, and pressure is the hot-forming thick sheet material of 1.0mm that obtains under the condition of 10MPa;
D, isothermal crystal: be that isothermal crystal obtained heat-proof polylactic acid blend after 70 minutes under 90 ℃ the condition in temperature with above-mentioned sheet material after hot-forming, it is as shown in table 2 to form different measured mechanical property and resistance toheats according to sample.
Embodiment 3
A, mixing: the composition according to the weight part of embodiment in the table 13 mixes, and puts into homogenizer after the mixing and stirs;
B, banburying: the composition of above-mentioned blend is put into the Banbury mixer banburying, and wherein banburying temperature is 190 ℃, and the banburying time is 5 minutes;
C, hot-forming: is 200 ℃ with the resin after the above-mentioned banburying in temperature, and pressure is the hot-forming thick sheet material of 1.0mm that obtains under the condition of 8MPa;
D, isothermal crystal: be that isothermal crystal obtained heat-proof polylactic acid blend after 120 minutes under 120 ℃ the condition in temperature with above-mentioned sheet material after hot-forming, it is as shown in table 2 to form different measured mechanical property and resistance toheats according to sample.
Embodiment 4～7
Composition according to the weight part of embodiment in the table 1 4～7 during mixing mixes; Temperature during isothermal crystal is 95 ℃, and crystallization time is 60 minutes.Other technical process is with embodiment 1; Repeat no more; It is as shown in table 2 to form different measured mechanical property and ageing-resistant performances according to sample.
The performance of the heat-proof polylactic acid blend that table 2: embodiment 1～7 is prepared
The heat-proof polylactic acid blend of the present invention's preparation not only has excellent heat resisting as can be seen from Table 2; And having an excellent mechanical property, the prepared heat-proof polylactic acid blend of the present invention is also biodegradable in addition.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (4)
1. the preparation method of a heat-proof polylactic acid blend is characterized in that, this method may further comprise the steps:
A, blend: get 100 parts of poly(lactic acid) by weight; Biodegradable heat-proof macromolecule material: 5～100 parts, described biodegradable heat-proof macromolecule material is poly butyric ester or 3-butyric ester-4-hydroxyl pentanoate copolymer or Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer or poly butylene succinate and the mixture of polyhydroxybutyrate ester mixture or 3-butyric ester-4-hydroxyl pentanoate copolymer and Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer or the mixture of poly butylene succinate, poly butyric ester and Succinic Acid/mutual-phenenyl two acid bromide two alcohol ester's multipolymer; Filler: 0～100 part is mixed, stirs after the mixing;
B, banburying: the composition of above-mentioned blend is put into the Banbury mixer banburying, and wherein banburying temperature is 150 ℃～190 ℃, and the banburying time is 5～20 minutes;
C, hot-forming: is 150 ℃～200 ℃ with the resin after the above-mentioned banburying in temperature, and pressure is hot-forming under the condition of 8～15MPa;
D, isothermal crystal: be that isothermal crystal obtained heat-proof polylactic acid blend after 5～120 minutes under 60 ℃～120 ℃ the condition with above-mentioned sheet material after hot-forming in temperature.
2. the preparation method of a kind of heat-proof polylactic acid blend according to claim 1 is characterized in that, the banburying temperature described in the step B is 170 ℃, and the banburying time is 10 minutes.
3. the preparation method of a kind of heat-proof polylactic acid blend according to claim 1 is characterized in that: the temperature during hot-forming described in the step C is 180 ℃, and pressure is 10MPa.
4. the preparation method of a kind of heat-proof polylactic acid blend according to claim 1 is characterized in that: the temperature during isothermal crystal described in the step D is 80 ℃～100 ℃, and crystallization time is 5～90 minutes.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101824210A (en) * | 2009-12-28 | 2010-09-08 | 天津国韵生物材料有限公司 | Multi-component film material capable of completely biological decomposition and preparation method thereof |
| CN101792579B (en) * | 2010-02-02 | 2012-04-04 | 淮安毅炀机械电子有限公司 | Biodegradable plastic motor shaft sleeve and preparation method thereof |
| CN102079849A (en) * | 2010-12-09 | 2011-06-01 | 楼仲平 | Biomass degradable material preparation method and straw |
| CN105602215B (en) * | 2016-01-26 | 2018-11-16 | 深圳市绿自然生物降解科技有限公司 | A kind of heat-resisting sheet material of biodegrade and preparation method thereof |
| CN108003581B (en) | 2017-11-27 | 2019-10-11 | 金发科技股份有限公司 | A kind of lactic acid composite material and its application |
| CN111393817B (en) * | 2020-05-08 | 2021-08-17 | 中国科学院长春应用化学研究所 | Completely-stereo high-toughness polylactic acid stereo compound and preparation method thereof |
| CN114311914A (en) * | 2021-12-13 | 2022-04-12 | 佛山碧嘉高新材料科技有限公司 | Biodegradable multilayer co-extrusion low-density heat-insulation sheet and preparation method and application thereof |
| CN114149668A (en) * | 2022-01-04 | 2022-03-08 | 浙江宏仕达科技股份有限公司 | Preparation method of PBAT (poly (butylene adipate-co-terephthalate)) based material with enhanced rigidity and toughness of mesomorphic phase |
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| CN101045810A (en) * | 2007-04-12 | 2007-10-03 | 上海交通大学 | Flexible modified method for poly beta-hydroxybutyric butyrate and poly beta-hydroxybutyric butyrate-beta hydroxyl valerate |
| CN101210101A (en) * | 2006-12-29 | 2008-07-02 | 天津国韵生物科技有限公司 | Composition containing polyhydroxy butyrate ester copolymer and polylactic acid for sheet, thin film, pipeline and fibrous material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101210101A (en) * | 2006-12-29 | 2008-07-02 | 天津国韵生物科技有限公司 | Composition containing polyhydroxy butyrate ester copolymer and polylactic acid for sheet, thin film, pipeline and fibrous material |
| CN101045810A (en) * | 2007-04-12 | 2007-10-03 | 上海交通大学 | Flexible modified method for poly beta-hydroxybutyric butyrate and poly beta-hydroxybutyric butyrate-beta hydroxyl valerate |
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