CN102504507A - Polylactic acid toughening and modifying agent and preparation method thereof - Google Patents
Polylactic acid toughening and modifying agent and preparation method thereof Download PDFInfo
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- CN102504507A CN102504507A CN2011103513886A CN201110351388A CN102504507A CN 102504507 A CN102504507 A CN 102504507A CN 2011103513886 A CN2011103513886 A CN 2011103513886A CN 201110351388 A CN201110351388 A CN 201110351388A CN 102504507 A CN102504507 A CN 102504507A
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Abstract
The invention relates to a polylactic acid toughening and modifying agent and a preparation method thereof. The method comprises the following steps of: proportioning the raw materials consisting of polyalcohol and hydroxy acid or polyacid/anhydride according to the mass ratio of 1:0.5 to 1:2,000, and carrying out condensation polymerization at 130-210 DEG C for 0.5-24 h to prepare a polyester polyol polylactic acid toughening and modifying agent polymer. Compared with the prior art, the polylactic acid toughening and modifying agent disclosed by the invention has the advantages of being nontoxic, harmless, completely biodegraded, free from negative effects on the environment and human health and the like.
Description
Technical field
The present invention relates to a kind of material and method of technical field of polymer materials, specifically is a kind of preparation method of POLYACTIC ACID plasticized modifier.
Background technology
Along with high speed development of national economy, the use of macromolecular material has been penetrated into people's various fields in life, brings great convenience for our life.Yet macromolecular material major part commonly used is a raw material with the oil, is discarded into after the use to be difficult to biological degradation in the environment, thereby has caused the serious environmental pollution problem, like " white pollution ".Be accompanied by worsening shortages and the people of the petroleum resources raising that requires with quality of life of showing great attention to environmental problem, exploitation totally biodegradable property macromolecular material has become studies focus now both at home and abroad.
(polylactic acid is to be converted into glucose by the starch that renewable plant resources such as corn, yam extracts PLA) to POLYACTIC ACID, and glucose becomes lactic acid after fermentation, aggregate into POLYACTIC ACID by lactic acid through single stage method or two-step approach again.The glass transition temperature Tg of PLA is approximately 55 ℃, and fusing point Tm is approximately 180 ℃, and excellent biological compatibility is arranged; And can complete biodegradable, the final product after the degraded is carbonic acid gas (CO2) and water, thereby; Nontoxic, can not pollute after the use environment, be a kind of green plastic.Simultaneously, the tensile strength of PLA, modulus of compression height, transparent good; Forming process is convenient, can on general processing units, extrude as synthetic macromolecules such as PP, PS and PET, forming process such as injection moulding, bottle blowing, thermoforming produce film, sheet material, bottle and various heat product and injection moulded products.In a word, PLA not only environmental friendliness, be widely used, see the consumption that can also reduce from its source to the Nonrenewable resources oil, the title of " green plastic " good reputation is arranged, caused people's extensive interest.But the shortcoming of PLA shows as mainly that matter is hard and crisp, shock resistance, wetting ability are poor, and degradation cycle is difficult to control.This has limited its application greatly, particularly at packaging field.Therefore, the modification of PLA is become the research focus, particularly aspect toughening modifying.
At present, doing a large amount of work aspect the toughness that improves PLA.As, adopting the common plasticizers citric acid ester type, various monomerics improve the toughness of PLA as glycerine, polylactic acid low polymer (OLA), lower molecular weight PEG and PLA blend.Though this method is simple to operate, can improve the toughness of PLA to a certain extent.But the poor stability of material, lower-molecular substance very easily permeates in material use and storage process, and transport phenomena finally makes material property descend.
Retrieval through to prior art finds that Kelly S.Anderson etc. has synthesized POLYACTIC ACID-polyethylene block multipolymer (PLLA-PE) earlier, makes solubilizing agent with linear low density polyethylene (LLDPE) and PLA blending toughening PLA with this segmented copolymer then.Peng Zhao etc. come toughness reinforcing PLA with blend such as PLA and PBS, PBAT.Though above method can well solve the phenomenon of small molecules softening agent infiltration migration, second component of being introduced is often poor with the consistency of PLA, causes that the transparency of PLA is seriously damaged after the modification.The Vilaterm of introducing simultaneously partly is difficult to biological degradation.
Further retrieval finds that Chinese patent document number CN1662603A discloses a kind of polylactic acid base polymer composition, its molding and film.Have polyethers and/or the segmental fluidizer of polyester joins in the POLYACTIC ACID through synthetic, form to have enough flexible polylactic acid base polymer composition.American documentation literature US2005/0159583A1 discloses a kind of POLYACTIC ACID plasticized modifier and mixture thereof.This method has at first been synthesized a kind of A-B type segmented copolymer, then this segmented copolymer is added among the PLA to reach the purpose of toughness reinforcing PLA.And kind and molecular weight size through changing A and B obtain optimum toughening effect.Though more than these methods can realize seldom producing fluidizer/toughner volatilization, ooze out, run off and bleach when heating and problem such as muddiness.But the cost of synthetic required fluidizer is higher, causes final polylactic acid base polymer composition cost to increase easily, is unfavorable for increasing its market competitiveness.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of nontoxic, fully biodegradable to be provided, and can not bring POLYACTIC ACID plasticized modifier of negative impact and preparation method thereof to environment and HUMAN HEALTH.
The object of the invention can be realized through following technical scheme: a kind of POLYACTIC ACID plasticized modifier is characterized in that the starting material of this properties-correcting agent comprise that the amount of substance ratio is 1: 0.5-1: 2000 polyvalent alcohol and alcohol acid or polyprotonic acid/acid anhydrides.
Described polyvalent alcohol is Viscotrol C, gather a kind of or its compsn in Viscotrol C, epoxy soybean oil, glycerine, linseed oil, the plam oil.
Described alcohol acid or polyprotonic acid/acid anhydrides are a kind of or its compsn in L-lactic acid, DL-lactic acid, D-lactic acid, oxalic acid, Succinic Acid, hexanodioic acid, Succinic anhydried, the dodecyl diacid.
A kind of preparation method of POLYACTIC ACID plasticized modifier; It is characterized in that; This method may further comprise the steps: is 1 with alcohol acid or polyprotonic acid/acid anhydrides by the amount of substance ratio with raw polyol: 0.5-1: 2000 carry out proportioning, under 130-210 ℃, carry out polycondensation 0.5-24h and make polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance.
Described polycondensation is carried out in liquid solvent, and the consumption of this liquid solvent is the 20-60% of raw material total mass.
Described liquid solvent is a kind of or its combination in benzene,toluene,xylene or the perhydronaphthalene.
Described polycondensation is carried out under rare gas element or vacuum, and described rare gas element is nitrogen or argon gas.
Described polycondensation is carried out under the condition that adds catalyzer, and the add-on of described catalyzer is the 0.01-1.5% of raw material total mass.
Described catalyzer is stannous octoate, tin protochloride, 2 ethyl hexanoic acid tin or Zinic stearas.
The number-average molecular weight of described polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance is 100-100000.
The properties-correcting agent that the present invention adopts raw material preparing nontoxic, with low cost to obtain not only can solve phenomenons such as migration of the prior art, infiltration.And the properties-correcting agent of gained is also nontoxic, fully biodegradable, can not bring negative impact to environment and HUMAN HEALTH.Compared with prior art, the present invention has the following advantages:
1, the consistency of prepared toughner and POLYACTIC ACID is good, can well solve migration, phenomenon of osmosis that the toughness reinforcing PLA of small molecules is brought.
2, prepared toughner cost is low, nontoxic, and fully biodegradable, can not bring harm to environment and HUMAN HEALTH.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment given detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
Viscotrol C and L-ammonium lacate amount of substance were fed intake than 1: 2, and tin protochloride is a catalyzer, and the reaction certain hour obtains toughner A after the purification of products under 150 ℃ of certain vacuum degree, and GPC records number-average molecular weight and is 6810, and is for use.
Embodiment 2
To gather Viscotrol C feeds intake than 1: 3 with DL-ammonium lacate amount of substance; Stannous octoate is a catalyzer, and temperature of reaction is 170 ℃, earlier reaction for some time under nitrogen atmosphere; The back is reaction under the certain vacuum degree; Reaction finish after product through purify toughner B, GPC records number-average molecular weight and is 18750, and is for use.
Embodiment 3
Viscotrol C and Succinic Acid are fed intake than 1: 1.5 by amount of substance, and 180 ℃ of following direct condensation, reaction is reaction for some time under nitrogen atmosphere earlier; The back is reaction under the certain vacuum degree; Get toughening agent C after reaction finishes, GPC records number-average molecular weight and is 3052, and is for use.
Embodiment 4
Glycerine and Succinic anhydried are fed intake than 1: 1.5 by amount of substance, and 170 ℃ of following direct condensation, reaction is reaction for some time under nitrogen atmosphere earlier; The back is reaction under the certain vacuum degree; Get toughner D after reaction finishes, GPC records number-average molecular weight and is 3865, and is for use.
PLA (provided by NatureWorks company, the trade mark is 2002D) is dried by the fire 12h under 50 ℃ of vacuum, after PLA and toughner A are carried out blend by mass ratio 95/5 in Haake, blending temperature is 150-170 ℃, rotating speed 60rad/min, the blend time is 5min.The blend appearance of gained is carried out compressing tablet on vulcanizing press, 180 ℃ of molding temperatures, hot pressing 2min under 10MPa, the 15min that colds pressing is pressed into 1mm and 3mm appearance.After process tensile bars respectively and impact batten.
In like manner, change toughner A into toughner B, C, D respectively, both mass ratioes are respectively 90/10,90/10,85/15, and other conditions are identical.
The contrast experiment
PLA at 50 ℃ of following vacuum baking 12h, is added in the Haake and carries out banburying, on vulcanizing press, be pressed into the sheet of 1mm and 3mm then respectively, process tensile bars and impact batten.Mold pressing parameter and aforementioned the same in identical on Haake banburying and the vulcanizing press.
Among the above embodiment blend appearance mechanical property as the table:
Embodiment 5
A kind of preparation method of POLYACTIC ACID plasticized modifier; This method may further comprise the steps: is to carry out proportioning at 1: 0.5 with raw material epoxy soybean oil and oxalic acid by the amount of substance ratio; Add in the benzene; The add-on of benzene is 20% of a raw material total mass, under 130 ℃, carries out polycondensation 24h and makes polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance.
Embodiment 6
A kind of preparation method of POLYACTIC ACID plasticized modifier; This method may further comprise the steps: with raw material linseed oil and D-ammonium lacate amount of substance ratio is to carry out proportioning at 1: 2000; Add in the toluene; The add-on of toluene is 60% of a raw material total mass, under 210 ℃, carries out polycondensation 0.5h and makes polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance.
Embodiment 7
A kind of preparation method of POLYACTIC ACID plasticized modifier; This method may further comprise the steps: with raw material plam oil and D-ammonium lacate amount of substance ratio is to carry out proportioning at 1: 1; Add catalyzer 2 ethyl hexanoic acid tin; Add-on is 0.01% of a raw material total mass, under 200 ℃, carries out polycondensation 0.5h and makes polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance, and the number-average molecular weight of gained polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance is 100.
Embodiment 8
A kind of preparation method of POLYACTIC ACID plasticized modifier; This method may further comprise the steps: with raw material plam oil and L-ammonium lacate amount of substance ratio is to carry out proportioning at 1: 1000; Add the catalyzer Zinic stearas; Add-on is 1.5% of a raw material total mass, under 150 ℃, carries out polycondensation 0.5h and makes polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance, and the number-average molecular weight of gained polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance is 100000.
Claims (10)
1. a POLYACTIC ACID plasticized modifier is characterized in that, the starting material of this properties-correcting agent comprise that the amount of substance ratio is 1: 0.5-1: 2000 polyvalent alcohol and alcohol acid or polyprotonic acid/acid anhydrides.
2. a kind of POLYACTIC ACID plasticized modifier according to claim 1 is characterized in that, described polyvalent alcohol is Viscotrol C, gather a kind of or its compsn in Viscotrol C, epoxy soybean oil, glycerine, linseed oil, the plam oil.
3. a kind of POLYACTIC ACID plasticized modifier according to claim 1; It is characterized in that described alcohol acid or polyprotonic acid/acid anhydrides are a kind of or its compsn in L-lactic acid, DL-lactic acid, D-lactic acid, oxalic acid, Succinic Acid, hexanodioic acid, Succinic anhydried, the dodecyl diacid.
4. the preparation method of a POLYACTIC ACID plasticized modifier according to claim 1; It is characterized in that; This method may further comprise the steps: is 1 with alcohol acid or polyprotonic acid/acid anhydrides by the amount of substance ratio with raw polyol: 0.5-1: 2000 carry out proportioning, under 130-210 ℃, carry out polycondensation 0.5-24h and make polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance.
5. the preparation method of a kind of POLYACTIC ACID plasticized modifier according to claim 4 is characterized in that, described polycondensation is carried out in liquid solvent, and the consumption of this liquid solvent is the 20-60% of raw material total mass.
6. the preparation method of a kind of POLYACTIC ACID plasticized modifier according to claim 5 is characterized in that, described liquid solvent is a kind of or its combination in benzene,toluene,xylene or the perhydronaphthalene.
7. the preparation method of a kind of POLYACTIC ACID plasticized modifier according to claim 4 is characterized in that, described polycondensation is carried out under rare gas element or vacuum, and described rare gas element is nitrogen or argon gas.
8. the preparation method of a kind of POLYACTIC ACID plasticized modifier according to claim 4 is characterized in that, described polycondensation is carried out under the condition that adds catalyzer, and the add-on of described catalyzer is the 0.01-1.5% of raw material total mass.
9. the preparation method of a kind of POLYACTIC ACID plasticized modifier according to claim 8 is characterized in that, described catalyzer is stannous octoate, tin protochloride, 2 ethyl hexanoic acid tin or Zinic stearas.
10. the preparation method of a kind of POLYACTIC ACID plasticized modifier according to claim 4 is characterized in that, the number-average molecular weight of described polyester polyol class POLYACTIC ACID plasticized modifier polymkeric substance is 100-100000.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146160A (en) * | 2013-03-14 | 2013-06-12 | 上海交通大学 | Fully-biodegradable composition and preparation method thereof |
| CN103726220A (en) * | 2013-12-17 | 2014-04-16 | 浙江理工大学 | Preparation method of toughened polylactic acid melt-blown nonwoven cloth |
| CN103965600A (en) * | 2014-05-23 | 2014-08-06 | 上海交通大学 | Method for toughening heat-resistant modified polylactic acid with plant-base composite environment-friendly modifier |
| CN104231582A (en) * | 2014-10-17 | 2014-12-24 | 中国科学院长春应用化学研究所 | Polylactic acid base composite material and preparation method thereof |
| CN104312121A (en) * | 2014-11-19 | 2015-01-28 | 威海共达塑胶化工制品有限公司 | High-toughness transparent polylactic acid film and preparing method thereof |
| CN106336636A (en) * | 2016-10-14 | 2017-01-18 | 西南大学 | Preparation method of polylactic acid/epoxy soybean oil resin alloy and product |
| CN106432698A (en) * | 2016-10-17 | 2017-02-22 | 杭州铭众生物科技有限公司 | Method for preparing polyglycolic acid through glycolic acid polymerization |
| CN106633017A (en) * | 2016-10-17 | 2017-05-10 | 杭州铭众生物科技有限公司 | Method for preparing modified polylactic acid |
| CN106674942A (en) * | 2017-01-05 | 2017-05-17 | 深圳立山环保材料有限公司 | Polylactic resin-based biodegradable plastics |
| CN114163621A (en) * | 2021-12-08 | 2022-03-11 | 合肥飞木生物科技有限公司 | Preparation method and application of epoxidized soybean oil and glycolide copolymerization bio-based elastomer |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103146160A (en) * | 2013-03-14 | 2013-06-12 | 上海交通大学 | Fully-biodegradable composition and preparation method thereof |
| CN103146160B (en) * | 2013-03-14 | 2015-09-09 | 上海交通大学 | Complete biodegradable composition and method of making the same |
| CN103726220A (en) * | 2013-12-17 | 2014-04-16 | 浙江理工大学 | Preparation method of toughened polylactic acid melt-blown nonwoven cloth |
| CN103965600A (en) * | 2014-05-23 | 2014-08-06 | 上海交通大学 | Method for toughening heat-resistant modified polylactic acid with plant-base composite environment-friendly modifier |
| CN103965600B (en) * | 2014-05-23 | 2016-07-06 | 上海交通大学 | A kind of method of the toughness reinforcing heat resistance modified polylactic acid of plant base composite environment-friendly modifying agent |
| CN104231582A (en) * | 2014-10-17 | 2014-12-24 | 中国科学院长春应用化学研究所 | Polylactic acid base composite material and preparation method thereof |
| CN104231582B (en) * | 2014-10-17 | 2016-06-01 | 中国科学院长春应用化学研究所 | A kind of polylactic acid-base composite material and its preparation method |
| CN104312121A (en) * | 2014-11-19 | 2015-01-28 | 威海共达塑胶化工制品有限公司 | High-toughness transparent polylactic acid film and preparing method thereof |
| CN106336636A (en) * | 2016-10-14 | 2017-01-18 | 西南大学 | Preparation method of polylactic acid/epoxy soybean oil resin alloy and product |
| CN106336636B (en) * | 2016-10-14 | 2018-06-29 | 西南大学 | The preparation method and product of a kind of polylactic acid/epoxy soybean oil resin alloy |
| CN106432698A (en) * | 2016-10-17 | 2017-02-22 | 杭州铭众生物科技有限公司 | Method for preparing polyglycolic acid through glycolic acid polymerization |
| CN106633017A (en) * | 2016-10-17 | 2017-05-10 | 杭州铭众生物科技有限公司 | Method for preparing modified polylactic acid |
| CN106432698B (en) * | 2016-10-17 | 2019-02-26 | 杭州铭众生物科技有限公司 | The method that hydroxyacetic acid polymerization prepares polyglycolic acid |
| CN106633017B (en) * | 2016-10-17 | 2019-03-29 | 杭州铭众生物科技有限公司 | A kind of preparation method of polydactyl acid |
| CN106674942A (en) * | 2017-01-05 | 2017-05-17 | 深圳立山环保材料有限公司 | Polylactic resin-based biodegradable plastics |
| CN106674942B (en) * | 2017-01-05 | 2018-10-19 | 深圳立山环保材料有限公司 | A kind of biodegradable plastic based on polylactic resin |
| CN114163621A (en) * | 2021-12-08 | 2022-03-11 | 合肥飞木生物科技有限公司 | Preparation method and application of epoxidized soybean oil and glycolide copolymerization bio-based elastomer |
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Application publication date: 20120620 |