CN102453318A - Toughened polylactic resin composition and preparation method thereof - Google Patents
Toughened polylactic resin composition and preparation method thereof Download PDFInfo
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- CN102453318A CN102453318A CN2010105201047A CN201010520104A CN102453318A CN 102453318 A CN102453318 A CN 102453318A CN 2010105201047 A CN2010105201047 A CN 2010105201047A CN 201010520104 A CN201010520104 A CN 201010520104A CN 102453318 A CN102453318 A CN 102453318A
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Abstract
The invention discloses a toughened polylactic resin composition and a preparation method thereof. The composition comprises the following components: 100 weight parts of polylactic resin and 3 to 20 weight parts of toughening agent which are blended, wherein the toughening agent is powdered rubber with the average particle size of 20-900nm and a cross-linked structure, and has the gel content of 60 weight percent or above; and the rubber particles of the powdered rubber have homogenous structures. The preparation method comprises the following step of: melting and blending the components including the polylactic resin and the toughening agent in the proportion to obtain the polylactic resin composition. In the polylactic resin composition, powdered rubber particles are uniformly distributed in a matrix material polylactic resin, the material has stable properties, the impact property is obviously improved, the tensile property cannot be greatly reduced due to the addition of the powdered rubber, and the material has good processability under the condition of not adding a lubricant.
Description
Technical field
The present invention relates to the toughened resin compsn, further say, it is good to relate to a kind of shock resistance, and material property isostatic poly (lactic acid) composition and preparation method thereof.
Background technology
Polylactic resin (PLA also claims polylactide) is owing to the recyclability in source and the biodegradable performance of itself, and it is used and more and more receives people's attention.POLYACTIC ACID can form lactic acid like the starch that from corn, wheat and yam, extracts through lactobacillus-fermented from the renewable resources preparation in a year beyond oil or the gas material, finally forms POLYACTIC ACID through polymerization then.Polylactic resin can be degraded under some compost treatment condition fast, finally is decomposed into water and carbonic acid gas.Because POLYACTIC ACID comes from bio-based, to human non-toxic, environmentally friendly property, the polylactic resin product obtains people's attention gradually, poly-lactic acid products can be widely used in fields such as medical treatment, agricultural, packing, clothes, building and daily living article.
The heat-drawn wire of polylactic resin low (60 ℃); Impact property is poor, and the socle girder notch shock can only reach 30J/M not through modification the time, and because its modulus in flexure is very big; This just causes material very crisp in use and rigidity is excessive, has limited application.
China applies for a patent in (application number 200810241319.8) and utilizes urethane to come plasticizing polylactic acid; Find that urethane has good toughening effect to POLYACTIC ACID; When the weight polyurethane umber surpasses 11 parts (POLYACTIC ACID keeps 100 parts); Shock strength improves more than 100%, and is a lot of but the tensile strength of material descends.And because urethane is a kind of polymkeric substance, and size of particles is bigger, dispersed bad in POLYACTIC ACID, thus the homogeneity of material can be influenced.
Summary of the invention
To the above-mentioned defective of mentioning of the prior art; One of the object of the invention is to provide a kind of plasticizing polylactic acid resin combination; When not adding lubricant, when can obviously improve the impact property of polylactic resin, make it have good mechanical property and processing characteristics again; And the balancing performance of material is to satisfy the urgent day by day demand from the productive life each side.
Two of the object of the invention is to provide this kind plasticizing polylactic acid resin combination.Described plasticizing polylactic acid resin combination includes the polylactic resin and the toughner of blend.In polylactic resin is 100 parts by weight; Toughner 3～20 parts by weight, preferred 5～18 parts by weight.
Polylactic resin as toughness reinforcing matrix resin of the present invention comprises the POLYACTIC ACID by prepared in various methods in the prior art.Because lactic acid has two kinds of optically active isomers; Be commonly called " D " and " L " enantiomorph; Therefore there are three kinds of configurations in rac-Lactide; That is: dimeric " the L-rac-Lactide " of two L-lactic acid molecules, the dimer of two D-lactic acid molecules " D-rac-Lactide ", and by 1 L_ lactic acid molecules and 1 " meso-rac-Lactide " dimer that the D-lactic acid molecules constitutes.POLYACTIC ACID used among the present invention is for having-CH (CH
3) polymkeric substance of repeating unit of C (O) O-, can be the L-lactic acid of arbitrary proportion and the polymkeric substance that D-lactic acid obtains, no matter these repeating units are how to constitute this polylactic resin.
In the production process of reality, polylactic resin can adopt known methods such as polycondensation method, ring-opening polymerization method.Polycondensation method is about to the polycondensation of directly dewatering of L-lactic acid or D-lactic acid or their mixture; The ring-opening polymerization method is about to the rac-Lactide open loop and carries out polymerization, uses polymerization regulator to regulate molecular weight in case of necessity.Be used for POLYACTIC ACID of the present invention, its weight-average molecular weight is 80,000～400,000.
Polylactic resin as matrix resin of the present invention can also include other monomers that can carry out copolymerization with rac-Lactide or lactic acid, like oxyalkylene (comprising oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran etc.) or annular lactone or carbonic ether.The content that these repeating units generally can account for the PLA resin is 0～10wt%, is preferably 0～5wt%.
In addition; As other compounds that can also comprise in the POLYACTIC ACID of matrix resin of the present invention through the melt strength of polymerization method molecular weight that add, that can improve POLYACTIC ACID, raising POLYACTIC ACID, as: isocyanic ester, acid anhydrides, epoxy compounds, organic peroxy compound.More concrete, described isocyanic ester comprises diphenylmethanediisocyanate (MDI), 2,4 toluene diisocyanate (TDI)/eylylene diisocyanate (XDI).Described organo-peroxide comprises alkyl peroxide, ketone peroxide, ester class superoxide, acyl class superoxide.
Said toughner in the plasticizing polylactic acid resin combination of the present invention is that median size is 20～900nm, powdered rubber with crosslinking structure, and its gel content is 60wt% or higher, preferred 75wt% or higher, more preferably 90wt% or higher.The rubber grain of said powdered rubber is equal phase structure.Said powdered rubber median size is preferably 30～500nm, more preferably 100～200nm.The kind of said powdered rubber is selected the rubber good with the polylactic resin consistency for use, at least a as in the following kind: tree elastomer, polyacrylic rubber, paracril.
Powdered rubber described in the present invention can be selected the various powdered rubbers that meet the above-mentioned parameter requirement in the prior art for use, preferred one Chinese patent application CN 1402752A and the disclosed fully vulcanized powder rubber of CN 1383439A.This kind fully vulcanized powder rubber is meant that gel content reaches 60wt% or higher, more preferably 75wt% or higher, and need not with separant after the drying is free flowable rubber micro mist.The median size of this fully vulcanized powder rubber is 20nm～2000nm.Each particulate in this fully vulcanized powder rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming.Under the observation of existing microtechnique, do not find layering in the particulate, divide the phenomenon that equates uneven phase.This powdered rubber is through with corresponding rubber latex cross-linking radiation and with rubber particles particle diameter fixed.
Powdered rubber according to the invention can also the preferred disclosed cross-linked powdered rubber of one Chinese patent application CN 1353131A.This kind cross-linked powdered rubber be a kind of be raw material with the cross-linking type synthetic rubber latex, through the dry powdered rubber that obtains.This cross-linked powdered rubber need not add separant both can unrestricted flow.Its median size is 50nm～300nm.Its gel content is consistent with gel content as the cross-linking type synthetic rubber latex of raw material, is 80wt% or higher, preferred 85wt% or higher.Each particulate in this cross-linked powdered rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and under the observation of existing microtechnique, does not find layering in the particulate, divides the phenomenon that equates uneven phase.
In order to improve ageing resistance, polylactic acid resin composition of the present invention also comprises oxidation inhibitor, and oxidation inhibitor can be selected resin various oxidation inhibitor commonly used in the prior art for use, and its consumption also is a conventional amount used.It is preferably composite oxidation inhibitor, by primary antioxidant with auxiliary antioxidant is composite forms.Primary antioxidant wherein is a hindered phenol compound, as: β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid octadecyl ester (antioxidant 1076), four [β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid] pentaerythritol ester (antioxidant 1010); Preferred antioxidant 1010.Auxiliary antioxidant is a phosphite ester compound, as: tricresyl phosphite (2, the 4-di-tert-butyl) esters (oxidation inhibitor 168), Tyox B (DLTP), thio-2 acid SUNSOFT Q-182S (DSTP); Preferred oxidation inhibitor 168.Total consumption of oxidation inhibitor is 100 parts by weight meters according to matrix resin, is 0.5～1.5 weight part, preferred 0.6～1.0 weight part.Wherein primary antioxidant and auxiliary antioxidant weight ratio are 1: 2～2: 1, preferred 1: 1.5～1.5: 1.
In addition; In the course of processing of plasticizing polylactic acid resin of the present invention, need not add lubricant, but the needs of the concrete processing of available basis; In the blend material, add processing aid commonly used in the polylactic resin modification technology; For example: softening agent, toughener, fire retardant, static inhibitor, dispersion agent, nucleator, weighting agent, pigment etc., its consumption is conventional amount used, or adjusts according to practical requirements.
Two of the object of the invention is to provide the preparation method of this kind plasticizing polylactic acid resin combination, realizes through following technical scheme: comprise the component that comprises said polylactic resin, toughner is made described polylactic acid resin composition by said content melt blending.
In the course of processing of polylactic acid resin composition of the present invention; Material melt blending temperature is used blending temperature in the common polylactic resin processing; Should select not only guaranteeing the complete fusion of matrix resin but also can not make in the scope of its decomposition; Be generally 165 ℃～210 ℃, preferred processing temperature is 170 ℃～190 ℃.In addition, according to the processing needs, can in the blend material, add some auxiliary agents such as dispersion agent, surface treatment agent etc. commonly used in the polylactic resin course of processing in right amount, its consumption is conventional amount used, or adjusts according to practical requirements.
More concrete, its step of preparation method of the present invention normally mixes all components earlier, carries out melt blending then, and step is following:
A. earlier with polylactic resin in 45 ℃～60 ℃ vacuum drying oven dry 24 hours;
B. polylactic resin, powdered rubber, oxidation inhibitor, lubricant are carried out proportioning by a certain percentage, in impeller, stir then;
C. carry out melt blending at twin screw extruder and extrude, 165 ℃～210 ℃ of extrusion temperatures, 200～300 rev/mins of screw speeds;
D. cooling, granulation, drying;
E. inject sample preparation.
The mixing equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, like stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the aforesaid method of the present invention, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Plasticizing polylactic acid resin of the present invention adds powdered rubber as toughner; Not only under the prerequisite of other balancing performances that keep poly (lactic acid) composition, improve the shock resistance of material, and can under the situation of not adding lubricant, significantly improve the processing characteristics of POLYACTIC ACID.This point is embodied in twin screw when extruding, and polylactic resin is extruded easily, production efficiency is high, in injector, carries easily when more being embodied in the injection sample preparation.Because the POLYACTIC ACID constitutional features determined its second-order transition temperature very high, about 60 ℃, so the flexural strength of POLYACTIC ACID and modulus in flexure are very big at normal temperatures, its modulus in flexure can reach more than the 3.0GPa.And POLYACTIC ACID has very high modulus; When extruding and inject sample preparation; Feeding section and delivery end at screw rod; Mobile modulus poor, that it is too high can make screw rod send sharp-pointed grating, cause moment of torsion too high because of friction because POLYACTIC ACID in the short period of time can't fusion, and locking or the screw rod that often causes screw rod rotates not smooth, cause processing difficulties and production efficiency lowly.So in common processing, pure POLYACTIC ACID is extruded, need be added a certain amount of lubricant when injecting.Among the present invention, described toughner is powdered rubber, is a kind of rubber bodies, and the second-order transition temperature of itself very low (being lower than normal temperature) can obviously reduce the second-order transition temperature (T of material in the time of in joining POLYACTIC ACID
g), and the powdered rubber that is added, as: propenoate powder rubber and powder nbr rubber etc. has certain polarity; Good with the consistency of PLA, poly-lactic acid mixture extrude, the mobile of blanking section, delivery end obviously improves when injecting, sharp-pointed grating disappears; Under the situation that does not need lubricant; Mixture can be in screw rod smooth delivery of power, extrude, obviously improved the processibility and the working (machining) efficiency of POLYACTIC ACID, reduced production cost.On the whole, the preparation method of plasticizing polylactic acid resin of the present invention, technology is simple, good processability, the plasticizing polylactic acid resin of gained has good strong and unyielding balance.
Embodiment
Embodiment 1～5
With full propylene sulfide acid esters powdered rubber (trade mark VP301; The Sinopec Beijing Chemical Research Institute, median size is 200nm, gel content 85wt%), (trade mark 2002D of the polylactic resin behind vacuum drying; U.S. Natureworks company), oxidation inhibitor (1010 and 168 composite; Switzerland Ciba company) and lubricant stearic acid zinc (Tianjin fine chemistry industry institute) according to certain mixed evenly after, mixture joined carries out melt blending in the twin screw extruder (German WP company, model ZSK-25) and extrude the back granulation; Extrusion temperature is 165 ℃～190 ℃, and screw speed is 250～300 rev/mins.Its concrete prescription is seen table 1, and wherein each component concentration is all in parts by weight.
Material is extruded, pelletizing, in 45 ℃～60 ℃ vacuum drying oven dry 24 hours then.Become the standard batten 180 ℃～210 ℃ injected, carry out the test of mechanical property.Each performance test standard is following: tensile property is pressed ASTM D638-2003 test; Bending property is pressed ASTM D790-2007 test; Impact property is pressed the ASYMD256-2006 test; Heat-drawn wire is tested according to ASTM D 648-2007.Test result is as shown in table 1.It is as shown in table 3 that the moment of torsion of the compsn of gained reduces the result.
Comparative Examples 1:
Except that concrete prescription difference, all the other conditions are all identical with previous embodiment 1～5.Concrete prescription is seen table 1, and wherein each component concentration is all in parts by weight.And it is carried out the test of mechanical property, and testing standard and test process are with embodiment 1～5, and test result is as shown in table 1; It is as shown in table 3 that its moment of torsion reduces the result.
Embodiment 6～9:
To vulcanize powder nbr rubber (trade mark VP401 entirely; The Sinopec Beijing Chemical Research Institute, median size is for being respectively 200nm, 300nm, 500nm, 800nm, gel content 85wt%), (trade mark 2002D of the polylactic resin behind vacuum drying; U.S. Natureworks company), oxidation inhibitor (1010 and 168 composite; Switzerland Ciba company) and lubricant stearic acid zinc (Tianjin fine chemistry industry institute) according to certain mixed evenly after, mixture joined carries out melt blending in the twin screw extruder (German WP company, model ZSK-25) and extrude the back granulation; Extrusion temperature is 165 ℃～190 ℃, and screw speed is 250～300 rev/mins.Concrete prescription is seen table 2, and wherein each component concentration is all in parts by weight.
Material is extruded, pelletizing, in 45 ℃～60 ℃ vacuum drying oven dry 24 hours then.Become the standard batten 180 ℃～210 ℃ injected, carry out the test of mechanical property, testing standard is with embodiment 1～5, and test result is as shown in table 2.It is as shown in table 3 that its moment of torsion reduces the result.
The moment of torsion of table 3 embodiment 1～9, Comparative Examples 1 reduces data relatively
| Routine number | Torque drop low value (%) |
| Comparative Examples 1 | 65～75％ |
| Embodiment 1 | 55～65％ |
| Embodiment 2 | 50～60％ |
| Embodiment 3 | 45～60％ |
| Embodiment 4 | 40～55％ |
| Embodiment 5 | 40～50％ |
| Embodiment 6 | 50～60％ |
| Embodiment 7 | 45～55％ |
| Embodiment 8 | 40～50％ |
| Embodiment 9 | 40～50％ |
Can find out that from table 1～3 compsn of the present invention had both been held good processing properties under the situation that need not add lubricant.Because the particle diameter of the powdered rubber that the present invention uses is very little; And be homogeneous phase particle with crosslinking structure; With the polylactic resin melt blending time, rubber particles is evenly distributed in the body material polylactic resin, and material property is stable; Impact property is improved significantly, and tensile property can not descend because of the adding of powdered rubber significantly; Adding powdered rubber separately, do not make under the situation with lubricator simultaneously, can either obviously reduce the modulus in flexure and the second-order transition temperature (Tg) of polylactic resin, its processing characteristics is significantly improved.
Claims (10)
1. plasticizing polylactic acid resin combination includes the following component of blend: polylactic resin 100 parts by weight, toughner 3～20 parts by weight; Wherein, described toughner is median size 20～900nm, has the powdered rubber of crosslinking structure that its gel content is 60wt% or higher; The kind of said powdered rubber is selected from least a of following kind: tree elastomer, polyacrylic rubber, paracril; The rubber grain of said powdered rubber is equal phase structure.
2. polylactic acid resin composition according to claim 1 is characterized in that:
The following component that includes blend: polylactic resin 100 parts by weight, toughner 5～18 parts by weight.
3. polylactic acid resin composition according to claim 1 is characterized in that:
The median size of said powdered rubber is 30nm～500nm.
4. polylactic acid resin composition according to claim 3 is characterized in that:
The median size of said powdered rubber is 100～200nm.
5. polylactic acid resin composition according to claim 1 is characterized in that:
The gel content of said powdered rubber is 75wt% or higher.
6. polylactic acid resin composition according to claim 5 is characterized in that:
The gel content of said powdered rubber is 90wt% or higher.
7. according to the arbitrary described polylactic acid resin composition of claim 1～6, it is characterized in that:
Described POLYACTIC ACID weight-average molecular weight is 80,000～400,000.
8. polylactic acid resin composition according to claim 7 is characterized in that:
Described powdered rubber is selected from least a in fully vulcanized powder rubber, the cross-linked powdered rubber.
9. polylactic acid resin composition according to claim 7 is characterized in that:
Include oxidation inhibitor; In polylactic resin by 100 parts by weight, oxidation inhibitor 0.5～1.5 parts by weight;
Described oxidation inhibitor is by primary antioxidant and auxiliary antioxidant is composite forms; Described primary antioxidant is a Hinered phenols, and described auxiliary antioxidant is phosphorous acid esters; The compound proportion of described primary antioxidant and auxiliary antioxidant is weight ratio 1: 2～2: 1.
10. a preparation method who prepares the described plasticizing polylactic acid resin combination of one of claim 1～9 is characterized in that: comprise the component that comprises said polylactic resin, toughner is made described polylactic acid resin composition by said content melt blending.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN103589126A (en) * | 2013-11-28 | 2014-02-19 | 青岛科技大学 | Nitrile rubber/polylactic acid thermoplastic vulcanizate and preparation method |
| CN105670252A (en) * | 2016-02-02 | 2016-06-15 | 青岛科技大学 | Toughened polylactic acid composition and preparation method thereof |
| CN107163526A (en) * | 2017-06-20 | 2017-09-15 | 苏州奥宇包装科技有限公司 | A kind of acrylonitrile butadiene rubber modified lactic acid composite material and preparation method thereof |
| CN107189304A (en) * | 2017-07-04 | 2017-09-22 | 青岛科技大学 | A kind of low resilience memory foam material and preparation method thereof |
| CN109836614A (en) * | 2019-01-31 | 2019-06-04 | 中粮集团有限公司 | Composite thermal stabilizer, the method for lactide ring-opening polymerisation production polylactic acid and polylactic acid and application |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN103467950B (en) * | 2013-09-29 | 2015-09-02 | 成都新柯力化工科技有限公司 | A kind of 3D prints modified polylactic acid material and preparation method thereof |
| CN103589126A (en) * | 2013-11-28 | 2014-02-19 | 青岛科技大学 | Nitrile rubber/polylactic acid thermoplastic vulcanizate and preparation method |
| CN103589126B (en) * | 2013-11-28 | 2015-08-05 | 青岛科技大学 | A kind of Nitrile rubber/polylactic acid thermoplastic vulcanizate and preparation method thereof |
| CN105670252A (en) * | 2016-02-02 | 2016-06-15 | 青岛科技大学 | Toughened polylactic acid composition and preparation method thereof |
| CN107163526A (en) * | 2017-06-20 | 2017-09-15 | 苏州奥宇包装科技有限公司 | A kind of acrylonitrile butadiene rubber modified lactic acid composite material and preparation method thereof |
| CN107189304A (en) * | 2017-07-04 | 2017-09-22 | 青岛科技大学 | A kind of low resilience memory foam material and preparation method thereof |
| CN107189304B (en) * | 2017-07-04 | 2019-05-10 | 青岛科技大学 | A kind of low resilience memory foam material and preparation method thereof |
| CN109836614A (en) * | 2019-01-31 | 2019-06-04 | 中粮集团有限公司 | Composite thermal stabilizer, the method for lactide ring-opening polymerisation production polylactic acid and polylactic acid and application |
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Application publication date: 20120516 |