CN105492543A - Biodegradable impact-modified polymer compositions - Google Patents
Biodegradable impact-modified polymer compositions Download PDFInfo
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- CN105492543A CN105492543A CN201480047462.7A CN201480047462A CN105492543A CN 105492543 A CN105492543 A CN 105492543A CN 201480047462 A CN201480047462 A CN 201480047462A CN 105492543 A CN105492543 A CN 105492543A
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- Prior art keywords
- core
- impact modifier
- biodegradable polymer
- impact
- polymer composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Abstract
The invention relates to an impact-modified bio-degradable polymer composition having large particle size impact modifiers dispersed in a continuous biodegradable polymer phase. The impact modifiers have a core-shell morphology and may have average sizes of greater than 250 nm. The impact-modified composition has good impact properties and low haze. The biodegradable polymer is preferably a polylactide or polyhydroxy butyrate. The composition comprises 30-99.9 weight percent of degradable polymer and 0.1 to 15 weight percent of one or more impact modifiers.
Description
Invention field
The present invention relates to the biodegradable polymer composition of impact modification, these polymer compositions have the particle size impact be scattered in the biodegradable polymer phase of continuous print and hit properties-correcting agent.These anti-impact modifiers have core-shell structure copolymer form and have the mean size being greater than 250nm.The composition of this impact modification has good impact property and low mist degree.
background of invention
The global concern growing to persistent plastic waste creates very large interest to the biodegradable polymkeric substance for everyday use.Biodegradable polymkeric substance based on poly(lactic acid) (PLA) is one of the most attractive material standed for, because they can easily be produced by renewable agricultural origin (such as corn).Recently by agricultural origin, the development manufactured economically in this polymkeric substance has accelerated the appearance of this base polymer in biodegradable plastics commodity market.
The acrylic copolymer having disclosed straight chain with the blend of biological polymer (such as polylactide) in be used as processing aid.(U. S. application 2007-0179218).Disclosed linear acrylic copolymers does not provide gratifying impact property.Additive such as anti-impact modifier can be used in this polylactide composition.
For many biodegradable polymkeric substance (such as polylactide), a problem is the character be highly brittle of pure polymkeric substance.This characteristic result in the low-down impact property of finished article, far below desired by the suitable product performance.Known anti-impact modifier, as MBS (MBS) and vinylformic acid core-shell structure copolymer or segmented copolymer, improves the impact property of PVC and polycarbonate Alloys.
Segmented copolymer and core-shell polymer has been described in biodegradable polymkeric substance in PCT/US07/84502.Granularity is not mentioned in this application.
WO2008/051443 describes the polylactide resins of transparent impact modification.The bimodal core-shell structure copolymer anti-impact modifier of these resins has carried out modification, and the number average particle size of all particles and agglomerate is less than 210 nanometers.
Unexpectedly, have been found that the core-shell structure copolymer anti-impact modifier with the number average particle size being greater than 250 may be used in biodegradable plastics, and still achieve excellent impact modification and low mist degree.
summary of the invention
The present invention relates to biodegradable polymer composition, this polymer composition comprises:
A) one or more biodegradable polymkeric substance of 30 to 99.9 weight percents;
B) one or more biological polymers of 0-69.9 weight percent; And
C) one or more core-shell structure copolymer anti-impact modifiers of 0.1 to 15 weight percent,
Wherein said anti-impact modifier has the number average particle size being greater than 250nm.
This biodegradable polymer composition can be transparent or translucent, and preferably has the mist degree being less than 15.
detailed description of the invention
Biodegradable polymkeric substance of the present invention can be single biodegradable polymkeric substance or the mixture of biodegradable polymkeric substance.Some examples of biodegradable polymkeric substance useful in the present invention include but not limited to polylactide and poly butyric ester.This biodegradable composition comprises this one or more biodegradable polymkeric substance of 30 to 99.9 weight percents.
Preferred polylactide and poly butyric ester can be normal or low-molecular-weight.
Except this one or more biodegradable polymkeric substance, other biological polymkeric substance can also be there is, such as but not limited to starch, Mierocrystalline cellulose and polysaccharide.Other biological polymer can also be there is, such as but not limited to polycaprolactam, polymeric amide 11 and aliphatic or aromatic polyester.Other biological polymkeric substance can exist with the weight percent from 0 to 69.9 in the composition.
One or more anti-impact modifiers can using from 0.1 to 15 weight percents with said composition.
This anti-impact modifier is core/shell anti-impact modifier.Core-shell structure copolymer (multilayer) anti-impact modifier can have soft (rubber or elastomerics) core and duricrust, is coated with stone and the duricrust of soft elastomer layer, or other core-shell structure copolymer forms known in the art.These rubber layers are made up of lower glass transition temperatures (Tg) polymkeric substance, these polymkeric substance comprise, but be not limited to, butyl acrylate (BA), ethylhexylacrylate (EHA), divinyl (BD), butyl acrylate/vinylbenzene and other combination multiple.Preferably, this core is complete acrylic acid homopolymer or multipolymer.Have been found that and use compared with diolefine nuclear polymer, vinylformic acid core result in the biodegradable polymer composition with more low haze.
The preferred second-order transition temperature (Tg) of this elastomer layer should lower than 25 DEG C.This elastomer layer or rubber layer normally with polyfunctional monomer crosslinked for improvement of energy absorption.Be adapted in this core/shell anti-impact modifier as linking agent use cross-linking monomer be well-known to those skilled in the art, and be generally with existing cholesterol monomers copolymerizable and there is the polyfunctional monomer having the reactive group be roughly equal to of ethylenic.Example includes but not limited to: Vinylstyrene, two-and the ethylene glycol of three-methacrylic ester and acrylate, triol triacrylates, methacrylic ester and allyl methacrylate(AMA) etc.Also use grafted monomer to strengthen interlayer grafting and the matrix/modified grain grafting of anti-impact modifier.These grafted monomer can be any polyfunctional cross-linking monomers.
For soft core multilayer anti-impact modifier, the scope of this core is from 30 to 95 per-cents by the weighing scale of this anti-impact modifier, and the scope of shell is from 15 to 70 weight percents.The scope of the linking agent in this elastomer layer is from 0 to 5.0%.The synthesis of core-shell structure copolymer anti-impact modifier is known in this area, and has a lot of reference, such as US3, and 793,402, US3,808,180, US3,971,835 and US3,671,610, these reference are combined in this by reference.The refractive index of these modified grains and/or matrix polymer can have the copolymerisable monomer of different refractive index by use and match each other.Preferred monomer includes but not limited to: have the vinylbenzene of unsaturated ethylenic group, α-methylstyrene and interpolymerized vinylidene fluoride monomer.
The anti-impact modifier of other non-core/shell also likely for the present invention, when super transparency and sharpness may not be required.Such as, divinyl rubber can be incorporated in acrylic substrate to realize high bullet-proof (ballisticresistance) characteristic.
In a preferred embodiment, this core-shell polymer is acrylic acid core of 80%-90%, and comprises the shell of Ethyl acrylate of the methyl methacrylate of 75-100wt%, the butyl acrylate of 0-20 weight percent and 0-25 weight percent.This acrylic acid core is preferentially selected from butyl acrylate homopolymer and ethylhexylacrylate homopolymer, or butyl acrylate and ethylhexylacrylate are by the multipolymer of any monomer ratio.
In one embodiment, acrylic copolymer anti-impact modifier is the multipolymer based on acrylate, this multipolymer has core-shell polymer, this core-shell polymer has the core like rubber, such as 1, the 3-diene multipolymer of vinyl aromatic compounds (also have with) or the alkyl acrylate with the alkyl containing 4 or more carbon; And this shell to be grafted on this core and to comprise various of monomer, such as vinyl aromatic compounds (such as, vinylbenzene), alkyl methacrylate (there is the alkyl of 1-4 carbon), alkyl acrylate (there is the alkyl of 1-4 carbon) and vinyl cyanide.
Core/the shell polymeric of preferred acrylic-type is following core/shell polymeric, this core/shell polymeric has the core comprising following item of 70%-90%: the butyl acrylate of 0-100wt%, the 2-ethylhexyl acrylate of 0-100% and the divinyl of 0-35%; And comprise the shell of following item: the ethyl propenoate of the methyl methacrylate of 75-100wt%, the butyl acrylate of 0-20 weight percent and 0-25 weight percent.
Core-shell structure copolymer anti-impact modifier of the present invention be have be greater than 250nm, preferably from 250 to 400nm and most preferably from 280 to 330nm the particle of number average particle size.This core-shell structure copolymer anti-impact modifier can be have the size of two or more or the blend of chemical constitution, but the number average particle size of all anti-impact modifier particles is greater than 250nm.Granularity can use NiComp380 dynamic light scattering particle size analyzer to measure under normal operating conditions.Gaussian intensity weight mean particle size can be reported.
Preferably, the anti-impact modifier of biodegradable polymer composition of the present invention is pellet or powder, and these pellets or powder packets contain following item, form or be made up of following item primarily of following item: the anti-impact modifier particle with number average particle size described here.
Anti-impact modifier pellet of the present invention comprises block that is little, that be shaped, and these blocks can have any shape, includes, but are not limited to circular, spherical, columniform etc.
The pellet of anti-impact modifier can use melt processing as extruded or other technologies formation.Wherein pellet is when using melt-processed to be formed, what what this pellet was passable extruded.Such as, the anti-impact modifier in pellet form can be by melt processing (as list or twin-screw extrusion) or extrude (mixing tank of kneader as reciprocating in Buss and banbury type) by the common kneading with reciprocating screw and obtain.Final pellet can be use wire rod method (strandmethod) or other granulation means to be formed.
Processing temperature can be undertaken controlling by the temperature of the barrel section (above, middle and below) controlling the correspondence of this forcing machine and can scope from about 150 °F-460 °F, preferably from about 200 °F-450 °F, even more preferably from about 300 °F to 400 °F.
Preferably this forcing machine can from about 140 to 300RPM, preferably run from the RPM of about 150 to 250RPM and the input speed/output of about 10Kg/hr.
Preferably, this method of granulating makes at the Shear heating (low shearing) formed when having a final pellet of desired size, shape, composition and molecular weight and these anti-impact modifiers is temperature minimized.Such as, the size of these anti-impact modifier pellets and/or shape can correspond essentially to it can as described in this and the size of the biodegradable polymeric aggregate of its combination and/or shape.
Alternately, these pellets can be cold compaction.
Anti-impact modifier in powder type may be problematic in some application are as injection-molded, and wherein such as powder can cluster and/or form undesirable piece.In view of will being expensive in powder feed to equipment and difficulty, anti-impact modifier pellet avoids these problems.
Another advantage of the granulation of anti-impact modifier is that its allows to be easy to, processing easily and do not produce the separation of component.Such as, the granulation of anti-impact modifier allows to mix or tumble mixed with the bag of other products of granulating, and has low or that even do not have independent component separation or sedimentation.Granulate and also substantially can reduce and even eliminate efflorescence and relevant potential problems, these potential problems sometimes can be relevant to the use of powder.
The use of anti-impact modifier pellet additionally provides and manufactures biodegradable polymer composition of the present invention with lower manufacturing cost, better efficiency, due to the larger consistence that needs less processing units, the finished product and the process ease increased.
Anti-impact modifier of the present invention can also be powder, and this powder packets contains following item, forms or be made up of following item primarily of following item: the anti-impact modifier particle with number average particle size described here.Anti-impact modifier powder can be use spraying dry or condensation to be formed.
Biodegradable polymer composition of the present invention can comprise this biodegradable polymkeric substance of 30-99.9 weight percent, the other biological polymkeric substance of 0-69.9 weight percent and these one or more acrylic copolymer from 0.1 to 15 weight percent.These compositions can carry out mixing or can combining in the process of one or more procedure of processing (such as melting-blending operations) before processing.This can be undertaken by such as Single screw extrusion, twin-screw extrusion, Buss kneader, two roller mill, vane type mixing.Acrylic acid-methacrylic acid multipolymer equally distributed any married operation in this biodegradable polymkeric substance is caused to be all acceptable.The formation of this blend is not limited to single step and is formed.Also expect that the acrylic acid-methacrylic acid multipolymer of 15% to 99% forms masterbatch in the carrier polymer of 1% to 85%, then adds in this biodegradable polymkeric substance subsequently to obtain final blend.This carrier polymer can be but be not limited to polylactide, acrylic acid-methacrylic acid multipolymer and methacrylic acid homo thing.
Except this biodegradable polymkeric substance, biological polymer and anti-impact modifier, amount to 100%, composition of the present invention can comprise multiple additives in addition, includes but not limited to thermo-stabilizer, inside and outside lubricant, other anti-impact modifiers, processing aid, melt strength additive, weighting agent and pigment.
Find that composition of the present invention considerably improves impact property compared with independent polylactide.These core-shell polymer anti-impact modifiers provide excellent impact modification, still provide low mist degree simultaneously.
The biodegradable polymer composition of this impact modification from almost transparent or translucent to opaque change, can depend on the level of composition and impact modification.In one embodiment, the biodegradable polymkeric substance of this impact modification to have when being measured by ASTM1003-00 lower than 15%, is preferably lower than the level of haze of 12%.
Composition of the present invention can use any known method (include but not limited to injection molding, extrude, roll, blow molding, foaming and hot compacting) to process.The useful article using these biodegradable compositions to make includes but not limited to wrapping material, film and bottle.Based at this disclosure content and example, those skilled in the art will envision that other useful article multiple and the method for the formation of these article.
example
example 1
Form the polylactide of 95% and 93.5% by using the melt extrusion of twin screw extruder, contain the blend of the acrylic acid-methacrylic acid copolymer impact modifier of by weight 5% and 7.5%.Processing temperature in extrusion and melt temperature remain on temperature of fusion (>152 DEG C) higher than polylactide to guarantee uniform melt.Use 3 roller storehouses and puller (rollstackandpuller) by this extrudate curtain coating flakiness (17-22 Mill).Haze measurement uses chromascope to carry out on this thin slice, and drop impact measurement carries out with the Gardner Impact tester (GardnerImpacttester) with 2lb semisphere knocker head.The data observed illustrate in table 1 below:
Table 1
example 2-uses the anti-impact modifier of twin screw rotating Vortex intermeshing extruder to granulate
Use following equipment that acrylic acid-methacrylic acid copolymer impact modifier is configured as pellet: co-rotating twin screw, there is intermeshing screw rod and be equipped with two ventages, there is the L/D (length/diameter) of 40/1, and be equipped with can air cooled heating zone temperature regulator.This twin screw is the commercially available twin screw with the 27mm of screw design, and this twin screw runs under the input speed/output of 260RPM and 10Kg/hr.
In this granulating process process, control the temperature profile curve of machine barrel, make 1/3 of this machine barrel centre 1/3 being arranged on (region before this), this machine barrel at about 455 DEG C be heated to about 437 DEG C and this part (comprising intake zone) is below heated to about 410 DEG C.The temperature profile curve of this machine barrel correspondingly can be adjusted according to the brand of this forcing machine and model and input speed.
Water-bath and wire rod nodulizer (strandpelletizer) are positioned over the downstream of this twin screw.The cutting speed in feet per minute of this nodulizer is adjusted based on desired pellet length.
Claims (13)
1. a biodegradable polymer composition, comprises:
A) one or more biodegradable polymkeric substance of 30 to 99.9 weight percents;
B) one or more biological polymers of 0 to 69.9 weight percent; And
C) one or more core-shell structure copolymer anti-impact modifiers of 0.1 to 15 weight percent,
Wherein said anti-impact modifier is the pellet comprising the particle with the number average particle size being greater than 250nm, and wherein said composition has the mist degree being less than 15 per-cents as measured by ASTM1003-00.
2. a biodegradable polymer composition, comprises:
A) one or more biodegradable polymkeric substance of 30 to 99.9 weight percents;
B) one or more biological polymers of 0 to 69.9 weight percent; And
C) one or more core-shell structure copolymer anti-impact modifiers of 0.1 to 15 weight percent,
Wherein said anti-impact modifier is the powder comprising the particle with the number average particle size being greater than 250nm, and wherein said composition has the mist degree being less than 15 per-cents as measured by ASTM1003-00.
3. biodegradable polymer composition as claimed in claim 1, wherein said biodegradable polymkeric substance is polylactide, poly butyric ester or its mixture.
4. biodegradable polymer composition as claimed in claim 1, wherein said anti-impact modifier has the number average particle size from being greater than 250nm to 400nm.
5. biodegradable polymer composition as claimed in claim 1, wherein said anti-impact modifier has the number average particle size from 280 to 330nm.
6. biodegradable polymer composition as claimed in claim 3, wherein said polylactide has from 10,000-3, the weight-average molecular weight of 000,000g/mol.
7. biodegradable polymer composition as claimed in claim 1, wherein this core-shell structure copolymer anti-impact modifier is the blend of two or more multipolymers.
8. biodegradable polymer composition as claimed in claim 1, wherein said biological polymer comprises one or more polymkeric substance being selected from lower group, and this group is made up of the following: starch, Mierocrystalline cellulose, polysaccharide, aliphatic or aromatic polyester and polycaprolactone.
9. biodegradable polymer composition as claimed in claim 1, wherein said core-shell structure copolymer anti-impact modifier is complete acrylic acid core/shell polymeric.
10. biodegradable polymer composition as claimed in claim 1, the core of wherein said core-shell structure copolymer anti-impact modifier comprises one or more monomeric unit being selected from lower group, and this group is made up of the following: butyl acrylate and ethylhexylacrylate.
11. biodegradable polymer compositions as claimed in claim 1, the core of wherein said core-shell structure copolymer anti-impact modifier is butyl polyacrylate.
12. biodegradable polymer compositions as claimed in claim 1, wherein this biological polymer comprises one or more in starch, Mierocrystalline cellulose and polycaprolactone.
13. biodegradable polymer compositions as claimed in claim 1, wherein the shell of this core/shell anti-impact modifier comprises the Ethyl acrylate of the methyl methacrylate of 75-100 % by weight, the butyl acrylate of 0-20 weight percent and 0-25 weight percent, and the core of wherein said core-shell structure copolymer anti-impact modifier comprises one or more monomeric unit being selected from lower group, and this group is made up of the following: butyl acrylate and ethylhexylacrylate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/013,225 US20130345363A1 (en) | 2008-06-13 | 2013-08-29 | Biodegradable impact-modified polymer compositions |
| US14/013,225 | 2013-08-29 | ||
| PCT/US2014/052637 WO2015031315A1 (en) | 2013-08-29 | 2014-08-26 | Biodegradable impact-modified polymer compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105492543A true CN105492543A (en) | 2016-04-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480047462.7A Pending CN105492543A (en) | 2013-08-29 | 2014-08-26 | Biodegradable impact-modified polymer compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP3039081A4 (en) |
| JP (1) | JP2016529375A (en) |
| CN (1) | CN105492543A (en) |
| WO (1) | WO2015031315A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872389A (en) * | 2018-08-31 | 2020-03-10 | 富士施乐株式会社 | Resin composition and resin molded article |
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2014
- 2014-08-26 CN CN201480047462.7A patent/CN105492543A/en active Pending
- 2014-08-26 JP JP2016539021A patent/JP2016529375A/en active Pending
- 2014-08-26 WO PCT/US2014/052637 patent/WO2015031315A1/en active Application Filing
- 2014-08-26 EP EP14839813.4A patent/EP3039081A4/en not_active Withdrawn
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| CN1934191A (en) * | 2004-03-05 | 2007-03-21 | 三菱丽阳株式会社 | Thermoplastic resin composition and molded article comprising the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2015031315A1 (en) | 2015-03-05 |
| JP2016529375A (en) | 2016-09-23 |
| EP3039081A4 (en) | 2017-04-12 |
| EP3039081A1 (en) | 2016-07-06 |
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Application publication date: 20160413 |