CN104769042B - The polyhydroxy-alkanoates composition of improved impact resistance is shown under the low-level of impact modifying agent - Google Patents
The polyhydroxy-alkanoates composition of improved impact resistance is shown under the low-level of impact modifying agent Download PDFInfo
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- CN104769042B CN104769042B CN201380058044.3A CN201380058044A CN104769042B CN 104769042 B CN104769042 B CN 104769042B CN 201380058044 A CN201380058044 A CN 201380058044A CN 104769042 B CN104769042 B CN 104769042B
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- 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 present invention relates to the impact modifying agent in polyhydroxy-alkanoates (PHA's) (including PLA (PLA)).These impact modifying agents include core-shell impact modifiers and the mixture of the ethylene copolymer (GMA copolymers) comprising GMA.Improved impact property is realized under the low-level of total impact modifying agent.
Description
Invention field
The present invention relates to the polyhydroxy-alkanoates with improved impact strength (PHA) composition.Total impact modified
Improved impact property is realized under the low-level of agent load capacity.
Background of invention
Polyhydroxy-alkanoates or the polymer of polyhydroxy phenylalkanoic acid (PHA) type (such as PLA (PLA)) are can be from
The polymer obtained in the monomer of plant origin.Due to their biodegradable characteristic, they are significant.So
And they are especially frangible polymer, it requires the enhancing for impact.
JP H09-316310 describe PLA compositions, and these compositions include and use polystyrene or poly dimethyl propylene
The ethylene-methyl methacrylate glycidyl ester copolymer of acid esters grafting or the polyolefin that maleic anhydride grafting is alternatively used.
WO 2005/059031 describes PLA compositions, said composition include ethene by mass from 3% to 40%,
The copolymer of carboxylate and ethylene oxidic ester.
US 2008/0071008 discloses polyhydroxy phenylalkanoic acid (polyhydroalkanoic acid) composition, the group
Compound includes the core-shell structure copolymer compound with the refractive index less than 1.5 from 0.2% to 10% and does not include any vinyl aromatic (co)
Fragrant race's monomer.
Although these compositions show improved impact strength, this intensity is not entirely satisfactory.
In addition, some in these compositions have the mobility of substantially less than PHA mobility.This in mobility
The substantial reduction of kind hampers the purposes for being most used in particular for thin and large scale injection molding part.
The purpose of the present invention is to propose to the PHA compositions of novelty, said composition is especially always born in the low of impact modifying agent
There is excellent impact strength under loading levels.
Summary of the invention
The present invention relates to polyhydroxy-alkanoates (PHA) composition, said composition also includes core-shell structure copolymer elastomer compounds
And the ethylenic copolymer comprising the ethylenic monomer with epoxy-functional (B) (A).
This special composition comprising impact modifying agent (combining core-shell structure copolymer compound and ethylenic copolymer) has Zhuo
Impact characteristics more, unexpectedly, more and special better than the impact characteristics of the composition of prior art of these impact characteristics
Than include by the ethylenic copolymer comprising the ethylenic monomer with epoxy-functional or core-shell structure copolymer compound group into impact change
The composition of property agent it is good more.
Said composition also has the advantages of superior fluidity during its use.
Said composition use comprising PLA (" PLA ") and core shell impact modifier with it is sweet comprising Glycidyl methacrylate
The composition of the mixture of the ethylene copolymer (" GMA copolymers ") of grease also has the advantages of performance excellent impact strength.
The embodiment provides following composition, said composition include polyhydroxy phenylalkanoic acid and：
(A) elastomer compounds of core-shell structure copolymer type, wherein the amount of (A) be based on the quality of said composition from 0.1% to
6%；And
(B) and the ethylenic copolymer of the ethylenic monomer with epoxy-functional is included；
The amount for being wherein somebody's turn to do (B) is to be from the mass ratio of 0.01% to 0.6% and (A)/(B) based on the quality of said composition
From 85/15 to 99.5/0.5.
Another aspect of the present invention provides following composition, said composition include PLA and：
(A) elastomer compounds of core-shell structure copolymer type；And
(B) ethylenic copolymer, the ethylenic copolymer include ethene, GMA and (methyl) propylene
Acid alkyl ester, the wherein alkyl chain include from 1 to 30 carbon atom, wherein the amount of (A) be based on the quality of said composition from
0.1% to 6%；
The amount of wherein (B) is that (A)+(B) amount is by the combination from 0.01% to 0.6% based on the quality of said composition
The quality meter of thing is from 0.1% to 6%, and (A)/(B) mass ratio is from 85/15 to 99.5/0.5.
The present invention provides the method for preparing such composition in another aspect, wherein the impact by (A) and (B)
The spherolite of modifier blends is combined with the polyhydroxy phenylalkanoic acid.
The ethylenic monomer with epoxy-functional is preferably (methyl) glycidyl acrylate.
The copolymer (B) can be ethene, GMA and optionally alkyl acrylate and/or
The copolymer of alkyl methacrylate, the wherein alkyl chain are included from 1 to 30 carbon atom, and the latter's monomer is in this manual
It is combined under term (methyl) alkyl acrylate.The amount of (methyl) alkyl acrylate is somebody's turn to do relative to the ethylenic copolymer
(B) gross mass can from 0 (that is, not comprising) to 40%, advantageously from 5% to 35% and preferably from 20% to 30%
In the range of.
Amount of the ethylenic monomer with epoxy-functional in the ethylenic copolymer (B) relative to its gross mass for example
Be from 0.1% to 20%, advantageously from 2% to 15% and preferably in the range of 5% to 10%.
Said composition can also include the other olefinic for including the ethylenic monomer with epoxy-functional that is different from and be copolymerized
The ethylenic polymer (C) of thing.Preferably, this other ethylenic polymer (C) is ethene and (methyl) alkyl acrylate
Copolymer, the copolymer of ethene and vinyl esters of carboxylic acids, ethene and (methyl) acrylic acid or the copolymer of ionomer, most preferably second
Alkene with scope from the alkyl acrylate of 1 to 20 alkyl chain (such as methyl acrylate, ethylene-acrylate or acrylic acid
N-butyl) copolymer.In this case, said composition advantageously has from 90/10 to 10/90 or from 75/25 to 40/
Mass ratio (B)/(C) in the range of 60.
Advantageously, in one embodiment of the invention mass ratio (A)/((B)+optional (C)) be from 90/10 to
In the range of 10/90, such as 85/15 to 40/60, either advantageously from 80/20 to 50/50 or from 75/25 to 60/40.
In an alternative embodiment of the invention, however, C) it is not present and mass ratio (A)/(B) is 85/15 or bigger, preferably 90/
10 or bigger.For example, in this embodiment, mass ratio (A)/(B) can be 85/15 to 99.5/0.5 or 89/11 to 96/
4.In another embodiment, as C) be not present when, mass ratio (A)/(B) is 20/1 to 18/1, preferably 19/1.As made herein
, term " quality " and " percentage by weight " look like with identical.
In one embodiment of the invention, the amount of modifying agent ((A)+(B)+optional (C)) can be by total composition
Quality meter from 1% to 30%, advantageously from 2% to 15% or in the range of 3% to 9%.In another of the present invention
In embodiment, the amount of modifying agent ((A)+(B) (when in the absence of C)) can be based on the quality of total composition from 0.5% to
6%, preferably from about 1% to about 5%, more preferably about 1% or about 5%.
In one embodiment of the invention, it is relative with the amount of the ethylenic monomer including epoxy-functional of polymerized form
In the quality of total composition can be from 0.01% to 2%, advantageously from 0.02% to 1% or from 0.03% to 0.7%
In the range of.
On the elastomer core-shell structure copolymer compound (A), the glass transition temperature of the core polymer is preferably less than 20
DEG C, such as between -140 DEG C and 0 DEG C.Preferably, the glass transition temperature of the core polymer is greater than 20 DEG C, such as
Between 30 DEG C and 250 DEG C.
On the elastomer core-shell structure copolymer compound (A), its shell parts preferably includes, with polymerized form：
■ alkyl methacrylates, the wherein alkyl chain are included from 1 to 12 and preferably from 1 to 4 carbon atom；
■ and/or including the vinyl aromatic organic compound from 6 to 12 carbon atoms, such as styrene；
■ and/or acrylonitrile；
This shell parts is probably crosslinking.
The core part of the core-shell structure copolymer compound (A) advantageously comprises, with polymerized form：
■ is included from 4 to 12 and preferably from the conjugated diene of 4 to 8 carbon atoms；
■ or alkyl acrylate, the wherein alkyl chain are included from 1 to 12 and preferably from 1 to 8 carbon atom.
The core-shell structure copolymer compound (A) can be selected from：
■ compounds, the compound have include the core of butadiene and including methyl methacrylate, acrylic acid second
Ester, butyl acrylate, the shell of methacrylic acid and/or styrene；
■ compounds, the compound have include butyl acrylate, n-octyl and/or 2-EHA
Core and shell including methyl methacrylate；
■ compounds, mixture of the compound with the core for including butadiene and including acrylonitrile and styrene
Shell.
On the core-shell structure copolymer compound, the quality of the core advantageously the core-shell structure copolymer compound gross mass from 10%
To in the range of 99%, such as from 60% to 95%.
The granularity of the core-shell structure copolymer compound is advantageously between 50 and 600nm.
Preferably, the PHA is selected from PLA (PLA) and polyglycolic acid (PGA).
Subject of the present invention is still used for the method for preparing the PHA compositions of the modification, wherein being prepared by extruding
PHA, (A), (B), optional (C) and the mixture of optionally one or more additives (such as nucleator).
According to one embodiment of the inventive method, carry out following：
■ mixes (A), (B) and optional (C) to form impact modifying agent in the first step, and then
■ in the second step, by the impact modifying agent obtained from the first step (for example, it may be at spherolite
Form) mixed with PHA.
According to another above-mentioned composition for being used to prepare the method for carrying out present subject matter, carry out following：
- wherein the copolymer be in melting form at a temperature of and in the range of from 60 DEG C to 180 DEG C most
The first step of the impact modifying agent is manufactured under high-temperature by mixing；
- by extrusion or by mixing the impact modifying agent obtained in the first step and described PHA manufacture polyhydroxy
The second step of alkanoic acid (PHA) composition.
Advantageously, the step of carrying out the impact modifying agent for manufacturing the first step so that the maximum temperature be from
In the range of 70 DEG C to 140 DEG C.
According to one embodiment, carried out in twin screw or single screw extruder, preferential single screw extrusion machine by extruding
The step of above-mentioned impact modifying agent for manufacturing first step.According to one embodiment, in corotating double screw extruder or
In the double screw extruder of reverse rotation or reciprocating kneader or banbury or single screw extrusion machine, preferentially in Single screw extrusion
In machine by melting form mixing to carry out the impact modifying agent for manufacturing the first step the step of.It should be understood that with
In manufacture the impact modifying agent all steps (including in melting form mixing) herein be considered as extrusion.Using usual
The known prilling process in polymer processing field, can prepare the impact modifying agent in pellets.
Preferably, residence time of the impact modifying agent in the first step is in the range of 10 to 300 seconds.
According to one embodiment, can carry out for manufacture the impact modifying agent obtained in the first step with it is above-mentioned
The second step of PHA mixture so that the mixing temperature is in the range of from 180 DEG C to 320 DEG C.Can required for ratio
Example combines the spherolite of the impact modifying agent and PHA spherolite to reach the desired water of impact modifying agent in the final composition
Put down and be subjected to melt-processed so as to nearly mix these components and realize these components of the impact modifying agent in the PHA
It is uniform scattered in matrix.
Subject of the present invention is the part or object for the PHA compositions for including the modification, such as packaging material
(wrapping)。
The invention further relates to the method for manufacturing the part or object, this method includes the step for forming the composition
Suddenly, such as by injection molding, compacting or calendering, the part or the object optionally it is subjected to annealing steps.
Detailed description of the invention
The present invention relates to polyhydroxy-alkanoates (PHA) composition, said composition also include core-shell structure copolymer compound (A) and
Polymer (B) comprising the ethylenic monomer with epoxy-functional.
According to the present invention, when one of said composition polymer or composition " including monomer ", this means it in institute
State and exist in polymerized form in one (or more) kinds of polymer of polymer or the composition.
The polymer of PHA types is biodegradable polymer.Some of which or bio-renewable, these
Monomer extracts production by bacterial fermentation processes or alternately from plant.Term " biodegradable " is if be applied to it
The material of microbial degradation can be passed through.The result of this degraded is water, CO2And/or CH4And do not have optionally for environment
The formation of the accessory substance (residue, new biomass) of poison.Such as there is a possibility that whether determine the material with standard EN13432
It is biodegradable.In order to determine whether polymer is " bio-renewable ", standard ASTM D6866 can be used.Biology
Reproducible polymer is characterised by that they include the carbon of renewable source, i.e.14C.Specifically, from the organism to live simultaneously
And especially from being three kinds same for forming all carbon samples that the plant material of these bio-renewable polymer takes out
Position element：12C、13C and14C mixture, wherein being made by carbon with continuous exchange of environment14C/12C ratio keeps constant and waited
In 1.2 × 10-12.Although14C is radioactive and therefore its concentration is reduced over time, and its half-life period is 5730, and
And in itself be considered as from the plant material extraction until these bio-renewable polymer manufacture and even one
Until the end of their purposes should14C content is constant.Should for example, working as14C/12C ratio shows more than or equal to 1 × 10-12When,
What be may think that is that the polymer is bio-renewable.
Bio-renewable polymer can be measured14C content, for example, according to following liquid scintillation spectrometry or mass spectrum
Technology.These are used for measurement of species14The method of C content is in standard ASTM D 6866 (especially D6866-06) and standard ASTM
Accurately described in D 7026 (especially 7026-04).These methods measure sample14C/12C ratio and by it
With the reference sample of 100% renewable source14C/12C ratio is compared to obtain the renewable source in the sample
The relative percentage of carbon.
In the case of bio-renewable polymer, the measuring method preferentially used is in standard ASTM D6866-06
Described in mass spectrography (accelerator mass spectrometry).
PHA is the polymer for including hydroxyalkanoate acid unit, such as comprising from 2 to 10 carbon atoms.The example that can be mentioned that
Including：Include the polymer of 6 hydroxycaproic acid (being referred to as polycaprolactone (PCL)), including 3- hydroxycaproic acids, diethoxalic acid or 3-
The polymer of hydroxyheptanoic acid.Especially it can be pointed out that comprising 5 carbon atoms or less polymer, such as including glycolic
(PGA), lactic acid (PLA), 3- hydroxy propionates, 2- butyric esters, 3-hydroxybutyrate ester (PHB), 4 hydroxybutyric acid ester, 3- hydroxyls
The polymer of base valerate, 4- hydroxyl valerates and 5- hydroxyl valerates.Preferable condensate is PGA, PCL, PLA and PHB.This
A little PHA can be aliphatic.
PHA can also be copolymer, i.e. they may include the first hydroxyl alkane acid and another unit, and the another kind is single
Member can be different from first second hydroxyl alkane acid either another monomer such as glycol (such as ethylene glycol, 1,
Ammediol and 1,4- butanediols) or diacid (such as butanedioic acid, adipic acid and terephthalic acid (TPA)).For example, the present invention includes PLA's
Both homopolymer and copolymer, the wherein copolymer include PLA and other monomers, and other monomers include for example another single
Member, another unit can be different from first second hydroxyl alkane acid either another monomer such as glycol
(such as ethylene glycol, 1,3- propane diols and 1,4- butanediols) or diacid (such as butanedioic acid, adipic acid and terephthalic acid (TPA)).
The composition of the present invention may also include the mixture of these polymer, such as the mixing including PLA He other PHA
Thing.
PHA is often polymerisation in bulk.PHA can be synthesized by the dehydration and condensation of the hydroxyl alkane acid.It can be with
By the dealcoholysis and condensation of the Arrcostab of hydroxyl alkane acid or pass through via corresponding lactone cyclic derivatives or cyclic ester two
The polymerisation synthesis of the ring opening of aggressiveness.Polymerisation in bulk is generally carried out by method in batches or continuously.Such as it is used to manufacture PHA
Continuation method example, it is mentioned that in patent application JP-A 03-502115, JP-A 07-26001 and JP-A 07-
Method in 53684.Patent US 2 668 162 and US 3 297 033 describe batch processes.
On the nuclear-shell copolymer (A), it is to be in core made of soft polymer and at least poly- by hardness
The fine grain form of shell made of compound, and the size of these particles be typically smaller than micron and advantageously 50 with
Between 600nm, more preferably between 250 and 400nm.
Preferably, the polymer of the core has less than 20 DEG C of glass transition temperature, for example, -140 DEG C with 0 DEG C it
Between and preferably between -120 DEG C and -30 DEG C.Preferably, the polymer of the shell has the glass transition temperature more than 20 DEG C
Degree, such as between 30 DEG C and 250 DEG C.
The glass transition temperature of the polymer of said composition can be according to standard ISO 11357-2:1999 measurements.
The example for the core polymer that can be mentioned that includes：Rubber, butadiene, butyl acrylate, methyl methacrylate, third
Olefin(e) acid ethyl ester, and/or the homopolymer of butyl acrylate and copolymer, the homopolymer of isoprene, isoprene-butadiene copolymerization
Thing, isoprene with by weight be not more than 98% vinyl monomer copolymer and butadiene with being not more than by weight
The copolymer of 98% vinyl monomer.The vinyl monomer can be styrene, ring-alkylated styrenes, acrylonitrile, (methyl) third
Olefin(e) acid Arrcostab, alkyl acrylate, butadiene or isoprene.The core polymer may also include siloxanes, optionally with
Alkyl acrylate copolymer.The core of the nuclear-shell copolymer can be completely or partially crosslinked.Therefore, in the core
It is sufficient that monomer of at least difunctionality is added in the preparation process of core, and these monomers can be selected from the poly- of polyalcohol
(methyl) acrylate, such as two (methyl) acrylic acid fourth diester and trimethylol-propane trimethacrylate.Other more officials
The monomer of energy is such as divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate and cyanogen urea
Sour triallyl.The core can also be by introducing undersaturated functional monomer, being grafted or in the course of the polymerization process thereto
It is crosslinked as comonomer, these monomers such as unsaturated carboxylic acid acid anhydrides, undersaturated carboxylic acid and undersaturated epoxy
Compound.The example that can be mentioned that includes：Maleic anhydride, (methyl) acrylic acid and GMA.It can also use
The intrinsic reactivity of monomer (such as diene) is crosslinked.
One or more shells are styrene, ring-alkylated styrenes, (methyl) acrylic acid C1-C4 Arrcostabs, methyl methacrylate
Ester, butyl acrylate, the homopolymer or copolymer of ethyl acrylate, or including in by weight at least 70% aforementioned monomer
One of and at least one comonomer selected from other aforementioned monomers, another kind (methyl) alkyl acrylate, vinyl acetate
With the copolymer of acrylonitrile.The shell can be by introducing undersaturated functional monomer, being grafted or in polymerization process thereto
It is middle as comonomer to carry out functionalization, these monomers such as unsaturated carboxylic acid acid anhydrides, undersaturated carboxylic acid and undersaturated
Epoxides.The example that can be mentioned that includes：Maleic anhydride, (methyl) acrylic acid, GMA, metering system
Sour hydroxyl ethyl ester and alkyl (methyl) acrylamide.The example that can be mentioned that includes：Core-shell structure copolymer with the shell made of polystyrene
Copolymer and the nuclear-shell copolymer with the shell made of PMMA.The shell can also include imide functionality, or pass through
With the copolymerization of maleimide, or the chemical modification by the PMMA and primary amine.Advantageously, moles the hundred of imide functionality
It is from 30% to 60% (generally speaking relative to the shell) to divide ratio.The nuclear-shell copolymer for including two shells, polystyrene also be present
Manufactured shell and another outside the shell made of PMMA.Copolymer and the example of the method for preparing them exist
It is described in following patent：US 4 180 494、US 3808 180、US 4 096 202、US 4 260 693、US 3
287 443、US 3 657 391、US 4299 928、US 3 985 704、US 5 773 520。
For example, the core is represented 5% to 95% based on the weight of the core-shell structure copolymer compound, preferably from 50% in the present invention
To 95%, more preferably from 60% to 90%, and the shell by weight 95% to 5%, more preferably from 50% to 5% and more
It is preferred that from 40% to 10%.
Be made up of following item one of one example of the copolymer that can be mentioned that：(i) in mol, from 50 to 95 parts
Core, including at least 93% butadiene, 5% styrene and 0.5% to 1% divinylbenzene, and (ii) from 5 to
50 parts of two shells, they have substantially the same weight, and internal one is made up and outside one of polystyrene
It is made up of PMMA.
Preferably, can use with made of butyl acrylate copolymer core and made of PMMA shell core-
Shell compound.These compounds have the advantages of especially transparent.
Further preferably having includes rubber, butyl acrylate homopolymer or copolymer, dienite or copolymer
Core and including one or more shells in methyl methacrylate, ethyl acrylate, and/or butyl acrylate
Core-shell structure copolymer compound.
All these core-shell structure copolymer compounds are referred to as soft/hardness by accident due to elastomer nuclear core.It is copolymerized using core-shell structure copolymer
Thing such as hardness/soft/rigid copolymer (that is, has being total to for the shell of rigid core, soft shell and hardness according to this order
Polymers) context for running counter to the present invention will not be formed.These rigid parts can be by the poly- of the shell of foregoing soft/rigid copolymer
Compound is formed and the soft component can be made up of the polymer of the core of foregoing soft/rigid copolymer.
The example that can be mentioned that includes：Those described in EP 270 865, and according to this order by following item group
Into those：
The core made of the copolymer of methyl methacrylate and ethyl acrylate,
The shell made of the copolymer of butyl acrylate and styrene,
The shell made of the copolymer of methyl methacrylate and ethyl acrylate.
Other kinds of nuclear-shell copolymer also be present, such as rigid (core)/soft/semi-hard copolymer.With foregoing copolymerization
Thing is compared, and difference is " semi-hard " shell, and it is by two shells：One centre and another outside composition.Among this
Shell is methyl methacrylate, styrene and at least one monomer selected from alkyl acrylate, butadiene and isoprene
Copolymer.The shell is PMMA homopolymer or copolymer.
The example that can be mentioned that includes：Those being made up of according to this order following item：
The core made of the copolymer of methyl methacrylate and ethyl acrylate,
The shell made of the copolymer of butyl acrylate and styrene,
The shell made of the copolymer of methyl methacrylate, butyl acrylate and styrene,
The shell made of the copolymer of methyl methacrylate and ethyl acrylate.
Compound (A) is with brand name by Arkema (Arkema) WithSell.
The polymer (B) includes the ethylenic monomer with epoxy-functional.Preferably, it is statistical copolymer.The band
The ethylenic monomer of oxygen functional group can be undersaturated epoxides, such as：
■ aliphatic glycidyls esters and ethers, such as allyl glycidyl ether, vinyl glycidyl ether, maleic acid
Ethylene oxidic ester and glycidyl itoconate, and (methyl) glycidyl acrylate, and
■ aliphatic glycidyls esters and ethers, as 2- cyclohexene -1- glycidol ethers, cyclohexene -4,5- bis- shrink
Glyceryl carboxylate, cyclohexene -4- glycidyls carboxylate, 5- ENBs -2- methyl -2- glycidyls carboxylate with
And cis-two ring (the 2.2.1) -5- heptene -2,3- diglycidyl dicarboxylic esters of inner mold.
GMA is preferably as the ethylenic monomer with epoxy-functional.
Preferably, the polymer (B) is the ethylenic copolymer for including the ethylenic monomer with epoxy-functional, i.e. it is
Above-mentioned ethylenic monomer and at least one alpha-olefin (it may include from 2 to 20 carbon atoms, such as ethene or propylene, preferential ethene)
Copolymer.
The ethylenic copolymer may also include at least one and be different from above-mentioned alpha-olefin and be different from the band epoxy-functional
Ethylenic monomer monomer.The non-limiting examples that can be mentioned that include：
- conjugated diene, such as Isosorbide-5-Nitrae-hexadiene；
- carbon monoxide；
- undersaturated carboxylate, such as (methyl) alkyl acrylate；
The vinyl esters of carboxylic acids of-saturation, such as ethyl acetate or propionate.
According to a favourable pattern, the ethylenic copolymer includes (methyl) alkyl acrylate.The alkyl chain can include
Up to 24 carbon.Preferably wherein the alkyl chain is included from 1 to 12, advantageously from 1 to 6 or even from 1 to 4 carbon atom
Those.Advantageously, the C1 of (methyl) acrylic acid is preferably to C4 Arrcostabs, including for example, n-butyl acrylate, acrylic acid
Isobutyl ester, 2-EHA, ethyl acrylate and methyl acrylate.Preferably, these (methyl) alkyl acrylates
It is n-butyl acrylate, ethyl acrylate and methyl acrylate.Most preferably, it is PMA or polyacrylic acid fourth
Ester.
Most preferred polymer is that the C1 of ethene-(methyl) acrylic acid is sweet to C4 Arrcostabs-(poly-) Glycidyl methacrylate
Grease copolymer, ethylene-methyl methacrylate glycidyl ester copolymer and ethene-(poly-) butyl propyleneglycol acid glycidyl ester
Copolymer.
Different from the ethylenic monomer with epoxy-functional and different from monomer (such as (methyl) third of the alpha-olefin
Olefin(e) acid Arrcostab) amount, the gross mass relative to the ethylenic copolymer (B) can be from 0 (that is, it does not include any) extremely
50%th, advantageously from 5% to 35% and preferably in the range of 20% to 30%.
Amount of the ethylenic monomer with epoxy-functional in the ethylenic copolymer (B) relative to its gross mass for example
Be from 0.1% to 20%, advantageously from 2% to 15% and preferably in the range of 5% to 10%.Further preferably wrap
The glycidyl methacrylate copolymer of the part of GMA, ethene and acrylic acid is included, at this
There is 10 percentage by weights or less GMA, and the wherein part of these acrylic acid in copolymer
It is included in the polymethacrylates from 0 to 50 percentage by weight and/or poly- butyl propyleneglycol acid esters.
Copolymer (B) is with brand name by Arkema (Arkema)Sell.
The composition of the present invention may also include other ethylenic polymer (C), such as different from (B) (that is, not including any
Any monomer with epoxy-functional) ethylene copolymer.These can be selected from include ethene and vinyl esters copolymer or
Person includes the copolymer of ethene and (methyl) alkyl acrylate, the copolymerization being such as made up of ethene and (methyl) alkyl acrylate
Thing.Being somebody's turn to do the alkyl chain of (methyl) acrylate can contain up to up to 20 carbon.Preferably wherein the alkyl chain include from 1 to
12nd, advantageously from 1 to 6 or even from 1 to 4 carbon atom those.Advantageously, these (methyl) alkyl acrylates are propylene
Sour N-butyl, isobutyl acrylate, 2-EHA, ethyl acrylate and methyl acrylate.Preferably, these (first
Base) alkyl acrylate is n-butyl acrylate, ethyl acrylate and methyl acrylate.Preferably, should (methyl) alkyl acrylate
The amount of base ester is from 1% to 40%, advantageously from 5% to 35% relative to the scope of the gross mass of the ethylenic copolymer (C)
And preferably from 20% to 30%.
Copolymer (C) is with brand name by Arkema (Arkema)Sell.
Be present in the present invention different polymer in different monomers amount can by infra-red sepectrometry (example as used in
Method described in standard ISO 8985) measurement.
Method for manufacturing these copolymers (B) and (C) is known.They can be for example anti-in tubular type or autoclave
Answer by high-pressure free radical to polymerize in device and manufacture.
According to an aspect of the present invention, polyhydroxy phenylalkanoic acid (PHA) composition also includes：
(A) elastomer compounds of core-shell structure copolymer type；
(B) copolymer of the copolymer selected from ethene and GMA；And
(C) copolymer of ethene and (methyl) alkyl acrylate, the wherein alkyl chain are included from 1 to 20 carbon atom.
Said composition may also include the additive of some characteristics for improving the PHA compositions, such as nucleator, plasticising
Agent, dyestuff, UV absorbents, stabilizer, antioxidant, filler, fire retardant, lubricant, anticaking agent, releasing agent, Huo Zheyong
In the additive for promoting this method, it is commonly known as " processing aid ".
Can be by the thermoplasticity processing means (such as extrusion or blending) of standard by mixed according to the composition of the present invention
Close heterogeneity manufacture.The banbury with blade or rotor, external mix machine, and corotating or reverse rotation can be used
Single screw rod or twin-screw extruder.In one embodiment, in the glass transition temperature more than or equal to the PHA or
Person prepares said composition at a temperature of being even greater than the temperature.For example, temperature that can be in the range of from 160 DEG C to 260 DEG C
Lower preparation said composition.
According to one embodiment of the inventive method, enter to be about to the step of impact modifying agent is mixed to the PHA, the impact
Modifying agent includes (A), (B) and optional (C) mixture.
Because compound (A) is powdery, promoted by mixing (A) with (B) and optional (C) for manufacturing this
The method of PHA compositions, the impact modifying agent then obtained in this way are probably the form in particle so that at this
It is physically easier to perform during PHA method for transformation.
In one embodiment of the invention, (A), (B) and the optionally blending of (C) in pellets are prepared
Thing.Then the spherical impact modifying agent blend is combined with the PHA to provide the composition according to the present invention.It has been found that
This method is generated compared with by the way that (A), (B) and optional (C) is added separately into the composition of PHA preparations, tool
There are more preferable and more consistent impact characteristics and the composition of more consistent optical characteristics.
The present invention another theme be from according to the present invention composition manufacture part or object, as packaging material,
Film or thin slice (sheet).
In order to manufacture this part or this article, known molding technique can be used, such as compacting or injection molding
Compacting, or alternately known extrusion-blown modling molding technique.These films or thin slice can also be extruded by casting films, blown film
Extrusion or the manufacture of the technology of calendering.
Method for manufacturing this part may also include for crystallizing the annealing steps of the PHA, and therefore improve
Its mechanical property.
The example of composition will be described in the following example now；These examples be given by way of illustration and not with appoint
Where formula limits the scope of invention claimed.
Example
In order to prepare the example of composition and structure according to the present invention, following product is used：
(a1)：Core-shell structure copolymer compound based on butadiene, methyl methacrylate, ethyl acrylate and butyl acrylate；
(a2)：Core-shell structure copolymer compound based on butyl acrylate and methyl methacrylate；
(a3)：Core-shell structure copolymer compound including acrylonitrile, butadiene and styrene；
(b)：Ethylene-methyl acrylate-glyceryl methacrylate copolymer, include by weight 25% propylene
Acid esters and 8% GMAIts fusing point passes through DSC (ISO 11357-
03) measurement is 65 DEG C；
(c)：Ethylene-butyl acrylate copolymer, include by weight 30% acrylate
Its fusing point is 78 DEG C by DSC (ISO 11357-03) measurements；
(d)：The PLA 2002D sold by NatureWorks companies.
Include being given in Table 1 ratio according to the composition (4) of the present invention and (5) and Comparative composition (1), (2) and (3)
Composition (a1), (a2), (a3), (b), (c) and (d) of example.
Composition (1) to (5) is prepared in a single step.By the composition for extruding the ratio being given in Table 1
Mixing.Diameter and 25 L/D ratio (Haake PTW16/25) with 16mm of the extrusion in corotating twin screw type
Extruder in carry out.Highest mixing temperature is 240 DEG C.
Because these compositions (a1), (a2) and (a3) are powder and above-mentioned extruder is equipped only with metering dress
Put, it is necessary to these compositions (b) and (d) are ground until obtaining fine powder by low temperature ball milling (cryomilling), to obtain
Correct metering in these compositions to the extruder for preparing mixture (2) to (5).
Then these compositions are injected at 30 DEG C by Krauss Maffei 60-210B1 types at 200 DEG C
Injector pressure machine control mould in.
After these samples are annealed into 1 hour with crystalline polylactic acid at 110 DEG C, according to standard ISO179:2000 survey
Breach Charpy impact characteristic is measured.Charp impact value is bigger, and impact strength is better.Under room temperature (23 DEG C) and in cool condition (0
DEG C and/or -40 DEG C) under measure these characteristics.The value obtained is arranged in table 2.
These breach Charpy impact characteristics are also at room temperature according to standard ISO 179:2000 measure without annealing is lower.Obtained
The value obtained is arranged in table 3.
Table 1
Table 2
Table 3 (is not annealed)
Composition prepared in accordance with the present invention has improved impact special when compared with those obtained from prior art
Property.
It is described according to three kinds of other exemplary compositions of the present invention in table 4.In these examples, this is more
Hydroxyl alkane acid is PLA, and (A) is core-shell structure copolymer compound manufactured according to the present invention and (B) is ethene/C1-4 metering systems
Acid esters/glycidyl methacrylate copolymer.The amount of each component is with quality % based on the gross mass of said composition
Meter.
Table 4.
| Component | Example 12 | Example 13 | Example 14 |
| PLA | 99 | 99 | 95 |
| (A) | 0.9 | 0.95 | 4.75 |
| (B) | 0.1 | 0.05 | 0.25 |
According to following procedure preparating example 15-26 (table 5), (example 15-18 is comparison example, while example 19-26 is shown
Different embodiments of the invention).Using double screw extruder 1-5 is included by what melt extrusion formd 95-99 mass %
The polylactide of quality % total impact modifying agent (the core-shell structure copolymer compound+copolymer containing GMA)
Blend.Processing temperature and melting temperature in extrusion be maintained at more than the fusion temperature of polylactide (>170 DEG C) with true
Protect uniform fused mass.Extrudate is cast flakiness (15 mil thick) using three roller storehouses and puller.Drop impact measures
It is to be carried out with the Gardner Impact tester of the hemispherical impactor head with 2lb according to ASTM D5420.Obtain and show in table 5
The data gone out.PLA, core-shell structure copolymer compound (A) and glycidyl methacrylate copolymer (B) amount are to be based on the combination
The gross mass of thing is in terms of quality %.
Table 5.
The result shown in table 5, which demonstrates, includes relatively even a small amount of glycidyl methacrylate copolymer
(0.10-0.50 mass %) typically results in significantly improving for the impact characteristics for the PLA based composition and use thereof in packaging for also including core-shell structure copolymer compound.
That is, when constant under the gross mass of impact modifying agent ((A)+(B)) is maintained at 2%, 3% or 4%, when with 90/10 (example 19-
22) or 95/5 (example 23-26) (A)/(B) mass ratioes introduce glycidyl methacrylate copolymer when average failure energy
Value significantly increases.
Claims (15)
1. a kind of composition, said composition include polyhydroxy phenylalkanoic acid and：
(A) elastomer compounds of core-shell structure copolymer type；And
(B) ethylenic copolymer of the ethylenic monomer with epoxy-functional is included；
The amount of wherein (B) be based on the quality of said composition from the mass ratio of 0.01% to 0.6% and (A)/(B) be from more than
90/10 to 99.5/0.5, wherein (A)+(B) amount is in the range of 0.5% to 6% based on the quality of said composition.
2. composition as claimed in claim 1, the wherein ethylenic monomer with epoxy-functional are the contractings of (methyl) acrylic acid
Water glyceride.
3. composition as claimed in claim 1, wherein (B) is ethene, GMA and optionally (first
Base) alkyl acrylate copolymer, the wherein alkyl chain includes from 1 to 30 carbon atom.
4. composition as claimed in claim 1, additionally include the ethylene linkage with epoxy-functional different from this comprising other
The ethylenic polymer (C) of the ethylenic copolymer of formula monomer.
5. composition as claimed in claim 4, the wherein other ethylenic polymer (C) are ethene and (methyl) alkyl acrylate
The copolymer of base ester, the copolymer of ethene and vinyl esters of carboxylic acids, ethene and (methyl) acrylic acid or the copolymer of ionomer.
6. composition as claimed in claim 4, the wherein other ethylenic polymer (C) be ethene with scope from 1 to
The copolymer of the alkyl acrylate of 20 alkyl chain.
7. composition as claimed in claim 4, wherein mass ratio (B)/(C) is in the range of 90/10 to 10/90.
8. composition as claimed in claim 1, wherein mass ratio (A)/(B) are from the scope more than 90/10 to 96/4
It is interior.
9. composition as claimed in claim 1, wherein should be with the ethylenic monomer comprising epoxy-functional of polymerized form
Amount is in the range of 0.005% to 0.05% based on the quality of said composition.
10. composition as claimed in claim 1, the wherein polymer of the core of the core-shell structure copolymer compound (A), which have, is less than 20 DEG C
Glass transition temperature and the polymer of the shell have more than 20 DEG C of glass transition temperature.
11. the amount of the quality of composition as claimed in claim 1, the wherein core is the gross mass in the core-shell structure copolymer compound
In the range of 60% to 95%.
12. composition as claimed in claim 1, wherein the core-shell structure copolymer compound are to be in particle form and the core-shell structure copolymer chemical combination
The granularity of thing is between 50 and 600nm.
13. composition as claimed in claim 1, wherein the polyhydroxy phenylalkanoic acid are selected from by PLA (PLA) and PVOH
The group of sour (PGA) composition.
14. a kind of composition, said composition include PLA and：
(A) elastomer compounds of core-shell structure copolymer type；And
(B) ethylenic copolymer, the ethylenic copolymer include ethene, GMA and (methyl) alkyl acrylate
Base ester, the wherein alkyl chain are included from 1 to 30 carbon atom；
The amount of wherein (B) is that (A)+(B) amount is by said composition from 0.05% to 0.6% based on the quality of said composition
Quality meter is from 0.5% to 6%, and (A)/(B) mass ratio is from more than 90/10 to 99/1.
A kind of 15. method for preparing composition as claimed in claim 1, wherein (A) and (B) impact modifying agent are total to
The spherolite of mixed thing is combined with the polyhydroxy phenylalkanoic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/669,529 | 2012-11-06 | ||
| US13/669,529 US8729156B2 (en) | 2009-07-17 | 2012-11-06 | Polyhydroxyalkanoate composition exhibiting improved impact resistance at low levels of impact modifier |
| PCT/US2013/067654 WO2014074377A1 (en) | 2012-11-06 | 2013-10-31 | Polyhydroxyalkanoate composition exhibiting improved impact resistance at low levels of impact modifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104769042A CN104769042A (en) | 2015-07-08 |
| CN104769042B true CN104769042B (en) | 2018-01-02 |
Family
ID=50685082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380058044.3A Expired - Fee Related CN104769042B (en) | 2012-11-06 | 2013-10-31 | The polyhydroxy-alkanoates composition of improved impact resistance is shown under the low-level of impact modifying agent |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2917281A4 (en) |
| CN (1) | CN104769042B (en) |
| WO (1) | WO2014074377A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4038156A4 (en) * | 2019-10-01 | 2023-10-18 | Henkel AG & Co. KGaA | Two-part, cyanoacrylate/free radically curable adhesive systems |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2801597B1 (en) * | 1999-11-26 | 2005-03-11 | Atofina | COMPOSITIONS OF THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES |
| FR2801596B1 (en) * | 1999-11-26 | 2004-12-03 | Atofina | THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES AND SHOCK MODIFIER COMPOSITIONS |
| EP1955845B1 (en) * | 2005-11-30 | 2013-04-10 | Mitsubishi Plastics, Inc. | Thermally shrinkable polyolefin film, molded article using the film, thermally shrinkable label, and container |
| EP2454321B1 (en) * | 2009-07-17 | 2015-01-07 | Arkema France | Polyhydroxyalkanoate composition with an improved impact resistance |
-
2013
- 2013-10-31 WO PCT/US2013/067654 patent/WO2014074377A1/en active Application Filing
- 2013-10-31 CN CN201380058044.3A patent/CN104769042B/en not_active Expired - Fee Related
- 2013-10-31 EP EP13852505.0A patent/EP2917281A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014074377A1 (en) | 2014-05-15 |
| EP2917281A1 (en) | 2015-09-16 |
| CN104769042A (en) | 2015-07-08 |
| EP2917281A4 (en) | 2016-04-13 |
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