CN101993584A - Transparent toughness polyactic acid composition - Google Patents
Transparent toughness polyactic acid composition Download PDFInfo
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Abstract
The invention discloses a transparent toughness polyactic acid composition, which consists of the following components in part by weight: (A) 100 parts of polymer of which the main body is polyactic acid, (B) 1 to 30 parts of biodegradable aliphat polyester resin, and (C) 0.1 to 5 parts of reactive compatilizer, wherein the reactive compatilizer is an acrylate polymer having an epoxy reactive functional group, and the epoxy functionality is 0.1 to 1 meq/g. The composition has high impact properties, and simultaneously and obtained product has high transparency; besides, in the processing process, the reactive compatilizer is adopted to control the epoxy functionality and the addition to ensure that the problems of over-high melt viscosity and oversized processing torque in the processing process are solved, the processing difficulty is reduced, and the processing cost is reduced.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of poly (lactic acid) composition, specifically, is a kind of poly (lactic acid) composition that has the transparency and impact property concurrently.
Background technology
In recent years; from global environment protection viewpoint; biodegradable material has been subjected to people's common concern; wherein; polylactic resin is the biodegradable plastic of first kind of large-scale industrial production in the world, and its raw material is polymerized by fermentation from corn; the transparency is excellent, and fusing point is higher relatively.
But polylactic resin is very crisp, and impact resistance is relatively poor, so cracking is broken easily in the use of moulding product.Therefore a lot of researchs have been launched in the world to the poly(lactic acid) toughening modifying.
Method as the aliphatic polyester except that the lactic acid resin such as combination polybutylene succinate, polybutylene succinate/adipate copolymer is disclosed as Japanese Patent H10-87976, but, this method is in order effectively to improve the resin shock resistance, need a large amount of aliphatic polyesters, so just had a strong impact on the original properties of transparency of polylactic resin.
Document Journal of Applied polymer Science, Vol.106,1813-1820 (2007) discloses a kind of at polylactic resin, add the research of isocyanic ester in the polybutylene succinate as the reaction compatilizer, this method can improve poly(lactic acid), the impact resistance of polybutylene succinate mixture relatively.But do not relate to the properties of transparency modification of goods in this document.
U.S. Pat 2005/0154114A1 discloses and has a kind ofly added compatilizer in the blend of poly(lactic acid) and polytetramethylene glycol hexanodioic acid/terephthaldehyde's acid copolymer, and the methacrylic acid segmented copolymer improves the impact resistance of blend product.But this piece patent is not mentioned the properties of transparency of blend product equally, and the epoxy goods that add are bigger owing to epoxy equivalent (weight), cause the problem that melt is crosslinked and viscosity increases in the course of processing easily, thereby can influence the transparency of goods yet.
Summary of the invention
The invention provides a kind of biodegradable poly (lactic acid) composition, not only goods have higher shock resistance, also have preferable properties of transparency simultaneously.Realization of the present invention can realize by following concrete grammar:
A kind of poly (lactic acid) composition, said composition mainly are made of following component:
(A) lactic acid is polymkeric substance 100 weight parts of main body,
(B) biodegradable aliphatic polyester resin 1～30 weight part,
(C) reactive compatibilizers 0.1～5 weight part; Wherein, reactive compatibilizers is the acrylic polymer of band oxygen reactive functionality, and the epoxy-functional degree is 0.1～1meq/g.Preferred epoxy-functional degree is 0.5～0.7meq/g.
Lactic acid among the present invention is the polymkeric substance of main body, the homopolymer and the multipolymer that comprise lactic acid can be from D lactic acid, L lactic acid or their mixtures, and perhaps lactic acid is with the multipolymer of aliphatic ester, also can use the mixture of two or more polylactic acid polymers, preferred poly(lactic acid).Poly(lactic acid) is made by the benzilate dimerization generation catalysis ring-opening polymerization of the lactic acid that is called " rac-Lactide " usually.
The multipolymer of lactic acid reacts by rac-Lactide or another lactic acid derivatives and one or more cyclic esters and/or benzilate dimerization generation catalyzed copolymerization usually and prepares.Typical comonomer is the benzilate dimerization of glycollide, oxyacetic acid; α, α '-dimethyl-β-b-rac-Lactide, 2, the cyclic ester of 2-dimethyl-3-hydroxy-propionic acid; The cyclic ester of the cyclic ester of beta-butyrolactone, 3-hydroxybutyric acid, δ-Wu Neizhi, 5-hydroxypentanoic acid; The cyclic ester of 6-caprolactone, 6 hydroxycaproic acid, with and methyl substituted derivative such as 2-methyl-6 hydroxycaproic acid, 3,3, the lactone of 5-trimethylammonium-6 hydroxycaproic acid etc., the cyclic ester of sabinic acid and 2-are to the cyclic ester of-diethyleno dioxide ketones, 2-(2-hydroxyethyl) oxyacetic acid.Also can use aliphatics and aromatic diacid and diol monomer, such as Succinic Acid, hexanodioic acid and terephthalic acid and ethylene glycol, 1, ammediol and 1,4-butyleneglycol.
About lactic acid is the molecular weight of the polymkeric substance of main body, and there is no particular limitation, as weight-average molecular weight, considers from certain impact resistance, preferred more than 50,000, further preferred more than 80,000.And for the upper limit, preferred below 500,000 from mobile viewpoint, further preferred below 300,000.
Weight-average molecular weight is polystyrene calibration, and tetrahydrofuran (THF) is the gel permeation chromatography of moving phase.
Biodegradable aliphatic polyester resin among the present invention is the blend of the multipolymer of the multipolymer of biodegradable aliphatic dibasic acid binary alcohol esters and/or biodegradable aliphatic dibasic acid binary alcohol esters.Its example can be enumerated and wait with poly-(EGS ethylene glycol succinate) and poly-(succinic acid-butanediol ester) be aliphatic polyester representative, that be made of dibasic alcohol and dicarboxylic acid, gather (6-caprolactone) is gathering (ω-hydroxyalkanoate) and then can enumerating the gathering of the demonstration biological degradability that can contain aromatic component (succinic acid-butanediol ester-co-mutual-phenenyl two acid bromide two alcohol ester) and (tetramethylene adipate-co-mutual-phenenyl two acid bromide two alcohol ester) of representative.Wherein preferred poly butylene succinate (being PBGS) is biodegradable aliphatic polyester representative, that be made of dibasic alcohol and dicarboxylic acid.
The multipolymer of described biodegradable aliphatic dibasic acid binary alcohol esters, be preferably 1, the multipolymer of 4-butyleneglycol and aliphatic dibasic acid and/or 1, the blend of the multipolymer of 4-butyleneglycol and aliphatic dibasic acid, more preferably PBGS.
The molecular weight of biodegradable aliphatic polyester resin has no particular limits, and serves as preferred with weight-average molecular weight 50,000～500,000, and 80,000～300,000 is further preferred.When weight-average molecular weight melt viscosity of resin combination less than 50,000 time is low excessively, opposite weight-average molecular weight descends greater than the plasticity of 300,000 o'clock resin combinations.Weight-average molecular weight is polystyrene calibration, and chloroform is the gel permeation chromatography of moving phase.
Biodegradable aliphatic polyester resin consumption in prescription serves as preferred with 1～30 weight part, when consumption less than 1 weight part, can not well improve the impact property of lactic acid resin, when consumption greater than 30 weight parts, will have a strong impact on the properties of transparency of goods.Wherein further preferred 1～20 weight part.
Reactive compatibilizers among the present invention is the acrylic polymer that has epoxy reaction functional group, comprise the acrylate of band oxygen functional group and the multipolymer of alkene class, epoxy-functional can and/or have the esters of acrylic acid unit of epoxy-functional for the glycidyl methacrylate unit.
The acrylic polymer of described band oxygen functional group is preferably the multipolymer of glycidyl methacrylate unit and acrylate monomer and/or vinyl monomer; Perhaps have the unitary graft acrylic acid esters polymer of glycidyl methacrylate for main chain.
Described acrylic ester monomer can be the acrylate of non-replacement, also can be the acrylate that replaces, for example alkyl acrylate.Acrylic ester monomer of the present invention is preferably methacrylic ester, methyl methacrylate, methyl acrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, ethyl acrylate, methacrylic acid-2-ethylhexyl, Octyl acrylate, Octyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, allyl methacrylate(AMA), allyl acrylate, vinylformic acid-2-hydroxybutyl ester, one or more in methacrylic acid-2-hydroxybutyl ester.
Vinyl monomer can be common alkene class and vinyl derivative monomer, optimal ethylene, and third is rare, butylene, different third is rare, iso-butylene, octene, vinylbenzene, vinyl toluene, vinyl acetate between to for plastic, vinyl cyanide.
Reactive compatibilizers among the present invention is the acrylic polymer that has epoxy reaction functional group, preferred main chain has the unitary graft type polymethylmethacrylate of glycidyl methacrylate, glycidyl methacrylate, methyl methacrylate, styrol copolymer and ethene, acrylate, glycidyl methacrylate copolymer.
Proportioning among the present invention during to each the monomeric polymerization in the acrylic polymer of band oxygen functional group does not have specific requirement, as long as above-mentioned three kinds of monomer polymerizations can be become the acrylic polymer of band oxygen functional group, and the epoxy-functional degree reaches requirement of the present invention and gets final product.
Reactive compatibilizers among the present invention has effectively been improved composition impact property and properties of transparency, and by selecting the compatilizer of certain epoxy functionalities for use, influences mist degree greatly thereby effectively avoid melt viscosity to become.In the present invention, its content serves as preferred with 0.1～5 weight part, and is too small when consumption, can not have tangible reaction to take place, and can not well improve the goods impact property; When consumption is excessive, causes in the course of processing melt viscosity excessive easily, and finally also can influence the goods properties of transparency.Wherein further preferred 0.5～3 weight part.Its epoxy-functional degree serves as preferred with 0.1～1meq/g then, further preferred 0.5～0.7meq/g; When its functional group's degree increases the problem that also can bring melt viscosity to increase.
Epoxy-functional degree meq/g=(1/ epoxy equivalent (weight)) * 1000, the resin epoxy equivalent (weight) can be provided or just can be recorded by chemical analysis method according to national standard by manufacturer, states no longer in detail here.
Above-mentioned poly (lactic acid) composition is preferably mainly composed of the following components: (A) poly(lactic acid) of 100 weight parts, (B) the biodegradable butyleneglycol of 1～20 weight part and aliphatic dibasic acid copolyesters, (C) glycidyl methacrylate of 0.5～3 weight part and acrylate monomer and/or vinyl monomer multipolymer or be the graft copolymer that has the monomeric methyl methacrylate of glycidyl methacrylate on the graft copolymer main chain of 0.5～3 weight part.
In the aliphatic polyester resin composition of the present invention, as long as its characteristic is not had big infringement, can add the common pigments, thermo-stabilizer, antioxidant, weather resisting agent, fire retardant, softening agent, lubricant, releasing agent, static inhibitor, packing material of routine dose etc.Thermo-stabilizer and antioxidant can use for example Hinered phenols, phosphorus compound, hindered amine, sulphur compound, copper compound, alkali-metal halogenide or their mixture.The additive of these thermo-stabilizers, antioxidant, weather resisting agent etc. generally adds when melting mixing or during polymerization.Inorganic filling material has been enumerated, talcum, lime carbonate, zinc carbonate, wollastonite, silicon-dioxide, aluminum oxide, magnesium oxide, Calucium Silicate powder, sodium aluminate, calcium aluminate, sodium silicoaluminate, Magnesium Silicate q-agent, glass sphere, carbon black, zinc oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zeolite, hydrotalcite, steel fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, glass fibre, carbon fiber etc.Organic filler material has been enumerated, naturally occurring polymkeric substance or their modifiers such as starch, cellulose fine particle, wood powder, residue from beans after making, rice husk, wheat bran, mestha.
Mixing other the thermoplastic resin and/or the method for filling agent in aliphatic polyester resin composition of the present invention has no particular limits.Can behind common heating and melting, use the mixing method of for example known single shaft extrusion machine, double-shafted extruder, roll-type mixing roll, Banbury etc. to come mixing.Also having, also is static(al) mixing tank and dynamic mixer merging use effective.
Aliphatic polyester resin composition of the present invention can use known manufacturing process to form various shaping things.Preferably use as manufacturing process and to be selected from injection forming, blow molding, curtain coating and to be shaped, die forming, the manufacturing process of one or more kinds in the extrusion molding, moulding product of the present invention can be used as various uses, as Electrical and Electronic equipment (for example electric appliance casing), material of construction, trolley part, daily necessities, medical usage and agricultural use.
Beneficial effect of the present invention compared with the prior art: compared with prior art, the product that the present invention obtains has higher impact property, the goods that obtain simultaneously have the preferable transparency, and in the course of processing, the reactive compatibilizers that the present invention adopts has been controlled epoxy functionalities and addition, make and avoided melt viscosity excessive in the course of processing that the appearance of excessive these problems of processing torque has reduced the difficulty of processing and reduced tooling cost.
Embodiment
By the following examples the present invention is described in further detail.Yet the present invention has more than and is limited to following embodiment (the every weight part of following examples is 200 grams).
The test and the forming method that use in embodiment and the Comparative Examples are as follows:
(1) extrusion moulding
The poly (lactic acid) composition certain proportion is extruded 170 ℃ in processing temperature hopper, 200 ℃ of melt blending sections, 190 ℃ of die orifices through adding the forcing machine melt blending after the blend.Obtain pellet at last.
(2) injection moulding
According to ISO179 size injection moulding batten, 170 ℃ of hopper temperatures, 200 ℃ of melt temperatures, 190 ℃ of die temperature.Pressure 60MPa.
(3) Impact Test
According to ISO179 mark test bars simple beam impact strength.
(4) mist degree haze test
Extrude and obtain the sheet material that pellet is pressed into 500 μ m thickness, use mist degree instrument test haze value according to ASTM D1003 standard.
Embodiment 1
Poly(lactic acid) 100 weight parts (4042D nature works weight-average molecular weight 20w), PBGS (bionolle1020, Showa polymer) 20 weight parts, main chain has the unitary graft type polymethylmethacrylate of glycidyl methacrylate, weight part 0.5 (GP301, East Asia is synthetic, epoxy-functional degree 0.5～0.7meq/g).Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 2～3
According to embodiment 1, all the other components are constant, and PBGS (bionolle 1020, Showa polymer) is respectively 5,10 weight parts.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 4～5
According to embodiment 1, all the other components are constant, and the GP301 component is respectively 1,3 weight part, add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 6
Poly(lactic acid) 100 weight parts (6251D nature works weight-average molecular weight 10w), polytetramethylene glycol Succinic Acid/adipic acid ester (bionolle 3001Showa polymer) 20 weight parts, glycidyl methacrylate/methyl methacrylate/styrol copolymer (MP20, KANEKA Corporation, epoxy-functional degree 0.5～0.7meq/g) 0.5 weight part.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 7～8
According to embodiment 6, all the other components are constant, and the MP20 component is respectively 1,3 weight part.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 9
(REVODE 101 for polylactic resin, the positive biotech firm in sea, weight-average molecular weight 20w), polytetramethylene glycol hexanodioic acid/terephthalate (Ecoflex, Basf) 20 weight parts, ethylene/methyl acrylate/glycidyl methacrylate copolymer (LotaderAX8900, Arkema epoxy functionalities 0.5～0.7meq/g) 0.5 weight part.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 10～11
According to embodiment 9, all the other components are constant, and the AX8900 component is respectively 1,3 weight part.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 12～14
(Plamate 150 for polylactic-acid block copolymer, DIC company) 100 weight parts, ethylene/butyl acrylate/glycidyl methacrylate copolymer (elvaloy PTW, dupont) 0.1 weight part immobilizes, PBGS (bionolle 1001, Showa polymer) quality is respectively 1,20,30 weight parts.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Embodiment 15～17
(Plamate 150 for polylactic-acid block copolymer, DIC company) 100 weight parts, ethylene/butyl acrylate/glycidyl methacrylate copolymer (elvaloy PTW, dupont) 5 weight parts immobilize, PBGS (bionolle1001, Showa polymer) quality is respectively 1,20,30 weight parts.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 1
Poly(lactic acid) 100 weight parts (4042D nature works weight-average molecular weight 20w), PBGS (bionolle1020, Showa polymer) 20 weight parts.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 2
Poly(lactic acid) 100 weight parts (4042D nature works weight-average molecular weight 20w), PBGS (bionolle1020, Showa polymer) 20 weight parts, main chain has the unitary graft type polymethylmethacrylate of glycidyl methacrylate, weight part 5 (GP301, East Asia is synthetic, epoxy-functional degree 0.5～0.7meq/g).Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 3
Poly(lactic acid) 100 weight parts (6251D nature works weight-average molecular weight 10w), polytetramethylene glycol Succinic Acid/adipic acid ester (bionolle 3001Showa polymer) 20 weight parts add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 4
Poly(lactic acid) 100 weight parts (6251D nature works weight-average molecular weight 10w), polytetramethylene glycol Succinic Acid/adipic acid ester (bionolle 3001Showa polymer) 20 weight parts, glycidyl methacrylate/methyl methacrylate/styrol copolymer (almatex PD6100, Arkema epoxy-functional degree 1.0～1.2meq/g) 1 weight parts add forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 5
Polylactic resin (REVODE 101, the positive biotech firm in sea, weight-average molecular weight 20w), polytetramethylene glycol hexanodioic acid/terephthalate (Ecoflex, Basf) 20 weight parts.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 6
(REVODE 101 for polylactic resin, the positive biotech firm in sea, weight-average molecular weight 20w), polytetramethylene glycol hexanodioic acid/terephthalate (Ecoflex, Basf) 20 weight parts, glycidyl methacrylate/methyl methacrylate/styrol copolymer (almatex PD6100, Arkema epoxy-functional degree 1.0～1.2meq/g) 3 weight parts.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Comparative Examples 7,8
(Plamate 150 for polylactic-acid block copolymer, DIC company) 100 weight parts, PBGS (bionolle1001, Showa polymer) quality is 20 weight parts, ethylene/butyl acrylate/glycidyl methacrylate copolymer (elvaloy PTW, dupont) be respectively 0.1,5 weight part.Add the forcing machine melt blending, extruding pelletization.Difference test performance after injection moulding and the press mold moulding.
Concrete data see table 1 for details
Table 1
The result: shown in table 1 data, use the poly(lactic acid) of compatilizer, aliphatic poly ester mixture impact property all is significantly improved, and properties of transparency also has bigger improvement.When compatibilizer content increased in the Comparative Examples 2, linear growth had not had influence on whole properties of transparency to impact property on the contrary thereupon increasing.When using the bigger compatilizer of epoxy-functional degree, also there is similar problem, as Comparative Examples 4 and 6.
Claims (9)
1. transparent toughness poly (lactic acid) composition, this poly (lactic acid) composition mainly is made of following component:
(A) lactic acid is polymkeric substance 100 weight parts of main body,
(B) biodegradable aliphatic polyester resin 1～30 weight part,
(C) reactive compatibilizers 0.1～5 weight part; Wherein, reactive compatibilizers is the acrylic polymer of band oxygen reactive functionality, and its epoxy-functional degree is 0.1～1meq/g.
2. poly (lactic acid) composition according to claim 1 is characterized in that, the epoxy-functional degree of the acrylic polymer of described band oxygen reactive functionality is 0.5～0.7meq/g.
3. poly (lactic acid) composition according to claim 1, it is characterized in that described lactic acid is that the polymkeric substance of main body is the homopolymer of lactic acid, the multipolymer of L and/or D lactic acid, lactic acid is with the multipolymer of aliphatic ester, or the mixture of two or more polylactic acid polymers.
4. poly (lactic acid) composition according to claim 1, it is characterized in that the blend of the multipolymer that described biodegradable aliphatic polyester resin is biodegradable aliphatic dibasic acid binary alcohol esters and/or the multipolymer of biodegradable aliphatic dibasic acid binary alcohol esters.
5. poly (lactic acid) composition according to claim 4, it is characterized in that, the multipolymer of described biodegradable aliphatic dibasic acid binary alcohol esters is 1, the multipolymer of 4-butyleneglycol and aliphatic dibasic acid and/or 1, the blend of the multipolymer of 4-butyleneglycol and aliphatic dibasic acid.
6. poly (lactic acid) composition according to claim 1, it is characterized in that, the acrylic acid esters polymer of described band oxygen reactive functionality is the multipolymer of glycidyl methacrylate and acrylate monomer and/or vinyl monomer, perhaps has the unitary graft type acrylic ester polymer of glycidyl methacrylate for main chain.
7. poly (lactic acid) composition according to claim 6, it is characterized in that, described acrylate monomer is a methacrylic ester, methyl methacrylate, methyl acrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, ethyl acrylate, methacrylic acid-2-ethylhexyl, Octyl acrylate, Octyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, allyl methacrylate(AMA), allyl acrylate, vinylformic acid-2-hydroxybutyl ester, one or more in methacrylic acid-2-hydroxybutyl ester.
8. poly (lactic acid) composition according to claim 6 is characterized in that, described vinyl monomer is an ethene, and third is rare, butylene, and different third is rare, iso-butylene, octene, vinylbenzene, vinyl toluene, vinyl acetate between to for plastic or vinyl cyanide.
9. according to the described poly (lactic acid) composition of claim 1～6, it is characterized in that said composition is mainly composed of the following components:
(A) poly(lactic acid) of 100 weight parts,
(B) the biodegradable butyleneglycol of 1～20 weight part and aliphatic dibasic acid copolyesters,
(C) glycidyl methacrylate of 0.5～3 weight part and acrylate monomer and/or vinyl monomer multipolymer or be the graft copolymer that has the monomeric methyl methacrylate of glycidyl methacrylate on the graft copolymer main chain of 0.5～3 weight part.
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