CN102838855A - Biodegradable composite, disposable product and preparation method thereof - Google Patents
Biodegradable composite, disposable product and preparation method thereof Download PDFInfo
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- CN102838855A CN102838855A CN2011101734140A CN201110173414A CN102838855A CN 102838855 A CN102838855 A CN 102838855A CN 2011101734140 A CN2011101734140 A CN 2011101734140A CN 201110173414 A CN201110173414 A CN 201110173414A CN 102838855 A CN102838855 A CN 102838855A
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Abstract
The invention relates to a biodegradable composite and a preparation method of the biodegradable composite. The composite is prepared through mixing and contacting of a mixture containing polylactic acid, branched aliphatic-aromatic copolyester and organic peroxide at 100-200 DEG C. The invention further relates to a disposable product which is prepared by the biodegradable composite. The biodegradable composite is good in biodegradability and toughness.
Description
Technical field
The present invention relates to a kind of biodegradable mixture, the preparation method of this biodegradable mixture, and a kind of disposable product that makes by above-mentioned biodegradable mixture.
Background technology
POLYACTIC ACID is as the Biodegradable material that comes from bio-based; Because it has broken away from unique dependency of petroleum resources; And product can degraded under microbial process after the use fully, and final product is carbonic acid gas and water, returns life round-robin nature track; Its significant low-carbon (LC) load property, biocompatibility, biodegradable characteristics and favorable mechanical performance and use properties, other any material all can't be equal to it at present.But poly-lactic acid material self is because higher second-order transition temperature (about 50-60 ℃) and the property that shows is crisp and self softening temperature is low and defectives such as poor heat resistance that cause have greatly limited the application of POLYACTIC ACID.Therefore investigators are devoted to the toughness reinforcing and thermotolerance of POLYACTIC ACID has been carried out a large amount of research one after another both at home and abroad.
POLYACTIC ACID is carried out toughening modifying mainly carry out through the mode of copolymerization and blend, the modification by copolymerization complex process, the production cycle is long, and cost is high, and difficult enforcement is difficult to the industriallization continuous production, and the mode of opposite blend is implemented relatively easily.Therefore, adopt the mode of blend on existing apparatus, POLYACTIC ACID to be carried out the preferred version that toughening modifying becomes toughening modifying.
Be directed to toughening modifying; Best toughner is exactly the elastomer material of rubber-like; Like the MBS that uses among the CN101875763A; The olefin(e) compound of ethylene copolymer that uses among CN101495568A, US20100112357 and the US20060263394 or band oxygen functional group is as anti-impact and plasticized modifier etc., but this type material self is non-degradable material, after POLYACTIC ACID mixes; Can influence the biodegradation character of material, lose the original environmental protection meliority that is superior to other material of POLYACTIC ACID on the contrary.
Therefore, using Biodegradable material is the optimal selection to the POLYACTIC ACID toughening modifying as the POLYACTIC ACID plasticized modifier.For example; The biodegradable polyester mixture of mentioning among the US20080281018; Contain aliphatic-aromatic copolyester, other biodegradable polyesters and contain the compound of epoxy-functional; Comprising containing fatty aromatic copolyesters, POLYACTIC ACID and contain the mixture of the compound of epoxy-functional, though compare the toughness that can improve the compsn that contains POLYACTIC ACID in this case with POLYACTIC ACID, and obtain biodegradable poly (lactic acid) composition; But the toughening modifying effect of this poly (lactic acid) composition still is limited, particularly aspect anti-impact and tensile property.
Summary of the invention
The objective of the invention is to overcome the existing above-mentioned defective that contains the compsn of POLYACTIC ACID, a kind of biodegradable mixture and preparation method thereof is provided.
The invention provides a kind of biodegradable mixture, this mixture makes through mixing to contact at the 100-200 ℃ of following mixture that will contain POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide; Said aliphatic-aromatic copolyester is generated by the esterification raw material reaction, and said esterification raw material contains: (a) C
8-C
20Aromatic dicarboxylic acid compounds and C
2-C
20The aliphatic dibasic acids compounds, (b) C
2-C
20Aliphatic dihydroxy alcohol and/or C
3-C
10Alicyclic divalent alcohol, (c) functionality greater than 2 polyvalent alcohol, functionality greater than at least a greater than in the acid anhydrides of 2 polycarboxylic acid of 2 polycarboxylic acid and functionality.
The present invention also provides a kind of preparation method of biodegradable mixture, and this method may further comprise the steps:
(1) make the esterification raw material reaction generate aliphatic-aromatic copolyester, wherein, said esterification raw material contains: (a) C
8-C
20Aromatic dicarboxylic acid compounds and C
2-C
20The aliphatic dibasic acids compounds, (b) C
2-C
20Aliphatic dihydroxy alcohol and/or C
3-C
10Alicyclic divalent alcohol, (c) functionality greater than 2 polyvalent alcohol, functionality greater than at least a greater than in the acid anhydrides of 2 polycarboxylic acid of 2 polycarboxylic acid and functionality;
(2) under 100-200 ℃, the mixture that will contain aliphatic-aromatic copolyester and the organo-peroxide of preparation in the POLYACTIC ACID, step (1) mixes and contacts.
The present invention also provides a kind of disposable product; This disposable product is processed by biodegradable mixture, and said biodegradable mixture is the biodegradable mixture that biodegradable mixture provided by the invention perhaps prepares according to method provided by the invention.
In said biodegradable mixture provided by the invention, said organo-peroxide can be promoted the consistency of POLYACTIC ACID and aliphatic-aromatic copolyester, plays the effect of chain extension increase-volume, has improved the toughness of this mixture simultaneously effectively.
And, because the aliphatic-aromatic copolyester itself in the said biodegradable mixture has good biodegradable performance, make said biodegradable mixture of the present invention have excellent biodegradability.
In addition, the organo-peroxide in the said biodegradable mixture is nontoxic, does not influence the environmental friendliness performance of this mixture.
Overcome the brittle shortcoming of traditional poly-lactic acid material according to said biodegradable mixture provided by the invention, thereby be suitable for extruding fields such as blown film, membrane, bottle blowing, injection moulding, foaming, compressing tablet, be particularly useful for disposable product.Said biodegradable mixture of the present invention is owing to have excellent biodegradability; Make the goods of processing by this biodegradable mixture (like disposable product) after discarded; Can degrade through conventional biodegradation method (like composting process), thereby can not cause environmental pollution.
Embodiment
According to said biodegradable mixture provided by the invention, this mixture makes through mixing to contact at the 100-200 ℃ of following mixture that will contain POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide.The temperature of said mixing contact is preferably 100-170 ℃.
Under preferable case, said biodegradable mixture is added to mix in the twin screw extruder through the mixture that will contain POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide and contacts granulation then.Under the most preferred situation, in the said twin screw extruder from the opening for feed to the extrusion temperature of each section be followed successively by 100-105 ℃, 165-170 ℃, 165-170 ℃ and 160-165 ℃.
According to said biodegradable mixture provided by the invention, said POLYACTIC ACID can be the various POLYACTIC ACIDs of routine use.Under preferable case, said POLYACTIC ACID is the mixture of L-POLYACTIC ACID (PLLA) or L-POLYACTIC ACID (PLLA) and D-POLYACTIC ACID (PDLA).Under preferred situation, the content of L-POLYACTIC ACID is 50-100 weight % in the said POLYACTIC ACID.Under above-mentioned preferable case, the available further raising of the toughness of said biodegradable mixture and biodegradability.
In the present invention; Said POLYACTIC ACID can be the poly-lactic acid products of commercially available various routines; Under the preferable case, said POLYACTIC ACID number-average molecular weight can be 50,000-200,000, can be the poly-lactic acid products of 4042D for the trade mark available from Nature Works LLC company for example.
According to said biodegradable mixture provided by the invention, said aliphatic-aromatic copolyester is generated by the esterification raw material reaction, and said esterification raw material contains: (a) C
8-C
20Aromatic dicarboxylic acid compounds and C
2-C
20The aliphatic dibasic acids compounds, (b) C
2-C
20Aliphatic dihydroxy alcohol and/or C
3-C
10Alicyclic divalent alcohol, (c) functionality greater than 2 polyvalent alcohol, functionality greater than at least a greater than in the acid anhydrides of 2 polycarboxylic acid of 2 polycarboxylic acid and functionality.
In the present invention, said C
8-C
20The aromatic dicarboxylic acid compounds can be C
8-C
20Aromatic acid, C
8-C
20Aromatic dicarboxylic anhydride and C
8-C
20The ester of aromatic acid in one or more.Under the preferable case, said C
8-C
20The aromatic dicarboxylic acid compounds be m-phthalic acid, dimethyl isophthalate, terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, phthalic acid, dimethyl phthalate, Tetra hydro Phthalic anhydride, 2,6-naphthalic acid, 2,6-naphthalene diformic acid dimethyl ester, 1; 5-naphthalic acid, 1; 5-naphthalene diformic acid dimethyl ester, 2,7-naphthalic acid, 2,7-naphthalene diformic acid dimethyl ester, 4; 4 '-biphenyl dicarboxylic acid, 4; 4 '-biphenyl dicarboxylic acid dimethyl ester, 3,4 '-biphenyl dicarboxylic acid and 3, one or more in 4 '-biphenyl dicarboxylic acid dimethyl ester.Under the further preferable case, said C
8-C
20The aromatic dicarboxylic acid compounds be terephthalic acid and/or DMT. Dimethyl p-benzenedicarboxylate.
In the present invention, said C
2-C
20The aliphatic dibasic acids compounds can be C
2-C
20Aliphatic dibasic acid, C
3-C
10Alicyclic diprotic acid, their ester and their acid anhydrides in one or more.Under the preferable case, said C
2-C
20Aliphatic dibasic acids compounds Succinic Acid, Succinic anhydried, dimethyl adipate, hexanodioic acid, adipic anhydride, nonane diacid, sebacic acid, dodecanedioic acid, 1; 4-cyclohexane diacid, 1; 2,4,5-hexanaphthene tetracarboxylic dianhydride, 1; In 4-cyclohexane diacid dimethyl ester and the norbornane diacid one or more further are preferably at least a in Succinic Acid, hexanodioic acid and the sebacic acid.
In the present invention, component (b) is preferably C
2-C
10Aliphatic dihydroxy alcohol and/or C
5-C
10Alicyclic divalent alcohol; Further be preferably in terepthaloyl moietie, glycol ether, Ucar 35, butyleneglycol, pentanediol, pinakon, cyclohexane diol and the norbornane dimethanol one or more, more preferably one or more in Ucar 35, butyleneglycol, pentanediol and the pinakon.
In the present invention, the purpose that in the process of preparation aliphatic-aromatic copolyester, adds component (c) is to impel to form the aliphatic-aromatic copolyester that has side chain.Therefore, there is not special qualification for component (c) among the present invention, as long as have the active function groups more than 3.In the present invention, said active function groups be meant can with the functional group of hydroxyl and/or carboxyl generation condensation reaction.
Functionality in the said component (c) is meant the organic cpds with at least two alcoholic extract hydroxyl groups greater than 2 polyvalent alcohol, can also have one or more carboxyls or other reactive group in this polyvalent alcohol.Likewise, said functionality is meant the organic cpds with at least two carboxyls greater than 2 polycarboxylic acid, and this polycarboxylic acid can also have one or more hydroxyls or other reactive group.
Under preferable case; Said component (c) is one or more in tartrate, Hydrocerol A, Malic acid, D-, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, polyether-tribasic alcohol, glycerine, trimesic acid, trimellitic acid, trimellitic anhydride, PMA, pyromellitic acid dianhydride and the hydroxyisophthalic acid, more preferably at least a in USP Kosher, tetramethylolmethane and the pyromellitic acid dianhydride.
According to said biodegradable mixture provided by the invention, in said esterification raw material, component (a), component (b) do not have special qualification with the consumption of component (c), as long as with forming aliphatic-aromatic copolyester after their mixing contacts.Yet, having better toughness and biodegradability in order to guarantee said biodegradable mixture of the present invention, the mol ratio of component (a) and component (b) is preferably 1: 0.5-2.5, more preferably 1: 0.7-1.5; The weight ratio of component (a) and component (c) is preferably 100-1000: 1, and 200-800 more preferably: 1.
Under further preferred situation, in component (a), be benchmark with component (a) gross weight, said C
8-C
20The content of aromatic dicarboxylic acid compounds be 5-75 weight %, more preferably 30-60 weight %; Said C
2-C
20The content of aliphatic dibasic acids compounds be 25-95 weight %, more preferably 40-70 weight %.
According to said biodegradable mixture provided by the invention, the reaction times of said esterification raw material can be 3.5-12 hour.
According to said biodegradable mixture provided by the invention; In the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide; Gross weight with this mixture is a benchmark, and the content of said POLYACTIC ACID can be 10-95 weight %, is preferably 45-80 weight %; The content of said aliphatic-aromatic copolyester can be 4-89 weight %, is preferably 19-54 weight %; The content of said organo-peroxide can be 0.01-2 weight %, is preferably 0.05-1 weight %.
According to said biodegradable mixture provided by the invention, said organo-peroxide can be for playing the organo-peroxide of the various routines of chain extension compatibilization in poly (lactic acid) composition.Under the preferable case, the transformation period (t of said organo-peroxide under 100-200 ℃
1/2) be 0.2-10 minute.In the present invention, the said transformation period is meant that the organo-peroxide in the 100-200 ℃ of down said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide decomposes to the required time of a half of initial concentration.
Under further preferable case; Said organo-peroxide is to be selected from dialkyl, peroxo-diacyl and the peroxyester one or more; Most preferably be Di Cumyl Peroxide 99,2; 5-dimethyl--2, one or more in two (tert-butyl peroxide) hexanes of 5-, two (t-butyl peroxy sec.-propyl) benzene, BPO, lauroyl peroxide and the tert-butyl hydroperoxide isobutyrate.Under above-mentioned preferable case, said biodegradable mixture has better toughness.
In a kind of preferred implementation; Have better machining property and stable mechanical property in order to ensure said biodegradable mixture, the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide preferably also contains slipping agent and/or oxidation inhibitor.Said slipping agent can be the various slipping agents that routine is used, and for example can be in erucicamide, amine hydroxybenzene and the stearic amide one or more.Said oxidation inhibitor also can be the various conventional antioxidant products that use, and under the preferable case, said oxidation inhibitor is hindered phenol type antioxidant.Said hindered phenol type antioxidant is preferably the two β of triglycol-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester and/or β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid octadecanol ester.In the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide, be benchmark with the gross weight of this mixture, the content of said slipping agent can be 0.01-1 weight %, is preferably 0.05-0.5 weight %; The content of said oxidation inhibitor can be 0.01-1 weight %, is preferably 0.05-0.5 weight %.
The present invention also provides a kind of preparation method of biodegradable mixture, and this method may further comprise the steps:
(1) make the esterification raw material reaction generate aliphatic-aromatic copolyester, wherein, said esterification raw material contains: (a) C
8-C
20Aromatic dicarboxylic acid compounds and C
2-C
20The aliphatic dibasic acids compounds, (b) C
2-C
20Aliphatic dihydroxy alcohol and/or C
3-C
10Alicyclic divalent alcohol, (c) functionality greater than 2 polyvalent alcohol, functionality greater than at least a greater than in the acid anhydrides of 2 polycarboxylic acid of 2 polycarboxylic acid and functionality;
(2) under 100-200 ℃, the mixture that will contain aliphatic-aromatic copolyester and the organo-peroxide of preparation in the POLYACTIC ACID, step (1) mixes and contacts.
According to said method provided by the invention, in step (1), the component (a) in the said esterification raw material, component (b) and component (c) all with preamble describe identical.
According to said method provided by the invention, in step (1), in said esterification raw material, component (a), component (b) do not have special qualification with the consumption of component (c), as long as with forming aliphatic-aromatic copolyester after their mixing contacts.Yet, having better toughness and biodegradability in order to guarantee said biodegradable mixture of the present invention, the mol ratio of component (a) and component (b) is preferably 1: 0.5-2.5, more preferably 1: 0.7-1.5; The weight ratio of component (a) and component (c) is preferably 100-1000: 1, and 200-800 more preferably: 1.
Under further preferred situation, in component (a), be benchmark with component (a) gross weight, said C
8-C
20The content of aromatic dicarboxylic acid compounds be 5-75 weight %, more preferably 30-60 weight %; Said C
2-C
20The content of aliphatic dibasic acids compounds be 25-95 weight %, more preferably 40-70 weight %.
According to said method provided by the invention; In step (1); The method of said esterification raw material reaction is preferably included: component (a), component (b) and component (c) in the said esterification raw material are reacted under the esterification condition, and the product of this reaction is reacted under the polycondensation condition.Said esterification condition can comprise: temperature of reaction is 150-240 ℃, and the reaction times is 0.5-5 hour; The condition of said polycondensation can comprise: temperature of reaction is 200-300 ℃, and reaction pressure is 0-800Pa, and the reaction times is 3-7 hour.
Under preferred situation, component (a), component (b) and the reaction process of component (c) under the esterification condition comprise: (1) makes the C in the component (a)
8-C
20Aromatic dicarboxylic acid compounds and at least a portion component (b) under first temperature, react; (2) with mixture that obtains after the reaction in (1) and the C in the component (a)
2-C
20Aliphatic dibasic acids compounds, component (c) and remaining component (b) under second temperature, react.Said second temperature is preferably than high 5-30 ℃ of said first temperature.Under the further preferred situation, said first temperature is 150-225 ℃, more preferably 180-210 ℃; Said second temperature is 160-240 ℃, more preferably 190-230 ℃.The component (b) that in above-mentioned (1), adds preferably accounts for the 40-100 weight % of the total amount of the component (b) that adds in above-mentioned (1) and (2), more preferably 50-80 weight %.
According to said method provided by the invention; In step (1); Carry out under the existence that is reflected at catalyzer of said esterification raw material; Said catalyzer can be the conventional various catalyzer that use in the preparation process of aliphatic-aromatic copolyester, and for example, said catalyzer can contain: (1) is selected from least a in oxide compound and the titanyl compound of oxide compound, antimony of titan-alkoxide, antimony acetate, zinc acetate, zinc; (2) be selected from least a in Dibutyltin oxide, tin tetraethyl, triphenyl hydroxyl tin, dibutyltin diacetate, two LAURIC ACID 99 MIN tin diphenyls, monobutyl-tin-trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxy White tin oxide, stannoacetic acid, ethyl stannonic acid and the butyl stannonic acid; And (3) general formula is RE (R
1)
3Compound, wherein, RE is a thulium, R
1For being selected from halogen, alkoxyl group, aryloxy, acetylacetone based and R
2At least a in the COO-group, R
2Be C
1-C
30Alkyl, for example can be in Triple Pressed Stearic Acid lanthanum, Lanthanum trichloride, methyl ethyl diketone lanthanum, isopropoxy scandium, three (2,6-di-t-butyl-4-methylphenoxy) lanthanum and the cerous acetate at least a.
According to said method provided by the invention, in step (2), said POLYACTIC ACID and organo-peroxide all with preamble describe identical.
According to said method provided by the invention; In step (2), in the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide, be benchmark with the gross weight of this mixture; The content of said POLYACTIC ACID can be 10-95 weight %, is preferably 45-80 weight %; The content of said aliphatic-aromatic copolyester can be 4-89 weight %, is preferably 19-54 weight %; The content of said organo-peroxide can be 0.01-2 weight %, is preferably 0.05-1 weight %.
According to said method provided by the invention, in step (2), the said mixture mixing that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide contacts and is preferably 100-170 ℃.
Under preferred situation, the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide is added to mix in the twin screw extruder contacts granulation then.Under the most preferred situation, in the said twin screw extruder from the opening for feed to the extrusion temperature of each section be followed successively by 100-105 ℃, 165-170 ℃, 165-170 ℃ and 160-165 ℃.
According to said method provided by the invention; In step (2); Said organo-peroxide and POLYACTIC ACID, aliphatic-aromatic copolyester method of mixing preferably included with organic solvent (like acetone) organo-peroxide is dissolved earlier; The mixture that will be dissolved with organo-peroxide then spreads on the mixture that contains POLYACTIC ACID and aliphatic-aromatic copolyester, and fully mixes.
In a kind of preferred implementation, in step (2), the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide preferably also contains slipping agent and/or oxidation inhibitor.Said slipping agent and oxidation inhibitor all with preamble describe identical.In the said mixture that contains POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide, be benchmark with the gross weight of this mixture, the content of said slipping agent can be 0.01-1 weight %, is preferably 0.05-0.5 weight %; The content of said oxidation inhibitor can be 0.01-1 weight %, is preferably 0.05-0.5 weight %.
The present invention also provides a kind of disposable product; This disposable product is processed by biodegradable mixture, and said biodegradable mixture is the biodegradable mixture that biodegradable mixture provided by the invention perhaps prepares according to method provided by the invention.Said disposable product for example can make through conventional forming method (as extruding blown film, membrane, bottle blowing, injection moulding, foaming, compressing tablet etc.), thereby said disposable product can be membrane product, injection-molded item, foaming product, sheet material etc.
Below through embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
Present embodiment is used for specification sheets said biodegradable mixture provided by the invention and preparation method thereof.
(1) preparation of aliphatic-aromatic copolyester
Catalyzer: the gross weight with this catalyzer is a benchmark, and this catalyzer contains the Triple Pressed Stearic Acid lanthanum (method according to embodiment A 5 among the CN 1807485A makes) of 57.8 weight %, the tetrabutyl titanate (available from Beijing chemical reagents corporation) of 23.2 weight %, the Dibutyltin oxide (available from Beijing Chemical Factory No. 3) of 10.0 weight % and the triphenyl hydroxyl tin (available from Beijing chemical reagents corporation) of 9.0 weight %.
In the reactor drum of 2.5L, add 1.72mol terephthalic acid (285.2g), 2.78mol 1, the above-mentioned catalyzer of 4-butyleneglycol and 1.058g is under nitrogen atmosphere; Be heated with stirring to backflow, with temperature regulation to 230 ℃ and about 100 minutes of reaction under this temperature, when the water that question response generates steams fully; To wherein adding 1 of 1.86mol, 1 of 4-Succinic Acid (220g), 2.22mol, the tetramethylolmethane of 4-butyleneglycol and 1.3g; Continue heated and stirred to refluxing, with temperature regulation to 200 ℃ and about 100 minutes of reaction under this temperature, when the water that question response generates steams fully; Pressure in the reaction kettle is adjusted to below the 200Pa; Temperature regulation to 240 ℃, and polycondensation 4 hours under this temperature and pressure obtain light yellow polymer A 1.
(2) preparation of biodegradable composite materials
The poly (l-lactic acid) (PLLA) that takes by weighing 300g is (available from Nature Works LLC company; The trade mark is 4042D) and (1) of 200g in polymer A 1 of preparation; And with they uniform mixing, add successively then 0.5g erucicamide (reaching chemical materials ltd) and 1.0g available from Beijing star shellfish 2,5-dimethyl--2; 5-two (tertiary butyl) peroxo-hexane is (available from joining chemical industry ltd, the t in the time of 177 ℃ together
1/2Be 1 minute), and mix.Mixed material is carried out extruding pelletization through twin screw extruder (section temperature of each in the forcing machine from the opening for feed to the extrusion is controlled to be 100 ℃, 170 ℃, 170 ℃ and 165 ℃ successively), obtain biodegradable mixture.Then, should carry out the fusion compressing tablet by biodegradable mixture, obtain mixture sheet material S1.
Embodiment 2
Present embodiment is used for specification sheets said biodegradable mixture provided by the invention and preparation method thereof.
(1) preparation of aliphatic-aromatic copolyester
Catalyzer: the gross weight with this catalyzer is a benchmark, and this catalyzer contains the Triple Pressed Stearic Acid lanthanum (method according to embodiment A 5 among the CN 1807485A makes) of 57.8 weight %, the tetrabutyl titanate (available from Beijing chemical reagents corporation) of 23.2 weight %, the Dibutyltin oxide (available from Beijing Chemical Factory No. 3) of 10.0 weight % and the triphenyl hydroxyl tin (available from Beijing chemical reagents corporation) of 9.0 weight %.
In the reactor drum of 2.5L, add terephthalic acid (119.5g), the 1mol of 0.72mol DMT. Dimethyl p-benzenedicarboxylate (194.2g), 2.55mol 1, the above-mentioned catalyzer of ammediol and 1.058g is under nitrogen atmosphere; Be heated with stirring to backflow, with temperature regulation to 230 ℃ and about 100 minutes of reaction under this temperature, when water that question response generates and methyl alcohol steam fully; To wherein adding 1 of 1.38mol; 1 of 6-hexanodioic acid (201.5g), 2.10mol, the PMA of ammediol and 2.5g (available from the Tianjin auspicious chemical industry of gold ltd) continues heated and stirred to refluxing; With temperature regulation to 200 ℃ and about 100 minutes of reaction under this temperature; When the water that question response generates steams fully, the pressure in the reaction kettle is adjusted to below the 200Pa temperature regulation to 240 ℃; And polycondensation 4 hours under this temperature and pressure, obtain light yellow polymer A 2.
(2) preparation of biodegradable composite materials
The poly (l-lactic acid) (PLLA) that takes by weighing 300g is (available from Nature Works LLC company; The trade mark is 4042D) and (1) of 200g in polymer A 2 of preparation; And with they uniform mixing; Pair (t-butyl peroxy sec.-propyl) benzene of the two β of triglycol-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (available from Guangzhou logical sequence Leech industrial chemicals ltd) and 1.0g of erucicamide (reaching chemical materials ltd available from Beijing star shellfish), 0.5g that add 0.5g then successively are (available from last maritime business's scape Industrial Co., Ltd., the t in the time of 185 ℃
1/2Be 1 minute), and mix.Mixed material is carried out extruding pelletization through twin screw extruder (section temperature of each in the forcing machine from the opening for feed to the extrusion is controlled to be 100 ℃, 170 ℃, 170 ℃ and 165 ℃ successively), obtain biodegradable mixture.Then, should carry out the fusion compressing tablet by biodegradable mixture, obtain mixture sheet material S2.
Embodiment 3
Present embodiment is used for specification sheets said biodegradable mixture provided by the invention and preparation method thereof.
(1) preparation of aliphatic-aromatic copolyester
Catalyzer: the gross weight with this catalyzer is a benchmark, and this catalyzer contains the Triple Pressed Stearic Acid lanthanum (method according to embodiment A 5 among the CN 1807485A makes) of 57.8 weight %, the tetrabutyl titanate (available from Beijing chemical reagents corporation) of 23.2 weight %, the Dibutyltin oxide (available from Beijing Chemical Factory No. 3) of 10.0 weight % and the triphenyl hydroxyl tin (available from Beijing chemical reagents corporation) of 9.0 weight %.
In the reactor drum of 2.5L, add 2mol terephthalic acid (332g), 1.8mol 1, the above-mentioned catalyzer of 4-butyleneglycol and 1.058g is under nitrogen atmosphere; Be heated with stirring to backflow, with temperature regulation to 230 ℃ and about 100 minutes of reaction under this temperature, when the water that question response generates steams fully; To wherein adding 1 of 2.5mol, 1 of 3-propanedioic acid (260g), 1.8mol, the Malic acid, D-of 4-butyleneglycol and 2.0g (available from the triumphant promise chemical industry in Guangzhou ltd); Continue heated and stirred to refluxing, with temperature regulation to 200 ℃ and about 100 minutes of reaction under this temperature, when the water that question response generates steams fully; Pressure in the reaction kettle is adjusted to below the 200Pa; Temperature regulation to 240 ℃, and polycondensation 7 hours under this temperature and pressure obtain light yellow polymer A 3.
(2) preparation of biodegradable composite materials
The poly (l-lactic acid) (PLLA) that takes by weighing 300g is (available from Nature Works LLC company; The trade mark is 4042D) and (1) of 200g in polymer A 3 of preparation; And with they uniform mixing; Add successively then the erucicamide (reaching chemical materials ltd) of 0.5g and the tert-butyl hydroperoxide isobutyrate of 1.0g available from Beijing star shellfish (available from the auxiliary reagent factory, Lanzhou, the t in the time of 118 ℃
1/2Be 6 minutes), and mix.Mixed material is carried out extruding pelletization through twin screw extruder (section temperature of each in the forcing machine from the opening for feed to the extrusion is controlled to be 100 ℃, 170 ℃, 170 ℃ and 165 ℃ successively), obtain biodegradable mixture.Then, should carry out the fusion compressing tablet by biodegradable mixture, obtain mixture sheet material S3.
Comparative Examples 1
Method according to embodiment 3 prepares biodegradable composite materials, and different is in the process of the biodegradable composite materials of preparation, not add tert-butyl hydroperoxide isobutyrate (being organo-peroxide), thereby make composite sheet DS1.
Comparative Examples 2
Method according to embodiment 3 prepares biodegradable composite materials; Different is; In the process of the biodegradable composite materials of preparation; Replace the tert-butyl hydroperoxide isobutyrate with the SY-Monomer G (available from the chemical ltd of the anti-Ji in last Hai'an) of 1g and the epoxy soybean oil (available from the long-range Science and Technology Ltd. in Chinese and Western, Beijing, the trade mark is SL830-HYDDY 25) of 5g, thereby make composite sheet DS2.
Embodiment 4
Present embodiment is used for specification sheets said biodegradable mixture provided by the invention and preparation method thereof.
Method according to embodiment 3 prepares biodegradable composite materials, and different is that in the process of the biodegradable composite materials of preparation, the consumption of aliphatic-aromatic copolyester is 75g, thereby makes mixture sheet material S4.
Embodiment 5
Present embodiment is used for specification sheets said biodegradable mixture provided by the invention and preparation method thereof.
Method according to embodiment 3 prepares biodegradable composite materials, and different is that in the process of the biodegradable composite materials of preparation, the consumption of aliphatic-aromatic copolyester is 300g, thereby makes mixture sheet material S5.
Test case
The mensuration of melting index (MI): the CS-127 type fusion index instrument that adopts U.S. scientific instrument manufacturing company to provide; Method according to ISO1133-2005; At 190 ℃, 2.16kg load down, the melt flow rate(MFR) of the biodegradable mixture that obtains among detection embodiment 1-5 and the Comparative Examples 1-2;
Detect stretching yield stress, tensile break stress and the elongation at break of mixture sheet material S1-S5 and DS1-DS2 according to the method for GB/T 1040.2-2006;
Detect the simple beam notched Izod impact strength of mixture sheet material S1-S5 and DS1-DS2 according to the method for GB/T 1043.1-2008;
Measure the biodegradability of the plastic pellet of preparation mixture sheet material S1-S5 and DS1-DS2 according to the method for GB/T 20197-2006;
Above-mentioned detected result is as shown in table 1 below.
Table 1
Can find out from the data of table 1; Said biodegradable mixture provided by the invention not only has excellent biodegradability can; But also have the shock resistance and the tension fracture performance of obvious raising, thereby can be used for making membrane product, injection-molded item, foaming product, sheet material etc. through extruding blown film, membrane, bottle blowing, injection moulding, foaming, compressing tablet etc.Particularly, through embodiment 3 is compared and can find out with Comparative Examples 1 and 2,, obviously improved the shock resistance and the tension fracture performance of biodegradable mixture through having added the organo-peroxide of chain extension compatibilization.
Above embodiment only is used to describe preferred implementation of the present invention; But; The present invention is not limited to the detail in the above-mentioned embodiment; In technical conceive scope of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (19)
1. a biodegradable mixture is characterized in that, this mixture makes through mixing to contact at the 100-200 ℃ of following mixture that will contain POLYACTIC ACID, aliphatic-aromatic copolyester and organo-peroxide;
Said aliphatic-aromatic copolyester is generated by the esterification raw material reaction, and said esterification raw material contains: (a) C
8-C
20Aromatic dicarboxylic acid compounds and C
2-C
20The aliphatic dibasic acids compounds, (b) C
2-C
20Aliphatic dihydroxy alcohol and/or C
3-C
10Alicyclic divalent alcohol, (c) functionality greater than 2 polyvalent alcohol, functionality greater than at least a greater than in the acid anhydrides of 2 polycarboxylic acid of 2 polycarboxylic acid and functionality.
2. mixture according to claim 1 wherein, is a benchmark with the gross weight of said mixture, and the content of said POLYACTIC ACID is 10-95 weight %, is preferably 45-80 weight %; The content of said aliphatic-aromatic copolyester is 4-89 weight %, is preferably 19-54 weight %; The content of said organo-peroxide is 0.01-2 weight %, is preferably 0.05-1 weight %.
3. mixture according to claim 1 and 2, wherein, said POLYACTIC ACID is the mixture of L-POLYACTIC ACID or L-POLYACTIC ACID and D-POLYACTIC ACID, and the content of L-POLYACTIC ACID is 50-100 weight % in the said POLYACTIC ACID.
4. mixture according to claim 1, wherein, in said esterification raw material, component (a) is 1 with the mol ratio of component (b): 0.5-2.5 is preferably 1: 0.7-1.5; Component (a) is 100-1000 with the weight ratio of component (c): 1, be preferably 200-800: 1; In component (a), be benchmark with component (a) gross weight, said C
8-C
20The content of aromatic dicarboxylic acid compounds be 5-75 weight %, more preferably 30-60 weight %; Said C
2-C
20The content of aliphatic dibasic acids compounds be 25-95 weight %, more preferably 40-70 weight %; The reaction times of said esterification raw material is 3.5-12 hour.
5. according to claim 1 or 4 described mixtures, wherein, in said esterification raw material, said C
8-C
20The aromatic dicarboxylic acid compounds be C
8-C
20Aromatic acid, C
8-C
20Aromatic dicarboxylic anhydride and C
8-C
20The ester of aromatic acid in one or more, be preferably m-phthalic acid, dimethyl isophthalate, terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, phthalic acid, dimethyl phthalate, Tetra hydro Phthalic anhydride, 2,6-naphthalic acid, 2; 6-naphthalene diformic acid dimethyl ester, 1,5-naphthalic acid, 1,5-naphthalene diformic acid dimethyl ester, 2; 7-naphthalic acid, 2; 7-naphthalene diformic acid dimethyl ester, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid dimethyl ester, 3; 4 '-biphenyl dicarboxylic acid and 3, one or more in 4 '-biphenyl dicarboxylic acid dimethyl ester; Said C
2-C
20The aliphatic dibasic acids compounds be C
2-C
20Aliphatic dibasic acid, C
3-C
10Alicyclic diprotic acid, their ester and their acid anhydrides in one or more; Be preferably Succinic Acid, Succinic anhydried, dimethyl adipate, hexanodioic acid, adipic anhydride, nonane diacid, sebacic acid, dodecanedioic acid, 1; 4-cyclohexane diacid, 1,2,4; 5-hexanaphthene tetracarboxylic dianhydride, 1, one or more in 4-cyclohexane diacid dimethyl ester and the norbornane diacid; Component (b) is C
2-C
10Aliphatic dihydroxy alcohol and/or C
5-C
10Alicyclic divalent alcohol, be preferably in terepthaloyl moietie, glycol ether, Ucar 35, butyleneglycol, pentanediol, pinakon, cyclohexane diol and the norbornane dimethanol one or more; Component (c) is one or more in tartrate, Hydrocerol A, Malic acid, D-, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, polyether-tribasic alcohol, glycerine, trimesic acid, trimellitic acid, trimellitic anhydride, PMA, pyromellitic acid dianhydride and the hydroxyisophthalic acid, is preferably at least a in USP Kosher, tetramethylolmethane and the pyromellitic acid dianhydride.
6. mixture according to claim 1 and 2; Wherein, The transformation period of said organo-peroxide under 100-200 ℃ is 0.2-10 minute, and is selected from dialkyl, peroxo-diacyl and the peroxyester one or more, is preferably Di Cumyl Peroxide 99,2; 5-dimethyl--2, one or more in two (tert-butyl peroxide) hexanes of 5-, two (t-butyl peroxy sec.-propyl) benzene, BPO, lauroyl peroxide and the tert-butyl hydroperoxide isobutyrate.
7. mixture according to claim 1, wherein, said mixture also contains slipping agent and/or oxidation inhibitor; Said slipping agent is preferably one or more in erucicamide, amine hydroxybenzene and the stearic amide; Said oxidation inhibitor is preferably hindered phenol type antioxidant, more preferably the two β of triglycol-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester and/or β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid octadecanol ester.
8. mixture according to claim 7 wherein, is a benchmark with the gross weight of said mixture, and the content of said slipping agent is 0.01-1 weight %, is preferably 0.05-0.5 weight %; The content of said oxidation inhibitor is 0.01-1 weight %, is preferably 0.05-0.5 weight %.
9. the preparation method of a biodegradable mixture, this method may further comprise the steps:
(1) make the esterification raw material reaction generate aliphatic-aromatic copolyester, wherein, said esterification raw material contains: (a) C
8-C
20Aromatic dicarboxylic acid compounds and C
2-C
20The aliphatic dibasic acids compounds, (b) C
2-C
20Aliphatic dihydroxy alcohol and/or C
3-C
10Alicyclic divalent alcohol, (c) functionality greater than 2 polyvalent alcohol, functionality greater than at least a greater than in the acid anhydrides of 2 polycarboxylic acid of 2 polycarboxylic acid and functionality;
(2) under 100-200 ℃, the mixture that will contain aliphatic-aromatic copolyester and the organo-peroxide of preparation in the POLYACTIC ACID, step (1) mixes and contacts.
10. method according to claim 9, wherein, in said esterification raw material, component (a) is 1 with the mol ratio of component (b): 0.5-2.5 is preferably 1: 0.7-1.5; Component (a) is 100-1000 with the weight ratio of component (c): 1, be preferably 200-800: 1; In component (a), be benchmark with component (a) gross weight, said C
8-C
20The content of aromatic dicarboxylic acid compounds be 5-75 weight %, more preferably 30-60 weight %; Said C
2-C
20The content of aliphatic dibasic acids compounds be 25-95 weight %, more preferably 40-70 weight %.
11. according to claim 9 or 10 described methods; Wherein, The method of said esterification raw material reaction is comprised: component (a), component (b) and component (c) in the said esterification raw material are reacted under the esterification condition, and the product of this reaction is reacted under the polycondensation condition.
12. method according to claim 11, wherein, said esterification condition comprises: temperature of reaction is 150-240 ℃, and the reaction times is 0.5-5 hour; The condition of said polycondensation comprises: temperature of reaction is 200-300 ℃, and reaction pressure is 0-800Pa, and the reaction times is 3-7 hour.
13. according to claim 9 or 10 described methods, wherein, in said esterification raw material, said C
8-C
20The aromatic dicarboxylic acid compounds be C
8-C
20Aromatic acid, C
8-C
20Aromatic dicarboxylic anhydride and C
8-C
20The ester of aromatic acid in one or more, be preferably m-phthalic acid, dimethyl isophthalate, terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, phthalic acid, dimethyl phthalate, Tetra hydro Phthalic anhydride, 2,6-naphthalic acid, 2; 6-naphthalene diformic acid dimethyl ester, 1,5-naphthalic acid, 1,5-naphthalene diformic acid dimethyl ester, 2; 7-naphthalic acid, 2; 7-naphthalene diformic acid dimethyl ester, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid dimethyl ester, 3; 4 '-biphenyl dicarboxylic acid and 3, one or more in 4 '-biphenyl dicarboxylic acid dimethyl ester; Said C
2-C
20The aliphatic dibasic acids compounds be C
2-C
20Aliphatic dibasic acid, C
3-C
10Alicyclic diprotic acid, their ester and their acid anhydrides in one or more; Be preferably Succinic Acid, Succinic anhydried, dimethyl adipate, hexanodioic acid, adipic anhydride, nonane diacid, sebacic acid, dodecanedioic acid, 1; 4-cyclohexane diacid, 1,2,4; 5-hexanaphthene tetracarboxylic dianhydride, 1, one or more in 4-cyclohexane diacid dimethyl ester and the norbornane diacid; Component (b) is C
2-C
10Aliphatic dihydroxy alcohol and/or C
5-C
10Alicyclic divalent alcohol, be preferably in terepthaloyl moietie, glycol ether, Ucar 35, butyleneglycol, pentanediol, pinakon, cyclohexane diol and the norbornane dimethanol one or more; Component (c) is one or more in tartrate, Hydrocerol A, Malic acid, D-, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, polyether-tribasic alcohol, glycerine, trimesic acid, trimellitic acid, trimellitic anhydride, PMA, pyromellitic acid dianhydride and the hydroxyisophthalic acid, is preferably at least a in USP Kosher, tetramethylolmethane and the pyromellitic acid dianhydride.
14. method according to claim 9 wherein, in step (2), is a benchmark with the gross weight of said mixture, the content of said POLYACTIC ACID is 10-95 weight %, is preferably 45-80 weight %; The content of said aliphatic-aromatic copolyester is 4-89 weight %, is preferably 19-54 weight %; The content of said organo-peroxide is 0.01-2 weight %, is preferably 0.05-1 weight %.
15. method according to claim 9, wherein, said POLYACTIC ACID is the mixture of L-POLYACTIC ACID or L-POLYACTIC ACID and D-POLYACTIC ACID, and the content of L-POLYACTIC ACID is 50-100 weight % in the said POLYACTIC ACID.
16. method according to claim 9; Wherein, The transformation period of said organo-peroxide under 100-200 ℃ is 0.2-10 minute, and is selected from dialkyl, peroxo-diacyl and the peroxyester one or more, is preferably Di Cumyl Peroxide 99,2; 5-dimethyl--2, one or more in two (tert-butyl peroxide) hexanes of 5-, two (t-butyl peroxy sec.-propyl) benzene, BPO, lauroyl peroxide and the tert-butyl hydroperoxide isobutyrate.
17. method according to claim 9, wherein, in step (2), said mixture also contains slipping agent and/or oxidation inhibitor; Said slipping agent is preferably one or more in erucicamide, amine hydroxybenzene and the stearic amide; Said oxidation inhibitor is preferably hindered phenol type antioxidant, more preferably the two β of triglycol-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester and/or β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid octadecanol ester.
18. method according to claim 17 wherein, is a benchmark with the gross weight of said mixture, the content of said slipping agent is 0.01-1 weight %, is preferably 0.05-0.5 weight %; The content of said oxidation inhibitor is 0.01-1 weight %, is preferably 0.05-0.5 weight %.
19. disposable product; This disposable product is processed by biodegradable mixture; It is characterized in that said biodegradable mixture is any described biodegradable mixture or according to the biodegradable mixture of any described method preparation among the claim 9-18 among the claim 1-8.
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