CN102838855B - Biodegradable composite, disposable product and preparation method thereof - Google Patents
Biodegradable composite, disposable product and preparation method thereof Download PDFInfo
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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 obtained by above-mentioned biodegradable mixture.
Background technology
Poly(lactic acid) is as the Biodegradable material coming from bio-based, because it has broken away from unique dependency of petroleum resources, and product after a procedure can be degradable under microbial process, final product is carbonic acid gas and water, return the natural track of Life Cycles, its significant low-carbon (LC) is load, biocompatibility, biodegradable characteristics and good mechanical property and use properties, and other any material all cannot be equal to it at present.But the property that poly-lactic acid material self shows because of higher second-order transition temperature (about 50-60 DEG C) is crisp and self softening temperature is low and the defect such as poor heat resistance caused significantly limit the application of poly(lactic acid).Therefore investigators are devoted to have carried out large quantifier elimination to the toughness reinforcing of poly(lactic acid) and thermotolerance one after another both at home and abroad.
Carry out toughening modifying to poly(lactic acid) to carry out mainly through copolymerization and blended mode, modification by copolymerization complex process, the production cycle is long, and cost is high, more difficult enforcement, is difficult to industrialization continuous seepage, and mode blended on the contrary is relatively easily implemented.Therefore, blended mode is adopted to carry out to poly(lactic acid) the preferred version that toughening modifying becomes toughening modifying on existing apparatus.
Be directed to toughening modifying, best toughner is exactly the elastomer material of rubber-like, as the MBS used in CN101875763A, the olefin(e) compound of the ethylene copolymer used in CN101495568A, US20100112357 and US20060263394 or band epoxy-functional is as anti-impact and plasticized modifier etc., but this kind of material self is non-degradable material, after mixing with poly(lactic acid), the biodegradation character of material can be affected, lose the original environmental protection superiority being better than other material of poly(lactic acid) on the contrary.
Therefore, Biodegradable material is used to be the optimal selection to poly(lactic acid) toughening modifying as polylactic acid toughening modifier.Such as, the biodegradable polyester mixture mentioned in US20080281018, containing aliphatic-aromatic copolyester, other biodegradable polyesters and the compound containing epoxy-functional, comprising containing fatty aromatic copolyesters, the mixture of poly(lactic acid) and the compound containing epoxy-functional, although the toughness of the composition containing poly(lactic acid) can be improved in this case compared with poly(lactic acid), and obtain biodegradable poly (lactic acid) composition, but the toughening modifying effect of this poly (lactic acid) composition or limited, particularly in anti-impact and tensile property.
Summary of the invention
The object of the invention is the above-mentioned defect overcoming the existing composition containing poly(lactic acid), provide a kind of biodegradable mixture and preparation method thereof.
The invention provides a kind of biodegradable mixture, this mixture by obtaining carrying out mixing to contact containing poly(lactic acid), aliphatic-aromatic copolyester and the mixture of organo-peroxide at 100-200 DEG C; Described aliphatic-aromatic copolyester is generated by esterification raw material reaction, and described esterification raw material contains: (a) C
8-C
20aromatic dicarboxylic acid compounds and C
2-C
20aliphatic dibasic acids compounds, (b) C
2-C
20aliphatic dihydroxy alcohol and/or C
3-C
10cycloaliphatic diols, polyvalent alcohol, functionality that (c) functionality is greater than 2 be greater than 2 polycarboxylic acid and functionality be greater than at least one in the acid anhydrides of the polycarboxylic acid of 2.
Present invention also offers a kind of preparation method of biodegradable mixture, the method comprises the following steps:
(1) make esterification raw material reaction generate aliphatic-aromatic copolyester, wherein, described esterification raw material contains: (a) C
8-C
20aromatic dicarboxylic acid compounds and C
2-C
20aliphatic dibasic acids compounds, (b) C
2-C
20aliphatic dihydroxy alcohol and/or C
3-C
10cycloaliphatic diols, polyvalent alcohol, functionality that (c) functionality is greater than 2 be greater than 2 polycarboxylic acid and functionality be greater than at least one in the acid anhydrides of the polycarboxylic acid of 2;
(2) at 100-200 DEG C, contact carrying out mixing containing the aliphatic-aromatic copolyester of preparation in poly(lactic acid), step (1) with the mixture of organo-peroxide.
Present invention also offers a kind of disposable product, this disposable product is made up of biodegradable mixture, the biodegradable mixture that described biodegradable mixture is biodegradable mixture provided by the invention or prepares according to method provided by the invention.
In described biodegradable mixture provided by the invention, described organo-peroxide can promote the consistency of poly(lactic acid) and aliphatic-aromatic copolyester, plays the effect of chain extension increase-volume, effectively improves the toughness of this mixture simultaneously.
And, because the aliphatic-aromatic copolyester itself in described biodegradable mixture has good biodegradable performance, make described biodegradable mixture of the present invention have excellent biodegradability.
In addition, the organo-peroxide in described biodegradable mixture is nontoxic, does not affect the environmental friendliness performance of this mixture.
Overcome the shortcoming of the fragility of traditional poly-lactic acid material according to described biodegradable mixture provided by the invention, thus be suitable for extruding the fields such as blown film, membrane, bottle blowing, injection moulding, foaming, compressing tablet, be particularly useful for disposable product.Described biodegradable mixture of the present invention is owing to having excellent biodegradability, make the goods (as disposable product) be made up of this biodegradable mixture after discarding, can be degraded by conventional biodegradation method (as composting process), thus can not environmental pollution be caused.
Embodiment
According to described biodegradable mixture provided by the invention, this mixture by obtaining carrying out mixing to contact containing poly(lactic acid), aliphatic-aromatic copolyester and the mixture of organo-peroxide at 100-200 DEG C.The temperature of described mixing contact is preferably 100-170 DEG C.
In the preferred case, described biodegradable mixture is by carrying out mixing contact being added in twin screw extruder containing poly(lactic acid), aliphatic-aromatic copolyester and the mixture of organo-peroxide, then granulation.In most preferred situation, in described twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100-105 DEG C, 165-170 DEG C, 165-170 DEG C and 160-165 DEG C.
According to described biodegradable mixture provided by the invention, described poly(lactic acid) can be the conventional various poly(lactic acid) used.In the preferred case, described poly(lactic acid) is the mixture of PLLA (PLLA) or PLLA (PLLA) and D-poly(lactic acid) (PDLA).In a more preferred case, in described poly(lactic acid), the content of PLLA is 50-100 % by weight.Under above-mentioned preferable case, the toughness of described biodegradable mixture and the available further raising of biodegradability.
In the present invention, described poly(lactic acid) can be the poly-lactic acid products of commercially available various routines, under preferable case, described poly(lactic acid) number-average molecular weight can be 50,000-20 ten thousand, such as, can be the poly-lactic acid products of 4042D for the trade mark purchased from Nature Works LLC company.
According to described biodegradable mixture provided by the invention, described aliphatic-aromatic copolyester is generated by esterification raw material reaction, and described esterification raw material contains: (a) C
8-C
20aromatic dicarboxylic acid compounds and C
2-C
20aliphatic dibasic acids compounds, (b) C
2-C
20aliphatic dihydroxy alcohol and/or C
3-C
10cycloaliphatic diols, polyvalent alcohol, functionality that (c) functionality is greater than 2 be greater than 2 polycarboxylic acid and functionality be greater than at least one in the acid anhydrides of the polycarboxylic acid of 2.
In the present invention, described C
8-C
20aromatic dicarboxylic acid compounds can be C
8-C
20aromatic acid, C
8-C
20aromatic dicarboxylic anhydride and C
8-C
20aromatic acid ester in one or more.Under preferable case, described C
8-C
20aromatic dicarboxylic acid compounds be m-phthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate (DMT), 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 further preferable case, described C
8-C
20aromatic dicarboxylic acid compounds be terephthalic acid and/or dimethyl terephthalate (DMT).
In the present invention, described C
2-C
20aliphatic dibasic acids compounds can be C
2-C
20aliphatic dibasic acid, C
3-C
10cycloaliphatic diacid, in their ester and their acid anhydrides one or more.Under preferable case, described 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, one or more in 4-cyclohexane diacid dimethyl ester and norbornane diacid, at least one more preferably in succinic acid, hexanodioic acid and sebacic acid.
In the present invention, component (b) is preferably C
2-C
10aliphatic dihydroxy alcohol and/or C
5-C
10cycloaliphatic diols, one or more more preferably in ethylene glycol, glycol ether, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexane diol and norbornane dimethanol, be more preferably in propylene glycol, butyleneglycol, pentanediol and hexylene glycol one or more.
In the present invention, the object adding component (c) in the process preparing aliphatic-aromatic copolyester impels the aliphatic-aromatic copolyester formed with side chain.Therefore, in the present invention, for component (c), there is no particular limitation, as long as have the active function groups of more than 3.In the present invention, described active function groups refer to can with the functional group of hydroxyl and/or carboxyl generation condensation reaction.
The polyvalent alcohol that functionality in described component (c) is greater than 2 refers to the organic compound with at least two alcoholic extract hydroxyl groups, can also have one or more carboxyl or other active group in this polyvalent alcohol.Similarly, the polycarboxylic acid that described functionality is greater than 2 refers to the organic compound with at least two carboxyls, and this polycarboxylic acid can also have one or more hydroxyl or other active group.
In the preferred case, described component (c) is tartrate, one or more in citric acid, hydroxy-butanedioic acid, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, polyether-tribasic alcohol, glycerine, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic acid dianhydride and hydroxyisophthalic acid, is more preferably at least one in glycerol, tetramethylolmethane and pyromellitic acid dianhydride.
According to described biodegradable mixture provided by the invention, in described esterification raw material, there is no particular limitation for the consumption of component (a), component (b) and component (c), as long as can form aliphatic-aromatic copolyester by after their mixing contacts.But in order to ensure that described biodegradable mixture of the present invention has better toughness and biodegradability, component (a) is preferably 1: 0.5-2.5 with the mol ratio of component (b), is more preferably 1: 0.7-1.5; Component (a) is preferably 100-1000: 1 with the weight ratio of component (c), is more preferably 200-800: 1.
In further preferred situation, in component (a), with component (a) gross weight for benchmark, described C
8-C
20the content of aromatic dicarboxylic acid compounds be 5-75 % by weight, be more preferably 30-60 % by weight; Described C
2-C
20the content of aliphatic dibasic acids compounds be 25-95 % by weight, be more preferably 40-70 % by weight.
According to described biodegradable mixture provided by the invention, the reaction times of described esterification raw material can be 3.5-12 hour.
According to described biodegradable mixture provided by the invention, described containing in the mixture of poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide, with the gross weight of this mixture for benchmark, the content of described poly(lactic acid) can be 10-95 % by weight, is preferably 45-80 % by weight; The content of described aliphatic-aromatic copolyester can be 4-89 % by weight, is preferably 19-54 % by weight; The content of described organo-peroxide can be 0.01-2 % by weight, is preferably 0.05-1 % by weight.
According to described biodegradable mixture provided by the invention, described organo-peroxide can for playing the organo-peroxide of the various routines of chain extension compatibilization in poly (lactic acid) composition.Under preferable case, the transformation period (t of described organo-peroxide at 100-200 DEG C
1/2) be 0.2-10 minute.In the present invention, the described transformation period to refer at 100-200 DEG C described containing the organic peroxide decomposes in the mixture of poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide to initial concentration a half needed for time.
Under further preferable case; described organo-peroxide be selected from dialkyl, diacyl peroxides and peroxyester one or more; most preferably be dicumyl peroxide, 2; one or more in 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, two (tert-butylperoxyiso-propyl) benzene, dibenzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide isobutyrates.Under above-mentioned preferable case, described biodegradable mixture has better toughness.
In a kind of preferred implementation, have good processing characteristics and stable mechanical property in order to ensure described biodegradable mixture, the described mixture containing poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide is preferably also containing slipping agent and/or oxidation inhibitor.Described slipping agent can be the conventional various slipping agents used, such as, can be one or more in erucicamide, amine hydroxybenzene and stearic amide.Described oxidation inhibitor also can be the antioxidant product that various routine uses, and under preferable case, described oxidation inhibitor is hindered phenol type antioxidant.Described hindered phenol type antioxidant is preferably two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of triglycol and/or β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid octadecanol ester.Contain in the mixture of poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide described, with the gross weight of this mixture for benchmark, the content of described slipping agent can be 0.01-1 % by weight, is preferably 0.05-0.5 % by weight; The content of described oxidation inhibitor can be 0.01-1 % by weight, is preferably 0.05-0.5 % by weight.
Present invention also offers a kind of preparation method of biodegradable mixture, the method comprises the following steps:
(1) make esterification raw material reaction generate aliphatic-aromatic copolyester, wherein, described esterification raw material contains: (a) C
8-C
20aromatic dicarboxylic acid compounds and C
2-C
20aliphatic dibasic acids compounds, (b) C
2-C
20aliphatic dihydroxy alcohol and/or C
3-C
10cycloaliphatic diols, polyvalent alcohol, functionality that (c) functionality is greater than 2 be greater than 2 polycarboxylic acid and functionality be greater than at least one in the acid anhydrides of the polycarboxylic acid of 2;
(2) at 100-200 DEG C, contact carrying out mixing containing the aliphatic-aromatic copolyester of preparation in poly(lactic acid), step (1) with the mixture of organo-peroxide.
According to described method provided by the invention, in step (1), the component (a) in described esterification raw material, component (b) and component (c) all with describe above identical.
According to described method provided by the invention, in step (1), in described esterification raw material, there is no particular limitation for the consumption of component (a), component (b) and component (c), as long as can form aliphatic-aromatic copolyester by after their mixing contacts.But in order to ensure that described biodegradable mixture of the present invention has better toughness and biodegradability, component (a) is preferably 1: 0.5-2.5 with the mol ratio of component (b), is more preferably 1: 0.7-1.5; Component (a) is preferably 100-1000: 1 with the weight ratio of component (c), is more preferably 200-800: 1.
In further preferred situation, in component (a), with component (a) gross weight for benchmark, described C
8-C
20the content of aromatic dicarboxylic acid compounds be 5-75 % by weight, be more preferably 30-60 % by weight; Described C
2-C
20the content of aliphatic dibasic acids compounds be 25-95 % by weight, be more preferably 40-70 % by weight.
According to described method provided by the invention, in step (1), the method of described esterification raw material reaction is preferably included: the component (a) in described esterification raw material, component (b) and component (c) are reacted under esterification condition, and the product of this reaction is reacted under polycondensation condition.Described esterification condition can comprise: temperature of reaction is 150-240 DEG C, and the reaction times is 0.5-5 hour; The condition of described polycondensation can comprise: temperature of reaction is 200-300 DEG C, and reaction pressure is 0-800Pa, and the reaction times is 3-7 hour.
In the preferred case, component (a), component (b) and component (c) reaction process under esterification condition comprises: (1) makes the C in component (a)
8-C
20aromatic dicarboxylic acid compounds react at a first temperature with component (b) at least partially; (2) by the C in the mixture that obtains after reaction in (1) and component (a)
2-C
20aliphatic dibasic acids compounds, component (c) and remaining component (b) react at the second temperature.Described second temperature is preferably than described first temperature height 5-30 DEG C.Further in preferred situation, described first temperature is 150-225 DEG C, is more preferably 180-210 DEG C; Described second temperature is 160-240 DEG C, is more preferably 190-230 DEG C.The component (b) added in above-mentioned (1) preferably accounts for the 40-100 % by weight of the total amount of the component (b) added in above-mentioned (1) and (2), is more preferably 50-80 % by weight.
According to described method provided by the invention, in step (1), the reaction of described esterification raw material is carried out in the presence of a catalyst, described catalyzer can be the conventional various catalyzer used in the preparation process of aliphatic-aromatic copolyester, such as, described catalyzer can contain: (1) is selected from least one in titan-alkoxide, antimony acetate, zinc acetate, the oxide compound of zinc, the oxide compound of antimony and titanyl compound; (2) at least one in Dibutyltin oxide, tin tetraethyl, fentin hydroxide, dibutyltin diacetate, tin dilaurate tin diphenyl, monobutyl-tin-trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxy stannic oxide, stannoacetic acid, ethyl stannonic acid and butyl stannonic acid is selected from; And (3) general formula is RE (R
1)
3compound, wherein, RE is thulium, R
1for being selected from halogen, alkoxyl group, aryloxy, acetylacetone based and R
2at least one in COO-group, R
2for C
1-C
30alkyl, can be such as at least one in Lanthanum Stearate, Lanthanum trichloride, lanthanum acetylacetone, isopropoxy scandium, three (2,6-di-t-butyl-4-methylphenoxy) lanthanums and cerous acetate.
According to described method provided by the invention, in step (2), described poly(lactic acid) and organo-peroxide all with describe above identical.
According to described method provided by the invention, in step (2), described containing in the mixture of poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide, with the gross weight of this mixture for benchmark, the content of described poly(lactic acid) can be 10-95 % by weight, is preferably 45-80 % by weight; The content of described aliphatic-aromatic copolyester can be 4-89 % by weight, is preferably 19-54 % by weight; The content of described organo-peroxide can be 0.01-2 % by weight, is preferably 0.05-1 % by weight.
According to described method provided by the invention, in step (2), the described mixture mixing containing poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide contact and is preferably 100-170 DEG C.
In a more preferred case, described to be added in twin screw extruder containing poly(lactic acid), aliphatic-aromatic copolyester and the mixture of organo-peroxide is carried out mixing and contacted, then granulation.In most preferred situation, in described twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100-105 DEG C, 165-170 DEG C, 165-170 DEG C and 160-165 DEG C.
According to described method provided by the invention, in step (2), the method that described organo-peroxide mixes with poly(lactic acid), aliphatic-aromatic copolyester being preferably included first uses organic solvent (as acetone) to be dissolved by organo-peroxide, then the mixture being dissolved with organo-peroxide is spread on the mixture containing poly(lactic acid) and aliphatic-aromatic copolyester, and be fully uniformly mixed.
In a kind of preferred implementation, in step (2), the described mixture containing poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide is preferably also containing slipping agent and/or oxidation inhibitor.Described slipping agent and oxidation inhibitor all with describe above identical.Contain in the mixture of poly(lactic acid), aliphatic-aromatic copolyester and organo-peroxide described, with the gross weight of this mixture for benchmark, the content of described slipping agent can be 0.01-1 % by weight, is preferably 0.05-0.5 % by weight; The content of described oxidation inhibitor can be 0.01-1 % by weight, is preferably 0.05-0.5 % by weight.
Present invention also offers a kind of disposable product, this disposable product is made up of biodegradable mixture, the biodegradable mixture that described biodegradable mixture is biodegradable mixture provided by the invention or prepares according to method provided by the invention.Described disposable product such as can be obtained by conventional forming method (as extruding blown film, membrane, bottle blowing, injection moulding, foaming, compressing tablet etc.), thus described disposable product can be membrane product, injection-molded item, foaming product, sheet material etc.
The invention will be further described by the following examples, but protection scope of the present invention is not limited in this.
Embodiment 1
The present embodiment is for illustration of book described biodegradable mixture provided by the invention and preparation method thereof.
(1) preparation of aliphatic-aromatic copolyester
Catalyzer: with the gross weight of this catalyzer for benchmark, this catalyzer contain 57.8 % by weight Lanthanum Stearate (obtaining according to the method for embodiment A 5 in CN 1807485A), the tetrabutyl titanate (purchased from Beijing chemical reagents corporation) of 23.2 % by weight, the Dibutyltin oxide (purchased from Beijing Chemical Factory No. 3) of 10.0 % by weight and 9.0 % by weight fentin hydroxide (purchased from Beijing chemical reagents corporation).
The terephthalic acid (285.2g) of 1.72mol is added in the reactor of 2.5L, 2.78mol 1, the above-mentioned catalyzer of 4-butyleneglycol and 1.058g, in a nitrogen atmosphere, be heated with stirring to backflow, temperature be adjusted to 230 DEG C and react about 100 minutes at such a temperature, when the water that question response generates steams completely, add 1 of 1.86mol wherein, 4-succinic acid (220g), 2.22mol 1, the tetramethylolmethane of 4-butyleneglycol and 1.3g, continue heated and stirred to backflow, temperature be adjusted to 200 DEG C and react about 100 minutes at such a temperature, when the water that question response generates steams completely, pressure in reactor is adjusted to below 200Pa, temperature is adjusted to 240 DEG C, and polycondensation 4 hours at this temperature and pressure, obtain yellow polymer A1.
(2) preparation of biodegradable composite materials
Take the poly (l-lactic acid) (PLLA) of 300g (purchased from Nature Works LLC company, the trade mark is 4042D) and 200g (1) in preparation polymer A 1, and by they Homogeneous phase mixing, then the erucicamide (purchased from Beijing Xing Beida chemical materials company limited) of 0.5g and 2 of 1.0g are added successively, 5-dimethyl-2,5-bis-(tertiary butyl) butylperoxyhexane (joins Chemical Co., Ltd., the t 177 DEG C time purchased from same
1/2be 1 minute), and be uniformly mixed.Mixed material is carried out extruding pelletization by twin screw extruder (each section of temperature in forcing machine from opening for feed to extrusion controls to be 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C successively), obtains biodegradable mixture.Then, this biodegradable mixture is carried out melting compressing tablet, obtain mixture sheet material S1.
Embodiment 2
The present embodiment is for illustration of book described biodegradable mixture provided by the invention and preparation method thereof.
(1) preparation of aliphatic-aromatic copolyester
Catalyzer: with the gross weight of this catalyzer for benchmark, this catalyzer contain 57.8 % by weight Lanthanum Stearate (obtaining according to the method for embodiment A 5 in CN 1807485A), the tetrabutyl titanate (purchased from Beijing chemical reagents corporation) of 23.2 % by weight, the Dibutyltin oxide (purchased from Beijing Chemical Factory No. 3) of 10.0 % by weight and 9.0 % by weight fentin hydroxide (purchased from Beijing chemical reagents corporation).
The terephthalic acid (119.5g) of 0.72mol is added in the reactor of 2.5L, the dimethyl terephthalate (DMT) (194.2g) of 1mol, 2.55mol 1, the above-mentioned catalyzer of ammediol and 1.058g, in a nitrogen atmosphere, be heated with stirring to backflow, temperature be adjusted to 230 DEG C and react about 100 minutes at such a temperature, when the water that question response generates and methyl alcohol steam completely, add 1 of 1.38mol wherein, 6-hexanodioic acid (201.5g), 2.10mol 1, the pyromellitic acid (purchased from Tianjin Jin Rui Chemical Co., Ltd.) of ammediol and 2.5g, continue heated and stirred to backflow, temperature be adjusted to 200 DEG C and react about 100 minutes at such a temperature, when the water that question response generates steams completely, pressure in reactor is adjusted to below 200Pa, temperature is adjusted to 240 DEG C, and polycondensation 4 hours at this temperature and pressure, obtain yellow polymer A2.
(2) preparation of biodegradable composite materials
Take the poly (l-lactic acid) (PLLA) of 300g (purchased from Nature Works LLC company, the trade mark is 4042D) and 200g (1) in preparation polymer A 2, and by they Homogeneous phase mixing, then the erucicamide (purchased from Beijing Xing Beida chemical materials company limited) of 0.5g is added successively, two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (purchased from Guangzhou logical sequence Leech industrial chemicals company limited) of triglycol of 0.5g and two (tert-butylperoxyiso-propyl) benzene of 1.0g are (purchased from upper maritime business's scape Industrial Co., Ltd., t 185 DEG C time
1/2be 1 minute), and be uniformly mixed.Mixed material is carried out extruding pelletization by twin screw extruder (each section of temperature in forcing machine from opening for feed to extrusion controls to be 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C successively), obtains biodegradable mixture.Then, this biodegradable mixture is carried out melting compressing tablet, obtain mixture sheet material S2.
Embodiment 3
The present embodiment is for illustration of book described biodegradable mixture provided by the invention and preparation method thereof.
(1) preparation of aliphatic-aromatic copolyester
Catalyzer: with the gross weight of this catalyzer for benchmark, this catalyzer contain 57.8 % by weight Lanthanum Stearate (obtaining according to the method for embodiment A 5 in CN 1807485A), the tetrabutyl titanate (purchased from Beijing chemical reagents corporation) of 23.2 % by weight, the Dibutyltin oxide (purchased from Beijing Chemical Factory No. 3) of 10.0 % by weight and 9.0 % by weight fentin hydroxide (purchased from Beijing chemical reagents corporation).
The terephthalic acid (332g) of 2mol is added in the reactor of 2.5L, 1 of 1.8mol, the above-mentioned catalyzer of 4-butyleneglycol and 1.058g, in a nitrogen atmosphere, be heated with stirring to backflow, temperature be adjusted to 230 DEG C and react about 100 minutes at such a temperature, when the water that question response generates steams completely, add 1 of 2.5mol wherein, 3-propanedioic acid (260g), 1 of 1.8mol, the hydroxy-butanedioic acid (purchased from Guangzhou Kai Nuo Chemical Co., Ltd.) of 4-butyleneglycol and 2.0g, continue heated and stirred to backflow, temperature be adjusted to 200 DEG C and react about 100 minutes at such a temperature, when the water that question response generates steams completely, pressure in reactor is adjusted to below 200Pa, temperature is adjusted to 240 DEG C, and polycondensation 7 hours at this temperature and pressure, obtain yellow polymer A3.
(2) preparation of biodegradable composite materials
Take the poly (l-lactic acid) (PLLA) of 300g (purchased from Nature Works LLC company, the trade mark is 4042D) and 200g (1) in preparation polymer A 3, and by they Homogeneous phase mixing, then add successively the erucicamide (purchased from Beijing Xing Beida chemical materials company limited) of 0.5g and 1.0g tert-butyl hydroperoxide isobutyrate (purchased from Lanzhou auxiliary reagent factory, the t 118 DEG C time
1/2be 6 minutes), and be uniformly mixed.Mixed material is carried out extruding pelletization by twin screw extruder (each section of temperature in forcing machine from opening for feed to extrusion controls to be 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C successively), obtains biodegradable mixture.Then, this biodegradable mixture is carried out melting compressing tablet, obtain mixture sheet material S3.
Comparative example 1
Biodegradable composite materials is prepared according to the method for embodiment 3, difference is, in the process of the biodegradable composite materials of preparation, do not add tert-butyl hydroperoxide isobutyrate (i.e. organo-peroxide), thus obtained composite sheet DS1.
Comparative example 2
Biodegradable composite materials is prepared according to the method for embodiment 3, difference is, in the process of the biodegradable composite materials of preparation, with the glycidyl methacrylate (purchased from Town in Shanghai Nai Ji Chemical Co., Ltd.) of 1g and the epoxy soybean oil of 5g (purchased from the long-range Science and Technology Ltd. in Chinese and Western, Beijing, the trade mark is SL830-HYDDY 25) replace tert-butyl hydroperoxide isobutyrate, thus obtained composite sheet DS2.
Embodiment 4
The present embodiment is for illustration of book described biodegradable mixture provided by the invention and preparation method thereof.
Prepare biodegradable composite materials according to the method for embodiment 3, difference is, in the process of the biodegradable composite materials of preparation, the consumption of aliphatic-aromatic copolyester is 75g, thus obtained mixture sheet material S4.
Embodiment 5
The present embodiment is for illustration of book described biodegradable mixture provided by the invention and preparation method thereof.
Prepare biodegradable composite materials according to the method for embodiment 3, difference is, in the process of the biodegradable composite materials of preparation, the consumption of aliphatic-aromatic copolyester is 300g, thus obtained mixture sheet material S5.
Test case
The mensuration of melting index (MI): adopt the CS-127 type fusion index instrument that American science instrument manufacturing company provides, according to the method for ISO1133-2005,190 DEG C, under 2.16kg load, detect the melt flow rate (MFR) of the biodegradable mixture obtained in embodiment 1-5 and comparative example 1-2;
The stretching yield stress of mixture sheet material S1-S5 and DS1-DS2, tensile break stress and elongation at break is detected according to the method for GB/T 1040.2-2006;
The simply supported beam notched Izod impact strength of mixture sheet material S1-S5 and DS1-DS2 is detected according to the method for GB/T 1043.1-2008;
Method according to GB/T 20197-2006 measures the biodegradability preparing the plastic pellet of mixture sheet material S1-S5 and DS1-DS2;
Above-mentioned detected result is as shown in table 1 below.
Table 1
As can be seen from the data of table 1, described biodegradable mixture provided by the invention not only has excellent biodegradability, but also there is the shock resistance and tension fracture performance that significantly improve, thus may be used for by extruding the obtained membrane product such as blown film, membrane, bottle blowing, injection moulding, foaming, compressing tablet, injection-molded item, foaming product, sheet material etc.Particularly, by embodiment 3 and comparative example 1 and 2 are compared and can be found out, by having added the organo-peroxide of chain extension compatibilization, shock resistance and the tension fracture performance of biodegradable mixture has been significantly improved.
Above embodiment is only for describing the preferred embodiment of the present invention; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive 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 (35)
1. a biodegradable mixture, is characterized in that, this mixture by obtaining carrying out mixing to contact containing poly(lactic acid), aliphatic-aromatic copolyester and the mixture of organo-peroxide at 100-200 DEG C;
Described aliphatic-aromatic copolyester is generated by esterification raw material reaction, and described esterification raw material contains: (a) C
8-C
20aromatic dicarboxylic acid compounds and C
2-C
20aliphatic dibasic acids compounds, (b) C
2-C
20aliphatic dihydroxy alcohol and/or C
3-C
10cycloaliphatic diols, polyvalent alcohol, functionality that (c) functionality is greater than 2 be greater than 2 polycarboxylic acid and functionality be greater than at least one in the acid anhydrides of the polycarboxylic acid of 2;
Described poly(lactic acid) is PLLA; The transformation period of described organo-peroxide at 100-200 DEG C is 0.2-10 minute; With the gross weight of described mixture for benchmark, the content of described poly(lactic acid) is 45-80 % by weight, and the content of described aliphatic-aromatic copolyester is 19-54 % by weight, and the content of described organo-peroxide is 0.05-1 % by weight.
2. mixture according to claim 1, wherein, in described esterification raw material, component (a) is 1:0.5-2.5 with the mol ratio of component (b); Component (a) is 100-1000:1 with the weight ratio of component (c); In component (a), with component (a) gross weight for benchmark, described C
8-C
20the content of aromatic dicarboxylic acid compounds be 5-75 % by weight, described C
2-C
20the content of aliphatic dibasic acids compounds be 25-95 % by weight; The reaction times of described esterification raw material is 3.5-12 hour.
3. mixture according to claim 2, wherein, in described esterification raw material, component (a) is 1:0.7-1.5 with the mol ratio of component (b); Component (a) is 200-800:1 with the weight ratio of component (c); In component (a), with component (a) gross weight for benchmark, described C
8-C
20the content of aromatic dicarboxylic acid compounds be 30-60 % by weight, described C
2-C
20the content of aliphatic dibasic acids compounds be 40-70 % by weight.
4. mixture according to claim 1 and 2, wherein, in described esterification raw material, described C
8-C
20aromatic dicarboxylic acid compounds be C
8-C
20aromatic acid, C
8-C
20aromatic dicarboxylic anhydride and C
8-C
20aromatic acid ester in one or more; Described C
2-C
20aliphatic dibasic acids compounds be C
2-C
20aliphatic dibasic acid, C
3-C
10cycloaliphatic diacid, in their ester and their acid anhydrides one or more; Component (b) is C
2-C
10aliphatic dihydroxy alcohol and/or C
5-C
10cycloaliphatic diols; Component (c) is tartrate, one or more in citric acid, hydroxy-butanedioic acid, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, polyether-tribasic alcohol, glycerine, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic acid dianhydride and hydroxyisophthalic acid.
5. mixture according to claim 4, wherein, described C
8-C
20aromatic dicarboxylic acid compounds be m-phthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate (DMT), 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.
6. mixture according to claim 4, wherein, described C
2-C
20aliphatic dibasic acids compounds be succinic acid, Succinic anhydried, dimethyl adipate, hexanodioic acid, adipic anhydride, nonane diacid, sebacic acid, dodecanedioic acid, 1, one or more in 4-cyclohexane diacid, Isosorbide-5-Nitrae-cyclohexane diacid dimethyl ester and norbornane diacid.
7. mixture according to claim 4, wherein, component (b) is ethylene glycol, one or more in glycol ether, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexane diol and norbornane dimethanol.
8. mixture according to claim 4, wherein, component (c) is glycerol, at least one in tetramethylolmethane and pyromellitic acid dianhydride.
9. mixture according to claim 1, wherein, described organo-peroxide be selected from dialkyl, diacyl peroxides and peroxyester one or more.
10. mixture according to claim 9, wherein, described organo-peroxide is dicumyl peroxide, 2, one or more in 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, two (tert-butylperoxyiso-propyl) benzene, dibenzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide isobutyrates.
11. mixtures according to claim 1, wherein, described mixture is also containing slipping agent and/or oxidation inhibitor.
12. mixtures according to claim 11, wherein, described slipping agent is one or more in erucicamide, amine hydroxybenzene and stearic amide.
13. mixtures according to claim 11, wherein, described oxidation inhibitor is hindered phenol type antioxidant.
14. mixtures according to claim 13, wherein, described oxidation inhibitor is two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of triglycol and/or β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid octadecanol ester.
15. according to the mixture in claim 11-14 described in any one, and wherein, with the gross weight of described mixture for benchmark, the content of described slipping agent is 0.01-1 % by weight, and the content of described oxidation inhibitor is 0.01-1 % by weight.
16. mixtures according to claim 14, wherein, with the gross weight of described mixture for benchmark, the content of described slipping agent is 0.05-0.5 % by weight, and the content of described oxidation inhibitor is 0.05-0.5 % by weight.
The preparation method of 17. 1 kinds of biodegradable mixtures, the method comprises the following steps:
(1) make esterification raw material reaction generate aliphatic-aromatic copolyester, wherein, described esterification raw material contains: (a) C
8-C
20aromatic dicarboxylic acid compounds and C
2-C
20aliphatic dibasic acids compounds, (b) C
2-C
20aliphatic dihydroxy alcohol and/or C
3-C
10cycloaliphatic diols, polyvalent alcohol, functionality that (c) functionality is greater than 2 be greater than 2 polycarboxylic acid and functionality be greater than at least one in the acid anhydrides of the polycarboxylic acid of 2;
(2) at 100-200 DEG C, contact carrying out mixing containing the aliphatic-aromatic copolyester of preparation in poly(lactic acid), step (1) with the mixture of organo-peroxide;
Described poly(lactic acid) is PLLA; The transformation period of described organo-peroxide at 100-200 DEG C is 0.2-10 minute; With the gross weight of described mixture for benchmark, the content of described poly(lactic acid) is 45-80 % by weight, and the content of described aliphatic-aromatic copolyester is 19-54 % by weight, and the content of described organo-peroxide is 0.05-1 % by weight.
18. methods according to claim 17, wherein, in described esterification raw material, component (a) is 1:0.5-2.5 with the mol ratio of component (b); Component (a) is 100-1000:1 with the weight ratio of component (c); In component (a), with component (a) gross weight for benchmark, described C
8-C
20the content of aromatic dicarboxylic acid compounds be 5-75 % by weight, described C
2-C
20the content of aliphatic dibasic acids compounds be 25-95 % by weight.
19. methods according to claim 18, wherein, in described esterification raw material, component (a) is 1:0.7-1.5 with the mol ratio of component (b); Component (a) is 200-800:1 with the weight ratio of component (c); In component (a), with component (a) gross weight for benchmark, described C
8-C
20the content of aromatic dicarboxylic acid compounds be 30-60 % by weight, described C
2-C
20the content of aliphatic dibasic acids compounds be 40-70 % by weight.
20. methods according to claim 17 or 18, wherein, the method of described esterification raw material reaction is comprised: the component (a) in described esterification raw material, component (b) and component (c) are reacted under esterification condition, and the product of this reaction is reacted under polycondensation condition.
21. methods according to claim 20, wherein, described esterification condition comprises: temperature of reaction is 150-240 DEG C, and the reaction times is 0.5-5 hour; The condition of described polycondensation comprises: temperature of reaction is 200-300 DEG C, and reaction pressure is 0-800Pa, and the reaction times is 3-7 hour.
22. methods according to claim 17 or 18, wherein, in described esterification raw material, described C
8-C
20aromatic dicarboxylic acid compounds be C
8-C
20aromatic acid, C
8-C
20aromatic dicarboxylic anhydride and C
8-C
20aromatic acid ester in one or more; Described C
2-C
20aliphatic dibasic acids compounds be C
2-C
20aliphatic dibasic acid, C
3-C
10cycloaliphatic diacid, in their ester and their acid anhydrides one or more; Component (b) is C
2-C
10aliphatic dihydroxy alcohol and/or C
5-C
10cycloaliphatic diols; Component (c) is tartrate, one or more in citric acid, hydroxy-butanedioic acid, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, polyether-tribasic alcohol, glycerine, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic acid dianhydride and hydroxyisophthalic acid.
23. methods according to claim 22, wherein, described C
8-C
20aromatic dicarboxylic acid compounds be m-phthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate (DMT), 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.
24. methods according to claim 22, wherein, described C
2-C
20aliphatic dibasic acids compounds be succinic acid, Succinic anhydried, dimethyl adipate, hexanodioic acid, adipic anhydride, nonane diacid, sebacic acid, dodecanedioic acid, 1, one or more in 4-cyclohexane diacid, Isosorbide-5-Nitrae-cyclohexane diacid dimethyl ester and norbornane diacid.
25. methods according to claim 22, wherein, component (b) is ethylene glycol, one or more in glycol ether, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexane diol and norbornane dimethanol.
26. methods according to claim 22, wherein, component (c) is glycerol, at least one in tetramethylolmethane and pyromellitic acid dianhydride.
27. methods according to claim 17, wherein, described organo-peroxide be selected from dialkyl, diacyl peroxides and peroxyester one or more.
28. methods according to claim 27, wherein, described organo-peroxide is dicumyl peroxide, 2, one or more in 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, two (tert-butylperoxyiso-propyl) benzene, dibenzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide isobutyrates.
29. methods according to claim 17, wherein, in step (2), described mixture is also containing slipping agent and/or oxidation inhibitor.
30. methods according to claim 29, wherein, described slipping agent is one or more in erucicamide, amine hydroxybenzene and stearic amide.
31. methods according to claim 29, wherein, described oxidation inhibitor is hindered phenol type antioxidant.
32. methods according to claim 31, wherein, described oxidation inhibitor is two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of triglycol and/or β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid octadecanol ester.
33. according to the method in claim 29-32 described in any one, and wherein, with the gross weight of described mixture for benchmark, the content of described slipping agent is 0.01-1 % by weight, and the content of described oxidation inhibitor is 0.01-1 % by weight.
34. methods according to claim 33, wherein, with the gross weight of described mixture for benchmark, the content of described slipping agent is 0.05-0.5 % by weight, and the content of described oxidation inhibitor is 0.05-0.5 % by weight.
35. 1 kinds of disposable products, this disposable product is made up of biodegradable mixture, it is characterized in that, described biodegradable mixture is the biodegradable mixture in claim 1-16 described in any one or the biodegradable mixture prepared according to the method in claim 17-34 described in any one.
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