CN103087488A - Biodegradable polylactic acid composite material, and preparation method and application thereof - Google Patents
Biodegradable polylactic acid composite material, and preparation method and application thereof Download PDFInfo
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- CN103087488A CN103087488A CN2013100420770A CN201310042077A CN103087488A CN 103087488 A CN103087488 A CN 103087488A CN 2013100420770 A CN2013100420770 A CN 2013100420770A CN 201310042077 A CN201310042077 A CN 201310042077A CN 103087488 A CN103087488 A CN 103087488A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention discloses a biodegradable polylactic acid composite material, and a preparation method and an application thereof. The biodegradable polylactic acid composite material comprises the components of, by weight, 100 parts of high-molecular-weight polylactic acid, 10-40 parts of low-molecular-weight polylactic acid, 10-30 parts of biodegradable copolyester, 0.1-3 parts of a chain extender, 0.1-3 parts of an anti-hydrolysis agent, 0.1-5 parts of a nucleating agent, 5-20 parts of an inorganic filler, and 0.1-0.8 parts of an antioxidant. The weight average molecular weight Mw of the high-molecular-weight polylactic acid is greater than 100000 and no greater than 200000, and the weight average molecular weight Mw of the low-molecular-weight polylactic acid is no lower than 60000 and no greater than 100000. The polylactic acid composite material provided by the invention has high melt strength, high toughness, high heat resistance, high water resistance and good processing properties. The material can be widely applied in the fields such as toys, offices, cars and electronic appliances.
Description
Technical field
The present invention relates to for polymeric material field, particularly a kind of biodegradable polylactic acid matrix material and its preparation method and application.
Background technology
At present, along with mouthful being becoming tight of petroleum resources, environmental pollution becomes again one of topmost several large problems of human survival, and degradable non-petroleum base macromolecular material more and more obtains people's attention.Poly(lactic acid) is a kind of macromolecular material that obtains from the corn fermentation repolymerization, is the environmental friendliness degradation material, and poly(lactic acid) has good stretchiness, bendability and light transmission simultaneously, can be used to each polymeric material field.But, poly(lactic acid) on the high side, and toughness, resistance toheat, hydrolytic resistance etc. still needs further improvement, could be used more widely.Therefore how making the toughness of poly(lactic acid) be improved and don't affect its biodegradability is to enlarge poly(lactic acid) to use problem needing to overcome.
Summary of the invention
In sum, the present invention is necessary to provide a kind of biodegradable polylactic acid matrix material.
Further, also be necessary to provide a kind of described biodegradable polylactic acid composite manufacture method.
Further, also be necessary to provide a kind of application of described biodegradable polylactic acid matrix material.
A kind of biodegradable polylactic acid matrix material, described biodegradable polylactic acid matrix material comprise the following component of calculating by weight:
100 parts of poly-lactic acid in high molecular weight;
10 ~ 40 parts of low molecular weights;
10 ~ 30 parts of Biodegradable Copolyesters;
0.1 ~ 3 part of chainextender;
0.1 ~ 3 part of hydrolysis-resisting agent;
0.1 ~ 5 part of nucleator;
5 ~ 20 parts of mineral fillers;
0.1 ~ 0.8 part, oxidation inhibitor;
The weight-average molecular weight of described poly-lactic acid in high molecular weight is 100,000＜Mw≤200,000; The weight-average molecular weight of described low molecular weight is 60,000≤Mw≤100,000.
A kind of biodegradable polylactic acid matrix material, described biodegradable polylactic acid matrix material is comprised of the following component of calculating by weight:
100 parts of poly-lactic acid in high molecular weight;
10 ~ 40 parts of low molecular weights;
10 ~ 30 parts of Biodegradable Copolyesters;
0.1 ~ 3 part of chainextender;
0.1 ~ 3 part of hydrolysis-resisting agent;
0.1 ~ 5 part of nucleator;
5 ~ 20 parts of mineral fillers;
0.1 ~ 0.8 part, oxidation inhibitor;
The weight-average molecular weight of described poly-lactic acid in high molecular weight is 100,000＜Mw≤200,000; The weight-average molecular weight of described low molecular weight is 60,000≤Mw≤100,000.
Wherein, described Biodegradable Copolyester can be for being obtained by di-carboxylic acid monomer and the reaction of dibasic alcohol monomer condenses.
Wherein, described di-carboxylic acid monomer can be selected from any one or its combination in the esterified derivative of esterified derivative, aromatic acid or aromatic acid of aliphatic dibasic acid, aliphatic dibasic acid;
Described dibasic alcohol monomer can be selected from aliphatic dihydroxy alcohol.
Wherein, in described di-carboxylic acid monomer, can contain 2 ~ 22 carbon atoms.
Wherein, in described dibasic alcohol monomer, can contain 2 ~ 22 carbon atoms.
Wherein, described Biodegradable Copolyester can be the multipolymer (PBSA) of poly butylene succinate (PBS), succinic acid-butanediol ester and tetramethylene adipate or tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer (PBAT).
There is no particular limitation for the weight-average molecular weight of described PBS, is this area PBS commonly used.Normally, its weight-average molecular weight Mw is between 10 ~ 300,000.
There is no particular limitation for the weight-average molecular weight of described PBSA, is this area PBSA commonly used.Normally, its weight-average molecular weight Mw is between 10 ~ 300,000.
There is no particular limitation for the molecular weight of described PBAT, is this area PBAT commonly used.Normally, its melt flow rate (MFR) (MFR) is 2 ~ 8g/10min (190 ° of C/2.16kg).
Wherein, described chainextender can be selected from Isosorbide-5-Nitrae-phenyl-two (2-dislikes quinoline), 2-glycidyl ester, two (2-dislikes quinoline), tolylene diisocyanate, all two any one or its combinations in phthalein amine, chainextender ADR-4370, isocyanuric acid three-glycidyl ester, hexamethylene diisocyanate, isophorone diisocyanate in oneself of benzene four acid anhydrides, diphenylmethanediisocyanate, bischloroformate, isophorone diisocyanate, isophthalic two phthalidyls.
Wherein, described hydrolysis-resisting agent can be selected from the Carbodiimides material.Described Carbodiimides material can be mixed by one or more carbodiimide and form.
Wherein, be preferably the carbodiimide that contains 1 ~ 30 carbodiimide groups in structure.
Wherein, preferred molar mass is the carbodiimide of 40 ~ 30000g/mol.
Wherein, described nucleator can be selected from polynite, 4,6-di-tert-butyl-phenyl sodium phosphate, hydroxide 2, any one or its combination in 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salt, phenyl zinc phosphite or dimethyl isophthalate 5-sodium sulfonate.
Wherein, described mineral filler can be selected from any one or its combination in calcium carbonate, talcum powder, silicon-dioxide, titanium dioxide, kaolin, diatomite.
Wherein, described oxidation inhibitor can be selected from [β-(3,5-di-t-butyl-4-alkyl phenyl) propionic acid] pentaerythritol ester, 2,2 '-methylene radical-two (4-methyl-6-tert-butylphenol), phosphorous acid 4, the different fork bis-phenol of 4-two (12-14) carbon alkyl ester, any one or its combination in three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.
Described biodegradable polylactic acid composite manufacture method comprises the steps:
In proportion poly-lactic acid in high molecular weight, low molecular weight, Biodegradable Copolyester are mixed in mixer, then dry, obtain Preblend;
Preblend and softening agent, mineral filler, oxidation inhibitor, lubricant in high-speed mixer and mixing, are obtained compound;
Compound is fed carry out fusion plastification in twin screw extruder, extrude, granulation namely gets described biodegradable polylactic acid matrix material.
Wherein, the design temperature of twin screw extruder is: a district: 130 ~ 150 ℃, and 2nd district: 160 ~ 180 ℃, 3rd district: 170 ~ 190 ℃, 4th district: 175 ~ 195 ℃, 5th district: 175 ~ 195 ℃, 6th district: 180 ~ 200 ℃, 7th district: 180 ~ 200 ℃, 8th district: 180 ~ 200 ℃, 9th district: 180 ~ 200 ℃, head: 175-195 ℃, screw speed: 200 ~ 400rpm.
Wherein, described twin screw extruder can be equidirectional parallel double-screw extruder, anisotropic parallel twin-screw extruding machine or conical double screw extruder.
Wherein, the screw slenderness ratio of described twin screw extruder can 40:1,56:1 or 60:1.
The application of described biodegradable polylactic acid matrix material in preparation biological degradation goods.
Described biodegradable polylactic acid matrix material has higher melt strength, toughness, thermotolerance, water tolerance and processing characteristics preferably, can make injection-molded item by the method for injection moulding.The injection-molded item of gained can be degraded under composting conditions, and the physical and chemical performance in gained injection-molded item 3 years can satisfy the routine use demand, can be widely used in toy, office, automobile and field of electronics.
Compared with prior art, the present invention has following beneficial effect:
(1) completely biological degradation polylactic acid matrix material of the present invention, by the choose reasonable to component, resistance to impact shock and the tension fracture elongation rate of poly(lactic acid) have effectively been improved, under the prerequisite of the degradation characteristic that does not affect matrix material, solved the major defect of poly(lactic acid) fragility, and the poly(lactic acid) of high molecular and the mixing of low-molecular-weight poly(lactic acid) can form bimodal molecular weight distribution, improve processing characteristics;
(2) the present invention selects poly-lactic acid in high molecular weight and low molecular weight with the composite use of certain proportion, poly(lactic acid) both, fully compatible, the poly(lactic acid) of high molecular can guarantee the mechanical property of product, and low-molecular-weight poly(lactic acid) can guarantee its workability energy, and due to the adding of low molecular weight, has played softening agent, make the second-order transition temperature of biodegradable polylactic acid matrix material reduce, further improved the toughness of matrix material;
(3) by hydrolysis-resisting agent, the C-terminal of poly(lactic acid) is carried out end-blocking, can improve the hydrolytic resistance of poly(lactic acid); Chainextender can improve the thermostability of poly(lactic acid), and introduces branched structure in system, thereby improves the melt strength of system; Nucleator can improve the thermotolerance of matrix material;
Reasonably combined by above-mentioned (1) ~ (3) point makes lactic acid composite material of the present invention have higher melt strength, toughness, thermotolerance, water tolerance and processing characteristics preferably, can make injection-molded item by the method for injection moulding.The injection-molded item of gained can be degraded under composting conditions, and the physical and chemical performance in gained injection-molded item 3 years can satisfy the routine use demand, can be widely used in toy, office, automobile and field of electronics.
Embodiment
Below in conjunction with some embodiments, biodegradable polylactic acid matrix material of the present invention and its preparation method and application is described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
The material that embodiment of the present invention is used and source thereof:
Poly-lactic acid in high molecular weight-1: available from U.S. Natureworks company, weight-average molecular weight is 110,000.
Poly-lactic acid in high molecular weight-2: available from U.S. Natureworks company, weight-average molecular weight is 200,000.
Poly-lactic acid in high molecular weight-3: available from U.S. Natureworks company, weight-average molecular weight is 400,000.
Low molecular weight-1: available from U.S. Natureworks company, weight-average molecular weight is 60,000.
Low molecular weight-2: available from U.S. Natureworks company, weight-average molecular weight is 100,000.
Low molecular weight-3: available from U.S. Natureworks company, weight-average molecular weight is 20,000.
PBSA:Mw=14-15 ten thousand, Japan clear and polymer company;
PBS:Mw=10-20 ten thousand, Anqing and Xinghua work limited liability company;
PBAT: German BASF AG, trade(brand)name Ecoflex@, MFR is) 3g/10min (190 ° of C/2.16kg);
Chainextender: tolylene diisocyanate, available from Yantai Wan Hua company, 8020.Hexamethylene diisocyanate is available from the sharp smart chemical preparations of Beijing benefit company limited.
Carbodiimide: available from TUV chemistry, stabaxol.
Nucleator: dimethyl isophthalate 5-sodium sulfonate changes into company available from Tokyo.The phenyl zinc phosphite is available from rich gloomy chemical industry company limited of upper Hisense.4,6-di-tert-butyl-phenyl sodium phosphate is available from rich gloomy chemical industry company limited of upper Hisense.
Mineral filler, oxidation inhibitor are the commercially available prod.
Detection method or standard that embodiment of the present invention is used are:
Tensile strength is pressed ISO 527 standard testings;
Elongation at break by standard ISO 527-2/5A/500 test, is tested under 23 ℃;
The socle girder notched Izod impact strength is pressed ISO 180 standard testings, and the type of socle girder breach is the category-A breach;
Biodegradation test method: with reference to the testing method of ISO 14855, with CO after 90 days compost of material
2Burst size is the degradation property index.
Heat-drawn wire: with reference to the method test of the regulation of ISO 75-2004.
Aging resistance: be 60 ℃ in temperature, the draw secondary strength retention of the condition of relative humidity 95% in next week represents.
Embodiment 1 ~ 6
Press the proportioning of table 1, first the poly(lactic acid) component is mixed in mixer with Biodegradable Copolyester, then dry, obtain Preblend; Then Preblend and softening agent, mineral filler, oxidation inhibitor, lubricant were carried out mechanical blending 5 minutes in high mixer, then feed carry out fusion plastification in twin screw extruder, extrude, granulation obtains the described biodegradable polylactic acid matrix material of embodiment 1 ~ 6.
Described twin screw extruder is equidirectional parallel double-screw extruder, its design temperature is: a district: 130 ~ 150 ℃, and 2nd district: 160 ~ 180 ℃, 3rd district: 170 ~ 190 ℃, 4th district: 175 ~ 195 ℃, 5th district: 175 ~ 195 ℃, 6th district: 180 ~ 200 ℃, 7th district: 180 ~ 200 ℃, 8th district: 180 ~ 200 ℃, 9th district: 180 ~ 200 ℃, head: 175-195 ℃, screw speed: 300rpm.
Screw slenderness ratio is 40:1.
Table 1
Comparative Examples 1 ~ 6
Press the proportioning of table 2, first the poly(lactic acid) component is mixed in mixer with Biodegradable Copolyester, then dry, obtain Preblend; Then Preblend and softening agent, mineral filler, oxidation inhibitor, lubricant were carried out mechanical blending 5 minutes in high mixer, then feed carry out fusion plastification in twin screw extruder, extrude, granulation obtains the described biodegradable polylactic acid matrix material of Comparative Examples 1 ~ 6.
Described twin screw extruder is equidirectional parallel double-screw extruder, its design temperature is: a district: 130 ~ 150 ℃, and 2nd district: 160 ~ 180 ℃, 3rd district: 170 ~ 190 ℃, 4th district: 175 ~ 195 ℃, 5th district: 175 ~ 195 ℃, 6th district: 180 ~ 200 ℃, 7th district: 180 ~ 200 ℃, 8th district: 180 ~ 200 ℃, 9th district: 180 ~ 200 ℃, head: 175-195 ℃, screw speed: 300rpm.
Screw slenderness ratio is 40:1.
Table 2
Can find out from Comparative Examples 1, the low molecular weight content that adds too much has negative impact to the tensile strength of gained completely biological degradation polylactic acid matrix material.Can find out from Comparative Examples 2 and Comparative Examples 6, when the low molecular weight content that adds is very few, help little to elongation at break and the shock strength of improving product.Can find out when the low molecular weight molecular weight of selecting is too low, the toughness of gained completely biological degradation polylactic acid matrix material is had negative impact from Comparative Examples 3.Can find out from Comparative Examples 4 and Comparative Examples 5, when the poly-lactic acid in high molecular weight molecular weight that adopts was too high, due to its poor processability, rapid attenuation, degradation easily appearred in molecular weight in the course of processing.Can find out from Comparative Examples 6, not add low molecular weight, the toughness of gained completely biological degradation polylactic acid matrix material has obviously been added the low of low molecular weight.
Embodiment 7 ~ 12
Press the proportioning of table 3, first the poly(lactic acid) component is mixed in mixer with Biodegradable Copolyester, then dry, obtain Preblend; Then Preblend and softening agent, mineral filler, oxidation inhibitor, lubricant were carried out mechanical blending 5 minutes in high mixer, then feed carry out fusion plastification in twin screw extruder, extrude, granulation obtains the described biodegradable polylactic acid matrix material of embodiment 7 ~ 12.
Described twin screw extruder is equidirectional parallel double-screw extruder, its design temperature is: a district: 130 ~ 150 ℃, and 2nd district: 160 ~ 180 ℃, 3rd district: 170 ~ 190 ℃, 4th district: 175 ~ 195 ℃, 5th district: 175 ~ 195 ℃, 6th district: 180 ~ 200 ℃, 7th district: 180 ~ 200 ℃, 8th district: 180 ~ 200 ℃, 9th district: 180 ~ 200 ℃, head: 175-195 ℃, screw speed: 400rpm.
Screw slenderness ratio is 60:1.
Table 3
Can reflect from the performance of table 1 and table 2, biodegradable polylactic acid matrix material of the present invention has high tenacity, be the mating reaction by reasonable composite and each component that poly(lactic acid) is formed, avoided degradable material to add conventional plastic in order to satisfy toughness and cause the problem of degradation property decline.Simultaneously, described biodegradable polylactic acid matrix material has higher melt strength, toughness, thermotolerance, water tolerance and processing characteristics preferably, its injection-molded item for preparing can be degraded under composting conditions, and the physical and chemical performance in gained injection-molded item 3 years can satisfy the routine use demand, can be widely used in toy, office, automobile and field of electronics.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (10)
1. a biodegradable polylactic acid matrix material, is characterized in that, described biodegradable polylactic acid matrix material comprises the following component of calculating by weight:
100 parts of poly-lactic acid in high molecular weight;
10 ~ 40 parts of low molecular weights;
10 ~ 30 parts of Biodegradable Copolyesters;
0.1 ~ 3 part of chainextender;
0.1 ~ 3 part of hydrolysis-resisting agent;
0.1 ~ 5 part of nucleator;
5 ~ 20 parts of mineral fillers;
0.1 ~ 0.8 part, oxidation inhibitor;
The weight-average molecular weight of described poly-lactic acid in high molecular weight is 100,000＜Mw≤200,000; The weight-average molecular weight of described low molecular weight is 60,000≤Mw≤100,000.
2. a biodegradable polylactic acid matrix material, is characterized in that, described biodegradable polylactic acid matrix material is comprised of the following component of calculating by weight:
100 parts of poly-lactic acid in high molecular weight;
10 ~ 40 parts of low molecular weights;
10 ~ 30 parts of Biodegradable Copolyesters;
0.1 ~ 3 part of chainextender;
0.1 ~ 3 part of hydrolysis-resisting agent;
0.1 ~ 5 part of nucleator;
5 ~ 20 parts of mineral fillers;
0.1 ~ 0.8 part, oxidation inhibitor;
The weight-average molecular weight of described poly-lactic acid in high molecular weight is 100,000＜Mw≤200,000; The weight-average molecular weight of described low molecular weight is 60,000≤Mw≤100,000.
3. biodegradable polylactic acid matrix material as claimed in claim 1 or 2, it is characterized in that, described di-carboxylic acid monomer is selected from any one or its combination in the esterified derivative of esterified derivative, aromatic acid or aromatic acid of aliphatic dibasic acid, aliphatic dibasic acid;
Described dibasic alcohol monomer is selected from aliphatic dihydroxy alcohol.
4. biodegradable polylactic acid matrix material as claimed in claim 3, it is characterized in that, described Biodegradable Copolyester is the multipolymer of poly butylene succinate, succinic acid-butanediol ester and tetramethylene adipate or tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer.
5. biodegradable polylactic acid matrix material as claimed in claim 1 or 2, it is characterized in that, described chainextender is selected from Isosorbide-5-Nitrae-phenyl-two (2-dislikes quinoline), 2-glycidyl ester, two (2-dislikes quinoline), tolylene diisocyanate, all two any one or its combinations in phthalein amine, chainextender ADR-4370, isocyanuric acid three-glycidyl ester, hexamethylene diisocyanate, isophorone diisocyanate in oneself of benzene four acid anhydrides, diphenylmethanediisocyanate, bischloroformate, isophorone diisocyanate, isophthalic two phthalidyls.
6. biodegradable polylactic acid matrix material as claimed in claim 1 or 2, is characterized in that, described hydrolysis-resisting agent is selected from the Carbodiimides material.
7. biodegradable polylactic acid matrix material as claimed in claim 1 or 2, it is characterized in that, described nucleator is selected from polynite, 4,6-di-tert-butyl-phenyl sodium phosphate, hydroxide 2, any one or its combination in 2-methylene-bis (4,6-di-tert-butyl-phenyl) sodium phosphate salt, phenyl zinc phosphite or dimethyl isophthalate 5-sodium sulfonate.
8. biodegradable polylactic acid matrix material as claimed in claim 1 or 2, is characterized in that, described mineral filler is selected from any one or its combination in calcium carbonate, talcum powder, silicon-dioxide, titanium dioxide, kaolin, diatomite.
9. the described biodegradable polylactic acid composite manufacture of any one claim method in claim 1 ~ 8, is characterized in that, comprises the steps:
In proportion poly-lactic acid in high molecular weight, low molecular weight, Biodegradable Copolyester are mixed in mixer, then dry, obtain Preblend;
Preblend and softening agent, mineral filler, oxidation inhibitor, lubricant in high-speed mixer and mixing, are obtained compound;
Compound is fed carry out fusion plastification in twin screw extruder, extrude, granulation namely gets described biodegradable polylactic acid matrix material.
10. the application of the described biodegradable polylactic acid matrix material of any one claim in preparation biological degradation goods in claim 1 ~ 8.
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