CN101717475A - Biodegradable foam plastic and preparation method thereof - Google Patents
Biodegradable foam plastic and preparation method thereof Download PDFInfo
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- CN101717475A CN101717475A CN200810223923A CN200810223923A CN101717475A CN 101717475 A CN101717475 A CN 101717475A CN 200810223923 A CN200810223923 A CN 200810223923A CN 200810223923 A CN200810223923 A CN 200810223923A CN 101717475 A CN101717475 A CN 101717475A
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Abstract
The invention discloses a biodegradable foam plastic and a preparation method thereof. The raw materials for preparing the foam plastic comprise 100 parts by weight of a or b and 0.01-10 parts by weight of UV photoinitiator, cross-linking agent and foaming agent, wherein a is poly(butylene succinate), and b is a copolymer formed by the poly(butylene succinate) and polyether; the number-average molecular weight of the poly(butylene succinate) is 10,000-100,000; and the number-average molecular weight of the copolymer formed by the poly(butylene succinate) and the polyether is 10,000-100,000. The method for preparing the biodegradable foam plastic comprises the steps of melting and mixing the raw materials of the foam plastic, then pressing into a sheet, carrying out UV irradiation on the obtained sheet, carrying out foaming and obtaining the biodegradable foam plastic.
Description
Technical field
The present invention relates to a kind of biodegradable foam plastic and preparation method thereof.
Background technology
Porous plastics is as a kind of lightweight material, has heat insulation, sound insulation, buffering, specific tenacity height, series of advantages such as cheap, therefore is widely used in fields such as packing business, industry, agricultural, transportation, daily necessities.Present principal item has urethane foam, polystyrene foamed plastics, foamed polyolefine plastic etc., these foam articles are when having made things convenient for the human being's production life, also brought great puzzlement to the mankind, because these foam article major parts have harmful substances in process of production, especially waste is difficult to recycle, in physical environment, be difficult to decompose voluntarily, or in discarded process, produce obnoxious flavour or material and cause cross infection, thereby the physical environment that the mankind depend on for existence is caused serious day by day pollution.Based on this, various countries have formulated some policies, rules in succession, and such non-degradable product is implemented to forbid or limit the use of.
Development biodegradable polymer and goods thereof provide a kind of possibility for the contradiction that solves between environmental pollution and the human's demand.Biodegradable material has good performance when it uses, can be carbonic acid gas and water through natural decomposition after discarding, and therefore seeks suitable biodegradable polymer, and preparing corresponding foam plastic product is the feasible method that takes stopgap measures and effect a permanent cure.
Biodegradable foam plastic concentrates on to aliphatic polyester-poly(lactic acid) the research of poly-epsilon-caprolactone and starch based biodegradable foamed plastics at present.Chinese patent CN1544525 and CN1544514 disclose a kind of biodegradable poly(lactic acid) plastics preparation method and a kind of biodegradable polylactic acid foam plastic of chainextender and preparation method thereof that contains respectively, but foam inhomogeneous by the product that these two kinds of technology obtain.Chinese patent CN1919926 discloses a kind of polylactic acid-starch foaming material and preparation method thereof, and wide but the poly(lactic acid) relative molecular weight of this method polymerization gained distributes, intensity often can not meet the demands, the fragility height, and heat-drawn wire is low, and shock resistance is poor.The poly(lactic acid) thermostability is bad, and serious thermal destruction easily takes place in the course of processing, causes molecular weight to descend significantly.Its price comparison simultaneously is expensive, and lactic acid price and polymerization technique have determined that the cost of poly(lactic acid) is higher.These have all limited the large-scale application of poly(lactic acid) and goods thereof.
Chinese patent CN1544526A, CN1618875A and CN1687231A disclose poly-epsilon-caprolactone respectively, peroxide crosslinking poly-epsilon-caprolactone and poly-epsilon-caprolactone/inorganic filler composite material porous plastics and preparation method thereof, though obtained corresponding porous plastics, the price limit of the decline of mechanical property and poly-epsilon-caprolactone costliness their use.
Aspect the starch-based, biodegradable porous plastics, Chinese patent CN1407006A is a raw material with vinylformic acid starch ester and vinylbenzene, acrylate, prepares a kind of starch base porous plastics through emulsion copolymerization and moulded from foam.The degradation property fully of its raw material certainly will influence the degradation property of final foam article.
Compare with aliphatic polyesters such as poly(lactic acid), poly-succinic fourth diester (PBS) is a kind of fusing point and the intensity higher aliphatic polyester that all compares, and is expected to replace general polyethylene or polypropylene and enters the general-purpose plastics field.Its wide material sources both can satisfy the demands by petrochemicals, also can be produced through the biological fermentation approach by regeneration farm crop product, thereby further reduce the cost of PBS.At present, PBS can scale operation.Clear and polymer company of Japan and the BASF trade(brand)name that released one after another is respectively: Bionolle, the commercialization poly-succinic fourth diester of Ecoflex.Poly-succinic fourth diester/copolyether that poly-succinic fourth diester and polyethers are prepared into by methods such as melt phase polycondensation, solution copolymerizations, hypotoxicity with polyethers, excellent biological compatibility, and other advantages of series of advantages such as broad mechanical property and poly-succinic fourth diester combine effectively, make the thermoplastic elastomer that obtains greatly improve the mechanical property of aliphatic polyester, make it be more suitable for being applied to resistance to impact shock is had the field of requirements at the higher level.
When adopting poly-succinic fourth diester and polyester copolyether thereof to foam as matrix, because of the melt strength of material itself lower, be prone to phenomenons such as bulla, string bubble during foaming, even can keep the gas that does not live wherein owing to melt strength is too low, cause melt fracture, the gas loss finally causes the foaming failure.People such as K.Bahari [Polym.Degrad.Stab.62,551-557. (1998)] adopt the chemical foaming method to obtain corresponding porous plastics after poly-succinic fourth diester is carried out radiotreatment raising melt strength, and its degradation property is better.But than higher, labour protection is strict, and environment is also easily polluted, and is difficult to realize industrialization to the requirement of equipment for this method.
Summary of the invention
The purpose of this invention is to provide a kind of biodegradable foam plastic and preparation method thereof.
Biodegradable foam plastic provided by the present invention, the raw material of making described porous plastics comprises: ultraviolet initiator, linking agent and the whipping agent of a of 100 mass parts or b, 0.01～10 mass parts; Described a is a poly-succinic fourth diester, and described b is the multipolymer that is formed by poly-succinic fourth diester and polyethers; The number-average molecular weight of described poly-succinic fourth diester is 10,000～100,000; The number-average molecular weight of the multipolymer of described poly-succinic fourth diester and polyethers is 10,000～100,000.
The mass parts of described linking agent can be 0.5～40; The mass parts of described whipping agent can be 0.1～20.
The raw material of making described porous plastics also can comprise at least a in frothing aid and the following additives: nucleator, suds-stabilizing agent, softening agent, tensio-active agent, fire retardant, static inhibitor, flow promotor, organic and inorganic filler, promotor and pigment.The used frothing aid of the present invention can be any known whipping agent that uses in the preparation of thermoplastics foam materials.
The number-average molecular weight that is used to prepare the polyethers of the described multipolymer that is formed by poly-succinic fourth diester and polyethers among the present invention is 500～20,000; The number-average molecular weight that is used to prepare the poly-succinic fourth diester of the described multipolymer that is formed by poly-succinic fourth diester and polyethers is 500～5000; Being used to prepare the described polyethers of the described multipolymer that is formed by poly-succinic fourth diester and polyethers and the mass ratio of described poly-succinic fourth diester is 1: 1～1: 20.
Described polyethers can be equal polyethers or copolyether; Described equal polyethers specifically can be polyoxyethylene glycol (PEG), polyethylene oxide (PEO), poly(propylene oxide) (PPG, PPO) or the polytetrahydrofuran polyethers (PTMO, PTMG);
Described copolyether can be random copolymerization ether or block co-polyether; Described random copolymerization ether mainly is oxyethane and propylene oxide random copolymerization ether; Described block co-polyether comprises PEO-PPO-PEO, PEO-PTMO-PEO, and various ways such as PPO-PTMO-PPO are preferably PEO-PPO-PEO.
Described ultraviolet initiator is a kind of in the following substances: bitter almond oil camphor and ether derivant thereof, α, alpha-alpha-dimethyl benzil ketals, dialkoxy methyl phenyl ketone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acyl group phosphorous oxides, aryl peroxy esters compound, halogenated methyl arone, sulfur-containing organic compound, benzoyl formiate, benzophenone, thioxanthone and derivative, anthraquinone, coumarone and camphorquinone;
Described linking agent is a kind of in the following substances: trimethylolpropane trimethacrylate, triallyl cyanurate, iso-cyanuric acid triallyl ester, season amylalcohol acrylate, season amylalcohol tetramethyl-acrylate, diallyl phthalic ester and Viscoat 295;
Described whipping agent is inorganic foaming agent or organic blowing agent;
Described inorganic foaming agent specifically can be carbonate, Citrate trianion, supercarbonate, nitrate, hydroborate or carbide, is preferably Citrate trianion or supercarbonate;
Described organic blowing agent can be nitroso compound, azo-compound or sulfonyl hydrazines compound;
Described nitroso compound specifically can be N, N-dinitroso five methyne tetramine (DPT) or N, N-dimethyl-N, N-two inferior terephthalamides (NTA);
Described azo-compound specifically can be Cellmic C 121 (ADC), diisopropyl azodiformate, diethyl azodiformate, azoformic acid barium; Be preferably Cellmic C 121.
Described sulfonyl hydrazines compound J specifically can be 4,4-disulfonyl hydrazide diphenyl ether (OBSH), p-toluene sulfonyl hydrazide, 3,3-disulfonyl hydrazide sulfobenzide, 4,4-two benzene disulfohydrazides, 1,3-benzene disulfohydrazide, 1,4-benzene disulfohydrazide;
The method for preparing biodegradable foam plastic provided by the present invention may further comprise the steps:
1) will make the raw material of porous plastics: multipolymer, ultraviolet initiator, linking agent and whipping agent that poly-succinic fourth diester or poly-succinic fourth diester and polyethers form are pressed into sheet material after the melting mixing;
2) sheet material of step 1) is obtained the multipolymer of the crosslinked poly-succinic fourth diester of different gel contents or itself and polyethers behind ultraviolet light irradiation, foam then, obtain described biodegradable foam plastic.
Described raw material carries out melting mixing in Banbury mixer or twin screw extruder, the temperature of described melting mixing can be 110～160 ℃, and the time is 1～30min.
The thickness of described sheet material is 0.1-5mm; Described sheet material specifically be by with the molten mixture of described raw material at 110～160 ℃, hot pressing 1～10min under 5～50MPa, naturally cooling or water cooling obtain.
Described ultraviolet source is medium pressure mercury lamp or high voltage mercury lamp, and the power of described mercury lamp can be 0.1～25kw, and irradiation time is 1～120min.
Described foaming is carried out in baking oven or on the thermocompressor, and the temperature of described foaming is 170～250 ℃, and foamed time is 5～30min.
The various raw materials that the present invention will prepare poly-succinic fourth diester and polyester copolyether porous plastics thereof are pressed into sheet material can be by various processing technology manufacturings, such as extrude, calendering, thermoforming, transfer molding or injection molding, wherein, hot-forming is preferable methods.
Poly-succinic fourth diester/copolyether used among the present invention can synthesize by following route:
(1) with Succinic Acid, butyleneglycol in molar ratio 1: mix (1～4), join in the reactor that has stirring, heating and nitrogen protection device, in temperature is 150～200 ℃ of following esterifications 3～6 hours, steam byproduct of reaction water, obtain number-average molecular weight and be 500～5000 poly-succinic fourth two ester oligomers;
(2) polyethers is joined in the oligopolymer of step (1) gained, the mass ratio that makes described polyethers and described oligopolymer is 1: 1～1: 20, with cadmium acetate, zinc acetate, antimonous oxide, butyl (tetra) titanate or their any mixture as catalyzer, put in the reactor by 0.05%～3% of the quality that always feeds intake (the quality summation of described polyethers and described oligopolymer), polymerization is 4～9 hours under 230～280 ℃, 5～10Pa, obtain thick poly-succinic fourth diester/copolyether melt, cooling crystallizes into white solid.Described rare gas element is nitrogen or argon gas etc.
The related polyethers of step (2) is equal polyethers and copolyether, and all polyethers has polyoxyethylene glycol (PEG), polyethylene oxide (PEO), poly(propylene oxide) (PPG, PPO) and the polytetrahydrofuran polyethers (PTMO, PTMG); Copolyether comprises random copolymerization ether (mainly being oxyethane and propylene oxide random copolymerization ether) and block co-polyether, as PEO-PPO-PEO, and PEO-PTMO-PEO, various ways such as PPO-PTMO-PPO.The number-average molecular weight of polyethers is 500～20,000.
The melt strength of poly-succinic fourth diester and polyester copolyether thereof itself is lower, is prone to phenomenons such as bulla, string bubble during the preparation of the foam article of being correlated with, and causes foaming to be failed, and this has limited their application aspect porous plastics.
The melt strength of polymkeric substance is relevant with numerous factors, wherein, crosslinkedly can form reticulated structure, and the excessive increase of restriction bubble improves the molecular weight of polymkeric substance simultaneously, overcomes the low problem of bringing of melt strength, obtains corresponding porous plastics through foaming.Mostly crosslinked chemically crosslinked and the physical crosslinking of being divided into, chemically crosslinked are to be undertaken by the peroxide radical hydrogen abstraction reaction, and its main chain DeR can take place causes molecular weight to reduce, and reaction is difficult to effective control.Physical method crosslinked mostly are the methods that adopt radiation crosslinking, this method facility investment height has source of radiation, labour protection is strict, easily environment is worked the mischief and can not effectively use.
The invention provides biodegradable foam plastic.This porous plastics is to utilize the preparation of foaming of the poly-succinic fourth diester of ultraviolet light cross-linking and polyester copolyether thereof.Poly-succinic fourth diester and polyester copolyether melt strength thereof that this is crosslinked are higher, can be used for preparing relevant foam article.Ultraviolet light cross-linking is the photosensitizing chemical cross-linking method, and light trigger is decomposed into free radical under the effect of UV-light or transferring excited state to by ground state captures hydrogen on the macromolecular chain, produces free radical and causes crosslinked.This method processing unit is simple, less investment; Easy handling, easy to maintenance, environmentally safe, safety precaution requires not harsh; While quantum yield height, operating cost is low; Radiation injury to polymkeric substance in the irradiation process is little.
Among the present invention in order to improve the cross-linking efficiency of poly-succinic fourth diester and polyester copolyether thereof, in ultraviolet lighting, add proper amount of cross-linking agent (polyfunctional monomer), can more effectively form crosslinking structure, improved the melt strength of cross-linking products, mechanical property also improves, and obtains even, fine and closely woven degradable poly-succinic fourth diester of abscess and polyester copolyether porous plastics thereof through traditional chemical foaming method.
Description of drawings
Fig. 1 is the stereoscan photograph of poly-succinic fourth two ester foamed plastics among the embodiment 2.
Fig. 2 is the H of the multipolymer that poly-succinic fourth diester and PTMG form among the embodiment 7
1-NMR schemes (CDCl
3, 300MHZ).
Embodiment
Ratio among the embodiment is mass ratio, and polymericular weight is number-average molecular weight.
Embodiment 1,
With 100 mass parts molecular weight is 30,000 poly-succinic fourth diester, the ultraviolet initiator bitter almond oil camphor of 1 mass parts, the linking agent trimethylolpropane trimethacrylate of 3 mass parts, the inorganic foaming agent modification carbonate of 3 mass parts (white hair infusion TH-308), the nucleator nanometer grade calcium carbonate of 2 mass parts, the additive of 10 mass parts (the promotor zinc oxide of 5 mass parts and the lubricant stearic acid of 5 mass parts) mixes 5min in 130 ℃ in twin screw extruder, after mixing, on thermocompressor in 150 ℃, 5～10Mpa presses down 2min, obtains the thin slice about 0.1mm behind the naturally cooling.Then with thin slice with 200w medium pressure mercury lamp irradiation 10min, gel content is 40.1% crosslinked poly-succinic fourth diester.
The mensuration of gel content adopts extraction process, and concrete grammar is as follows: the sample behind the uv irradiation is placed Soxhlet extractor, is solvent with the chloroform, takes out behind the backflow 72h, dries to constant weight in 80 ℃ of vacuum drying ovens.Gel content is according to formula: gel content=(W/W
0) * 100% calculates, and wherein, W is the quality of sample after the extracting oven dry, W
0Be the sample initial mass.200 ℃ of foaming 10min get poly-succinic fourth two ester foamed plastics in baking oven subsequently.Foam density is 352Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, used enzyme is pseudomonas biological enzyme (Sigma-Aldrich, an article No.: 62309).Concrete experimental technique is as follows: the sample that will be of a size of 10mm * 10mm * 10mm, place phosphoric acid buffer (pH=6.82) solution that is dissolved with an amount of biological enzyme, and the ratio of bioenzyme activity unit and froth quality is 5U/mg in the control solution, the Erlenmeyer flask that above-mentioned buffered soln will be housed is then put into 45 ℃ Water Tank with Temp.-controlled constant temperature, every for some time sample is taken out, after washing repeatedly with distilled water, vacuum-drying is 3 hours in 45 ℃ vacuum drying oven, weighs.The foamy palliating degradation degree is weighed with rate of weight loss, and rate of weight loss can be calculated as follows: weightlessness=[(W
1-W
2)/W
1] * 100%, wherein, W
1Be foam initial weight, W
2For remaining foam wt behind certain degradation time.The biological degradation experiment shows resulting porous plastics degradable, a week degraded 5.5%.
Embodiment 2
With 100 mass parts molecular weight is 40,000 poly-succinic fourth diester, the light trigger alpha-hydroxyalkyl benzophenone of 2 mass parts, the linking agent triallyl cyanurate of 7 mass parts, the whipping agent Cellmic C 121 of 5 mass parts, the nucleator nanometer grade silica of 3 mass parts, the additive of 5 mass parts (promotor zinc oxide) mixes 10min in 140 ℃ in twin screw extruder, after mixing, on thermocompressor in 140 ℃, 5～10Mpa presses down 10min, obtains the thin slice about 0.3mm behind the naturally cooling.Then with thin slice with 1000w medium pressure mercury lamp irradiation 2min, gel content is 35.6% crosslinked poly-succinic fourth diester.The measuring method of gel content is with embodiment 1.
On thermocompressor 180 ℃ subsequently, foaming 20min gets poly-succinic fourth two ester foamed plastics.The sem photograph (see figure 1) of gained porous plastics has obtained even fine and closely woven foamy structure.Foam density is 187Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 6.7%.
Embodiment 3
With 100 mass parts molecular weight is 50,000 poly-succinic fourth diester, the light trigger dialkoxy methyl phenyl ketone of 3 mass parts, the linking agent season amylalcohol tetramethyl-acrylate of 10 mass parts, 7.5 the whipping agent 4 of mass parts, the 4-disulfonyl hydrazide diphenyl ether, the nucleator nano level talcum powder of 1 mass parts, the additive of 5 mass parts (the softening agent glycerine of the lubricant stearic acid of 3 mass parts and 2 mass parts) mixes 20min in 160 ℃ in twin screw extruder, after mixing, in 160 ℃, 5～10Mpa presses down 5min on thermocompressor, obtains the thin slice about 0.5mm behind the naturally cooling.Then with thin slice with 400w medium pressure mercury lamp irradiation 5min, gel content is 28.7% crosslinked poly-succinic fourth diester.Get poly-succinic fourth two ester foamed plastics at 210 ℃ of foaming 30min subsequently.Foam density is 159Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 10.1%.
With 100 mass parts molecular weight is 60,000 poly-succinic fourth diester, the ultraviolet initiator benzophenone of 4 mass parts, the linking agent diallyl phthalic ester of 15 mass parts, the whipping agent diisopropyl azodiformate of 10 mass parts in Banbury mixer 110 ℃ mix 30min, after mixing, on thermocompressor in 130 ℃, 5～10Mpa presses down 8min, obtains the thin slice about 1mm behind the naturally cooling.Then with thin slice with 500w medium pressure mercury lamp irradiation 5min, obtain gel content and be 31.4% crosslinked poly-succinic fourth diester.Get poly-succinic fourth two ester foamed plastics at 180 ℃ of foaming 30min subsequently.Foam density is 128Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 7.6%.
Embodiment 5
With 100 mass parts molecular weight is 70,000 poly-succinic fourth diester, the light trigger alpha-hydroxyalkyl benzophenone of 6 mass parts, the linking agent trimethylolpropane trimethacrylate of 20 mass parts, the whipping agent N of 12.5 mass parts, N-dinitroso five methyne tetramines be 120 ℃ of mixing 20min in Banbury mixer, after mixing, in 140 ℃, 5～10Mpa presses down 6min on thermocompressor, obtains the thin slice about 1mm behind the naturally cooling.Then with thin slice with 2000w high voltage mercury lamp irradiation 1min, obtain gel content and be 30% crosslinked poly-succinic fourth diester.Get poly-succinic fourth two ester foamed plastics at 180 ℃ of foaming 10min subsequently.Foam density is 105Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 7.8%.
Embodiment 6
With 100 mass parts molecular weight is 40,000 poly-succinic fourth diester, light trigger α-amine the alkyl phenones of 8 mass parts, the linking agent season amylalcohol acrylate of 35 mass parts, the whipping agent azoformic acid barium of 15 mass parts in Banbury mixer 130 ℃ mix 15min, after mixing, on thermocompressor in 160 ℃, 5～10Mpa presses down 10min, obtains the thin slice about 0.5mm behind the naturally cooling.Then with thin slice with 500w medium pressure mercury lamp irradiation 3min, obtain gel content and be 25% crosslinked poly-succinic fourth diester.Get poly-succinic fourth two ester foamed plastics at 240 ℃ of foaming 5min subsequently.Foam density is 87Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 11.3%.
Embodiment 7
1: 1.5 in molar ratio (253g altogether) mixes with Succinic Acid and butyleneglycol; join in the reactor that has stirring, heating and nitrogen protection device; in temperature is under 170 ℃; heated and stirred 6 hours; steam water byproduct; obtain the 210g number-average molecular weight and be the oligopolymer of 800 poly-succinic fourth diester, the molecular weight of this oligopolymer is by nuclear-magnetism (H
1NMR) ratio of hydroxyl and methylene peak area calculates gained in the spectrogram.Add the 15.7g number-average molecular weight subsequently and be 1000 PTMG PTMG, making the mass ratio of PTMG and described poly-succinic fourth two ester oligomers is 1: 13.4, at 250 ℃, mixture (the zinc acetate 0.05g that adds 0.2g (be equivalent to total charging capacity 0.09%) zinc acetate, antimonous oxide, antimonous oxide 0.15g) as catalyzer, 250～260 ℃ of vacuum reaction polymerizations 6 hours, obtain thick melt, cooling, crystallize into white solid, obtain poly-succinic fourth diester/PTMG multipolymer.The molecular weight that adopts gel permeation chromatography (GPC) to measure gained poly-succinic fourth diester/PTMG multipolymer is 40,000.
The structural formula of poly-succinic fourth diester/PTMG multipolymer is as follows:
Poly-succinic fourth diester/PTMG copolymer structure is identified collection of illustrative plates as shown in Figure 1.
Spectrum analysis sees the following form:
With the synthetic 100 mass parts molecular weight that obtain is 40, poly-succinic fourth diester/PTMG multipolymer of 000, the light trigger benzophenone of 2 mass parts, the linking agent triallyl cyanurate of 15 mass parts, the whipping agent azoformic acid barium of 4 mass parts in Banbury mixer 150 ℃ mix 20min, after mixing, on thermocompressor in 130 ℃, 5～10Mpa presses down 5min, obtains the thin slice about 1mm behind the naturally cooling.Then with thin slice with 2000w high voltage mercury lamp irradiation 1min, obtain gel content and be 33% crosslinked poly-succinic fourth diester.Get poly-succinic fourth diester/PTMG copolymer foam plastic at 240 ℃ of foaming 10min subsequently.Foam density is 210Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 8.9%.
Embodiment 8
Succinic Acid and butyleneglycol were total to 298g in 1: 2 in molar ratio; add and have heating, in the four-hole bottle of stirring and nitrogen protection device, after 190 ℃ of following heated and stirred are reacted 5 hours; steam water byproduct, obtain the 260g number-average molecular weight and be the oligopolymer of 1500 poly-succinic fourth diester.The Macrogol 4000 that adds 72g subsequently, making the mass ratio of Macrogol 4000 and described poly-succinic fourth two ester oligomers is 1: 3.6, mixture (the zinc acetate 0.25g that adds 0.3g (be equivalent to total charging capacity 0.09%) zinc acetate and zinc oxide again, zinc oxide 0.05g),, obtains thick melt 250 ℃ of following vacuum polymerizations 9 hours as catalyzer, cooling, crystallize into white solid, obtain molecular weight and be poly-succinic fourth diester/ethylene glycol copolymer of 30,000.
With 100 mass parts molecular weight is 30,000 poly-succinic fourth diester/ethylene glycol copolymer, the light trigger benzoyl formiate of 3 mass parts, the linking agent triallyl isocyanuric acid fat of 15 mass parts, the whipping agent diisopropyl azodiformate of 5 mass parts in Banbury mixer 130 ℃ mix 0.5h, after mixing, on thermocompressor in 150 ℃, 5～10Mpa presses down 3min, obtains the thin slice about 0.5mm behind the naturally cooling.Then with thin slice with 1000w medium pressure mercury lamp irradiation 2min, obtain gel content and be 35% crosslinked poly-succinic fourth diester.Get poly-succinic fourth diester/copolyether porous plastics at 200 ℃ of foaming 15min subsequently.Foam density is 175Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 13.3%.
Embodiment 9
Succinic Acid and butyleneglycol were total to 194g in 1: 3 in molar ratio; add and to have heating, stir and the four-hole bottle of nitrogen protection device in, in 180 ℃ of following heated and stirred after 5 hours; steam water byproduct, obtain the 176g number-average molecular weight and be the oligopolymer of 2500 poly-succinic fourth diester.Adding the 30.8g molecular weight subsequently is 10,000 poly(propylene oxide) ether PPG, making the mass ratio of PPG and described poly-succinic fourth two ester oligomers is 1: 5.7, adds 0.2～0.3g (be equivalent to total charging capacity 0.1%～0.15%) butyl (tetra) titanate simultaneously as catalyzer.260 ℃ of following vacuum polymerizations 5 hours, obtain thick melt, cooling crystallizes into white solid, and the number-average molecular weight that obtains is 40,000 poly-succinic fourth diester/PPG multipolymers.
With 100 mass parts molecular weight is 40,000 poly-succinic fourth diester/PPG multipolymer, light trigger α-amine the alkyl phenones of 4 mass parts, the linking agent trimethylolpropane trimethacrylate of 10 mass parts, the whipping agent N of 6 mass parts, N-dinitroso five methyne tetramines be 120 ℃ of mixing 10min in forcing machine, after mixing, in 150 ℃, 5～10Mpa presses down 5min on thermocompressor, obtains the thin slice about 0.3mm behind the naturally cooling.Then with thin slice with 500w medium pressure mercury lamp irradiation 5min, obtain gel content and be 34% crosslinked poly-succinic fourth diester.Get poly-succinic fourth diester/copolyether porous plastics at 210 ℃ of foaming 10min subsequently.Foam density is 133Kg/m
3
The biological degradation experiment shows resulting porous plastics degradable.
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 11.7%.
Embodiment 10
Succinic Acid and butyleneglycol were total to 253g in 1: 1.5 in molar ratio; add and have heating, in the four-hole bottle of stirring and nitrogen protection device, after 180 ℃ of following heated and stirred are reacted 5 hours; steam byproduct of reaction water, obtain the 210g number-average molecular weight and be the oligopolymer of 4600 poly-succinic fourth diester.Add 0.3g cadmium acetate, zinc acetate, butyl (tetra) titanate (cadmium acetate 0.05g, zinc acetate 0.1g, butyl (tetra) titanate 0.15g) as catalyzer, add 94g oxyethane and propylene oxide random copolymerization ether (BASF AG simultaneously, trade mark P103, molecular weight 4950), making the mass ratio of oxyethane and propylene oxide random copolymerization ether and described poly-succinic fourth two ester oligomers is 1: 2.2.260 ℃ of following vacuum polymerizations 5 hours, obtain thick melt, cooling crystallizes into white solid, and the molecular weight that obtains is 70,000 poly-succinic fourth diester/copolyethers.
With the molecular weight of 100 mass parts is 70,000 poly-succinic fourth diester/copolyether, light trigger α-amine the alkyl phenones of 3 mass parts, the linking agent season amylalcohol tetramethyl-acrylate of 5 mass parts, the whipping agent N of 10 mass parts, N-dinitroso five methyne tetramines, the nucleator nano level talcum powder of 1 mass parts in twin screw extruder 130 ℃ mix 20min, after mixing, on thermocompressor in 160 ℃, 5～10Mpa presses down 7min, obtains the thin slice about 1mm behind the naturally cooling.Then with thin slice with 400w medium pressure mercury lamp irradiation 5min, obtain gel content and be 31% crosslinked poly-succinic fourth diester.Get poly-succinic fourth diester/copolyether porous plastics at 200 ℃ of foaming 0.5h subsequently.Foam density is 78Kg/m
3
Adopt enzyme liberating to test the degradation capability that characterizes the gained porous plastics, experimental technique is with embodiment 1.The result shows resulting porous plastics degradable, a week degraded 17.6%.
Claims (10)
1. biodegradable foam plastic, the raw material of making described porous plastics comprises: ultraviolet initiator, linking agent and the whipping agent of a of 100 mass parts or b, 0.01～10 mass parts; Described a is a poly-succinic fourth diester, and described b is the multipolymer that is formed by poly-succinic fourth diester and polyethers; The number-average molecular weight of described poly-succinic fourth diester is 10,000～100,000; The number-average molecular weight of the multipolymer of described poly-succinic fourth diester and polyethers is 10,000～100,000.
2. porous plastics according to claim 1 is characterized in that: the mass parts of described linking agent is 0.5～40; The mass parts of described whipping agent is 0.1～20.
3. porous plastics according to claim 1 and 2 is characterized in that: the number-average molecular weight that is used to prepare the polyethers of the described multipolymer that is formed by poly-succinic fourth diester and polyethers is 500～20,000; The number-average molecular weight that is used to prepare the poly-succinic fourth diester of the described multipolymer that is formed by poly-succinic fourth diester and polyethers is 500～5000; Being used to prepare the described polyethers of the described multipolymer that is formed by poly-succinic fourth diester and polyethers and the mass ratio of described poly-succinic fourth diester is 1: 1～1: 20;
Described polyethers is equal polyethers or copolyether; Described equal polyethers is a kind of in following four kinds of materials: polyoxyethylene glycol, polyethylene oxide, poly(propylene oxide) and polytetrahydrofuran polyethers; Described copolyether is random copolymerization ether or block co-polyether; Described random copolymerization ether is oxyethane propylene oxide random copolymerization ether.
4. porous plastics according to claim 1 and 2, it is characterized in that: described ultraviolet initiator is a kind of in the following substances: bitter almond oil camphor and ether derivant thereof, α, alpha-alpha-dimethyl benzil ketals, dialkoxy methyl phenyl ketone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acyl group phosphorous oxides, aryl peroxy esters compound, halogenated methyl arone, sulfur-containing organic compound, benzoyl formiate, benzophenone, thioxanthone and derivative, anthraquinone, coumarone and camphorquinone;
Described linking agent is a kind of in the following substances: trimethylolpropane trimethacrylate, triallyl cyanurate, iso-cyanuric acid triallyl ester, season amylalcohol acrylate, season amylalcohol tetramethyl-acrylate, diallyl phthalic ester and Viscoat 295;
Described whipping agent is inorganic foaming agent or organic blowing agent;
Described inorganic foaming agent is carbonate, Citrate trianion, supercarbonate, nitrate, hydroborate or carbide;
Described organic blowing agent is nitroso compound, azo-compound or sulfonyl hydrazines compound.
5. porous plastics according to claim 4 is characterized in that: described inorganic foaming agent is Citrate trianion or supercarbonate;
Described nitroso compound is N, N-dinitroso five methyne tetramine or N, N-dimethyl-N, N-two inferior terephthalamides;
Described azo-compound is Cellmic C 121, diisopropyl azodiformate, diethyl azodiformate or azoformic acid barium, is preferably Cellmic C 121.
Described sulfonyl hydrazines compound is 4,4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 3,3-disulfonyl hydrazide sulfobenzide, 4,4-two benzene disulfohydrazides, 1,3-benzene disulfohydrazide or 1,4-benzene disulfohydrazide.
6. method for preparing arbitrary described biodegradable foam plastic among the claim 1-5 may further comprise the steps:
1) will prepare the raw material of arbitrary described porous plastics among the claim 1-5: a or b, ultraviolet initiator, linking agent and whipping agent, melting mixing is pressed into sheet material then; Wherein, described a is a poly-succinic fourth diester, and described b is the multipolymer that is formed by poly-succinic fourth diester and polyethers;
2) sheet material that step 1) is obtained foams behind ultraviolet light irradiation, obtains described biodegradable foam plastic.
7. method according to claim 6 is characterized in that: described raw material carries out melting mixing in Banbury mixer or twin screw extruder, and the temperature of described melting mixing is 110～160 ℃, and the time is 1～30min.
8. method according to claim 6 is characterized in that: the thickness of described sheet material is 0.1-5mm; Described sheet material be will be described the mixture that obtains after mixing of raw materials melt at 110～160 ℃, hot pressing 1～10min under 5～50MPa, naturally cooling or water cooling obtain.
9. method according to claim 6 is characterized in that: the light source of described UV-light is medium pressure mercury lamp or high voltage mercury lamp, the power 0.1～25kw of described mercury lamp, and irradiation time is 1～120min.
10. according to arbitrary described method among the claim 6-9, it is characterized in that: described foaming is carried out in baking oven or on the thermocompressor, and the temperature of described foaming is 170～250 ℃, and foamed time is 5～30min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899200A (en) * | 2010-06-03 | 2010-12-01 | 上海交通大学 | Preparation method of biodegradable poly butylene succinate (PBS) foam materials |
| CN103589302A (en) * | 2013-11-12 | 2014-02-19 | 惠州市长润发涂料有限公司 | Low-odor ultraviolet curing primer |
| CN104497392A (en) * | 2014-12-09 | 2015-04-08 | 黑龙江省润特科技有限公司 | Ultraviolet cross-linking polyolefin foaming material and preparation method thereof |
| CN110920018A (en) * | 2019-11-21 | 2020-03-27 | 佛山碧嘉高新材料科技有限公司 | Polylactic acid foaming method |
| CN113583400A (en) * | 2021-08-27 | 2021-11-02 | 浙江新恒泰新材料有限公司 | Degradable foaming material and preparation method thereof |
| CN116675960A (en) * | 2023-07-03 | 2023-09-01 | 美瑞新材料创新中心(山东)有限公司 | Degradable polyester material capable of being used for foaming and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4066683B2 (en) * | 2002-03-18 | 2008-03-26 | 東レ株式会社 | Foamable resin composition and cross-linked foam thereof |
| CN1600814A (en) * | 2003-09-24 | 2005-03-30 | 赖文正 | Method for foaming poly lactic acid and foamed body |
| JP2006070178A (en) * | 2004-09-02 | 2006-03-16 | Sekisui Chem Co Ltd | Biodegradable foamed container |
| CN1995137A (en) * | 2006-12-25 | 2007-07-11 | 刘津平 | Biodegradable high polymer foaming material, foam article and its production method |
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- 2008-10-09 CN CN2008102239238A patent/CN101717475B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899200A (en) * | 2010-06-03 | 2010-12-01 | 上海交通大学 | Preparation method of biodegradable poly butylene succinate (PBS) foam materials |
| CN103589302A (en) * | 2013-11-12 | 2014-02-19 | 惠州市长润发涂料有限公司 | Low-odor ultraviolet curing primer |
| CN104497392A (en) * | 2014-12-09 | 2015-04-08 | 黑龙江省润特科技有限公司 | Ultraviolet cross-linking polyolefin foaming material and preparation method thereof |
| CN110920018A (en) * | 2019-11-21 | 2020-03-27 | 佛山碧嘉高新材料科技有限公司 | Polylactic acid foaming method |
| CN113583400A (en) * | 2021-08-27 | 2021-11-02 | 浙江新恒泰新材料有限公司 | Degradable foaming material and preparation method thereof |
| CN116675960A (en) * | 2023-07-03 | 2023-09-01 | 美瑞新材料创新中心(山东)有限公司 | Degradable polyester material capable of being used for foaming and preparation method and application thereof |
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| CN101717475B (en) | 2011-09-14 |
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