CN102153838B - Biodegradable polycarbonate butylene terephthalate composite material and preparation method of biodegradable polycarbonate butylene terephthalate composite material - Google Patents
Biodegradable polycarbonate butylene terephthalate composite material and preparation method of biodegradable polycarbonate butylene terephthalate composite material Download PDFInfo
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Abstract
The invention relates to a biodegradable polycarbonate butylene terephthalate composite material and a preparation method of the biodegradable polycarbonate butylene terephthalate composite material. The biodegradable polycarbonate butylene terephthalate composite material is characterized in that the material comprises the following components in part by weight: 30 to 70 parts of aliphatic polycarbonate butylene terephthalate, 10 to 40 parts of other biodegradable materials, 1.0 to 10 parts of filler, 0.5 to 1.5 parts of rare earth composite nucleating agent, 0.5 to 1.5 parts of dispersant, 4.0 to 15 parts of plasticizer, 1.5 to 4 parts of heat resistance stabilizer, 0.05 to 1.5 parts of antioxidant, 0.5 to 1.0 part of lubricant, 0.1 to 1.0 part of anti-block agent and 0.05 to 0.5 part of biodegradation accelerator. The composite material has high melt strength, good film forming ability, high tensile strength, high tearing strength and good light-conversion effect.
Description
Technical field
The present invention relates to a kind of bio-degradable plastics material, be specifically related to a kind of biodegradable polytetramethylene carbonate diol type matrix material and preparation method thereof.
Background technology
The conventional plastic industrial expansion is when satisfying social development demand and people's living needs, and the environment of also depending on for existence to the mankind has brought immeasurable negative impact.Discarded amount after these conventional plastic goods use is up to 50%-60%.According to incompletely statistics, the annual plastic refuse total amount in the whole world is up to 5,000 ten thousand tons, and they decompose fully at occurring in nature and need 200-400, and the problem of environmental pollution that these depleted plastics are caused is serious day by day.In order to solve " white pollution " problem that plastics cause, the friendly complete biodegradable polymkeric substance of environment for use substitutes traditional petroleum-based plastics, has become the current research hot of research and development.
At present, the more Biodegradable material of research report mainly contains mikrobe synthetic polyhydroxyalkanoate, PHA (PHA) etc. both at home and abroad; The POLYACTIC ACID of chemosynthesis (PLA), gather acid (PCL), poly butylene succinate (PBS), aliphatic/aromatic copolyesters, aliphatic polycarbonate (APC), Z 150PH (PVA) etc. in oneself, part commercialization.But because development stages property, the prior biological degraded macromolecular material exists certain deficiency, and is comparatively cheap like POLYACTIC ACID, but its melt strength is lower, causes it to be difficult to blown film, and the prepared film fragility of two-way stretch is big, tear strength is low; All there are problems such as poor mechanical property in other the film that makes like polyhydroxyalkanoate (PHA, PHB, PHBV), aliphatic polycarbonate (APC), Z 150PH (PVA) etc.; And traditional biological degradable film ultraviolet-resistent property is poor, do not have the photosensitiveness of commentaries on classics, and these large-scale promotion that all significantly impact biodegradable plastic are used.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, biodegradable aliphatics polytetramethylene carbonate diol type matrix material that a kind of melt strength is high, mechanical property is excellent, uvioresistant performance is good and preparation method thereof is provided.
The objective of the invention is to realize like this:
A kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material, said material comprises following parts by weight proportioning:
Aliphatics polytetramethylene carbonate diol (poly (butylene carbonate) is called for short PBC) 30-70 part, other Biodegradable materials 10-40 part, weighting agent 1.0-10 part, rare earth compound nucleating agent 0.5-1.5 part, dispersion agent 0.5-1.5 part, softening agent 4.0-15 part, heat-resisting stabilizing agent 1.5-4 part, oxidation inhibitor 0.05-1.5 part, lubricant 0.5-1.0 part, opening agent 0.1-1.0 part, biodegradation promotor 0.05-0.5 part;
Wherein: the number-average molecular weight 60000～150000 of said aliphatics polytetramethylene carbonate diol;
Said other Biodegradable materials: POLYACTIC ACID (PLA), gather a kind of in own lactones (PCL), poly butylene succinate (PBS), aliphatic/aromatic copolyesters, aliphatic polycarbonate (APC), Z 150PH (PVA), the polyhydroxyalkanoate (PHA, PHB, PHBV).
Said rare earth compound nucleating agent is: main nucleator: nano-cerium oxide; Auxiliary nucleator: nano europium oxide, the ratio of main nucleator and auxiliary nucleator are 60:40～95:5;
Said dispersion agent: cage anilino methyl sesquisiloxane octamer.
The particle diameter of said nano-cerium oxide, nano europium oxide all is nano materials of 10nm～100nm level.
Said softening agent is: any one in phthalic ester (as: DBP, DOP, DIDP), polyoxyethylene glycol, Roplex400, the epoxy soybean wet goods epoxy resin softening agent.
Said heat-resisting stabilizing agent is: a kind of in maleic dibutyl tin, calcium stearate, zinc oxide, the Natural manganese dioxide.
Said oxidation inhibitor is: any one in dihydroxyphenyl propane, phosphorous acid ethyl ester, triphenyl phosphite or the phosphorous acid dihydroxyphenyl propane.
Said lubricant: Triple Pressed Stearic Acid.
Said opening agent: particle diameter is 3～4 microns a silicon-dioxide.
Said biodegradation promotor: a kind of in oxalic acid, propanedioic acid, Hydrocerol A, oxysuccinic acid, the Succinic anhydried.
Said weighting agent: a kind of in lime carbonate, talcum, WHITE CARBON BLACK, mica, the kaolin.
Said aliphatics polytetramethylene carbonate diol preparation method comprises transesterify and two steps of polycondensation, and concrete steps are following:
Step 1:
Transesterify: in inert gas atmosphere; Divalent alcohol and carbonic ether heated up under the effect of transesterification catalyst accomplish transesterification reaction, and remove the prepolymer that the by product that produces in the transesterification reaction obtains aliphatics polytetramethylene carbonate diol (poly (butylene carbonate));
Step 2:
Polycondensation: in the reaction system of above-mentioned step 1, add polycondensation catalyst, vacuum is carried out polycondensation, obtains aliphatics polytetramethylene carbonate diol provided by the invention (poly (butylene carbonate)).
In said preparing method's the step 1, divalent alcohol is: 1, and the 4-butyleneglycol; Carbonic ether is: methylcarbonate or diethyl carbonate; Transesterification catalyst is any one in Pottasium Hydroxide, sodium hydroxide, the titanium isopropylate; Polycondensation catalyst is: any one in titanium oxide, titanium sesquioxide, the aluminum oxide.
A kind of preparation method of biodegradable aliphatics polytetramethylene carbonate diol type matrix material; It is characterized in that: said preparation process and condition are: the good matrix resin of weighing in proportion; 20～60 ℃ of dryings 5～10 hours in baking oven mix in proportion load weighted nano-cerium oxide, nano europium oxide simultaneously in advance, and the matrix resin that will dry by the fire then after good drops into impeller; The beginning stirring at low speed; When stirring, add load weighted rare earth compound nucleating agent, dispersion agent, softening agent, heat-resisting stabilizing agent, oxidation inhibitor, lubricant, opening agent, biodegradation promotor and weighting agent successively, stirring at low speed 5～10 minutes adds high-speed stirring after 5～10 minutes afterwards again; After stirring, get in the parallel dual-screw extruding machine.Be 60～190 ℃ in temperature and carry out extruding pelletization, promptly obtain product.
Compared with prior art, the invention has the beneficial effects as follows:
In the biodegradable aliphatics polytetramethylene carbonate diol of the present invention type matrix material; Select a kind of high-molecular weight aliphatics polytetramethylene carbonate diol (poly (butylene carbonate) is called for short PBC) for use, number-average molecular weight is 60000～150000; Its advantage is that cost is low, melt strength is high, good heat resistance; Can the blowing film forming after itself and the blend of other biological degradable material, the film snappiness is good, and tear strength is high.
To the slow problem of PBC crystallization velocity, it is rare earth compound nucleating agent that the present invention has adopted a kind of Compositional type rare earth beta nucleater, and this rare earth compound nucleating agent is made by main nucleator nano-cerium oxide and the composite of auxilliary nucleator nano europium oxide.In melt isothermal crystal process; Nano-cerium oxide plays the effect that increases nucleus on the one hand; Macromole is at the interfacial free energy that folds perpendicular to the molecular chain direction when having reduced crystalline growth on the other hand; Make macromolecular chain more be prone to enter lattice, promptly play the effect that promotes crystalline growth, improve crystallization rate.But the beta crystal of its formation is poor in the thermodynamics upward stability, thus composite nano europium oxide, because the crystal face spacing of lattice of three valence state europiums is little; Improved its stability after the composite use,, thereby converted blood orange light to simultaneously owing to europium element ability absorbing ultraviolet light; Make polytetramethylene carbonate diol type biodegradable composite have the commentaries on classics optical property; The film that makes can transfer deleterious UV-light to useful blood orange light, thereby helps photosynthesis of plants, promotes growth; Reduce the chemical fertilizer usage quantity, play the effect of ecological, environmental protective.
The nano-cerium oxide that the present invention selects for use, nano europium oxide all are nano materials of 10nm～100nm level; Because the nano-component particle diameter is little, specific surface area is big; Very easily assemble and form larger-size coacervate, make nanoparticle because of gathering can not be in polymeric matrix homodisperse, to this problem; The present invention has selected a kind of cage anilino methyl sesquisiloxane octamer for use, and cagelike silsesquioxane is one type and had not only had nanometer microtexture but also special nanoparticle that can functionalization.Have the cage type core/shell structure, its shell is generally 8 organo-functional groups, and wherein 7 functional groups are the inertia organic group, 1 functional group for having reactive behavior.Its organic group can realization and the excellent compatibility of organic solvent and polymeric matrix, thereby significantly reduces the agglomeration of nanoparticle, makes its dispersion more even.
Problems such as the melt strength that the invention solves existing biodegradable polymer is lower, is difficult to blown film, and the fragility of film is big, and the commentaries on classics photosensitiveness of film is poor.Have that melt strength is higher, good film-forming property, characteristics that the commentaries on classics light effect is good.
Embodiment
Embodiment 1:
Nano europium oxide 65:35) 1.0, cage anilino methyl sesquisiloxane octamer press the row weight part and take by weighing each component: PBC:50.0, PLA: 36.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide:: 1.0, polyoxyethylene glycol: 5.0, maleic dibutyl tin: 2.5, dihydroxyphenyl propane: 0.5, Triple Pressed Stearic Acid: 0.7, silicon-dioxide: 1.0, propanedioic acid: 0.05, lime carbonate: 4.0.
Preparation process and condition are:
The good matrix resin of weighing in proportion; 30 ℃ of dryings 6 hours in baking oven mix in proportion load weighted nano-cerium oxide, nano europium oxide simultaneously in advance, and the matrix resin that will dry by the fire then after good drops into impeller; The beginning stirring at low speed; When stirring, add load weighted rare earth compound nucleating agent, dispersion agent, softening agent, heat-resisting stabilizing agent, oxidation inhibitor, lubricant, opening agent, biodegradation promotor and weighting agent successively, stirring at low speed 10 minutes adds high-speed stirring after 5 minutes afterwards again; After stirring, get in the parallel dual-screw extruding machine.Be 60～190 ℃ in temperature and carry out extruding pelletization, promptly obtain product.Utilize the matrix material master batch of above-mentioned technological process preparation to carry out blow molding, obtain film article.
The performance comparison of gained film article is seen table 1.
Table 1:
Embodiment 2:
Press the row weight part and take by weighing each component: PBC:55.0, gather sour PCL in oneself: 30.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide: nano europium oxide 60:40): 1.5, cage anilino methyl sesquisiloxane octamer: 0.5, Roplex400: 5.0, zinc oxide: 2.5, phosphorous acid ethyl ester: 0.5, Triple Pressed Stearic Acid: 0.7, silicon-dioxide: 1.0, propanedioic acid: 0.05, lime carbonate: 4.0;
Preparation process and condition are seen embodiment 1.
The performance comparison of gained film article is seen table 2.
Table 2:
Press the row weight part and take by weighing each component: PBC:50.0, PBS: 35.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide: nano europium oxide 70:30): 1.0, cage anilino methyl sesquisiloxane octamer: 0.5, epoxy soybean oil: 10.0, calcium stearate: 3.0, phosphorous acid ethyl ester: 0.5, Triple Pressed Stearic Acid: 1.0, silicon-dioxide: 1.0, oxalic acid: 0.05, WHITE CARBON BLACK: 4.0;
Preparation process and condition are seen embodiment 1.
The performance comparison of gained film article is seen table 3.
Table 3:
Press the row weight part and take by weighing each component: PBC:60.0, PHB: 30.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide: nano europium oxide 75:25): 1.0, cage anilino methyl sesquisiloxane octamer: 1.0, phthalic ester: 12.0, Natural manganese dioxide: 3.5, phosphorous acid dihydroxyphenyl propane: 1.0, Triple Pressed Stearic Acid: 1.0, silicon-dioxide: 1.0, Succinic anhydried: 0.15, WHITE CARBON BLACK: 4.0;
Preparation process and condition are seen embodiment 1.
The performance comparison of gained film article is seen table 4.
Table 4:
embodiment 5:
Press the row weight part and take by weighing each component: PBC:70.0, PHBV: 25.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide: nano europium oxide 80:20): 1.0, cage anilino methyl sesquisiloxane octamer: 0.8, polyoxyethylene glycol: 10.0, maleic dibutyl tin: 3.0, phosphorous acid dihydroxyphenyl propane: 1.0, Triple Pressed Stearic Acid: 1.0, silicon-dioxide: 1.0, propanedioic acid: 0.15, WHITE CARBON BLACK: 4.0;
Preparation process and condition are seen embodiment 1.
The performance comparison of gained film article is seen table 5.
Table 5:
Press the row weight part and take by weighing each component: PBC:65.0, PHA: 30.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide: nano europium oxide 85:15): 1.0, cage anilino methyl sesquisiloxane octamer: 1.0, polyoxyethylene glycol: 10.0, calcium stearate: 3.0, phosphorous acid dihydroxyphenyl propane: 1.0, Triple Pressed Stearic Acid: 1.0, silicon-dioxide: 1.0, oxalic acid: 0.2, lime carbonate: 4.0;
Preparation process and condition are seen embodiment 1.
The performance comparison of gained film article is seen table 6.
Table 6:
Press the row weight part and take by weighing each component: PBC:65.0, PVA: 30.0, Compositional type rare earth beta nucleater is a rare earth compound nucleating agent (nano-cerium oxide: nano europium oxide 74:26): 0.8, cage anilino methyl sesquisiloxane octamer: 1.1, polyoxyethylene glycol: 10.0, Natural manganese dioxide: 3.0, dihydroxyphenyl propane: 1.0, Triple Pressed Stearic Acid: 1.0, silicon-dioxide: 1.0, propanedioic acid: 0.2, lime carbonate: 5.0;
Preparation process and condition are seen embodiment 1.
The performance comparison of gained film article is seen table 7.
Table 7:
The high-molecular weight aliphatics polytetramethylene carbonate diol that the present invention uses, its general structure is as follows:
In the said structure general formula, n=345～875.
Above-mentioned aliphatics polytetramethylene carbonate diol (poly (butylene the carbonate)) preferred manufacturing procedure that the present invention uses comprises transesterify and two steps of polycondensation, and concrete steps are following:
Step 1:
Transesterify: in inert gas atmosphere; Divalent alcohol and carbonic ether heated up under the effect of transesterification catalyst accomplish transesterification reaction, and remove the prepolymer that the by product that produces in the transesterification reaction obtains aliphatics polytetramethylene carbonate diol (poly (butylene carbonate));
Step 2:
Polycondensation: in the reaction system of above-mentioned step 1, add polycondensation catalyst, vacuum is carried out polycondensation, obtains aliphatics polytetramethylene carbonate diol provided by the invention (poly (butylene carbonate)).
In above-mentioned preparing method's the step 1, divalent alcohol is: 1, and the 4-butyleneglycol; Carbonic ether is: methylcarbonate or diethyl carbonate; Transesterification catalyst is any one in Pottasium Hydroxide, sodium hydroxide, the titanium isopropylate; Polycondensation catalyst is: any one in titanium oxide, titanium sesquioxide, the aluminum oxide.
Claims (5)
1. biodegradable aliphatics polytetramethylene carbonate diol type matrix material, it is characterized in that: said material comprises following parts by weight proportioning:
Aliphatics polytetramethylene carbonate diol 30-70 part, other Biodegradable materials 10-40 part, weighting agent 1.0-10 part, rare earth compound nucleating agent 0.5-1.5 part, dispersion agent 0.5-1.5 part, softening agent 4.0-15 part, heat-resisting stabilizing agent 1.5-4 part, oxidation inhibitor 0.05-1.5 part, lubricant 0.5-1.0 part, opening agent 0.1-1.0 part, biodegradation promotor 0.05-0.5 part;
Wherein: the number-average molecular weight 60000～150000 of said aliphatics polytetramethylene carbonate diol;
Said other Biodegradable materials are: a kind of in POLYACTIC ACID, polycaprolactone, poly butylene succinate, aliphatic/aromatic copolyesters, aliphatic polycarbonate, Z 150PH, the polyhydroxyalkanoate;
Said rare earth compound nucleating agent is: main nucleator: nano-cerium oxide; Auxiliary nucleator: nano europium oxide, the ratio of main nucleator and auxiliary nucleator are 60:40～95:5;
Said dispersion agent: cage anilino methyl sesquisiloxane octamer;
Said opening agent: particle diameter is 3～4 microns a silicon-dioxide;
Said biodegradation promotor: a kind of in oxalic acid, propanedioic acid, Hydrocerol A, oxysuccinic acid, the Succinic anhydried;
The method for preparing said aliphatics polytetramethylene carbonate diol comprises transesterify and two steps of polycondensation, and concrete steps are following:
Step 1:
Transesterify: in inert gas atmosphere, divalent alcohol and carbonic ether heated up under the effect of transesterification catalyst accomplish transesterification reaction, and remove the prepolymer that the by product that produces in the transesterification reaction obtains the aliphatics polytetramethylene carbonate diol;
Step 2:
Polycondensation: in the reaction system of above-mentioned step 1, add polycondensation catalyst, vacuum is carried out polycondensation, obtains said aliphatics polytetramethylene carbonate diol;
In said preparing method's the step 1, divalent alcohol is: 1, and the 4-butyleneglycol; Carbonic ether is: methylcarbonate or diethyl carbonate; Transesterification catalyst is any one in Pottasium Hydroxide, sodium hydroxide, the titanium isopropylate;
Said polycondensation catalyst is: a kind of in titanium oxide, titanium sesquioxide, the aluminum oxide.
2. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said nano-cerium oxide, nano europium oxide all are nano materials of 10nm～100nm level.
3. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said softening agent is: a kind of in phthalic ester, polyoxyethylene glycol, the epoxy soybean oil epoxy resin softening agent.
4. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said heat-resisting stabilizing agent is: a kind of in maleic dibutyl tin, calcium stearate, zinc oxide, the Natural manganese dioxide.
5. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said oxidation inhibitor is: a kind of in dihydroxyphenyl propane, phosphorous acid ethyl ester, triphenyl phosphite or the phosphorous acid dihydroxyphenyl propane.
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