CN103665789A - Fully biodegradable polyester material, and preparation method and application thereof - Google Patents
Fully biodegradable polyester material, and preparation method and application thereof Download PDFInfo
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- CN103665789A CN103665789A CN201310632253.6A CN201310632253A CN103665789A CN 103665789 A CN103665789 A CN 103665789A CN 201310632253 A CN201310632253 A CN 201310632253A CN 103665789 A CN103665789 A CN 103665789A
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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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
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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
-
- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/54—Screws with additional forward-feeding elements
-
- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/55—Screws having reverse-feeding elements
Abstract
The invention belongs to the technical field of biodegradable polyester material, and discloses fully biodegradable polyester material in composting conditions, and a preparation method and the application thereof. The polyester material comprises the following constituents by mass percent: 93 to 99.5 percent of long chain branched polyester, 0.1 to 3 percent of a chain extender, 0.1 to 1 percent of an antioxidant, 0.1 to 1 percent of a lubricant, 0.1 to 1 percent of a stabilizer, and 0.1 to 1 percent of a nucleating agent. The material adopts the efficient chain extender to be mixed with aliphatic-aromatic copolyester and various types of additives, utilizes unique screw combination design and side feeding refueling design, improves the ageing property and the processing property of PBSA products, and meanwhile ensures that the fully biodegradable polyester material has excellent degradation property and aging property. The biodegradability of the material meets the use requirements of biodegradable plastics EN13432, and excellent membrane material mechanical property can be guaranteed after membrane blowing forming processing is performed.
Description
Technical field
The invention belongs to Biodegradable polyester material technology field, particularly a kind of can be at the polyester material of complete biodegradable under composting conditions and its preparation method and application.
Background technology
The aliphatic polyester-based resin that meets composting conditions biodegradability comprises poly-Alpha-hydroxy alkyl acid esters (as poly(lactic acid)), poly-beta-hydroxy alkyl acid esters (as poly-beta-hydroxy-butanoic acid ester, beta-hydroxy-butanoic acid ester-beta-hydroxy valerate multipolymer), poly-ω-hydroxyalkyl acid esters (as gathered acid esters in oneself), the copolyesters that also comprises diprotic acid dibasic alcohol, the latter's structure has good composting conditions biodegradability when the diprotic acid by even carbon and dibasic alcohol form.The material in polyester resin that an other class has larger cost advantage is a class aliphatic-aromatic copolyester material, as poly butylene succinate (PBS) or poly-(tetramethylene adipate/mutual-phenenyl two acid bromide two alcohol ester) (PBAT), poly-(succinic acid-butanediol ester-tetramethylene adipate) (PBSA) etc.
PBS is classical biodegradable material, has very important theoretical significance and actual application value.PBS base polyester, as degradable wrapping material, bio-medical material, meets national environmental protection and strategy of sustainable development requirement.But the molecular weight of binary homopolymer synthetic product is lower, the fragility that obtains product is large, and bad mechanical property is high due to crystallizing polyester degree again, causes its degradation property in physical environment poor, and degradation speed is slower.
In prior art, be engaged in design molecular structure, use polyester, polymerization single polymerization monomer aliphatic monomer or the aromatic monomer of specified property to carry out copolymerization or blending and modifying to former polyester based biodegradable material; Another is to add chainextender in the process of polyreaction, and the end group that utilizes chainextender and polymkeric substance carries out chain extending reaction and obtains the better polymkeric substance of mechanical property as hydroxyl, carboxyl etc.Adding just the end group contracting chain reaction of former polyester based material of chainextender, significantly improve the molecular weight of polyester material, promote processing characteristics, the molecular chain structure of former polyester and molecular weight distribution can not changed, thereby can not have influence on the complete biodegradable characteristic of polyester self.The complete biodegradable polyester material of prior art modification has problems, wherein first one be exactly high cost, at present, generally admit both at home and abroad, due to production technique and raw materials cost problem, the similar existing conventional plastic product of biodegradable plastic cost ratio is high, simultaneously in the industrialization course of processing, aliphatic-aromatic copolyester, because exist two reaction process of tackify and degraded in the middle of process systems, is found a kind of suitable complete processing and economic modified formula and is combined into the focus of chasing for industry inside.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of complete biodegradable polyester material.This material not only has superior degradation property and aging resistance, and has good mechanical property and blown film processing characteristics.
Another object of the present invention is to provide a kind of preparation method of above-mentioned complete biodegradable polyester material.
Still a further object of the present invention is to provide the application of above-mentioned complete biodegradable polyester material in the processing of film series products.
Object of the present invention realizes by following proposal:
A complete biodegradable polyester material, comprises following component by mass percentage:
Described long-branched polyester refers at least one in long-branched aliphatic polyester and long-branched aliphatic-aromatic copolyester.
Preferably, described long-branched aliphatic polyester is that weight-average molecular weight is more than 80000, its molecular chain is formed by connecting by polyfunctional groups such as polyvalent alcohol or polyprotonic acids at more than 4000 aliphatic polyester copolymers by weight-average molecular weight, and it contains organic dibasic acid residue and organic residue of dihydric alcohol, can be represented by general formula (1):
Wherein, R1 represents that carbonatoms is 2～12 fatty group, and R2 represents that carbonatoms is 4～12 fatty group, and R3 represents the organic molecule that contains polyvalent alcohol or polyprotonic acid polyfunctional group structure, and n represents number of repeat unit.
Described long-branched aliphatic-aromatic copolyester is that weight-average molecular weight is more than 80000, its molecular chain is formed by connecting by polyfunctional group mechanisms such as polyvalent alcohols at more than 4000 aliphatic-aromatic polyester copolymers by weight-average molecular weight, and it contains organic dibasic acid residue and organic residue of dihydric alcohol; By general formula (2), represented:
Wherein, R1 represents that carbonatoms is 2～12 fatty group, and R2 represents that carbonatoms is 4～12 fatty group, R4 represents the organic molecule containing aromatic structure, R5 represents the polyfunctional group building stones such as polyvalent alcohol, and m1 is more than or equal to 20 natural number, the natural number that m2 is 1～5.
Preferably, long-branched aliphatic-aromatic copolyester of the present invention refers to succinic acid-butanediol ester-tetramethylene adipate multipolymer (PBSA).
Described chainextender is selected from least one in Isosorbide-5-Nitrae-phenyl-bis-(2-oxazolines), two (2-oxazolines), tolylene diisocyanate, diphenylmethanediisocyanate, bischloroformate, isophorone diisocyanate, novel chainextender ADR-4370, isocyanuric acid three-glycidyl ester, hexamethylene diisocyanate and isophorone diisocyanate.
Described oxidation inhibitor is selected from dihydroxyphenyl propane, 1,4-dual-tert-butyl peroxy isopropyl base benzene, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide), phosphorous acid dihydroxyphenyl propane ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 4,4 '-bis--(α, α '-dimethyl benzyl) at least two kinds in pentanoic, ten dithio propyl ester and 1,4 bis tert butyl peroxy isopropyl benzene.
Described lubricant is selected from least two kinds in polymer complex ester, ethylene bis stearamide and the polyethylene wax of hard esteramides, amine hydroxybenzene, erucicamide, Zinic stearas, metallic soap.
Described stablizer is selected from least one in calcium stearate, zinc oxide, magnesium oxide, silicon-dioxide, kaolin and polynite.
Described nucleator is selected from least one in aluminium carbonate, terephthalic acid, talcum powder, aluminium hydroxide and aluminum oxide.
Complete biodegradable polyester material of the present invention can also include end-capping reagent, the reagent that deacidifies, the stabilization aid 0.1～3wt% such as reagent that dewater, and described stabilization aid is the organic molecule material containing oxazolyl, isocyanate group, isothiocyanate group, epoxy group(ing), activated silica alkyl or their mixed base.
A kind of preparation method of complete biodegradable polyester material, comprise following steps: long-branched polyester 93～99.5wt%, chainextender 0.1～3wt%, oxidation inhibitor 0.1～1wt%, lubricant 0.1～1wt%, stablizer 0.1～1wt%, nucleator 0.1～1wt% adds blender and mixing, in feeding twin screw extruder, fusion plastification, extruding pelletization, obtain complete biodegradable polyester material.
Described long-branched polyester carries out predrying in dehumidifying heat pump before using.
Before described feeding twin screw extruder, use weighing balance accurate-metering.
Described Assembled Twin Screw Extruder Screw is banburying element, delivery element assembled arrangement successively.
Preferably, described banburying element comprises shearing screwing element and hybrid element;
Described delivery element comprises reverse thread element and carries screwing element.
Preferably, described Assembled Twin Screw Extruder Screw is as shown in Fig. 2～3.
More preferably, when long-branched molecular weight of polyesters narrow distribution used, described Assembled Twin Screw Extruder Screw is the screw combinations that is provided with more conveying screwing element and reverse thread element, as shown in Figure 2; When long-branched molecular weight of polyesters wider distribution used, described Assembled Twin Screw Extruder Screw is the screw combinations that is provided with more shearing screwing element, as shown in Figure 3.
Described twin screw extruder is equidirectional parallel double-screw extruder, anisotropic parallel twin-screw extruding machine or conical double screw extruder; Its length-to-diameter ratio is 56:1 or 60:1; Forcing machine power is 65D or 75D model.
Preferably, twin screw extruder leading portion increases side and feeds oiling design, comprises small-bore oil nozzle, and refueling position is twin screw extruder blanking place, and choke size schematic diagram as shown in Figure 1.
Described side is fed to refuel and is designed for interpolation chainextender.Chainextender for confirmation accurately adds in forcing machine.
Described mixing machine is frequency-conversion high-speed mixing machine, and metering is called weight-loss metering and claims.
The mode of described pelletizing is that tie rod is crossed tank and entered the granulation of white steel knife dicing machine, underwater cutpellet or water ring pelletizing.
Complete biodegradable polyester material of the present invention can be applicable to film series products field.
Mechanism of the present invention is:
Screwing element mainly divides (1) to carry screwing element, and Main Function is convey materials; (2) reverse thread element, effect is to make material form and stop in the process of carrying, and promotes melting, strengthens mixed effect, increases the residence time of material; (3) shear screwing element, the inside has comprised the cutout of various angles, works and is mainly to provide high shearing, thereby promote good distribution mixing and dispersing and mixing, and stagger arrangement angle is larger, and the degree of filling of melt and the residence time just increase thereupon; (4) hybrid element, also possesses material is shunted possessing on the function basis of common cutout, and the function of minimum energy input is provided, and is more conducive to distribute and mixes.The present invention, by screw combinations, side hello refueling device and composition of raw materials are designed, utilizes efficient chainextender, obtains having superior degradation property and aging resistance, and has the polyester material of good mechanical property and blown film processing characteristics.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention utilizes efficient chainextender with aliphatic-aromatic copolyester blend, assist a ruler in governing a country with various additives, utilizing unique screw combinations design and side to feed to refuel designs, improved aging resistance and the processing characteristics of PBSA goods, guaranteed that complete biodegradable polyester material has superior degradation property and aging resistance simultaneously.Its biodegradability meets the service requirements of biodegradable plastic EN13432, and after carrying out blowfilm shaping processing, can guarantee good film material mechanical property.
(2) gordian technique of the present invention has more been to quote the different screw combinations of two covers on same formula basis, realized the processing on 65D type and 75D type, guarantee its processing stability, thereby obtained having the complete biodegradable polyester material of good aging resistance and blown film processing characteristics.
(3) complete biodegradable polyester material provided by the present invention can be prepared by the method for blow molding the membrane product of good physical and chemical performance.The biological degradation of this membrane product is to degrade under composting conditions, at the physical and chemical performance of 1 year inner membrance material, meets routine use demand, can be widely used in packaging industry, and product for agriculture.
Accompanying drawing explanation
Fig. 1 is oil nozzle schematic diagram.
Fig. 2 is the screw combinations element schematic diagram that embodiment 1 is used.
Fig. 3 is the screw combinations element schematic diagram that embodiment 2 is used.
The screw combinations element schematic diagram that Fig. 4 is used for comparative example.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: the preparation of complete biodegradable polyester material
Press row weight percent and take each component (%):
Preparation technology is as follows:
PBSA is put into baking oven, under 50～80 ℃ of conditions, carry out removal moisture drying 8 hours, moisture control is below 300ppm;
Dried compound and interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning;
Use weighing balance accurate measurement feeding forcing machine; Fig. 1 is shown in oil nozzle design.
Forcing machine length-to-diameter ratio is 60:1;
Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder;
Melting temperature is as follows: one section 90～100 ℃; Two sections 120～140 ℃; Three sections 190～200 ℃; Four sections 210～220 ℃; Five sections 210～220 ℃; Six sections 210～220 ℃; Seven sections 210～220 ℃; Eight sections 210～220 ℃; Nine sections 210～220 ℃; Ten sections 210～220 ℃; 11 sections 210～220 ℃; 12 sections 190～200 ℃; 13 sections 190～200 ℃; 14 sections 190～200 ℃; 180～190 ℃ of heads;
Fig. 2 is shown in by screw combinations schematic diagram.
Shown in Fig. 2,1 is helical pitch 56, length 56A screw thread transfer block;
Shown in 2 be helical pitch 96, length 96 transfer block;
Shown in 3 be helical pitch 72, length 72 transfer block;
Shown in 4 be helical pitch 56, length 56 transfer block;
Shown in 5 be 6 and mediate 30 degree that sheets form, three of length 72 and double end are mixed and are sheared threaded block;
Shown in 6 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 56;
Shown in 7 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 8 be helical pitch 72, length 36 left-hand transfer block;
Shown in 9 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 10 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 36;
Shown in 11 be helical pitch 128, length 128 transfer block;
Shown in 12 be feed opening;
Shown in 13 be side feeding oil port;
Shown in 14 be vaccum exhaust outlet;
Select underwater cutpellet to obtain complete biodegradable polyester material.
Embodiment 2: usage example 1 screw rod used, adjust PBSA consumption, and prepare complete biodegradable polyester material
Press row weight percent and take each component (%):
Preparation technology is as follows:
PBSA is put into baking oven, under 50～80 ℃ of conditions, carry out removal moisture drying 8 hours, moisture control is below 300ppm;
Dried compound and interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning;
Use weighing balance accurate measurement feeding forcing machine;
Forcing machine length-to-diameter ratio is 60:1;
Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder;
Melting temperature is as follows: one section 90～100 ℃; Two sections 120～140 ℃; Three sections 190～200 ℃; Four sections 210～220 ℃; Five sections 210～220 ℃; Six sections 210～220 ℃; Seven sections 210～220 ℃; Eight sections 210～220 ℃; Nine sections 210～220 ℃; Ten sections 210～220 ℃; 11 sections 210～220 ℃; 12 sections 190～200 ℃; 13 sections 190～200 ℃; 14 sections 190～200 ℃; 180～190 ℃ of heads;
Fig. 2 is shown in by screw combinations schematic diagram.
Shown in Fig. 2,1 is helical pitch 56, length 56A screw thread transfer block;
Shown in 2 be helical pitch 96, length 96 transfer block;
Shown in 3 be helical pitch 72, length 72 transfer block;
Shown in 4 be helical pitch 56, length 56 transfer block;
Shown in 5 be 6 and mediate 30 degree that sheets form, three of length 72 and double end are mixed and are sheared threaded block;
Shown in 6 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 56;
Shown in 7 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 8 be helical pitch 72, length 36 left-hand transfer block;
Shown in 9 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 10 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 36;
Shown in 11 be helical pitch 128, length 128 transfer block;
Shown in 12 be feed opening;
Shown in 13 be side feeding oil port;
Shown in 14 be vaccum exhaust outlet;
Select underwater cutpellet to obtain complete biodegradable polyester material.
Embodiment 3: usage example 1 screw rod used, adjust PBSA consumption, and prepare complete biodegradable polyester material
Press row weight percent and take each component (%):
PBSA 99.5 of an established trade mark
Tolylene diisocyanate 0.5
Preparation technology is as follows:
PBSA is put into baking oven, under 50～80 ℃ of conditions, carry out removal moisture drying 8 hours, moisture control is below 300ppm;
Dried compound and interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning;
Use weighing balance accurate measurement feeding forcing machine;
Forcing machine length-to-diameter ratio is 60:1;
Forcing machine power and model: 65D type, equidirectional parallel double-screw extruder;
Melting temperature is as follows: one section 90～100 ℃; Two sections 120～140 ℃; Three sections 190～200 ℃; Four sections 210～220 ℃; Five sections 210～220 ℃; Six sections 210～220 ℃; Seven sections 210～220 ℃; Eight sections 210～220 ℃; Nine sections 210～220 ℃; Ten sections 210～220 ℃; 11 sections 210～220 ℃; 12 sections 190～200 ℃; 13 sections 190～200 ℃; 14 sections 190～200 ℃; 180～190 ℃ of heads;
Fig. 2 is shown in by screw combinations schematic diagram.
Shown in Fig. 2,1 is helical pitch 56, length 56A screw thread transfer block;
Shown in 2 be helical pitch 96, length 96 transfer block;
Shown in 3 be helical pitch 72, length 72 transfer block;
Shown in 4 be helical pitch 56, length 56 transfer block;
Shown in 5 be 6 and mediate 30 degree that sheets form, three of length 72 and double end are mixed and are sheared threaded block;
Shown in 6 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 56;
Shown in 7 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 8 be helical pitch 72, length 36 left-hand transfer block;
Shown in 9 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 10 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 36;
Shown in 11 be helical pitch 128, length 128 transfer block;
Shown in 12 be feed opening;
Shown in 13 be side feeding oil port;
Shown in 14 be vaccum exhaust outlet;
Select underwater cutpellet to obtain complete biodegradable polyester material.
Embodiment 4: the preparation of complete biodegradable polyester material
Press row weight percent and take each component (%):
Preparation technology is as follows:
PBSA is put into baking oven, under 50～80 ℃ of conditions, carry out removal moisture drying 8 hours, moisture control is below 300ppm;
Dried compound and various interpolation auxiliary agent are dropped into high mixer high speed mixing 30s according to proportioning;
Use weighing balance accurate measurement feeding forcing machine;
Forcing machine length-to-diameter ratio is 60:1;
Forcing machine power and model: 75D type, equidirectional parallel double-screw extruder;
Melting temperature is as follows: one section 80～90 ℃; Two sections 80～90 ℃; Three sections 90～100 ℃; Four sections 90～100 ℃; Five sections 100～110 ℃; Six sections 140～150 ℃; Seven sections 180～190 ℃; Eight sections 180～190 ℃; Nine sections 180～190 ℃; Ten sections 180～190 ℃; 11 sections 180～180 ℃; 12 sections 180～190 ℃; 13 sections 170～180 ℃; 14 sections 170～180 ℃; 170～180 ℃ of heads;
Fig. 3 is shown in by screw combinations schematic diagram.
Shown in Fig. 3,1 is helical pitch 56, length 56A screw thread transfer block;
Shown in 2 be helical pitch 96, length 96 transfer block;
Shown in 3 be helical pitch 96, length 32 toothed disc;
Shown in 4 be helical pitch 72, length 72 transfer block;
Shown in 5 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 36;
Shown in 6 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 56;
Shown in 7 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 8 helical pitches 72, length 36 left-hand transfer block;
Shown in 9 be helical pitch 128, length 128 transfer block;
Shown in 10 be helical pitch 56, length 56 transfer block;
Shown in 11 be feed opening;
Shown in 12 be side feeding oil port;
Shown in 13 be vaccum exhaust outlet
Select water ring pelletizing to make complete biodegradable polyester material.
Comparative example 1
Use the material formula identical with embodiment 1, but use common screw rod, and do not configure side hello oiling design.
Preparation technology is as follows:
PBSA is put into baking oven, under 50～80 ℃ of conditions, carry out removal moisture drying 8 hours, moisture control is below 300ppm;
Dried compound and various auxiliary agent filler are dropped into high mixer high speed mixing 30s according to proportioning;
Use weighing balance accurate measurement feeding as forcing machine;
Forcing machine length-to-diameter ratio is 60:1;
Forcing machine power and model: 75D type, equidirectional parallel double-screw extruder;
Melting temperature is as follows: one section 90～100 ℃; Two sections 120～140 ℃; Three sections 190～200 ℃; Four sections 210～220 ℃; Five sections 210～220 ℃; Six sections 210～220 ℃; Seven sections 210～220 ℃; Eight sections 210～220 ℃; Nine sections 210～220 ℃; Ten sections 210～220 ℃; 11 sections 210～220 ℃; 12 sections 190～200 ℃; 13 sections 190～200 ℃; 14 sections 190～200 ℃; 180～190 ℃ of heads;
Fig. 4 is shown in by screw combinations schematic diagram.
Shown in Fig. 4,1 is helical pitch 56, length 56A screw thread transfer block;
Shown in 2 be helical pitch 96, length 96 transfer block;
Shown in 3 be helical pitch 72, length 72 transfer block;
Shown in 4 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 36;
Shown in 5 be 5 and mediate 45 degree that sheets form, the shearing threaded block of length 56;
Shown in 6 be 5 and mediate 90 degree that sheets form, the shearing threaded block of length 56;
Shown in 7 helical pitches 72, length 36 left-hand transfer block;
Shown in 8 be helical pitch 128, length 128 transfer block;
Shown in 9 be helical pitch 56, length 56 transfer block;
Shown in 10 be feed opening;
Shown in 11 be side feeding oil port;
Shown in 12 be vaccum exhaust outlet;
Selecting tie rod to cross 15 meters of tanks enters the granulation of white steel knife dicing machine and makes goods.
The polyester material that embodiment 1～4 and comparative example are prepared carries out performance test according to GB, the results are shown in Table 1.
The performance index of table 1 complete biodegradable polyester material
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Tensile strength/MPa | 22.8 | 23.5 | 19.5 | 21 | 16.8 |
| Elongation at break/% | 685 | 668 | 688 | 660 | 680 |
| Flexural strength/MPa | 7.2 | 8.4 | 6.9 | 7.5 | 7.4 |
| Modulus in flexure/MPa | 81 | 92 | 78 | 79 | 62 |
| Melt index/g10min -1 | 3.04 | 2.88 | 6.8 | 3.55 | 42.8 |
| Density/gcm -3 | 1.221 | 1.24 | 1.215 | 1.219 | 1.19 |
The polyester material that embodiment 1～4 and comparative example are prepared carries out compost degraded test, and complete biodegradable polyester material of the present invention degradation rate of 90 days under composting conditions reaches 90%.The polyester material of comparative example is because molten finger is too large, and insufficient strength, therefore can not process film forming.In addition when granulation is produced, because do not limit the design of oil port, chainextender is difficult to accurate-metering and joins in the middle of forcing machine, add screw combinations and do not limit order, therefore cause starting material can not in forcing machine, realize complete chain extension tackify process, and then cause carrying out the processing of film material.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a complete biodegradable polyester material, is characterized in that comprising following component by mass percentage:
2. complete biodegradable polyester material according to claim 1, is characterized in that: described long-branched polyester refers at least one in long-branched aliphatic polyester and long-branched aliphatic-aromatic copolyester.
3. complete biodegradable polyester material according to claim 1, it is characterized in that: described chainextender is selected from least one in Isosorbide-5-Nitrae-phenyl-bis-(2-oxazolines), two (2-oxazolines), tolylene diisocyanate, diphenylmethanediisocyanate, bischloroformate, isophorone diisocyanate, novel chainextender ADR-4370, isocyanuric acid three-glycidyl ester, hexamethylene diisocyanate and isophorone diisocyanate.
4. complete biodegradable polyester material according to claim 1, it is characterized in that: described oxidation inhibitor refers to dihydroxyphenyl propane, 1, 4-dual-tert-butyl peroxy isopropyl base benzene, N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxybenzene propionic acid amide), phosphorous acid dihydroxyphenyl propane ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, four [β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 4, 4 '-bis--(α, α '-dimethyl benzyl) pentanoic, ten dithio propyl ester and 1, in 4-dual-tert-butyl peroxy isopropyl base benzene at least two kinds.
5. complete biodegradable polyester material according to claim 1, is characterized in that: described lubricant refers at least two kinds in polymer complex ester, ethylene bis stearamide and the polyethylene wax of hard esteramides, amine hydroxybenzene, erucicamide, Zinic stearas, metallic soap; Described stablizer refers at least one in calcium stearate, zinc oxide, magnesium oxide, silicon-dioxide, kaolin and polynite; Described nucleator refers at least one in aluminium carbonate, terephthalic acid, talcum powder, aluminium hydroxide and aluminum oxide.
6. complete biodegradable polyester material according to claim 1, is characterized in that: described long-branched polyester refers to succinic acid-butanediol ester-tetramethylene adipate multipolymer; Described complete biodegradable polyester material also include 0.1～3wt% end-capping reagent, the reagent that deacidifies, the stabilization aids such as reagent dewater.
7. one kind according to the preparation method of the complete biodegradable polyester material described in claim 1～6 any one, it is characterized in that comprising following steps: long-branched polyester 93～99.5wt%, chainextender 0.1～3wt%, oxidation inhibitor 0.1～1wt%, lubricant 0.1～1wt%, stablizer 0.1～1wt%, nucleator 0.1～1wt% adds blender and mixing, in feeding twin screw extruder, fusion plastification, extruding pelletization, obtain complete biodegradable polyester material.
8. the preparation method of complete biodegradable polyester material according to claim 7, is characterized in that: described Assembled Twin Screw Extruder Screw is banburying element, delivery element assembled arrangement successively; Described twin screw extruder leading portion increases side and feeds oiling design, comprises small-bore oil nozzle, and refueling position is twin screw extruder blanking place.
9. the preparation method of complete biodegradable polyester material according to claim 8, is characterized in that: described banburying element comprises shears screwing element and hybrid element; Described delivery element comprises reverse thread element and carries screwing element; When long-branched molecular weight of polyesters narrow distribution used, described Assembled Twin Screw Extruder Screw is the screw combinations that is provided with a large amount of delivery elements and reverse thread element; When long-branched molecular weight of polyesters wider distribution used, described Assembled Twin Screw Extruder Screw is the screw combinations that is provided with more high-shear screwing element.
10. the application in preparing film product according to the complete biodegradable polyester material described in claim 1～6 any one.
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Effective date of registration: 20170524 Address after: 430000, No. 3, erudite Road, Wuhan economic and Technological Development Zone, Wuhan, Hubei Patentee after: WUHAN JINFA TECHNOLOGY CO., LTD. Address before: Ke Feng Lu Science City high tech Industrial Development Zone of Guangzhou City, Guangdong Province, No. 33 510663 Patentee before: Kingfa Technology Co., Ltd. |