CN103980685B - A kind of shock resistance biodegradable polyesters composition and method of making the same - Google Patents

A kind of shock resistance biodegradable polyesters composition and method of making the same Download PDF

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CN103980685B
CN103980685B CN201410230598.3A CN201410230598A CN103980685B CN 103980685 B CN103980685 B CN 103980685B CN 201410230598 A CN201410230598 A CN 201410230598A CN 103980685 B CN103980685 B CN 103980685B
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shock resistance
composition
ester
biodegradable polyesters
pha
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CN103980685A (en
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马丕明
蔡晓霞
陈明清
东为富
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Jiangnan University
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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
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92266—Mechanical properties
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature

Abstract

The invention discloses a kind of shock resistance biodegradable polyesters composition and method of making the same, be made up of according to respective weight following raw material: PHA 40 ~ 60 parts, poly butylene succinate 20 ~ 40 parts, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's copolymer 10 ~ 40 part, radical initiator 0.01 ~ 3 part.The shock resistance biodegradable polyesters composition excellent combination property obtained according to preparation method provided by the invention, shock resistance are outstanding, fully biodegradable, solve the defect of PHA class material with storage time embrittlement, and its preparation method simply, easily realizes industrialization.

Description

A kind of shock resistance biodegradable polyesters composition and method of making the same
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of shock resistance biodegradable polyesters composition and method of making the same.
Background technology
Using in a large number and discarding of conventional polymer material not only causes the day by day in short supply of petroleum resources, but also does great damage to ecotope.PHA (PHA) comprises 3 hydroxybutyric acid ester homopolymers (P3HB), 3 butyric ester-3 hydroxyl pentanoate copolymers (PHBV), 3 butyric ester-4 hydroxybutyric acids ester copolymer (P3HB-4HB) and 3 butyric ester-3 hydroxyhexanoate copolymer (PHBH) etc. and is considered to one of material of the most promising and competitive power in biodegradable plastic family, and these esters polymers can degradablely be CO under composting conditions 2and H 2o, can not cause any pollution to environment.PHA is mainly synthesized by microbial method at present, and its molecular weight is generally between hundreds of thousands of is extremely millions of.Composition and the content of the mechanical property of PHA and thermal characteristics and its polymerization single polymerization monomer are closely related.3 hydroxybutyric acid ester homopolymers (P3HB) are that (notched Izod impact strength is less than 2kJ/m to a kind of extremely crisp thermoplastic polyester 2, elongation is less than 3%), fusing point is about 175 DEG C, and second-order transition temperature is about 0 DEG C, and crystal growth rate is very fast but crystal nucleation rate is very slow.When comonomer in PHA (as 4HB, 3HV, 3HH etc.) molar content improves, the snappiness of PHA increases, and tensile strength reduces, fusing point reduces, crystallization rate reduces.Along with the increase of molar comonomer percentage composition, the melt-processable of PHA is deteriorated, physically aged phenomenon is remarkable, thus constrains its large-scale application.As a result, PHA is mainly used as rigid plastics or medical material at present.
Poly butylene succinate (PBS) is a kind of biodegradable petroleum base esters polymer, its comprehensive mechanical performance is good, tensile strength is about 35MPa, fusing point is 112 DEG C, second-order transition temperature is about-30 DEG C, and crystallization rate is very fast, and PBS processing characteristics is excellent in addition, its shortcoming is that shock resistance is poor, and elongation at break is not high.
Tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer (PBAT) is another kind of biodegradable esters polymer.PBAT ductility and kindliness good, tensile strength is about 20MPa, and elongation is up to 700%, and fusing point is 120 DEG C, and second-order transition temperature is about-30 DEG C, conventional do plasticized modifier or prepares various wrapping material with starch blending.
Existing open report adopts PBS or PBAT to carry out modification to PHA, but adopts PBS and PBAT to there is no report to PHA modified synergic simultaneously.Such as publication number is that the Chinese invention patent of CN101475735A discloses a kind of alloy material comprising PHA, poly butylene succinate, starch, filler and other auxiliary agents, although the mechanical property of alloy material improves to some extent, but alloy material shock resistance is still poor, and the fusing point of resulting composition (120-132 DEG C) on the low side, limit material application at high temperature.And due to poor compatibility between PHA and poly butylene succinate, the alloy material micron-scale phase separation obtained by simple blend is remarkable, and microscopic pattern is unstable.Publication number is that the patent of invention of CN101045810A discloses a kind of PBS or the poly(lactic acid) method of modifying by the toughness reinforcing PHBV of dynamic crosslinking in Banbury mixer, improve the elongation at break of composition, but to obtain the resistance to impact shock of composition lower, be difficult to realize continuous seepage, be unfavorable for industrialization.
The physically aged phenomenon of PHA is remarkable, and namely mechanical property changes after formation in time, and wherein brittle phenomenon is particularly remarkable, is embodied in shock strength and declines in time significantly.This is that when melt-processed is shaping, crystallization imperfection, occurs caused by secondary crystal in storage process because PHA purity is high.This problem seriously constrains forming process and the application of PHA, there is no mature technology at present and solves.The mechanical property reported in existing document or patent mostly be shaping after the mechanical property of (as 24 hours, CN101045810A) in a short time.
Summary of the invention
In view of this, the object of the invention is to propose a kind of shock resistance biodegradable polyesters composition and method of making the same, to obtain, shock strength is high, the polymer blend of biodegradable, storage process stable mechanical performance, melt-processable excellence.
Based on above-mentioned purpose, a kind of shock resistance biodegradable polyesters composition provided by the invention is made up of according to respective weight following raw material: PHA 40 ~ 60 parts, poly butylene succinate 20 ~ 40 parts, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's copolymer 10 ~ 40 part, radical initiator 0.01 ~ 3 part.
Alternatively, described PHA is selected from least one in 3 hydroxybutyric acid ester homopolymers, 3 butyric ester-3 hydroxyl pentanoate copolymers, 3 butyric ester-4 hydroxybutyric acid ester copolymers and 3 butyric ester-3 hydroxyhexanoate copolymer.
Alternatively, in described hydroxy alkanoic acid ester copolymer the molar content of 3 hydroxyl valerate monomers or 4 hydroxybutyrate monomer or 3 hydroxycaproic ester monomers lower than 20%.
Alternatively, described radical initiator is selected from bis(t-butylperoxy)diisopropylbenzene, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexin, 1, 1-di-t-butyl peroxy-3, 3, 5-trimethyl-cyclohexane, di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, dilauroyl peroxide, dibenzoyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, at least one in di-cyclohexylperoxy dicarbonate and 2,2'-Azobis(2,4-dimethylvaleronitrile).
Present invention also offers a kind of method preparing described shock resistance biodegradable polyesters composition, comprise the following steps:
First by PHA, poly butylene succinate, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer, radical initiator are at room temperature mixed by homogenizer according to weight proportion and obtain pre-composition, again above-mentioned pre-composition is extruded by twin screw extruder melt blending, namely obtain described shock resistance biodegradable polyesters composition.
Alternatively, described twin screw extruder feeding section temperature is 20 ~ 80 DEG C, and all the other each section of temperature are 130 ~ 180 DEG C.
Alternatively, the screw speed of described twin screw extruder is 100 ~ 450 revs/min.
In addition, add a small amount of functional aid, such as oxidation inhibitor, stablizer, nucleator, lubricant, tinting material etc. can not affect the basic mechanical property of this shock resistance biodegradable polyesters composition, but also can improve its processing characteristics, thermostability etc.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
By 3 hydroxybutyric acid ester homopolymer 50kg, poly butylene succinate 30kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 20kg, dicumyl peroxide 0.5kg premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C and 160 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 160 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Embodiment 2
By 3 butyric ester-3 hydroxyl pentanoate copolymers (3 hydroxyl valerate monomer molar percentage compositions are 2%) 45kg, poly butylene succinate 35kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 20kg, dibenzoyl peroxide 0.4kg premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C and 160 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 160 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Embodiment 3
By 3 butyric ester-3 hydroxyl pentanoate copolymers (3 hydroxyl valerate monomer molar percentage compositions are 3%) 50kg, poly butylene succinate 25kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 25kg, dicumyl peroxide 0.6kg premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 155 DEG C, 155 DEG C, 160 DEG C, 160 DEG C, 160 DEG C and 165 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 180 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Embodiment 4
By 3 butyric ester-4 hydroxybutyric acid ester copolymer (4 hydroxybutyrate monomer molar contents are 5%) 60kg, poly butylene succinate 25kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 30kg, dicumyl peroxide 1.0kg premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 160 DEG C, 160 DEG C and 165 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 200 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Embodiment 5
By 3 hydroxybutyric acid ester homopolymer 30kg, 3 butyric ester-3 hydroxyhexanoate copolymer (3 hydroxycaproic ester monomer molar content are 7%) 18kg, poly butylene succinate 30kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 25kg, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.6kg is premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C and 165 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 200 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Embodiment 6
By 3 hydroxybutyric acid ester homopolymer 40kg, 3 butyric ester-4 hydroxybutyric acid ester copolymer (4 hydroxybutyrate monomer molar content are 5%) 15kg, poly butylene succinate 30kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 25kg, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 1.0kg is premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 150 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C and 165 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 300 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Comparative example 1
3 hydroxybutyric acid ester homopolymer 50kg are joined melt blending in parallel double-screw extruder to extrude and obtain 3 hydroxybutyric acid ester homopolymer extruded stocks.Wherein twin screw extruder is respectively 40 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C and 160 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 160 revs/min.By this 3 hydroxybutyric acid ester homopolymer extruded stock adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
Comparative example 2
By 3 hydroxybutyric acid ester homopolymer 50kg, poly butylene succinate 30kg, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer 20kg premix evenly (720 revs/min in homogenizer, 5 minutes), then above-mentioned pre-composition is joined melt blending in parallel double-screw extruder and extrude and obtain shock resistance biodegradable polyesters composition.Wherein twin screw extruder is respectively 40 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 165 DEG C and 160 DEG C from feeding section to the temperature of mouth mould section, and screw speed is 160 revs/min.By this shock resistance biodegradable polyesters composition adopt plastic injection equipment according to ASTM standard injection become be used for Elongation test dumbbell shaped batten and be used for notch shock, non-notch impact and bending property test rectangle batten.Every test result is listed in table 1 and table 2.
It should be noted that, PHA used, poly butylene succinate and tetramethylene adipate in above each embodiment-mutual-phenenyl two acid bromide two alcohol ester's multipolymer is all vacuum-drying 8 hours at 70 DEG C before using.3 butyric ester-4 hydroxybutyric acid ester copolymers used are U.S. Metabolix Products, 3 hydroxybutyric acid ester homopolymers used, 3 butyric ester-3 hydroxyl pentanoate copolymers are Ningbo Tianan Biological Material Co., Ltd.'s product, 3 butyric ester-3 hydroxyhexanoate copolymer used are Japanese Kaneka Products, poly butylene succinate used is Hangzhou Xin Fu medicine company group company product, and tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer is BASF Aktiengesellschaft's product.
Wherein double-screw extruder screw diameter is 25 millimeters, and length-to-diameter ratio is 41.Wherein plastic injection equipment from charging opening to nozzle between temperature be set as 160 DEG C, 170 DEG C, 170 DEG C, 170 DEG C and 175 DEG C respectively, injector screw diameter is 25 millimeters, and length-to-diameter ratio is 28.
Wherein tensile strength and elongation at break adopt electronic tensile test machine (Instron4465) at room temperature to record according to ASTMD638, and rate of extension is 50mm/min; Notch shock and non-notch impact and adopt the MZ-2056 shock-testing machine of Jiangdu Mingzhu Testing Machinery Co., Ltd. to test according to ASTMD256; Flexural strength and modulus in flexure adopt electronic tensile test machine (Instron4465) at room temperature to record according to ASTMD790.Wherein melt temperature adopts differential scanning calorimeter (TA instrument company of the U.S.) to record, and temperature rise rate is 10 DEG C/min.
Wherein in table 1, data are that sample injection moulding is complete and at room temperature store after 60 days and record.
Table 1: the performance perameter of composition in embodiment and comparative example
From data in table 1, with do not add poly butylene succinate in comparative example 1, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer is compared with the poly butyric ester of radical initiator, notched Izod impact strength and the unnotched impact strength of the shock resistance biodegradable polyesters composition obtained in embodiment 1-6 improve more than 20 times and 15 times respectively.With do not add in comparative example 2 radical initiator poly butyric ester/poly butylene succinate/tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer composition compared with, notched Izod impact strength and the unnotched impact strength of the shock resistance biodegradable polyesters composition obtained in embodiment 1-6 improve more than 4.8 times and 2.0 times respectively.Compare with comparative example 2 with comparative example 1, the shock resistance biodegradable polyesters composition modulus in flexure obtained in embodiment 1-6 reduces, and elongation significantly improves, and does not obviously affect other mechanical propertys simultaneously.These results illustrate that the shock resistance biodegradable polyesters composition obtained by the present invention has excellent comprehensive mechanical performance, especially can improve shock resistance and the toughness of the combination of PHA and PHA/poly butylene succinate/tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer.In addition, the shock resistance biodegradable polyesters combination obtained in embodiment 1-6 has higher fusing point, illustrates that it may use at relatively high temperatures.
Table 2: the unnotched impact strength that embodiment records under the different storage time from composition injected sample in comparative example
From data in table 2, compared with the composition of poly butyric ester/poly butylene succinate/tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer in poly butyric ester, comparative example 2 in comparative example 1, the unnotched impact strength of the shock resistance biodegradable polyesters composition obtained in embodiment 1-6 is not remarkable with storage time change, illustrate that the shock resistance biodegradable polyesters composition physically aged phenomenon in storage process obtained by the present invention is not obvious, its shock resistance has excellent stability in storage.
PHA, poly butylene succinate and tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer three kinds degradable polyester in mechanical property, thermal characteristics (second-order transition temperature, fusing point, Tc etc.), degradation rate etc. on respectively have relative merits, respective advantage can be given full play to by blended for three, make up respective deficiency, thus obtain the novel material of excellent combination property.But each polyester components thermodynamics is incompatible in shock resistance biodegradable polyesters composition described in melt blending process.Therefore, be separated in the mixing process of twin screw extruder, disperse phase phase size is large, and cohesive force is poor between phase and phase, thus affects over-all properties and improve comprehensively, and microcosmic phase morphology and macro-mechanical performance instability in storage process.In the present invention, PHA under the mixing effect of twin screw extruder, reacted by radical initiator generation interface crosslinking between poly butylene succinate and tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer three kinds degradable polyester, in-situ preparation grafting or based block copolymer are as expanding material, both refinement and stabilize the microcosmic phase morphology of composition, facilitate the rapid crystallization of PHA, turn improve mechanical property and the stability of performance in storage process of composition, thus provide precondition for said composition large-scale production and practical application.The introducing of radical initiator, can not change the existence form of ester bond in polymer blend, therefore can not sacrifice PHA, poly butylene succinate and tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer biodegradable originally.
Shock resistance biodegradable polyesters composition provided by the invention can be directly used in extrusion moulding, compression molding, injection moulding, flow casting molding or plastics sucking moulding, to prepare various thermoplastic articles.In addition, add a small amount of functional aid, such as oxidation inhibitor, stablizer, nucleator, lubricant, tinting material etc. not only can not affect the basic mechanical property of this shock resistance biodegradable polyesters composition, but also can improve its processing characteristics, thermostability etc.
As can be seen from above, a kind of shock resistance biodegradable polyesters composition and method of making the same provided by the invention has following beneficial effect:
(1) radical initiator causes PHA, poly butylene succinate, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer three kinds polyester micro interface place generation in-situ chemical graft reaction, improve micro interface bounding force, thus the consistency of three kinds of polyester and the stability of microtexture can be significantly improved;
(2) the shock resistance biodegradable polyesters composition obtained according to preparation method provided by the invention has the features such as toughness is good, physical strength is high, modulus is high, excellent heat resistance, can be directly used in extrusion moulding, compression molding, injection moulding with, calendering formation and plastics sucking moulding to prepare various plastics;
(3) poly butylene succinate and the tetramethylene adipate-modification of mutual-phenenyl two acid bromide two alcohol ester's multipolymer to PHA have synergistic effect, under the prerequisite of initiator induction interfacial chemistry graft reaction, not only significantly improve the comprehensive mechanical performance of composition, and facilitate the crystallisation process of PHA, thus significantly improve the stability of shock-resistant degradable polymer blend shock strength in storage process that the present invention obtains;
(4) the shock resistance biodegradable polyesters composition and method of making the same obtained according to the present invention can realize on existing processing of high molecular material equipment, and cost is low, environmental friendliness, easily realize large-scale industrial production.
It will be understood by those skilled in the art that: the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (2)

1. a shock resistance biodegradable polyesters composition, it is characterized in that, be made up of according to respective weight following raw material: PHA 40 ~ 60 parts, poly butylene succinate 20 ~ 40 parts, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's copolymer 10 ~ 40 part, dicumyl peroxide 0.01 ~ 3 part;
Wherein said PHA is 3 butyric ester-3 hydroxyl pentanoate copolymers, at least one in 3 butyric ester-4 hydroxybutyric acid ester copolymers and 3 butyric ester-3 hydroxyhexanoate copolymer that microbial method obtains;
In wherein said hydroxy alkanoic acid ester copolymer, the molar content of 3 hydroxyl valerate monomers or 4 hydroxybutyrate monomer or 3 hydroxycaproic ester monomers is lower than 20%.
2. prepare a preparation method for shock resistance biodegradable polyesters composition according to claim 1, it is characterized in that, said method comprising the steps of:
First by polyhydroxyalkanoate copolymer, poly butylene succinate, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer, dicumyl peroxide are at room temperature mixed by homogenizer according to weight proportion and obtain pre-composition, again above-mentioned pre-composition is extruded by twin screw extruder melt blending, namely described shock resistance biodegradable polyesters composition is obtained, wherein feeding section temperature is 20 ~ 80 DEG C, all the other each section of temperature are 130 ~ 180 DEG C, and the screw speed of twin screw extruder is 100 ~ 450 revs/min.
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CN102618003A (en) * 2012-04-13 2012-08-01 中国科学院长春应用化学研究所 Polylactic acid composition and polylactic acid product

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