CN103992626A - Polyhydroxybutyrate valerate polyester composite material - Google Patents
Polyhydroxybutyrate valerate polyester composite material Download PDFInfo
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- CN103992626A CN103992626A CN201410086467.2A CN201410086467A CN103992626A CN 103992626 A CN103992626 A CN 103992626A CN 201410086467 A CN201410086467 A CN 201410086467A CN 103992626 A CN103992626 A CN 103992626A
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Abstract
The invention provides a polyhydroxybutyrate valerate polyester composite material, which uses polyhydroxybutyrate valerate polyester as a matrix, jute fiber as a reinforcement. The composite materials is light in weight, cheap, biodegradable and pollution-free to the environment, and has high specific strength and specific modulus.
Description
Technical field
The present invention relates to a kind of polyhydroxybutyrate valeric acid copolyesters matrix material.
Background technology
Many type materials, bring the various whiles easily to the mankind, also bring unthinkable trouble to people.Because some rejected material is non-degradable under field conditions (factors), burning can discharge obnoxious flavour again, has caused the pollution that is difficult to improvement to ecotope.
Therefore, be necessary to design a kind of matrix material that can not pollute environment generation.
Summary of the invention
The defect existing for prior art, the object of the present invention is to provide a kind of matrix material that can not pollute environment generation.
The invention provides a kind of polyhydroxybutyrate valeric acid copolyesters matrix material, it is matrix that described polyhydroxybutyrate valeric acid copolyesters matrix material be take polyhydroxybutyrate valeric acid copolyesters, take jute fibre as reinforcement.
Preferably, described jute fibre intensity 4.9-5.2cN/dtex.
Preferably, described jute fibre cutting length is 51 ± 5mm.
Preferably, the scope of the quality proportioning of described jute fibre and polyhydroxybutyrate valeric acid copolyesters is 30/70-55/45.
Compared with prior art, the present invention at least has following technique effect: this matrix material quality is light, inexpensive, can biological degradation, environmentally safe.
Embodiment
A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar popularization without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public specific embodiment.
Polyhydroxybutyrate valeric acid copolyesters (PHBV) is a kind of biopolymer polyester, and it has similar character to polypropylene.This material is after discarding, even if be also stable under moist environment, but in the situation that having microorganism, it will be degraded to carbonic acid gas and water.Therefore it has good biocompatibility, biological degradability and Bioabsorbable.The raw material sources of polyhydroxybutyrate valeric acid copolyesters (PHBV) are very abundant, and the remains of each kind of plant all can be prepared PHBV through fermentation, separation.
PBHV has completely biocompatibility and to high barrier of water, gas etc.Therefore at aspects such as medical material (suture, nail), thin-film material (mulch film, shopping bag, compost bag), disposable product (pen, tableware), wrapping material (particularly food product pack), have a wide range of applications.Take PHBV as matrix, and all kinds of inorganic matter fiber cellulose fibers such as starch of take are reinforcement or weighting material, can make the different biodegradable matrix material of performance, to meet the service requirements of different occasions.Quite wide such as adopting polyhydroxybutyrate valeric acid copolyesters (PHBV) to produce biological self-destruction plastics purposes in medical treatment.For example, in fracture operation, it can serve as the support between bone.Along with the healing of bone, it also can decompose gradually voluntarily.Holland scientist invents a kind of plastics, implants and just decomposes voluntarily for about 2 years, becomes carbonic acid gas and water.Also have the biological self-destruction plastics of a kind of wire, can replace traditional Medical surgical suturing with thread management wound.This plastics surgical thread, can be absorbed gradually by health, exempts the worries of taking out stitches.In addition, the capsule for medicine made from biological self-destruction plastics, can slowly dissolve in vivo, and the speed of controlled pharmacy intravasation.
China Shi Chanma big country, jute accounts for numb output 80%.The quality of jute fibre is light, inexpensive, can biological degradation, environmentally safe, has higher specific tenacity and specific modulus.This project adopts jute fibre intensity 4.9-5.2cN/dtex, and cutting length is 51 ± 5mm.
Present method take that cost of development is low, the simple biodegradable composite material of manufacture craft is target, and Choice and process flow process is short, cost is low, without woven needling non-woven working method, make jute fibre strongthener.By selecting polyhydroxybutyrate valeric acid copolyesters (PHBV) as the matrix of matrix material, select reinforcement or weighting material that jute fibre is matrix material, after repetition test, adopt certain technical process and processing condition, develop biodegradable jute fibre reinforced composite.
A preparation method for polyhydroxybutyrate valeric acid copolyesters matrix material, comprises raw material processing, lapping acupuncture, compression molding.
Raw material is processed:
Jute fibre is before carrying out shredding mixing, need carry out alkaline purification, alkaline purification operation is as follows: jute fibre is soaked in the NaOH solution of massfraction 5% after 1 hour, water washes away unnecessary alkaline solution, then the diluted acid that adds massfraction 10%, drier after cleaning with clear water.
Polyhydroxybutyrate valeric acid copolyesters (PHBV) is a kind of biopolymer polyester, its fusing point lower (165 ℃), and initial decomposition temperature is 180 ℃ of left and right, and it has good biocompatibility, biological degradability and Bioabsorbable.The matrix that the PHBV of take is matrix material, take jute fibre as reinforcement or weighting material, can make the different biodegradable matrix material of performance, to meet the service requirements of different occasions.
Lapping acupuncture:
Technical process: shredding, give cotton, combing, lapping, charging, pre-needling, rolling, acupuncture.
Machinery corresponding to this technical process is respectively: teaser → cotton feeder → carding machine → lapping machine → charger → needle loom → lapper → needle loom.
Equipment used: WL-GK-1-600 type teaser, WL-J-500 type cotton feeder, WL-GS-A-600 type carding machine, WL-ZGS.Z-Y-800 type pre-needling machine, WL-ZGS.Z-Z-800 type needle loom, WL-800 type lapper, above equipment is manufactured by Chinese granary Shuan Feng non-interlaced fabric equipment company limited.
Teaser is comprised of comb and parallel cotton fibers prior to spinning blower fan, main plucker roller, hook groove roller, charging curtain etc.In operating process, because have cotton knot, comb and parallel cotton fibers prior to spinning blower fan director's phase not to process, can cause cacophonia because of overheap, affect comb and parallel cotton fibers prior to spinning progress.
Pre-needling machine traverse 50mm, every meter of cloth pin amount is by 3500 pieces of cloth pins, as need increase needling density.Must improve main frame frequency and reduce charging and discharging speed, as need reduce needling density, contrary, regulate in addition depth of needling.Pre-needling machine is mainly that between and fiber fluffy for height after one-tenth net operation, the very little web layer of cohesive force is carried out acupuncture, and its basic object is to guarantee that high fluffy web layer feeds acupuncture district smoothly, does not produce congested and excessive false draft.The traverse of main needle loom is 30mm, and every meter of cloth pin amount is by 5000 pieces of cloth pins, and other are identical with pre-needling machine.The main processing object of main needle loom is the fibre web through pre-needling, and its fibre web after to pre-needling is done further to reinforce.The stripping web plate of main needle loom and the distance between off-grid plate are dwindled, and acupuncture traverse diminishes, and bestock increases, and pricker frequency improves, and speed also has significantly raising.Each operation design variable is as table 1:
Each operation design variable of table 1
With the nonwoven material that pinprick reinforcement is produced, there is good mechanical property, for next step, make the compound good condition that provides, make tensile strength and the flexural strength of this reinforced composite better simultaneously, at aspects such as automobile, construction industries, have a good application prospect.
Compression molding:
Jute fibre through acupuncture lapping and polyhydroxybutyrate valeric acid copolyesters (PHBV) are evenly mixed according to a certain ratio and put into mould and carry out hot-forming, molding apparatus is the vulcanizing press that Shanghai Qi Cai hydraulic machinery company limited produces, fusing point lower (165 ℃) due to PHBV, initial decomposition temperature is 180 ℃ of left and right, so mold temperature is selected 165 ℃-180 ℃, selection of time 3min-6min, pressure is selected 5MPa-14MPa, obtains biodegradable jute fibre needling non-woven reinforced composite.
Mold pressing parameter is selected:
In order to analyze proportioning, hot pressing temperature, hot pressing time and the impact of hot pressing pressure on composite materials property of jute fibre/PHBV, explore optimum jute fibre/PHBV reinforced composite preparation technology, get jute fibre/PHBV proportioning, hot pressing temperature, hot pressing time, four factors of hot pressing pressure and four levels are respectively set and carry out orthogonal design.Each experimental level of jute fibre/PHBV proportioning, hot pressing temperature, hot pressing time, four factors of hot pressing pressure is in Table 2.
Table 2 orthogonal experiment four factor four levels
The design of orthogonal experiment is with reference to L16 (45), and respectively the jute fibre without alkaline purification and the jute fibre after alkaline purification carried out to orthogonal experiment.It is as follows that jute fibre/PHBV matrix material of preparing by orthogonal experiment obtains its tensile strength after tested afterwards, table 3 is without alkaline purification jute fibre/PHBV matrix material orthogonal test analysis table, and table 4 is through alkaline purification jute fibre/PHBV matrix material orthogonal test analysis table.
Untreated jute fibre/the PHBV of table 3 matrix material orthogonal experiment analytical table
Table 4 alkaline purification jute fibre/PHBV matrix material orthogonal experiment analytical table
From table 3 and table 4, the tensile strength of jute fibre/PHBV matrix material is known, after joining in PHBV using jute fibre as reinforcement, no matter jute fibre has or not through alkali lye and processes, the tensile break strength of its matrix material is all greater than the tensile break strength of pure PHBV sheet material substantially, and the tensile break strength of the matrix material of the jute fibre of processing through alkali lye and PHBV is higher.This explanation adds after jute fibre in PHBV, reinforced effects is obvious, tensile break strength obviously promotes, and particularly after alkali lye is processed, it is combined improvement to jute fibre with PHBV interface, and the more undressed jute fibre of improvement of its tensile break strength and the matrix material of PHBV are more remarkable.
The performance test analysis of jute fibre/PHBV reinforced composite:
(1) without alkali lye, process jute fibre/PHBV reinforced composite
The primary and secondary pass that affects of the known tensile break strength for undressed jute fibre/PHBV reinforced composite of numerical value of each factor from table 3 is: the impact of jute fibre/PHBV proportioning is main, is secondly hot pressing pressure, hot pressing time, hot pressing temperature.That is: A → D → C → B
By the tensile strength in table 3, determined, untreated jute fibre/PHBV matrix material proportioning level 4 is best, hot pressing temperature level 3 is best, hot pressing time level 2 is best, hot pressing pressure level 4 is best, the tensile strength of matrix material is up to 60.01MPa, so optimum combination technique is A4B3C2D4, and jute fibre/PHBV proportioning is 40/60, hot pressing temperature is that 175 ℃, hot pressing time are that 4min, hot pressing pressure are 14MPa.
The trend changing with jute fibre/PHBV proportioning in order further to research and analyse jute fibre/PHBV matrix material, adopting hot pressing temperature is that 175 ℃, hot pressing time are that 4min, hot pressing pressure are under 14MPa condition, change jute fibre/PHBV proportioning this because usually analyzing the impact of this factors vary on the tensile break strength of jute fibre/PHBV matrix material.The stretching of untreated jute fibre/PHBV matrix material is emphasized in Table 5.
The tensile strength of the untreated jute fibre/PHBV of table 5 reinforced composite
As can be seen from Table 5, the tensile break strength of untreated jute fibre/PHBV matrix material presents and first increases the trend reducing afterwards with the increase of jute fibre proportion.This is less owing to starting the proportion of jute fibre in matrix material, increase along with jute fibre, enhancement to matrix material constantly increases, therefore the tensile break strength of matrix material also constantly increases, but in matrix material, the proportion of jute fibre is over after a certain amount of, in matrix material, the proportion of matrix reduces relatively, this makes matrix can not well be coated jute fibre, can not form and invade profit completely jute fibre, therefore the proportion along with jute fibre constantly increases, and the tensile break strength of matrix material presents downtrending.As known from Table 5, for the best proportioning of jute fibre/PHBV of the matrix material of processing without alkali lye, be 35/65-55/45, its tensile strength, all over 55MPa, is up to 60.01MPa.
(2) through alkaline purification jute fibre/PHBV reinforced composite
The tensile break strength of the known jute fibre/PHBV reinforced composite for processing through alkali lye of extreme value of each factor from table 4 has the greatest impact with jute fibre/PHBV proportioning, is secondly hot pressing time, hot pressing pressure, hot pressing temperature.That is: A → C → D → B
By the tensile strength in table 4, determined, proportioning level 4 through alkaline purification jute fibre/PHBV reinforced composite is best, hot pressing temperature level 3 is best, hot pressing time level 2 is best, hot pressing pressure level 4 is best, therefore optimum combination technique is A4B3C2D4, and jute fibre/PHBV proportioning is 40/60, hot pressing temperature is that 175 ℃, hot pressing time are that 4min, hot pressing pressure are 14MPa.
In order further to research and analyse the trend that jute fibre/PHBV reinforced composite changes with jute fibre/PHBV proportioning after alkaline purification, adopting hot pressing temperature is that 175 ℃, hot pressing time are that 4min, hot pressing pressure are under 14MPa condition, change jute fibre/PHBV proportioning this because usually analyzing the impact of this factors vary on the tensile break strength of jute fibre/PHBV matrix material.Stretching through alkaline purification jute fibre/PHBV matrix material is emphasized in Table 6.
Table 6 is through the tensile strength of alkaline purification jute fibre/PHBV reinforced composite
As can be seen from Table 6, the tensile break strength of processing jute fibre/PHBV reinforced composite through alkali lye along with the proportioning of jute fibre/PHBV in the increase of jute fibre proportion start to increase then and reduce, but the tensile strength integral body of the jute fibre/PHBV reinforced composite after alkali lye is processed strengthens the tensile strength of PHBV matrix material higher than the jute fibre of processing without alkali lye, this is because jute fibre is after alkali lye is processed, its surface property improves, the consistency of jute fibre and matrix gets a new look, make the interface bonding condition improved of jute fibre and matrix, show on matrix material to be exactly the lifting of its mechanical property.As known from Table 6, for the best proportioning of passing through jute fibre/PHBV reinforced composite of alkaline purification, be 30/70-55/45, its tensile strength, all over 60MPa, is up to 74.42MPa.
The present invention compared with prior art, has following beneficial effect:
Present method take that cost of development is low, the simple jute fibre matrix material of manufacture craft is target, adopt jute fibre needling non-woven thing and polyhydroxybutyrate valeric acid copolyesters (PHBV) evenly to mix and put into mould according to a certain ratio, carry out hot-forming manufacture reinforced composite under certain condition, the method work flow is short, cost is low, without woven needling non-woven mixture, by suitable composite curing explained hereafter jute fibre needling non-woven reinforced composite.The composite materials property of present method development surpasses similar engineering plastics level, can be applicable to the fields such as medicine, automobile, building industry and military aviation.
The present invention select jute fibre as the reinforcement of matrix material, polyhydroxybutyrate valeric acid copolyesters (PHBV) as matrix.Polyhydroxybutyrate valeric acid copolyesters (PHBV) is a kind of biopolymer polyester, it has good biocompatibility, and biological degradability and Bioabsorbable also have its exclusive feature simultaneously: 1. abundant raw material, the remains of each kind of plant are through fermentation, and separation all can be prepared PHBV; 2. performance and resins for universal use are suitable, can be used as the substitute products of resin, and development potentiality is huge; 3. crystal property is good, and the model that can be used as flexible polymer is studied; 4. the biocompatibility that PHBV is good, Bioabsorbable and certain bio-absorbable cycle and higher fusing point provide condition for its application in medical treatment and some other particular surroundings.Therefore this matrix material can be applied to some special dimensions, and the rejected material of product can biological degradation, is conducive to environment protection, therefore has broad application prospects.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; can make possible change and modification, so protection scope of the present invention should be as the criterion with the scope that the claims in the present invention were defined.
Claims (4)
1. a polyhydroxybutyrate valeric acid copolyesters matrix material, is characterized in that: it is matrix that described polyhydroxybutyrate valeric acid copolyesters matrix material be take polyhydroxybutyrate valeric acid copolyesters, take jute fibre as reinforcement.
2. polyhydroxybutyrate valeric acid copolyesters matrix material according to claim 1, is characterized in that: described jute fibre intensity 4.9-5.2cN/dtex.
3. polyhydroxybutyrate valeric acid copolyesters matrix material according to claim 1, is characterized in that: described jute fibre cutting length is 51 ± 5mm.
4. polyhydroxybutyrate valeric acid copolyesters matrix material according to claim 1, is characterized in that: the scope of the quality proportioning of described jute fibre and polyhydroxybutyrate valeric acid copolyesters is 30/70-55/45.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106626535A (en) * | 2016-11-08 | 2017-05-10 | 江南大学 | PHBV mono-polymer composite material having high fiber volume content and preparation method thereof |
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| CN102268180A (en) * | 2011-08-16 | 2011-12-07 | 浙江省林业科学研究院 | Biobased degradable composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102268180A (en) * | 2011-08-16 | 2011-12-07 | 浙江省林业科学研究院 | Biobased degradable composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A.K.MOHANTY ET AL: "Surface modification of jute and its influence on performance of biodegradable jute-fabric/Biopol composites", 《COMPOSITES SCIENCE AND TECHNOLOGY》 * |
| LIFANG LIU ET AL: "Biodegradability of poly(butylene succinate)(PBS) composite reinforced with jute fibre", 《POLYMER DEGRADATION AND STABILITY》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106626535A (en) * | 2016-11-08 | 2017-05-10 | 江南大学 | PHBV mono-polymer composite material having high fiber volume content and preparation method thereof |
| CN106626535B (en) * | 2016-11-08 | 2019-04-09 | 江南大学 | Mono- polymer composites of a kind of high microsteping volume content PHBV and preparation method thereof |
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