CN106426973A - Method for preparing orientated-state polylactic acid profile - Google Patents
Method for preparing orientated-state polylactic acid profile Download PDFInfo
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- CN106426973A CN106426973A CN201610798903.8A CN201610798903A CN106426973A CN 106426973 A CN106426973 A CN 106426973A CN 201610798903 A CN201610798903 A CN 201610798903A CN 106426973 A CN106426973 A CN 106426973A
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- Prior art keywords
- polylactic acid
- section bar
- alignment state
- described step
- method preparing
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
-
- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
-
- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
- B29C2071/025—Quenching, i.e. rapid cooling of an object
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/046—PLA, i.e. polylactic acid or polylactide
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials For Medical Uses (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a method for preparing an orientated-state polylactic acid profile. The method comprises the following steps of 1, conducting injection molding on dried polylactic acid raw materials through an injection molding machine, so that a billet material is obtained, or heating and pressurizing the polylactic acid raw materials, so that the polylactic acid raw materials are made into the billet material through forging; 2, conducting oriented intensification on the billet material obtained in step 1, wherein extrusion or forging is adopted as the oriented intensification method; and 3, conducting cooling and quenching on the billet material obtained in step 2, so that after the billet material is stabilized, the profile is formed. According to the method for preparing the orientated-state polylactic acid profile, technological parameters for preparing the polylactic acid profile are controlled, so that the orientation effect of polylactic acid molecules and a crystalline region is improved to the greatest extent; and the unexpected technical effect is gained, and thus the polylactic acid profile which is excellent in mechanical performance is obtained. The orientated-state polylactic acid profile prepared through the method is stable in performance, healthy, harmless and good in biocompatibility.
Description
Technical field
The present invention relates to producing the technique of organic polymer section bar, especially a kind of side producing alignment state polylactic acid section bar
Method.
Background technology
Polylactic acid, as a kind of degradation material, has good histocompatibility, therefore medically has been widely used,
But the poly-lactic acid material of routine is due to its low intensity, constrain it in medical science, the particularly application on orthopaedics.
Chinese patent CN103540111A discloses a kind of high intensity, resistant to elevated temperatures fully-degradable polylactic acid sheet material and its preparation
Method, by the polylactic acid of 50%-78%, the toughening element of 10%-30%, the inorganic filler of 10%-30% and 1%-3% other
Auxiliary agent mix homogeneously, using extrusion mechanism standby blending master batch, then passes through extrusion mechanism for sheet material.The method helps because adding
The problem of agent, therefore Presence of an interface matching difference.
Chinese patent CN101525812A prepares the polylactic acid of high intensity by spin processes, is former with polylactic acid slice
Material, using high velocity air jet stretch, improves the degree of orientation of continuous filament yarn, to obtain enough fibre strengths；Using being higher than
The roller temperature of the milling train line pressure of 100N/mm and 125 DEG C～157 DEG C, to obtain optimal bonding strength.The method rolling mill line
Pressure and air-flow shower nozzle are difficult to control to, and the purity requirement to equipment, raw material, polylactic acid is harsh, thus practical operation is complicated.
Content of the invention
In order to solve problem of the prior art, the invention provides a kind of method preparing alignment state polylactic acid section bar, bag
Include following steps：
1) polylactic acid raw material is molded by injection machine and makes embryo material or polylactic acid raw material is forced through with forging and stamping system
Become embryo material；
2) by step 1) gained embryo material carry out orientation strengthening, described orientation intensifying method be extrusion (extrusion) or forge and press；
3) by step 2) products therefrom carries out Cooling Quenching, forms alignment state polylactic acid section bar after product is stable.
Preferably, described step 1) forging and stamping method be vacuum forging and stamping.
Preferably, described step 1) in polylactic acid raw material be Poly-L-lactic acid, its specific rotatory power is at -155 °～-160 °
Between, intrinsic viscosity is 1dL/g-7dL/g.
Preferably, described step 1) forging and stamping embryo heating-up temperature be 160 DEG C -210 DEG C, pressure be 5Mpa-30Mpa,
Heat time heating time is 1min-5min.
Preferably, described step 2) in extrusion preheating temperature be 120 DEG C -200 DEG C, preheating time be 1min-5min.
Described step 2) in forging method preheating temperature be 140 DEG C -180 DEG C, preheating time be 1min-5min.
Preferably, described step 2) in extruded velocity be 10-200cm3/s.
Preferably, described step 3) hardening heat be -20 DEG C to 30 DEG C, cool time be 1-2min, quenching cooling speed
Rate is 50 DEG C/min-150 DEG C/min.
Preferably, step 3) in the degree of crystallinity of section bar be 50%-90%, grain shape is platelet, extended chain is brilliant or string
Crystalline substance, microstructure linearly arranges.
The invention has the beneficial effects as follows：
1st, process is simple, easy to operate, low for equipment requirements, it is suitable for large-scale production.The inventive method is highly oriented
The preparation of degree polylactic acid section bar provides rational process conditions and technology path, in the synergism of selected process conditions
Under, the arrangement of strand is more regular in order, polylactic acid crystalline region recurring structure weight under certain briquetting pressure and forming temperature
Row, is formed at microcosmic and the height-oriented polylactic acid section bar of macrostructure, and effectively overcomes its conventional polylactic acid article power
Learn the defects such as performance is undesirable, thus expanding the practical application area of polylactic acid article further.
2nd, by correlations such as injecting rate, preheating temperature, pressurize temperature, pressurize pressure, cooldown rate and time parameters
The setting of condition, improves the orientation effect of polylactic acid molecule and crystalline region to the full extent, achieves unforeseeable technology
Effect, thus obtain the polylactic acid section bar with excellent mechanical property.On the one hand it is in elastomeric state poly-lactic acid material strand
Section can occur being arranged of preferred orient along stress direction under extraneous stress, and script random arrangement is non-in the process
Crystalline state polylactic acid molecule regular arrangement form extended chain crystalline substance or shish-kebab, the crystalline state meanwhile originally mainly being existed with spherocrystal form
Part recurring structure is reset along stress direction distribution, is significantly better than through the mechanical performance of the poly-lactic acid material of orientation process
Common poly-lactic acid material product.The present invention, under the conditions of 120 DEG C 200 DEG C, strengthens to polylactic acid embryo material, makes polylactic acid edge
There is preferred orientation in special die die cavity, be significantly improved through the mechanical performance of the polylactic acid section bar of orientation, particularly
The bending strength of product improves about 100% compared with market existing procucts.The present invention is during machine-shaping by the course of processing
The regulation of middle temperature and control, the rational degree of crystallinity controlling polylactic acid, thus further improve the mechanical performance of product.
On the other hand, under the conditions of 120 DEG C 200 DEG C, polylactic acid embryo material is strengthened, the type after the strengthening obtaining
Material passes through low temperature quenching, so that the orientation texture in material is effectively preserved, and prevents the generation of its deorientation it is ensured that type
Material has excellent mechanical performance；Meanwhile, low temperature quenching can prevent section bar crystallization from excessively so that the fragility of product is increased.
3rd, pass through low temperature quenching during the embryo material processing preparing polylactic acid section bar, so that the temperature of embryo material is rapidly reduced
To below the vitrification point of polylactic acid, it is effectively controlled the crystallization of polylactic acid, it is qualified to provide for follow-up strengthening process
Embryo material.
4th, stable performance.Because this technique is to temperature, pressure, the isoparametric adjustment of injecting rate, be not added with nucleator,
The auxiliary agents such as plasticizer, so the problem that problem of Presence of an interface and small molecule are not overflowed, strong mechanical property.
5th, more healthy harmless.Because raw materials used, without any auxiliary agent, biocompatibility is good for pure polylactic acid,
In medical treatment ＆ health industry using more healthy harmless.With generally add other reinforcing agents to improve the machinery of material in the feed
The method of performance compares, and the present invention adopts brand-new processing molding method, without other any reinforcing agents or auxiliary agent, widens
The range of application of material, improves the value of poly-lactic acid products, particularly in the medical treatment neck that control strict to product raw material
The application in domain.
Brief description
Fig. 1 prepares the longitudinal section scanning electron microscope (SEM) photograph of polylactic acid section bar according to the method for the present invention；
Fig. 2 prepares the cross-sectional scans electron microscope of polylactic acid section bar according to the method for the present invention.
Specific embodiment
Embodiment A：
A kind of method preparing alignment state polylactic acid section bar, according to the following step：
[1]. standby after Poly-L-lactic acid vacuum is fully dried.
[2]. injection machine parameters are preheated after setting completed；After preheating completes, add the poly- breast of drying
Acid starts injection molding.
[3]. cooled rapidly by special cooling system after the embryo material demoulding of injection mo(u)lding and make polylactic acid embryo material.
[4]. extrusion die is heated to 180 DEG C, after stablizing, embryo material is put into heating 2min in mold cavity.
[5]. after completing heating, embryo material is clamp-oned in the shaping mold cavity being preheating to 120 DEG C by starting device, is prepared into alignment state
Polylactic acid section bar.
[6]. after completing extruding, polylactic acid section bar is obtained final poly- breast together with the quick Cooling Quenching of shaping mold cavity
Acid type material.Under other working condition the same terms, using specific rotatory power be -150 °～-160 °, viscosity be 4dL/g poly- breast
Acid is raw material, the relevant parameter in producing is adjusted, concrete adjusting parameter is referring to as table 1 below.
Table 1 relevant parameter adjusts list
Table 2 is the result being curved strength test according to the material that the parameter of embodiment 1-8 and comparative example 1-3 produces
(average bending strength of 7 samples of randomization), experimental condition is as follows:
Test speed：2mm/minSpan (L)：15mmSpecimen shape：BarSpecimen finish：4mm
| Maximum, force | Bending strength (meansigma methodss) | |
| Unit | N | MPa |
| Embodiment 1 | 395.0 | 235.9 |
| Embodiment 2 | 458.5 | 273.8 |
| Embodiment 3 | 408.6 | 244.0 |
| Embodiment 4 | 391.6 | 233.8 |
| Embodiment 5 | 331.5 | 198.0 |
| Embodiment 6 | 352.2 | 210.4 |
| Embodiment 7 | 273.6 | 163.4 |
| Embodiment 8 (most preferred embodiment) | 509.7 | 304.3 |
| Comparative example 1 | 314.3 | 187.7 |
| Comparative example 2 | 286.8 | 171.2 |
| Comparative example 3 | 342.0 | 204.2 |
By table 1,2 it can be seen that raw material injection temperature, embryo material rate of cooling, preheating temperature, preheating time, cooling temperature
The associated production conditions such as degree have a great impact to the bending strength of polylactic acid section bar.Examination by the polylactic acid to different viscosities
Issue after examination and approval existing preheating temperature be 120 DEG C -200 DEG C, preheating time be 1min-5min, embryo material rate of cooling be 50 DEG C -200 DEG C, poly- breast
Acid type material chilling temperature is that the bending strength of the polylactic acid section bar obtaining when -20 DEG C -30 DEG C reaches maximum, and every mechanical property reaches
To optimum.
Embodiment B：
A kind of method preparing alignment state polylactic acid section bar, according to the following step：
[1]. the Poly-L-lactic acid that degree of crystallinity is 8.5% is placed in vacuum environment standby after being fully dried.
[2]. embryo material processing mold is heated to 200 DEG C and constant temperature, after preheating completes, particles of polylactic acid is put into mould
In and carry out under vacuum conditions rising gentle pressurization.
[3]. after polylactic acid heats 3min in a mold, forged and pressed, forging and stamping pressure is 10MPa, time 3min, is formed
Embryo material.
[4]. poly lactic acid type forming mold is heated to 180 DEG C and constant temperature, then embryo material is put into heating in mould
3min.
[5]. to be heated complete, the equipment of starting is forged and pressed, and forging and stamping pressure is 15MPa, and pressurize 20s.
[6]. rapidly polylactic acid section bar is quenched under dwell condition after the completion of pressurize, the cool time is 10 minutes.
[7]. to be quenched complete to obtain poly lactic acid type material.
Under other working condition the same terms, the method according to forging and stamping is adjusted to relevant parameter, concrete adjustment ginseng
Number is referring to such as table 3 below.
Table 3 adjusts relevant parameter according to forging method
Wherein table 1, "-" represents (0.1Mpa) or natural cooling under room temperature (10-25 DEG C), normal pressure in table 3.
Table 4 is the result row carrying out degree of crystallinity, bending strength test according to the embodiment resulting materials that the parameter of table 3 produces
Table：
Accompanying drawing 1 is the scanning according to the polylactic acid section bar (longitudinal section) being obtained under the Parameter Conditions of most preferred embodiment 8 in table 1
Ultramicroscope (SEM) photo：Amplification is 60 times, 100 times, 1000 times and 2000 times from low to high respectively, can from figure
Either macroscopical (60 times, 100 times) to find out, or microcosmic (1000 times, 2000 times) structure, the poly- breast being obtained by the present invention
Acid type material orientation is substantially；This is because under the synergism of selected initial process conditions, polylactic acid is in certain molding pressure
There is structural rearrangement, the arrangement of strand is more regular in order, forms effective orientation texture under power and forming temperature, thus, it is possible to
The defect such as effectively overcome mechanical property undesirable, thus expand the practical application area of polylactic acid article further.Accompanying drawing 2 be by
According to the SEM photograph of the polylactic acid section bar (cross section) being obtained under the Parameter Conditions of the most preferred embodiment 8 in table 1, permissible from figure
Find out, the fracture mode of the polylactic acid section bar of present invention preparation is typical ductile rupture, and its mechanism is by the course of processing
In the control of temperature the degree of crystallinity of polylactic acid is controlled in a preferable scope, so that the polylactic acid section bar tool of preparation
There is good toughness.
Can draw in conjunction with table 1, table 2, table 3, table 4 and accompanying drawing 1, accompanying drawing 2, under suitable temperature, intensified condition, especially
It is that the polylactic acid section bar of gained under optimum condition has good orientation texture.Therefore the inventive method is the poly- of high-crystallinity
Lactic acid preparation provides rational process conditions and route.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to invention
In the scope of the claims that a little modifications and changes should also be as fall into the present invention.Although additionally, employing in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limit to the present invention.
Claims (10)
1. a kind of method preparing alignment state polylactic acid section bar is it is characterised in that comprise the steps：
1) polylactic acid raw material through drying is molded by injection machine and makes embryo material or polylactic acid raw material is forced through
Embryo material is made in forging and stamping；
2) by step 1) gained embryo material carry out orientation strengthening, described orientation intensifying method be extrusion or forge and press；
3) by step 2) products therefrom carries out Cooling Quenching, forms alignment state polylactic acid section bar after product is stable.
2. a kind of method preparing alignment state polylactic acid section bar, is characterized in that, described step 1) forging and stamping method be vacuum forging
Pressure.
3. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 1)
In polylactic acid raw material be Poly-L-lactic acid, its specific rotatory power is at -155 °～-160 °.
4. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 1)
In polylactic acid raw material intrinsic viscosity be 1dL/g-7dL/g.
5. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 1)
In forging and stamping embryo heating-up temperature be 160 DEG C -210 DEG C, pressure be 5Mpa-30Mpa, heat time heating time be 1min-5min.
6. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 2)
In extrusion preheating temperature be 120 DEG C -200 DEG C, preheating time be 1min-5min.
7. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 2)
In forging method preheating temperature be 140 DEG C -180 DEG C, preheating time be 1min-5min.
8. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 2)
In extruded velocity be 10-200cm3/s.
9. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step 3)
Hardening heat be -20 DEG C to 30 DEG C, cool time be 1-2min, quenching cooling rate be 50 DEG C/min-150 DEG C/min.
10. a kind of method preparing alignment state polylactic acid section bar according to claim 1 is it is characterised in that described step
3) degree of crystallinity of the section bar in is 50%-90%, and grain shape is platelet, extended chain is brilliant or shish-kebab, linear in microstructure
Arrangement.
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| CN201610798903.8A CN106426973B (en) | 2016-08-31 | 2016-08-31 | A method of preparing alignment state polylactic acid proximate matter |
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| CN201610798903.8A CN106426973B (en) | 2016-08-31 | 2016-08-31 | A method of preparing alignment state polylactic acid proximate matter |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915967A (en) * | 2017-12-14 | 2018-04-17 | 中国石油大学(北京) | A kind of method of high molecular material spontaneous nucleation |
| CN108340529A (en) * | 2018-02-10 | 2018-07-31 | 郑州轻工业学院 | A method of supercharging prepares amorphous polylactic acid plank at a slow speed |
| CN108454074A (en) * | 2018-03-28 | 2018-08-28 | 中国航发北京航空材料研究院 | A kind of orientation intensifying method of thermoplastic resin |
| CN109130233A (en) * | 2018-07-31 | 2019-01-04 | 西华大学 | A kind of preparation method with the poly-lactic acid material of long acting antibiotic |
| CN110887857A (en) * | 2018-09-07 | 2020-03-17 | 吉林大学 | Method for detecting polyacrylonitrile fiber generalized crystallinity by two-dimensional X-ray diffraction |
| CN111978693A (en) * | 2019-05-24 | 2020-11-24 | 中国科学院宁波材料技术与工程研究所 | High-strength physical aging-resistant polylactic acid material, and preparation method and application thereof |
| CN112521733A (en) * | 2019-09-17 | 2021-03-19 | 中国科学院宁波材料技术与工程研究所 | Physical aging-resistant polylactic acid two-dimensional material, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168105A (en) * | 1995-09-14 | 1997-12-17 | 多喜兰株式会社 | Osteosynthetic material, composite implant material, and process for preparing same |
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2016
- 2016-08-31 CN CN201610798903.8A patent/CN106426973B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168105A (en) * | 1995-09-14 | 1997-12-17 | 多喜兰株式会社 | Osteosynthetic material, composite implant material, and process for preparing same |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915967A (en) * | 2017-12-14 | 2018-04-17 | 中国石油大学(北京) | A kind of method of high molecular material spontaneous nucleation |
| CN108340529A (en) * | 2018-02-10 | 2018-07-31 | 郑州轻工业学院 | A method of supercharging prepares amorphous polylactic acid plank at a slow speed |
| CN108340529B (en) * | 2018-02-10 | 2019-11-05 | 郑州轻工业学院 | A method of pressurization prepares amorphous polylactic acid plate at a slow speed |
| CN108454074A (en) * | 2018-03-28 | 2018-08-28 | 中国航发北京航空材料研究院 | A kind of orientation intensifying method of thermoplastic resin |
| CN109130233A (en) * | 2018-07-31 | 2019-01-04 | 西华大学 | A kind of preparation method with the poly-lactic acid material of long acting antibiotic |
| CN110887857A (en) * | 2018-09-07 | 2020-03-17 | 吉林大学 | Method for detecting polyacrylonitrile fiber generalized crystallinity by two-dimensional X-ray diffraction |
| CN111978693A (en) * | 2019-05-24 | 2020-11-24 | 中国科学院宁波材料技术与工程研究所 | High-strength physical aging-resistant polylactic acid material, and preparation method and application thereof |
| CN111978693B (en) * | 2019-05-24 | 2022-03-15 | 中国科学院宁波材料技术与工程研究所 | High-strength physical aging-resistant polylactic acid material, and preparation method and application thereof |
| CN112521733A (en) * | 2019-09-17 | 2021-03-19 | 中国科学院宁波材料技术与工程研究所 | Physical aging-resistant polylactic acid two-dimensional material, and preparation method and application thereof |
| CN112521733B (en) * | 2019-09-17 | 2022-03-15 | 中国科学院宁波材料技术与工程研究所 | Physical aging-resistant polylactic acid two-dimensional material, and preparation method and application thereof |
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