CN107304247A - Beta-hydroxybutyrate and β hydroxyl pentanoate copolymer powder for selective laser sintering and preparation method thereof - Google Patents
Beta-hydroxybutyrate and β hydroxyl pentanoate copolymer powder for selective laser sintering and preparation method thereof Download PDFInfo
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- CN107304247A CN107304247A CN201610258419.6A CN201610258419A CN107304247A CN 107304247 A CN107304247 A CN 107304247A CN 201610258419 A CN201610258419 A CN 201610258419A CN 107304247 A CN107304247 A CN 107304247A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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Abstract
The invention provides a kind of beta-hydroxybutyrate for selective laser sintering and β hydroxyl pentanoate copolymer powder and preparation method thereof.The preparation method is by selecting suitable solvent, especially it is selected under specific temperature and pressure, by the suitable heating of design and cooling method, so as to obtain beta-hydroxybutyrate and β hydroxyl valerate toner raw materials that form, character etc. are particularly suitable for the selective laser sintering of selective laser sintering.
Description
Technical field
The present invention relates to technical field of polymer processing, further say, be related to a kind of suitable for selective laser sintering
Beta-hydroxy-butanoic acid ester and beta-hydroxy valerate copolymers powder and preparation method thereof.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) technology is a kind of rapid shaping technique,
It is most widely used and most market prospects technology in current increases material manufacturing technology, becoming for fast development is showed in recent years
Gesture.Selective Laser Sintering is that 3D solid is scanned first by computer, is then irradiated by high intensity laser beam
The material powder spread on workbench or parts optionally molten sintering layer by layer in advance, so realize by
The technology of formable layer.Selective Laser Sintering has the design of height flexible, can produce accurate model and prototype,
The parts that can directly use with reliable structure can be molded, and it is with short production cycle, and technique is simple, therefore especially fits
Together in the exploitation of new product.
The moulding material species that can be used in Selective Laser Sintering is relatively broad, including macromolecule, paraffin, gold
Category, ceramics and their composite.Sintered into however, the performance of moulding material, character are Selective Laser Sinterings
One key factor of work(, it also directly affects the shaping speed of molding part, precision, and physics, chemical property and its synthesis
Performance.Although applicable moulding material species is various, can directly apply at present Selective Laser Sintering and into
The polymer powder powder stock that work(produces the moulded work that scale error is small, surface is regular, porosity is low is fresh few.Prior art
In, the powder stock of selective laser sintering is generally prepared using comminuting method, such as deep cooling crush method, this not only needs specific
Equipment, the particles of powdered ingredient surface for preparing is rougher, particle diameter is not uniform enough, in irregular shape, is unfavorable for sinter molding
The formation of body, and influence the performance of formed body.It is former suitable for the polymer powder of Selective Laser Sintering in the market
Material is deficient, therefore the corresponding solid powder raw material of various type of polymer is urgently developed.
Beta-hydroxy-butanoic acid ester and beta-hydroxy valerate copolymers (PHBV) are a kind of biodegradable resin materials, are had
Good mechanical performance and bio-compatibility, therefore the PHBV solids with biocompatibility of exploitation selective laser sintering
Powder, can meet the demand of the applications such as the bio-medical carrier material of personalization.However, not yet occurring generally fitting in the market
Selective laser sintering PHBV solid powders.
The content of the invention
It is an object of the invention to provide it is a kind of suitable for the PHBV toners of selective laser sintering and its preparation
Method.The PHBV toners have suitably sized size, well-balanced particle profile, and particle diameter distribution is uniform, powder stream
Dynamic property is good, and its preparation method is easily operated.
One aspect of the present invention provides a kind of beta-hydroxy-butanoic acid ester for selective laser sintering and beta-hydroxy valerate
Copolymer powder (PHBV toners), the particle of the powder is spherical and/or spherical, and the particle size of the particle is
20-120 μm, particle diameter distribution is：D10=24-43 μm, D50=48-65 μm, D90=82-115 μm.There is provided according to the present invention
PHBV toners with as above feature are particularly suitable for use in selective laser sintering to prepare various moulded works.
There is provided a kind of preparation of the PHBV toners for selective laser sintering according to another aspect of the present invention
Method, comprises the following steps：
A) beta-hydroxy-butanoic acid ester and beta-hydroxy valerate copolymers are dissolved in organic solvent and obtain copolymer solution, plus
The heat copolymer solution；
B) copolymer solution after will be heated in step a) is cooled, and makes solid Precipitation；With
C) precipitation is separated and is dried；
Wherein, the organic solvent is selected from C3-C8Ring-type or non-annularity ketone and C4-C8In oxygen helerocyclics at least
It is a kind of.
According to the preferred embodiment of the present invention, the organic solvent is selected from C3-C5Ring-type or non-annularity ketone and C4-C6
At least one of oxygen helerocyclics, is more preferably selected from acetone, butanone, 2 pentanone, propione, cyclopentanone, isopropyl methyl
At least one of ketone, tetrahydrofuran and dioxane, particularly preferred acetone and/or butanone.
Although organic solvent deposit technology has been used for separating and purifying biochemical substances, especially protein, Huo Zheyong
Crystal is prepared in precipitation, still, is still rarely burnt at present on being prepared using organic solvent precipitation method for selective laser
The report of the resin material powder of knot technology.Especially not yet have been reported that for preparing the PHBV suitable for selective laser sintering
Toner.The present inventor in experiments it is found that, when from appropriate solvent when, organic solvent, passes through solvent as previously discussed
The precipitation method can obtain the PHBV toners suitable for selective laser sintering.
According to the preferred embodiment of the present invention, using the beta-hydroxy-butanoic acid ester and beta-hydroxy valerate copolymers as 100
Parts by weight meter, the consumption of the organic solvent is 600-1200 parts by weight, preferably 800-1000 parts by weight.In the solvent
Use in the range of, PHBV resins can be made fully to dissolve in a heated condition, can fully be separated out again during cooling, and produce shape
Looks, dispersiveness preferably PHBV toners.
According to the preferred embodiment of the present invention, in step a), the copolymer solution is heated to 120-160 DEG C,
It is preferred that 130-140 DEG C of heating-up temperature.It is preferred that being stirred in heating process.Further, it is preferable to which the copolymer is molten
Liquid is kept for 30-90 minutes, more preferably 45-75 minutes in the heating-up temperature.
Preferably, in step a), the copolymer solution is heated under inert atmosphere, such as nitrogen atmosphere.
Preferably, in step a), the copolymer solution is begun to warm up under 0.1-0.35MPa pressure.
The beta-hydroxy-butanoic acid ester used in step a) and beta-hydroxy valerate copolymers are preferably powdered or graininess,
It can make by oneself or commercially available；Particle diameter can be conventional particle size, and preferably average grain diameter is in below 2mm, more preferably in below 1mm.To
The beta-hydroxy-butanoic acid ester is dissolved in before organic solvent with beta-hydroxy valerate copolymers, can be crushed by conventional meanses
To suitable particle diameter, the particle diameter of such as aforementioned range.According to the present invention it is possible to implement institute in reactor, such as autoclave
State method.
Preferably, in step b), the cooling is carried out under the conditions of self-generated pressure.That is, preferably solution is in confined reaction
Heat and cool down in kettle, until solution temperature is down to target temperature.
According to the preferred embodiment of the present invention, in step b), the average rate of temperature fall of the cooling for 0.1 DEG C/
Min-1.2 DEG C/min, such as 0.1,0.2,0.5,0.8,1.0 DEG C/min.
According to the preferred embodiment of the present invention, in step b), the copolymer solution is cooled to cooling target temperature
Degree, and kept for 30-90 minutes in cooling target temperature；It is preferred that the cooling target temperature is 10-30 DEG C, such as room temperature.
In the method that the present invention is provided, the temperature-fall period of the PHBV resin solutions after heating can at the uniform velocity cool, and also may be used
With stage cooling.The present invention some preferred embodiment in, in step b), be cooled to cooling target temperature it
Before, the copolymer solution is cooled to one or more medium temperatures, and kept for 30-90 minutes in the medium temperature；Institute
It is preferably 50-100 DEG C to state medium temperature, also preferably 60-90 DEG C, more preferably 70-80 DEG C.Especially, when only relating to one
During medium temperature, the intermediate temperature range is preferably 70-80 DEG C.It is readily appreciated that, heating of the medium temperature between step a)
Between temperature and step b) cooling target temperature.
According to the specific embodiment of the present invention, in step b), before cooling target temperature is cooled to, by institute
State copolymer solution and be cooled to the first medium temperature, and kept for 30-90 minutes in first medium temperature；Then proceed to cooling
Kept for 30-90 minutes to the second medium temperature, and in second medium temperature；Wherein, first medium temperature is in 80-
100 DEG C of scope, scope of second medium temperature at 50-75 DEG C.
By using the above-mentioned preferred interim cooling method of the present invention, moderate in grain size, particle diameter distribution are obtained more equal
It is even, and the powder of good fluidity, thus it is particularly suitable for selective laser sintering application.
In step c), preferably by centrifuging out precipitation, and preferably dried by vacuum drying mode separated
Precipitation, obtain for laser sintered PHBV powder.
The above-mentioned preparation method provided according to the present invention, can prepare PHBV toners as characterized above,
The particle of i.e. described powder is spherical and/or spherical, and the particle size of particle is 20-120 μm, particle diameter distribution D10=24-43
μm, D50=48-65 μm, D90=82-120 μm.The powder is particularly suitable for use in Selective Laser Sintering, sinters success rate
Height, obtained sintered products and predetermined prod scale error are small, and section cavity is few.
Present invention also offers a kind of selective laser sintering method, using the present invention provide it is as characterized above
PHBV toners or the PHBV toners that are prepared by the method that provides of the present invention be used as raw material and carry out selectivity
Laser sintered operation.
The selective laser sintering method provided by the present invention, can be prepared even with irregular figure, surface
Claim smooth, satisfactory mechanical property PHBV moulded works.
Provided by the present invention for the preparation method of the PHBV toners of selective laser sintering, operating procedure is simple,
It is easily operated, by selecting suitable solvent, under specific temperature and pressure, the suitable heating of design and cooling method, from
And the PHBV toner raw materials that form, character etc. are particularly suitable for selective laser sintering are obtained, it is expected to fill up such product
Gaps in market.
In addition, another advantage protruded of the present invention is, without using other auxiliary agents or additive, just to result in chi
It is very little be of moderate size, surface is round and smooth, dispersed and good fluidity, particle diameter distribution are uniform, the PHBV trees of (on apparent) heap appropriate density
Cosmetics end, it can prepare that scale error is small, hole is few, profile is well-balanced, mechanicalness when for Selective Laser Sintering
The good moulded work of energy.
Thus, the invention provides a kind of PHBV toner raw materials of good performance suitable for selective laser sintering
And preparation method thereof, only selective laser sintering does not provide new qualified raw materials for sintering, is also the processing of PHBV resins
New direction is provided with application.
Brief description of the drawings
Wherein, identical part identical reference in the accompanying drawings；Accompanying drawing is not drawn according to actual ratio.
Fig. 1 is SEM (SEM) figure of the PHBV toners provided according to the present invention.
Fig. 2 is the scanning electron microscope diagram for the polyamide powder for being commercially for selective laser sintering.
Embodiment
The present invention will be described further by specific embodiment below, it should be appreciated that the scope of the present invention is not
It is limited to this.
In the examples below, obtained PHBV is characterized using SEM (XL-30, FEI Co. of the U.S.)
The pattern of toner and the polyamide powder for being commercially for selective laser sintering.Using laser particle analyzer
(Mastersizer 2000, Malvern companies of Britain) characterizes the particle size and particle diameter point of obtained PHBV toners
Cloth.
Embodiment 1
The acetone of the PHBV resins of 100 parts by weight and 1000 parts by weight is placed in autoclave.It is passed through high pure nitrogen
To 0.2MPa.135 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes.
After constant temperature terminates, 80 DEG C are down to 1.0 DEG C/min speed through cooling water, at this temperature constant temperature 60 minutes；After
It is continuous that room temperature is down to 1.0 DEG C/min speed.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
The pattern of the PHBV toners obtained is as shown in figure 1, particle size and particle diameter distribution are listed in Table 1 below.
Embodiment 2
The acetone of the PHBV resins of 100 parts by weight and 800 parts by weight is placed in autoclave.It is passed through high pure nitrogen extremely
0.1MPa.140 DEG C are then raised temperature to, at this temperature constant temperature 80 minutes.
After constant temperature terminates, 70 DEG C are down to 1.0 DEG C/min speed through cooling water, at this temperature constant temperature 70 minutes；With
0.5 DEG C/min speed is down to 20 DEG C, and is kept for 30 minutes at 20 DEG C.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
Characterized using SEM obtained PHBV toners pattern (result is similar to Example 1,
This SEM is not shown), particle size and particle diameter distribution are listed in Table 1 below.
Embodiment 3
The butanone of the PHBV resins of 100 parts by weight and 1200 parts by weight is placed in autoclave.It is passed through high pure nitrogen
To 0.3MPa.130 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes.
After constant temperature terminates, room temperature is down to 0.1 DEG C/min speed.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
Characterized using SEM obtained PHBV toners pattern (result is similar to Example 1,
This SEM is not shown), particle size and particle diameter distribution are listed in Table 1 below.
Embodiment 4
The butanone of the PHBV resins of 100 parts by weight and 1200 parts by weight is placed in autoclave.It is passed through high pure nitrogen
To 0.3MPa.130 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes.
After constant temperature terminates, 80 DEG C are down to 0.5 DEG C/min speed through cooling water, at this temperature constant temperature 60 minutes；With
0.1 DEG C/min speed is down to room temperature, is kept for 30 minutes at room temperature.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
Characterized using SEM obtained PHBV toners pattern (result is similar to Example 1,
This SEM is not shown), particle size and particle diameter distribution are listed in Table 1 below.
Embodiment 5
The butanone of the PHBV resins of 100 parts by weight and 1000 parts by weight is placed in autoclave.It is passed through high pure nitrogen
To 0.1MPa.140 DEG C are then raised temperature to, at this temperature constant temperature 30 minutes.
After constant temperature terminates, 30 DEG C are down to 0.5 DEG C/min speed through cooling water, and kept for 60 minutes at 30 DEG C.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
Characterized using SEM obtained PHBV toners pattern (result is similar to Example 1,
This SEM is not shown), particle size and particle diameter distribution are listed in Table 1 below.
Embodiment 6
The propione of the PHBV resins of 100 parts by weight and 1200 parts by weight is placed in autoclave.It is passed through High Purity Nitrogen
Gas is to 0.3MPa.130 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes.
After constant temperature terminates, 90 DEG C are down to 1.0 DEG C/min speed through cooling water, at this temperature constant temperature 60 minutes；So
60 DEG C are down to 0.5 DEG C/min speed afterwards, at this temperature constant temperature 45 minutes；Room temperature is down to 0.1 DEG C/min speed again,
Kept for 30 minutes at room temperature.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
Characterized using SEM obtained PHBV toners pattern (result is similar to Example 1,
This SEM is not shown), particle size and particle diameter distribution are listed in Table 1 below.
Embodiment 7
The tetrahydrofuran of the PHBV resins of 100 parts by weight and 1000 parts by weight is placed in autoclave.It is passed through high-purity
Nitrogen is to 0.2MPa.140 DEG C are then raised temperature to, at this temperature constant temperature 30 minutes.
After constant temperature terminates, 30 DEG C are down to 0.5 DEG C/min speed through cooling water, and kept for 60 minutes at 30 DEG C.
Material is centrifuged into out precipitation, vacuum drying precipitation obtains the PHBV resins suitable for selective laser sintering
Powder.
Characterized using SEM obtained PHBV toners pattern (result is similar to Example 1,
This SEM is not shown), particle size and particle diameter distribution are listed in Table 1 below.
Table 1
As seen from Figure 1, the character for the PHBV toners that the method according to the invention is prepared is spherical and/or class ball
Shape, such as potato character, the surface of particle are more smooth, and preferably, the aggregation caking of particle is few, is therefore particularly suitable for for dispersiveness
Selective laser sintering.From the point of view of granulometry result (table 1), the PHBV toner particle diameters that the method according to the invention is obtained
In 20-120 μm, distribution uniform.
Fig. 2 is the scanning electron microscope diagram for the polyamide powder for being commercially for selective laser sintering.From Fig. 2 and figure
From the point of view of 1 contrast, the shape of commercially available polyamide powder particle is regular, even not as the PHBV resinous powder particles that the present invention is provided
Claim, and particle adhesion than serious shown by Fig. 1.
As can be seen here, generally, for PHBV resin materials, prepared and burnt for selective laser by the method for the present invention
The PHBV toners of knot, obtain good effect, are suitable for the raw material of selective laser sintering.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that each side of the invention recorded, different embodiments
Each several part and the various features enumerated can be combined or all or part of exchange.In each above-mentioned embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, and this is by by this area skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that description above is only the mode of example, not purport
In the limitation present invention.
Claims (11)
1. the preparation method of a kind of beta-hydroxy-butanoic acid ester for selective laser sintering and beta-hydroxy valerate copolymers powder,
Comprise the following steps：
A) beta-hydroxy-butanoic acid ester and beta-hydroxy valerate copolymers are dissolved in organic solvent and obtain copolymer solution, heat institute
State copolymer solution；
B) copolymer solution after will be heated in step a) is cooled, and makes solid Precipitation；With
C) precipitation is separated and is dried；
Wherein, the organic solvent is selected from C3-C8Ring-type or non-annularity ketone and C4-C8At least one of oxygen helerocyclics.
2. preparation method according to claim 1, it is characterised in that the organic solvent is selected from C3-C5Ring-type or non-annularity
Ketone and C4-C6At least one of oxygen helerocyclics, is preferably selected from acetone, butanone, 2 pentanone, propione, cyclopentanone, first
At least one of base isopropyl-ketone, tetrahydrofuran and dioxane, more preferably acetone and/or butanone.
3. preparation method according to claim 1 or 2, it is characterised in that with the beta-hydroxy-butanoic acid ester and beta-hydroxy penta
Acid ester copolymer is 100 parts by weight meters, and the consumption of the organic solvent is 600-1200 parts by weight, preferably 800-1000 weights
Measure number.
4. the preparation method according to any one of claim 1-3, it is characterised in that in step a), by the copolymerization
Thing solution is heated to 120-160 DEG C, preferably 130-140 DEG C of heating-up temperature；It is preferred that by the copolymer solution in the heating
Temperature is kept for 30-90 minutes, preferably 45-75 minutes.
5. the preparation method according to any one of claim 1-4, it is characterised in that in step a), in 0.1-
The copolymer solution is begun to warm up under 0.35MPa pressure, preferably described copolymer solution is heated under an inert atmosphere；
And/or
In step b), the cooling is carried out under the conditions of self-generated pressure.
6. the preparation method according to any one of claim 1-5, it is characterised in that in step b), the cooling
Average rate of temperature fall is 0.1 DEG C/min-1.2 DEG C/min.
7. the preparation method according to any one of claim 1-6, it is characterised in that in step b), by the copolymerization
Thing solution is cooled to cooling target temperature, and is kept for 30-90 minutes in cooling target temperature；It is preferred that the cooling target temperature is
10-30℃。
8. the preparation method according to any one of claim 1-6, it is characterised in that in step b), is being cooled to
Before warm target temperature, the copolymer solution is cooled to one or more medium temperatures, and keep in the medium temperature
30-90 minutes；The medium temperature is preferably 60-90 DEG C, preferably 70-80 DEG C.
9. the preparation method according to any one of claim 1-6, it is characterised in that in step b), is being cooled to
Before warm target temperature, the copolymer solution is cooled to the first medium temperature, and 30- is kept in first medium temperature
90 minutes；Then proceed to be cooled to the second medium temperature, and kept for 30-90 minutes in second medium temperature；Wherein, it is described
Scope of first medium temperature at 80-100 DEG C, scope of second medium temperature at 50-75 DEG C.
10. the β for selective laser sintering that the preparation method according to any one of claim 1-9 is prepared-
Butyric ester and beta-hydroxy valerate copolymers powder, the particle of the powder be it is spherical and/or spherical, the particle
Particle size is 20-120 μm, and particle diameter distribution is：D10=24-43 μm, D50=48-65 μm, D90=82-120 μm.
11. a kind of selective laser sintering method, using beta-hydroxy-butanoic acid ester as claimed in claim 10 and beta-hydroxy
Valerate copolymers powder or the beta-hydroxy-butanoic acid prepared by preparation method as claimed in any one of claims 1-9 wherein
Ester carries out selective laser sintering operation with beta-hydroxy valerate copolymers powder as raw material.
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| CN201610258419.6A CN107304247A (en) | 2016-04-22 | 2016-04-22 | Beta-hydroxybutyrate and β hydroxyl pentanoate copolymer powder for selective laser sintering and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3812416A1 (en) | 2019-10-23 | 2021-04-28 | Acondicionamiento Tarrasense | Process for producing polymers in powder form |
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| CN102399371A (en) * | 2011-10-17 | 2012-04-04 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide powder used for selective laser sintering |
| CN104497323A (en) * | 2014-12-17 | 2015-04-08 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder for selective laser sintering |
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| CN101138651A (en) * | 2007-09-14 | 2008-03-12 | 华中科技大学 | Method of preparing organization bracket performing selectivity laser sintering by using macromolecule microsphere |
| CN102140246A (en) * | 2010-12-21 | 2011-08-03 | 湖南华曙高科技有限责任公司 | Method for preparing nylon powder for selective laser sintering |
| CN102399371A (en) * | 2011-10-17 | 2012-04-04 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide powder used for selective laser sintering |
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| EP3812416A1 (en) | 2019-10-23 | 2021-04-28 | Acondicionamiento Tarrasense | Process for producing polymers in powder form |
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Application publication date: 20171031 |