CN106521688A - High strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) filament and preparation method thereof - Google Patents
High strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) filament and preparation method thereof Download PDFInfo
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- CN106521688A CN106521688A CN201610842357.3A CN201610842357A CN106521688A CN 106521688 A CN106521688 A CN 106521688A CN 201610842357 A CN201610842357 A CN 201610842357A CN 106521688 A CN106521688 A CN 106521688A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a high strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) (PHBV) filament and a preparation method thereof. The filament comprises the following raw materials in parts by weight: 93 to 100 parts of PHBV, 0 to 5 parts of inorganic nucleating agent, and 0 to 2 parts of antioxidant. The preparation method comprises the following steps: (1) weighting dry PHBV, an inorganic nucleating agent, and an antioxidant according to the abovementioned ratio, pre-mixing the raw materials, blending the raw materials, and carrying out granulation to obtain PHBV master batch; and (2) melting and extruding PHBV master batch, and performing water bath cooling, primary water bath stretching, secondary hot air stretching, hot moulding, oiling and reeling to obtain the high strength coarse denier PHBV filament. The provided filament has the characteristics of high strength and high modulus, and can be used as a raw material of textiles.
Description
Technical field
The present invention relates to polymeric material field, and in particular to the poly- (3-hydroxybutyrate ester-co-3- hydroxyls penta of high-strength thick denier
Acid esters) (PHBV) monofilament and preparation method thereof.
Background technology
Poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerates) (PHBV) be a class Jing fermentable synthesis non-petroleum
Based thermoplastic polyester material, its resource are renewable, biodegradable, melt-processable, and performance is similar to polypropylene.Although PHBV
Possess many excellent characteristics, but which there is also some intrinsic performance deficiencies, it is main to include being susceptible to thermal degradation, it is corresponding
Material is crisp etc..In numerous defects of PHBV, urgent need to resolve is the crisp problem of its corresponding material, and the defect almost makes which without making
With value.
According to PHBV tenacity of fibre difference Producing reason, people try by change melt spinning process outfield method come
Regulate and control their condensed state structure to improve its toughness, wherein Iwata of Japan Chemical institute (RIKEN) etc.【Strong Fibers
and Films of Microbial Polyesters.Macromol.Biosci.2005,5(8),689-701.】Using special
Spinning technique the monofilament of high-strength and high-modulus has been obtained, PHBV fibers obtained by melt-spun are quenched without fixed in ice-water bath by first
The PHBV fibers of shape, and (temperature is close to the glass transition temperature of PHBV, T in ice-water bathg=-4 DEG C) in isothermal crystal 24 it is little
When to form more small crystal nucleus, then under normal temperature on drafting machine by drawing of fiber to original 10 times, partly positioned at tiny crystalline substance
Internuclear strand develops into β type crystal in the presence of stretching outfield, and wherein strand is in the zigzag conformations of plane, most
Afterwards PHBV fibers are processed 30 minutes under conditions of 60 DEG C and constant-tension, moieties chain are on the one hand made with established thin
Alpha type crystal is piled into based on small crystal nucleus, and wherein strand is in 21Helical conformation, to increase the degree of crystallinity of PHBV fibers, separately
On the one hand fix the strand of the zigzag conformations in plane, it is to avoid the generation of secondary crystallization.It is fine due to avoiding PHBV
The secondary crystallization of dimension, the reduction of crystalline size, and β type crystal are formed such that the intensity and modulus of PHBV monofilament have exceeded often
Rule polyster fibre, and with higher elongation at break.But regrettably Iwata etc. prepare PHBV monofilament process it is very multiple
Miscellaneous, condition has high demands, and efficiency is low, it is virtually impossible to practical.Therefore, develop the work for efficiently producing high-strength thick denier PHBV monofilament
Skill, realizes that its industrialized production is most important.
The content of the invention
The purpose of the present invention is the present situation for high-strength thick denier PHBV monofilament, high-strength thick denier PHBV monofilament in developing,
And provide its preparation method.
Poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerates) (PHBV) high-strength coarse denier monofilaments, by the raw material of following mass parts
Make：
PHBV：97～100 parts；
Inorganic nucleator：0～5 part；
Antioxidant：0～2 part；
The wherein viscosity average molecular weigh of PHBV is：1.0×105～1.0 × 106；
In PHBV, the content of 3- hydroxyl valerates (HV) construction unit is：0～20mol%, when HV contents are 0, PHBV
For poly- (3-hydroxybutyrate ester) (PHB)；
Inorganic nucleator be clay, CNT, boron nitride, talcum powder, terbium oxide, lanthana, hydroxyapatite (HA),
One kind in calcium phosphate and sesquialter cage type siloxanes (POSS)；
Antioxidant be three (2,4- di-tert-butyls) phosphite ester, 2,6 di tert butyl 4 methyl phenol, four [β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites,
β-positive 18 carbonic acid the alcohol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, thiobis (3 methy 6 tert butyl phenol), 4,
4- butylidene-bis(3-methyl-6-t-butyl phenol)s, 2,2 '-methylene bis (4- methyl-6-tert-butylphenols), tri- (4- of 1,3,5-
The tert-butyl group -3-2,6- dimethyl benzyls) -1,3,5- triazine -2,4,6- (1H, 3H, 5H)-triketone, 3,9- it is double [1,1- dimethyl -
2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyl] -2,4,8,10- four oxaspiros [5,5] hendecanes, 4,
It is 4 '-methylene-bis(2,6-di-t-butyl phenol), 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid, thio
Double-(3,5- di-tert-butyl -4- hydroxy benzenes benzyls), N, N '-bis--[3- (3,5- di-tert-butyl-hydroxy phenyls) benzoyl group] oneself two
One or two in double-β-(3- tertiary butyl -4- hydroxy-5-methyl base phenyl) propionic ester of amine, triethylene-glycol.
The preparation method of described high-strength thick denier PHBV, comprises the steps：
(1) PHBV, inorganic nucleator and antioxidant are dried into 8～48h in vacuum drying oven in advance, baking temperature is 50
～105 DEG C；
(2) 0～2 part of 93～100 parts of PHBV, 0～5 part of inorganic nucleator and antioxidant are taken and puts into super mixer
In dry-mixed 3～5 minutes, the then blending granulation in twin-screw blender obtains PHBV master batches, and prilling temperature is 130～200 DEG C,
Rotating speed is 50～150rmp, and the melt blending time is 3～8 minutes；
(3) spinning on melt spinning machine by PHBV master batches, Jing melting extrusions water-bath cool down one water-bath and draw
Stretch two road hot-airs stretching thermal finalizations to oil winding, the high-strength coarse denier monofilaments of prepared PHBV, Screw Extrusion temperature
For 130～200 DEG C, the temperature of cooling bath is 0～25 DEG C, and a roller winding speed is 1～25m/min, one water-bath stretching
Temperature is 20～80 DEG C, and draw ratio is 2～15 times, and the temperature of two road hot-airs stretchings is 20～80 DEG C, draw ratio is 1～
10 times, heat setting temperature is 60～120 DEG C.
Beneficial effect：
The present invention introduces inorganic nano-particle in PHBV as heterogeneous nucleation agent, it is to avoid the formation of large scale spherocrystal, separately
Outward, add antioxidant, improve the heat endurance during PHBV melt-processeds, it is to avoid molecular weight significantly under
Drop.
The preparation method of present invention conventional monofilament has been obtained high-strength thick denier PHBV monofilament, process is simple, and efficiency high can work
Metaplasia is produced.A diameter of 0.08mm～5mm of the high-strength thick denier PHBV monofilament of gained, fracture strength is up to 9.5cN/dtex.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
And do not limit the scope of the invention.In addition, it is to be understood that after the content for having read instruction of the present invention, those skilled in the art can
So that to various changes of the invention or modification, these equivalent form of values equally fall into the model limited by the application appended claims
Enclose.
Embodiment 1
(1) 98 parts of PHBV (HV contents are 2.5mol%), 1 part of boron nitride and 1 part of four [β-(bis- tertiary fourths of 3,5- is weighed first
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester respectively in vacuum drying oven be dried 12 hours (80 DEG C), 12 hours (80 DEG C) and
24 hours (60 DEG C), then put into them dry-mixed 4 minutes in super mixer, then are blended in twin-screw blender and make
Grain, obtains PHBV master batches.Prilling temperature is 170 DEG C, and screw speed is 75rmp, and the melt blending time is 5 minutes.
(2) spinning on melt spinning machine by PHBV master batches, Jing melting extrusions water-bath cool down one water-bath and draw
Stretch two road hot-airs stretching thermal finalizations to oil winding, prepared high-strength thick denier PHBV monofilament, Screw Extrusion temperature
For 170 DEG C, the temperature of cooling bath is 15 DEG C, and a roller winding speed is 10m/min, and the temperature of one water-bath stretching is 45 DEG C,
Draw ratio is 5 times, and the temperature of two road hot-air stretchings is 60 DEG C, and draw ratio is 2 times, and heat setting temperature is 100 DEG C.Gained
A diameter of 0.3mm of PHBV monofilament, fracture strength are 6.0cN/dtex, and elongation at break is 30.8%.
Embodiment 2
(1) 98.5 parts of PHBV (HV contents are 5.0mol%), 1 part of boron nitride and 0.5 part of 2,2 '-methylene bis are weighed first
(4- methyl-6-tert-butylphenols) is dried 12 hours (80 DEG C), 12 hours (80 DEG C) and 24 hours (60 respectively in vacuum drying oven
DEG C), then they are put into dry-mixed 3 minutes in super mixer, then the blending granulation in twin-screw blender, obtain PHBV female
Grain.Prilling temperature is 165 DEG C, and screw speed is 75rmp, and the melt blending time is 8 minutes.
(2) spinning on melt spinning machine by PHBV master batches, Jing melting extrusions water-bath cool down one water-bath and draw
Stretch two road hot-airs stretching thermal finalizations to oil winding, the high-strength coarse denier monofilaments of prepared PHBV, Screw Extrusion temperature
For 165 DEG C, the temperature of cooling bath is 10 DEG C, and a roller winding speed is 5m/min, and the temperature of one water-bath stretching is 45 DEG C, is drawn
Multiple is stretched for 8 times, the temperature of two road hot-air stretchings is 60 DEG C, and draw ratio is 2 times, and heat setting temperature is 90 DEG C.Gained
A diameter of 0.2mm of PHBV monofilament, fracture strength are 6.5cN/dtex, and elongation at break is 25.7%.
Embodiment 3
(1) 98.7 parts of PHBV (HV contents are 2.5mol%), 1 part of talcum powder and 0.3 part of β-(bis- tertiary fourth of 3,5- is weighed first
Base -4- hydroxy phenyls) the positive 18 carbonic acid alcohol ester of propionic acid respectively in vacuum drying oven be dried 12 hours (80 DEG C), 12 hours (80 DEG C)
With 48 hours (40 DEG C), then they are put into dry-mixed 3 minutes in super mixer, then be blended in twin-screw blender and make
Grain, obtains PHBV master batches.Prilling temperature is 170 DEG C, and screw speed is 75rmp, and the melt blending time is 8 minutes.
(2) spinning on melt spinning machine by PHBV master batches, Jing melting extrusions water-bath cool down one water-bath and draw
Stretch two road hot-airs stretching thermal finalizations to oil winding, the high-strength coarse denier monofilaments of prepared PHBV, Screw Extrusion temperature
For 150 DEG C, the temperature of cooling bath is 10 DEG C, and a roller winding speed is 5m/min, and the temperature of one water-bath stretching is 30 DEG C, is drawn
Multiple is stretched for 8 times, the temperature of two road hot-air stretchings is 60 DEG C, and draw ratio is 2 times, and heat setting temperature is 80 DEG C.Gained
A diameter of 0.15mm of PHBV monofilament, fracture strength are 6.2cN/dtex, and elongation at break is 29%.
Embodiment 4
(1) 98 parts of PHBV (HV contents are 2.5mol%), 1.5 parts of boron nitride and 0.5 part of triethylene-glycol is weighed first
Double-β-(3- tertiary butyl -4- hydroxy-5-methyl base phenyl) propionic ester is dried 12 hours (80 DEG C), 12 little respectively in vacuum drying oven
When (80 DEG C) and 48 hours (50 DEG C), then they are put into dry-mixed 3 minutes in super mixer, then in twin-screw blender
Middle blending granulation, obtains PHBV master batches.Prilling temperature is 170 DEG C, and screw speed is 75rmp, and the melt blending time is 8 minutes.
(2) spinning on melt spinning machine by PHBV master batches, Jing melting extrusions water-bath cool down one water-bath and draw
Stretch two road hot-airs stretching thermal finalizations to oil winding, the high-strength coarse denier monofilaments of prepared PHBV, Screw Extrusion temperature
For 170 DEG C, the temperature of cooling bath is 10 DEG C, and a roller winding speed is 5m/min, and the temperature of one water-bath stretching is 30 DEG C, is drawn
Multiple is stretched for 10 times, the temperature of two road hot-air stretchings is 60 DEG C, and draw ratio is 2 times, and heat setting temperature is 100 DEG C.Gained
A diameter of 0.1mm of PHBV monofilament, fracture strength are 9.5cN/dtex, and elongation at break is 18.5%.
Claims (2)
1. a kind of high-strength thick denier poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerates) (PHBV) monofilament, by the original of following mass parts
Material is made：
PHBV：97～100 parts；
Inorganic nucleator：0～5 part；
Antioxidant：0～2 part；
The wherein viscosity average molecular weigh of PHBV is：1.0×105～1.0 × 106；
In PHBV, the content of 3- hydroxyl valerates (HV) construction unit is：0～20mol%, when HV contents are 0, PHBV is poly-
(3-hydroxybutyrate ester) (PHB)；
Inorganic nucleator is clay, CNT, boron nitride, talcum powder, terbium oxide, lanthana, hydroxyapatite (HA), phosphoric acid
One kind in calcium and sesquialter cage type siloxanes (POSS)；
Antioxidant is three (2,4- di-tert-butyls) phosphite ester, 2,6 di tert butyl 4 methyl phenol, four [β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, β-
The positive 18 carbonic acid alcohol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, thiobis (3 methy 6 tert butyl phenol), 4,4-
Butylidene-bis(3-methyl-6-t-butyl phenol), 2,2 '-methylene bis (4- methyl-6-tert-butylphenols), tri- (uncles 4- of 1,3,5-
Butyl -3-2,6- dimethyl benzyls) double [1,1- dimethyl -2- of -1,3,5- triazine -2,4,6- (1H, 3H, 5H)-triketone, 3,9-
[(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyl] -2,4,8,10- four oxaspiros [5,5] hendecanes, 4,
It is 4 '-methylene-bis(2,6-di-t-butyl phenol), 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid, thio
Double-(3,5- di-tert-butyl -4- hydroxy benzenes benzyls), N, N '-bis--[3- (3,5- di-tert-butyl-hydroxy phenyls) benzoyl group] oneself two
One or two in double-β-(3- tertiary butyl -4- hydroxy-5-methyl base phenyl) propionic ester of amine, triethylene-glycol.
2. the preparation method of high-strength thick denier PHBV according to claim 1, comprises the steps：
(1) PHBV, inorganic nucleator and antioxidant be dried in vacuum drying oven in advance 8～48h, baking temperature is 50～
105℃；
(2) take during 0～2 part of 93～100 parts of PHBV, 0～5 part of inorganic nucleator and antioxidant put into super mixer and do
Mixed 3～5 minutes, the then blending granulation in twin-screw blender obtains PHBV master batches, and prilling temperature is 130～200 DEG C, rotating speed
For 50～150rmp, the melt blending time is 3～8 minutes；
(3) spinning on melt spinning machine by PHBV master batches, Jing melting extrusions water-bath cool down one water-bath and draw
Stretch two road hot-airs stretching thermal finalizations to oil winding, the high-strength coarse denier monofilaments of prepared PHBV, Screw Extrusion temperature
For 130～200 DEG C, the temperature of cooling bath is 0～25 DEG C, and a roller winding speed is 1～25m/min, one water-bath stretching
Temperature is 20～80 DEG C, and draw ratio is 2～15 times, and the temperature of two road hot-airs stretchings is 20～80 DEG C, draw ratio is 1～
10 times, heat setting temperature is 60～120 DEG C.
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| CN201610842357.3A CN106521688A (en) | 2016-09-22 | 2016-09-22 | High strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) filament and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109825892A (en) * | 2018-12-24 | 2019-05-31 | 江苏杜为新材料科技有限公司 | A kind of poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerate) monofilament of hollow high-strength large-diameter and preparation method thereof |
| CN112962151A (en) * | 2021-02-02 | 2021-06-15 | 广东永锐实业有限公司 | Degradable silk and preparation method thereof |
| CN117802595A (en) * | 2024-02-29 | 2024-04-02 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate monofilament and continuous preparation method thereof |
| WO2024104374A1 (en) * | 2022-11-18 | 2024-05-23 | 北京微构工场生物技术有限公司 | Degradable filament, preparation method therefor, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825892A (en) * | 2018-12-24 | 2019-05-31 | 江苏杜为新材料科技有限公司 | A kind of poly- (3-hydroxybutyrate ester-co-3- hydroxyl valerate) monofilament of hollow high-strength large-diameter and preparation method thereof |
| CN109825892B (en) * | 2018-12-24 | 2021-11-30 | 江苏杜为新材料科技有限公司 | Hollow high-strength large-diameter poly (3-hydroxybutyrate-co-3-hydroxyvalerate) monofilament and preparation method thereof |
| CN112962151A (en) * | 2021-02-02 | 2021-06-15 | 广东永锐实业有限公司 | Degradable silk and preparation method thereof |
| WO2024104374A1 (en) * | 2022-11-18 | 2024-05-23 | 北京微构工场生物技术有限公司 | Degradable filament, preparation method therefor, and use thereof |
| CN117802595A (en) * | 2024-02-29 | 2024-04-02 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate monofilament and continuous preparation method thereof |
| CN117802595B (en) * | 2024-02-29 | 2024-05-28 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate monofilament and continuous preparation method thereof |
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Application publication date: 20170322 |