CN106480535B - A kind of method that melt spinning prepares polyformaldehyde fibre - Google Patents
A kind of method that melt spinning prepares polyformaldehyde fibre Download PDFInfo
- Publication number
- CN106480535B CN106480535B CN201610930007.2A CN201610930007A CN106480535B CN 106480535 B CN106480535 B CN 106480535B CN 201610930007 A CN201610930007 A CN 201610930007A CN 106480535 B CN106480535 B CN 106480535B
- Authority
- CN
- China
- Prior art keywords
- pom
- pbs
- polyformaldehyde
- spinning
- fibre
- Prior art date
- 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.)
- Active
Links
Classifications
-
- 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
- D01F6/94—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 other polycondensation products
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- 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
Abstract
The invention discloses a kind of preparation methods of polyformaldehyde (POM) fiber, its key step: succinic acid butanediol (PBS) kind polyester is mixed in a high speed mixer with POM, mixed raw material is carried out to two step method melt spinning on melt spinning machine, obtains modified POM fiber after hot gas spring, thermal finalization, the present invention uses low melting point, PBS kind polyester and POM co-blended spinning with hydroxyl, ester group, the crystallinity and crystallizing power of POM are reduced, the mechanical property of POM fiber is improved；Present invention process is simple, is not necessarily to special installation, industrialization easy to accomplish.
Description
Technical field
The present invention relates to a kind of methods that technical field of polyformaldehyde more particularly to melt spinning prepare polyformaldehyde fibre.
Background technique
Polyformaldehyde (POM) is a kind of engineering plastics of excellent combination property, such as excellent rigidity, intensity, creep recovery
Energy, alkaline-resisting, solvent resistance etc., by the fiber that POM resin stretches preparation through excessively high draw ratio have good tensile strength and
Elasticity modulus can give full play to the potentiality of polyformaldehyde structural material, especially alkali resistance, and therefore, POM fiber enhances in concrete
The fields such as material, meshed filter material and rope are with a wide range of applications.
The crystallization rate of POM resin is fast, and thermal stability is poor, and when direct melt spinning, fibrinogen is easily broken off, and polyformaldehyde is fine
The production efficiency of dimension is low, industrialized production by must limit, meanwhile, drawing of fiber multiple is too low, and fibre strength is not high, fiber system
The market application of product is severely limited.
The prior art, which is concentrated mainly on, changes three chemical structure, control processing technology and addition modifying agent aspects.As led to
It crosses polymerization and controls second, third content of monomer, change the molecular structure of POM, reduce crystallization rate, to improve the product of fiber
Spinnability improves the intensity of fiber.Such as WO-2008001924, CN1715464A patent is by adjusting oxyalkylene ratio, control
The flexible chain of POM is greater than 30s, prepares fiber by melt spinning；In terms of controlling processing technology, as CN1555430A,
The patents such as CN102011201A, CN101792938A carry out heating slow cooling after leaving spinneret to as-spun fibre, while using and adding
The drawing process or water-bath for pressing steam stretch, and prepare high-intensitive fiber.Addition modifying agent mainly includes addition in-lubricant
The intensity that POM crystallinity improves POM fiber is reduced with addition crystallization inhibitor.As CN104499087A selects cellulose acetate class
Polymer and POM, which are blended, is used as spinning material, then controls spinning technique, prepares the POM fiber of high-strength and high-modulus.
CN105386151A is mixed in the preparation of POM fiber, by POM with in-lubricant, improves the mobility of POM, improves spinnability,
Prepare high-intensitive POM fiber.
But the above method still has some problems, such as exploitation for spinning-grade POM raw material, mainly from molecule knot
Structure angle is set out, and technical requirements are high, and cost of material is higher；Multistage slow cooling-quenching process the high requirements on the equipment of technique is controlled, is needed
Existing equipment or investment new equipment is transformed.It is limited to the crystalline modified effect of POM to add modifying agent, still needs to pressurize using clearance-type
The defect of POM fiber surface micropore is eliminated in thermal finalization, different from conventional melt spinning, heat-setting equipment is needed to have centainly
Pressure maintaining ability.Adding in-lubricant is mostly low molecular weight substance, and volume is small, limited to the mechanical property castering action of POM fiber.
Summary of the invention
In order to solve the above technical problems, The present invention provides a kind of meltings of PBS kind polyester modified polyacetal fiber to spin
Silk method.Preparation method wide adaptability provided by the invention, can improve the mobility of polyformaldehyde matrix, reduce the crystallization of polyformaldehyde
Degree, improves the mechanical property of polyformaldehyde fibre.
The present invention provides a kind of methods that melt spinning prepares polyformaldehyde fibre, specifically comprise the following steps:
(1) preparation of POM/PBS blend composition: PBS kind polyester, polyformaldehyde (POM) resin are mixed in a high speed mixer,
POM/PBS blend composition is obtained, is then cooled to room temperature；
(2) melt spinning: by POM/PBS blend composition spinning in melt spinning machine made from step (1), through Screw Extrusion
Machine, fondant filter, spinning manifold and component, are prepared as-spun fibre；
(3) preparation of polyformaldehyde fibre: by as-spun fibre made from step (2) after second level hot gas spring, thermal finalization
To the polyformaldehyde fibre of high-strength and high-modulus；
PBS kind polyester described in step (1) mixes in acetal resin high-speed mixer, mixing temperature be 80 DEG C-
120 DEG C, mixing time 2-5min；
The spinning temperature of POM/PBS blend composition described in step (2) is 200 DEG C -230 DEG C, the winding speed of as-spun fibre
Degree is 200-1000m/min；
Second level hot gas spring condition described in step (3): first order hot gas spring temperature is 90-120 DEG C, second level hot gas spring temperature
Degree is 140-160 DEG C；The heat set conditions: heat setting temperature is 140-145 DEG C, heat-setting time 5-10min.
PBS (succinic acid butanediol) kind polyester is poly butylene succinate (PBS), poly-succinic-terephthaldehyde
The mixture of any one or two kinds in acid-butanediol ester (PBST), poly-succinic-adipic acid-butanediol ester (PBSA).
Preferably, the melt index of the acetal resin is 5-12g/10min, and weight average molecular weight is 10-30 ten thousand, to poly-
It closes for object, melt index is closely related with molecular weight, when melt index is too low, the molecular weight height of POM, mobility when processing
Difference is unable to melt spinning, when melt index is too high, indicates that the molecular weight of POM is low, the fibrous mechanical property of preparation is lower, answers
It is little with value.
The quality of the PBS kind polyester is the 5%-40% of acetal resin quality, and PBS is the crystallinity and stream of polyformaldehyde
The modifying agent of dynamic property, when PBS kind polyester additional amount is low, small to the modifying function of polyformaldehyde, effect is unobvious；Additional amount is excessively high
When, PBS kind polyester cannot be uniformly dispersed in polyformaldehyde matrix, generate stress concentration point, and fracture of wire, lousiness are generated when spinning.
Feature of the present invention and its utility model has the advantages that (1) present invention by acetal resin be added PBS kind polyester, not only
The crystallization that can inhibit acetal resin reduces the crystallinity of polyformaldehyde, and can improve the mobility of acetal resin, mentions
The spinnability and drawability of high polyformaldehyde, prepare the polyformaldehyde fibre of high-strength and high-modulus；(2) preparation process of the invention letter
It is single, traditional meltspun equipment can be directly utilized, without being transformed to existing equipment, is easy to industrialize, have very strong practical
Property.
Specific embodiment
Next in conjunction with the embodiments, technical scheme of the present invention will be described in further detail, but the present invention never office
Limit and this, any equivalent change or modification in accordance with the spirit of the invention, should all cover protection scope of the present invention it
It is interior.
Raw material used in the embodiment of the present invention is marketable material, and all degrees are weight percent
Than.
Tensile strength of the present invention and the test method of elasticity modulus refer to national standard (GB/T19975-2005).
Polyformaldehyde used in the present invention (POM) resin, Yuntianhua Group Co., Ltd
Poly butylene succinate (PBS) resin, Dongguan City Ren Ju Biotechnology Co., Ltd, TH804
Poly-succinic-terephthalic acid (TPA)-butanediol ester (PBST) resin, Jiangsu and Shi Li new material Co., Ltd
Poly-succinic-adipic acid-butanediol ester (PBSA) resin, Japanese Showa, 3A40
Embodiment 1
The preparation of raw material: being warming up to 120 DEG C for high-speed mixer, weighs the polyformaldehyde (POM) of 1000g, the polybutadiene of 50g
Acid-hexanedioic acid-butanediol ester (PBSA) raw material is put into mixing machine, and unlatching is stirred 2min releasing, is cooled to room temperature, is obtained
Spinning material, the melt index of acetal resin are 12g/10min, and molecular weight Mw is 283758.
Fiber preparation: the spinning in melt spinning machine by spinning material, through screw extruder, fondant filter, manifold
Body and component, winding obtain as-spun fibre, and spinning temperature is 220 DEG C, and as-spun fibre rolling speed is 200m/min, then will be come into being
Silk carries out thermal finalization 8min after carrying out second level hot gas spring at 120 DEG C, 150 DEG C respectively under the conditions of 140 DEG C, obtains being modified poly- first
Aldehyde fiber.
Embodiment 2
The preparation of raw material: being warming up to 100 DEG C for high-speed mixer, weighs the polyformaldehyde (POM) of 1000g, the poly- fourth of 150g
Diacid-terephthalic acid (TPA)-butanediol ester (PBST) raw material is put into mixing machine, and unlatching is stirred 4min releasing, is cooled to room
Temperature obtains spinning material, and the melt index of acetal resin is 9g/10min, and molecular weight Mw is 203586.
Fiber preparation: the spinning in melt spinning machine by spinning material, through screw extruder, fondant filter, manifold
Body and component, winding obtain as-spun fibre, and spinning temperature is 200 DEG C, and as-spun fibre rolling speed is 800m/min, then will be come into being
Silk carries out thermal finalization 5min after carrying out second level hot gas spring at 100 DEG C, 140 DEG C respectively under the conditions of 145 DEG C, obtains being modified poly- first
Aldehyde fiber.
Embodiment 3
The preparation of raw material: being warming up to 80 DEG C for high-speed mixer, weighs the polyformaldehyde (POM) of 1000g, the polybutadiene of 400g
Sour butanediol ester (PBS) raw material is put into mixing machine, and unlatching is stirred 2min releasing, is cooled to room temperature, is obtained spinning material.
The melt index of acetal resin is 5g/10min, and molecular weight Mw is 135062.
Fiber preparation: the spinning in melt spinning machine by spinning material, through screw extruder, fondant filter, manifold
Body and component, winding obtain as-spun fibre, and spinning temperature is 200 DEG C, and as-spun fibre rolling speed is 600m/min, then will be come into being
Silk carries out thermal finalization 10min after carrying out second level hot gas spring at 90 DEG C, 140 DEG C respectively under the conditions of 142 DEG C, obtains being modified poly- first
Aldehyde fiber.
Embodiment 4
The preparation of raw material: being warming up to 90 DEG C for high-speed mixer, weighs the polyformaldehyde (POM) of 1000g, the polybutadiene of 100g
Acid-adipic acid-butanediol ester (PBST) raw material is put into mixing machine, and unlatching is stirred 5min releasing, is cooled to room temperature, is obtained
Spinning material.The melt index of acetal resin is 5g/10min, and molecular weight Mw is 135062.
Fiber preparation: the spinning in melt spinning machine by spinning material, through screw extruder, fondant filter, manifold
Body and component, winding obtain spun filament, and spinning temperature is 210 DEG C, and as-spun fibre rolling speed is 1000m/min, then will be come into being
Fiber carries out thermal finalization 5min after carrying out second level hot gas spring at 110 DEG C, 150 DEG C respectively under the conditions of 145 DEG C, obtains modified poly-
Formaldehyde fibers.
Embodiment 5
The preparation of raw material: being warming up to 100 DEG C for high-speed mixer, weighs the polyformaldehyde (POM) of 1000g, the poly- fourth of 100g
Succinate adipate (PBS), 100g poly-succinic-adipic acid-butanediol ester (PBST) raw material are put into mixing machine, open stirring
It mixes 3min to release, is cooled to room temperature, obtains spinning material.The melt index of acetal resin is 9g/10min, molecular weight Mw
It is 203586.
Fiber preparation: the spinning in melt spinning machine by spinning material, through screw extruder, fondant filter, manifold
Body and component, winding obtain as-spun fibre, and spinning temperature is 200 DEG C, and as-spun fibre rolling speed is 1000m/min, then will be first
Raw silk carries out thermal finalization 10min after carrying out second level hot-stretch at 120 DEG C, 160 DEG C respectively under the conditions of 140 DEG C, is modified
Polyformaldehyde fibre.
Embodiment 6
The preparation of raw material: being warming up to 100 DEG C for high-speed mixer, weighs polyformaldehyde (POM), the 50g polybutadiene of 1000g
Acid-adipic acid-butanediol ester (PBST), 150g poly-succinic-terephthalic acid (TPA)-butanediol ester (PBSA) raw material be put into mixing
In machine, unlatching is stirred 3min releasing, is cooled to room temperature, obtains spinning material.The melt index of acetal resin is 9g/
10min, molecular weight Mw are 203586.
Fiber preparation: the spinning in melt spinning machine by spinning material, through screw extruder, fondant filter, manifold
Body and component, winding obtain spun filament, and spinning temperature is 210 DEG C, and as-spun fibre rolling speed is 500m/min, then by nascent fibre
Dimension carries out thermal finalization 10min after carrying out second level hot gas spring at 110 DEG C, 155 DEG C respectively under the conditions of 140 DEG C, obtains modified poly-
Formaldehyde fibers.
Comparative example
Polyformaldehyde raw material spinning in melt spinning machine of PBS kind polyester will not be added, through screw extruder, melt filtration
Device, spinning manifold and component, winding obtain spun filament, and spinning temperature is 200 DEG C, and as-spun fibre rolling speed is 500m/min,
Thermal finalization 10min is carried out under the conditions of 140 DEG C after as-spun fibre is carried out second level hot gas spring respectively at 120 DEG C, 150 DEG C again,
Obtain modified polyacetal fiber.
The mechanical property of the modified polyacetal fiber made from testing example and comparative example, as shown in table 1.
The method of the present invention in acetal resin by being added PBS kind polyester it can be seen from data in table 1, to mention
The spinnability and drawability of high polyformaldehyde, prepare the polyformaldehyde fibre of high-strength and high-modulus, fine with the polyformaldehyde of comparative example preparation
Dimension is compared, and tensile strength obviously increases with elasticity modulus.
Claims (4)
1. a kind of method that melt spinning prepares polyformaldehyde fibre, which is characterized in that specifically comprise the following steps:
(1) preparation of POM/PBS blend composition: PBS kind polyester, polyformaldehyde (POM) resin are mixed in a high speed mixer, obtained
POM/PBS blend composition, then cools to room temperature；
(2) melt spinning: by POM/PBS blend composition spinning in melt spinning machine made from step (1), through screw extruder,
Fondant filter, spinning manifold and component, are prepared as-spun fibre；
(3) as-spun fibre made from step (2) preparation of polyformaldehyde fibre: is obtained into height after second level hot gas spring, thermal finalization
The polyformaldehyde fibre of strong Gao Mo；
PBS kind polyester described in step (1) mixes in acetal resin high-speed mixer, and mixing temperature is 80 DEG C -120 DEG C,
Mixing time is 2-5min；
The spinning temperature of POM/PBS blend composition described in step (2) is 200 DEG C -230 DEG C, and the rolling speed of as-spun fibre is
200-1000m/min；
Second level hot gas spring condition described in step (3): first order hot gas spring temperature is 90-120 DEG C, and second level hot gas spring temperature is
140-160℃；The heat set conditions: heat setting temperature is 140-145 DEG C, heat-setting time 5-10min.
2. the method that a kind of melt spinning according to claim 1 prepares polyformaldehyde fibre, which is characterized in that the PBS
Kind polyester be poly butylene succinate (PBS), poly-succinic-terephthalic acid (TPA)-butanediol ester (PBST), poly-succinic-oneself
The mixture of any one or two kinds in diacid-butanediol ester (PBSA).
3. the method that a kind of melt spinning according to claim 2 prepares polyformaldehyde fibre, which is characterized in that the poly- first
The melt index of urea formaldehyde is 5-12g/10min, and weight average molecular weight is 10-30 ten thousand.
4. the method that a kind of melt spinning according to claim 3 prepares polyformaldehyde fibre, which is characterized in that the PBS
The quality of kind polyester is the 5%-40% of acetal resin quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610930007.2A CN106480535B (en) | 2016-10-31 | 2016-10-31 | A kind of method that melt spinning prepares polyformaldehyde fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610930007.2A CN106480535B (en) | 2016-10-31 | 2016-10-31 | A kind of method that melt spinning prepares polyformaldehyde fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106480535A CN106480535A (en) | 2017-03-08 |
| CN106480535B true CN106480535B (en) | 2019-01-15 |
Family
ID=58271572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610930007.2A Active CN106480535B (en) | 2016-10-31 | 2016-10-31 | A kind of method that melt spinning prepares polyformaldehyde fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106480535B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586373A (en) * | 2017-10-18 | 2018-01-16 | 江苏苏博特新材料股份有限公司 | A kind of crystal property adjustable spinning polyoxymethylene resin and its spinning process |
| CN109913960B (en) * | 2019-03-14 | 2020-05-22 | 唐山开滦化工科技有限公司 | Preparation method of low-orientation high-stretch polyformaldehyde nascent fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412242C (en) * | 2006-11-16 | 2008-08-20 | 东华大学 | Prepn process of paraphthalic acid-butanediol succinate copolymer fiber |
| US8785526B2 (en) * | 2010-12-16 | 2014-07-22 | Ticona Llc | Polyoxymethylene fibers in concrete |
| CN105401254B (en) * | 2015-10-27 | 2017-07-11 | 唐山开滦化工科技有限公司 | A kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method |
| CN105386151A (en) * | 2015-12-17 | 2016-03-09 | 云南云天化股份有限公司 | Polyformaldehyde fiber preparation method |
-
2016
- 2016-10-31 CN CN201610930007.2A patent/CN106480535B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106480535A (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103290497B (en) | A kind of industry functional form 66 nylon fiber and preparation method thereof | |
| CN101768791B (en) | Polyacrylonitrile-based hollow carbon fiber precursor preparation method | |
| CN102493016B (en) | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof | |
| CN103741258B (en) | A kind of hydrophilic polyester fibers and preparation method thereof | |
| CN103774272B (en) | A kind of ultra-thin light-weight fabric ultraviolet resistant nylon 6 fiber and preparation method thereof | |
| CN105908283B (en) | A kind of semi-dull POY polyster fibre and its processing method | |
| CN105544000B (en) | High-temperature oxidation resistant composite Nano PPS/Ti SiOx chopped fibers and preparation method thereof | |
| CN104499087B (en) | The preparation method of a kind of polyoxymethylene fiber | |
| CN109537088B (en) | Method for manufacturing different-shrinkage polyester low-stretch yarns | |
| CN102251308A (en) | Method for preparing colored light-extinction polyester filament | |
| CN105401254B (en) | A kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method | |
| CN105926060A (en) | Melt direct spinning superfine denier polyester filament and making method thereof | |
| CN111206300A (en) | Elastic composite fiber and preparation method thereof | |
| CN106480535B (en) | A kind of method that melt spinning prepares polyformaldehyde fibre | |
| CN110257947A (en) | A kind of antibacterial polyester industrial yarn and preparation method thereof | |
| CN112941657A (en) | Spinning forming method of poly (p-phenylene-benzobisoxazole) fibers | |
| CN109161973A (en) | The production technology of acid fiber by polylactic | |
| CN106521704B (en) | A kind of preparation method of polyketone-polyformaldehyde composite fibre | |
| CN101381905A (en) | Method for producing low shrink corn modified polylactic acid fibre | |
| CN108048946A (en) | A kind of hydrophilic fire-retardant polyester fibre material and preparation method thereof | |
| CN101824666B (en) | Production method of polyster fiber | |
| CN114703561B (en) | Preparation method of high-strength high-toughness bionic fiber | |
| CN103628172B (en) | A kind of preparation method of ternary copolyimide fiber | |
| CN107586373A (en) | A kind of crystal property adjustable spinning polyoxymethylene resin and its spinning process | |
| CN103060939B (en) | Preparation method of cellulose acetate fiber through polybasic carboxylic acid crosslinking |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |