CN106478932A - A kind of hydrolysis high-speed spinning spun-bonded non-woven polyester and its synthetic method - Google Patents
A kind of hydrolysis high-speed spinning spun-bonded non-woven polyester and its synthetic method Download PDFInfo
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- CN106478932A CN106478932A CN201510524799.9A CN201510524799A CN106478932A CN 106478932 A CN106478932 A CN 106478932A CN 201510524799 A CN201510524799 A CN 201510524799A CN 106478932 A CN106478932 A CN 106478932A
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Abstract
The invention discloses a kind of hydrolysis high-speed spinning spun-bonded non-woven polyester and its synthetic method.Which adopts PTA to be esterified with EG low temperature, using Ti-Sb composite catalyst, add hydrolysis monomer, aid in the inorganic additive of spunbond high speed super drawing, add UV resistant agent inherent viscosity is obtained for 0.68-0.72dl/g after precondensation and whole polycondensation reaction, content of carboxyl end group is 28-34mmol/t, DEG content is less than 0.8%, fusing point is more than 260 DEG C, moisture content is less than 0.1%, content of powder is less than 0.01%, and content of ashes is less than 0.01% and suitable spin-drawing speed is the hydrolysis high-speed spinning spun-bonded non-woven polyester of 5000-6000m/min.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of hydrolysis high-speed spinning spun-bonded non-woven polyester
And its synthetic method.
Background technology
Polyester (polyethylene terephthalate, PET) is polymerized by terephthalic acid (TPA) (PTA) and ethylene glycol (EG), and it has
Have excellent machinery, physics and chemical property, good processing characteristics, be widely used as fiber, film, resin and its
The production of his layered product.But as polyester end base is to water vapor sensitive, the particularly hydrolytic resistance under hot humid environment
Difference, is easily hydrolyzed by its remaining terminal carboxylate group catalysis, causes the deterioration of mechanical property and other performances, largely the upper limit
Its application is industrially made.Generally, polyester content of carboxyl end group is higher, and the hydrolysis type of polyester is poorer, and this is
Because containing ester bond in polyester backbone, terminal groups are carboxyl and hydroxyl, cause the anti-hydrolytic performance of polyester poor, particularly because
Self-accelerating reaction is hydrolyzed to for polyester, acid content increase can accelerate hydrolysis.
The hydrolytic resistance of polyester is improved at present to add the end-capping reagent containing functional functional group mostly.Patent CN1312327A
Disclose improves the hydrolytic resistance of polyester using epoxy radicals and amino group macromolecule end-capping reagent, but the preparation process of end-capping reagent
Complexity, the blending reaction activity for adding epoxy functional compounds be not high, needs a large amount of interpolations in course of reaction, causes cost to increase.
Furthermore Bhatt is disclosed by adding by some pre-blended in another thermoplastic in international application WO83/1253
Stable polyester agent can improve the hydrolytic stability of monofilament polyester, it is recommended that stabilizer be carbodiimides.But, it is mixed into
The thermoplastic of stabilizer may be had adverse effect on to the other performance of polyester article.
Spunbonded nonwoven is distributed in late 1950s, by du pont company's industrialized production first, subsequent countries in the world
Begin one's study the development and application technology in succession.Through the development of decades, spun-bonded non-woven is in production technology, product
The aspect such as energy and production efficiency has significant progress and raising.The speed of production of spun-bonded non-woven from initial per point
Tens meters of clock has improved 800 ms/min up till now, and spinning speed highest has reached 6000～8000 ms/min, into the net
Uniformity and product quality are become better and better, and its purposes covers civilian, industry use, agricultural, medical, health and uses and building work
The every field such as journey.One of non-weaving cloth major product object due to spun-bond process production is durability engineering material, for example, gather
Ester fiber non-weaving cloth becomes composite for replacing traditional asbestos bitumen waterproof roll with pitch or polyurethane etc., therefore
The key that the due physical and mechanical properties of polyester fiber is durability is kept under high temperature, many wet environments.Improve the durable of polyester
Property can be set about from the following aspects, first have to guarantee to be highly resistant to ultraviolet by high polymer that (i.e. light aging, polyolefin is most
Difference, best containing naphthalene nucleus), the hydrolytic resistance (the especially high polymer facile hydrolysis of polyesters) of its secondary raising high polymer has again
Seek to improve high polymer heat-resisting creep properties (i.e. stress relaxation, rubber band is exactly most typically example, long-term stretch, elimination
External force, follows the string).
Although spun-bonded non-woven spinning speed height mainly depends on equipment designed capacity itself, for a production line,
Improve spinning speed and yield can not only be improved, more importantly filament strength can be improved, improve sub-wire quality, so as to change significantly
The kind finished product uniformity.Spinning technique is had a certain impact using different polyester slices, and end product quality is also had very big
Impact.Normal polyester is used in high-speed spinning spun-bonded non-woven spinning process, with the raising of spinning speed, polyester is big
Molecule has little time orientation, causes degree of crystallinity to reduce, and fibre strength reduces, and spinning break rate increases, and lousiness accordingly can increase.
Therefore how spinning speed is improved on the same device, the problem for having become spinning user extremely in the urgent need to address.
Content of the invention
In order to polyester facile hydrolysis is solved the problems, such as, and spinning speed is improved on the basis of existing spunbonded equipment, the invention provides
A kind of hydrolysis high-speed spinning spun-bonded non-woven polyester and its synthetic method.The technical solution adopted in the present invention is as follows.
The present invention provides a kind of synthetic method of hydrolysis high-speed spinning spun-bonded non-woven polyester, its with terephthalic acid (TPA) with
Ethylene glycol is raw material, first carries out esterification under the ethylene glycol solution effect of Titanium series catalyst, reacts and be at least to esterification yield
92%；Again in the presence of antimony-based catalyst ethylene glycol solution, hydrolysis monomer, inorganic additive and UV resistant agent, warp
Cross prepolymerization reaction and obtain the prepolymer that inherent viscosity is 0.3～0.5dl/g；Finally whole polycondensation reaction is carried out, obtain polyester and melt
Body, through Cast Strip, cooling and dicing, obtains hydrolysis high-speed spinning spun-bonded non-woven polyester after drying.
In the present invention, the hydrolysis monomer is selected from trimethyl phosphate, triethyl phosphate, phosphonoacetate or double (3,5-
Di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) in calcium salt Irganox1330 any one, its addition is 0.01-0.08%, with
Polyester theoretical weight meter.
In the present invention, the one kind or many of the inorganic additive in nano level barium sulfate, titanium dioxide or silica
Kind, its addition is 0.25-0.45%, in terms of polyester theoretical weight.
In the present invention, the UV resistant agent is selected from 2- (2H- BTA -2- base) -4,6- bis- (1- methyl isophthalic acid-phenylethyl) phenol
(UV-234), 2- (- 2 base of 4,6- diphenyl -1,3,5- triazine) -5- [(hexyl) epoxide]-phenol (UV-1577) or double benzoxazoles
One or more in talan, its addition are 0.01-0.08%, in terms of polyester theoretical weight.
In the present invention, the mol ratio of the terephthalic acid (TPA) and ethylene glycol is 1：1.05-1：2.5；Preferably, terephthaldehyde
Acid is 1 with ethylene glycol mol ratio:1.05-1:1.8.The Titanium series catalyst is selected from titanium ethylene glycolate, butyl titanate or metatitanic acid four
One or more in isopropyl ester, the Titanium series catalyst ethylene glycol solution concentration are 0.01-0.1wt%, in Titanium series catalyst
Titanium atom content is 0.00005-0.0005%, in terms of polyester theoretical weight；The antimony-based catalyst is selected from antimony glycol, three oxygen
Change at least one of two antimony or antimony acetate, the antimony atoms content of antimony-based catalyst is 0.01～0.03%, with polyester theoretical weight
Calculate；Antimony-based catalyst ethylene glycol solution concentration is 2～8wt%.
In the present invention, during esterification, temperature is 220-280 DEG C, and gauge pressure is 0.05-0.15MPa, time of staying 2-3 hour；
During prepolymerization reaction, absolute pressure is 2000～5000Pa, and temperature is 260～290 DEG C, time of staying 0.5-1.5 hour；
During whole polycondensation reaction, absolute pressure is 10～2000Pa, and temperature is 270～300 DEG C, time of staying 2-3 hour；Preferably,
Esterification reaction temperature is 230～265 DEG C, gauge pressure is 0.08～0.12MPa；During the prepolymerization reaction, absolute pressure is
2000～5000Pa, temperature are 265～285 DEG C；During whole polycondensation reaction, absolute pressure be 10～2000Pa, temperature be 275～
288℃.
The present invention furthermore provides the spunbond special polyester of hydrolysis high-speed spinning that above-mentioned preparation method obtains, and its inherent viscosity is
0.68-0.72dl/g, content of carboxyl end group are 18-24mmol/t, and DEG content is less than 0.8%, and fusing point is more than 260 DEG C, moisture content
Less than 0.1%, ash content is less than 0.01% and suitable spin-drawing speed is spunbond for the hydrolysis high-speed spinning of 5000-6000m/min
Non-weaving cloth polyester.
Compared with prior art, the beneficial effects of the present invention is：
(1) present invention adopts antimony titanium complex catalyst, on the one hand improves polymerization rate, it is ensured that hydrolysis is special poly-
Ester section is more environmentally-friendly, and in polyester fondant, metal impurities are less, effectively improve the viscosity of polyester slice；
(2) present invention participates in polymerization process by adding special hydrolysis agent and UV resistant agent, effectively can drop
The content of carboxyl end group of oligoester section, it is ensured that polyester product has hydrolytic resistance and anti-ultraviolet radiation and ageing resistance；
(3) present invention passes through to improve polyester fondant inherent viscosity and molecular weight, and passes through elite inorganic additive, Ke Yifu
The degree of crystallinity improved in fiber formation process is helped, increases fiber strength, so as to improve spinning speed and stretching ratio.
Specific embodiment
Technical scheme is described further below according to specific embodiment.Protection scope of the present invention be not limited to
Lower embodiment, enumerates these examples and limits the present invention merely for exemplary purpose never in any form.
Performance test methods
The performances such as inherent viscosity, fusing point, end carboxyl form and aspect, DEG residual content, fine according to GB GB/T 14190-2008
Dimension grade polyester chip (PET) measurement of test method.
The test (BB%) of hydrolytic resistance：The hydrolysis system for handling that a certain amount of copolyester pellets are placed in sealing is taken, 155
DEG C, process 6h under the water vapor conditions of 0.46MPa, then will determine its inherent viscosity after the sample drying after process, compare
The change of the change of polyester slice viscosity, i.e. BB% after before processing,
BB%=0.27 × ([IV1]-4/3-[IV0]-4/3)
In equation, IV0Represent the intrinsic viscosity of polyester before hydrolysis process, IV1Represent the intrinsic viscosity of polyester after hydrolysis process.
Raw material in following examples, are such as not particularly illustrated, and are commercially available.
Embodiment 1-8：
By terephthalic acid (TPA), ethylene glycol, the slurry mixing tanks being added to stirring in proportion, Titanium series catalyst (ethylene glycol
Titanium) enter modulator zone after, add ethylene glycol and catalyst concn be diluted to 0.04wt%, after modulating, be delivered to slurry preparation
Tank, participates in slurry modulation, and is quantitatively continuously introduced into Horizontal band with gear pump after slurry supply tank is measured stirring esterification
Kettle, at gauge pressure 0.08-0.12MPa, temperature 230-265 DEG C, stirring is esterified, and generates intermediate terephthalic acid (TPA) double
Hydroxyl ethyl ester, reacts to esterification yield and is at least 92%, and the water that esterification process is generated is steamed with ethylene glycol, is fractionated into after tower separates water,
In the ethylene glycol backflow kettle of 99wt%, esterification time of staying 2-3 hour.Bishydroxyethyl terephthalate passes through intermediate
Pipeline enters prepolymerization reaction kettle.
Hydrolysis agent, UV resistant agent and inorganic additive add the additive for having added virgin ethylene glycol according to a certain percentage
Modulation tank, and hydrolysis agent is modulated into 5wt% ethylene glycol solution.Middle fluid line is delivered to after modulating, and above-mentioned
Intermediate mixes；From glycol antimony catalyst enter modulator zone after, add ethylene glycol, antimony glycol be modulated into 4wt%
Ethylene glycol solution, is delivered to middle fluid line after modulating, after mixing with above-mentioned intermediate, pumped with gear
Enter up flow type precondensation kettle, prepolymerization reaction 0.5-1 is carried out at temperature 265-285 DEG C, 2000～5000pa of absolute pressure
Hour, obtain precondensation product.
Prepolymer is delivered to the whole batch condensation polymerization reactor of Horizontal band squirrel-cage stirring by pressure reduction, 10～2000Pa of absolute pressure,
It is stirred continuously at temperature 275-288 DEG C, the poly- 2-3 hour of final minification is carried out, to reach reaction end, final polyester fondant tooth
Wheel pump is continuously discharged, cooling and dicing after fondant filter.
The content control of catalyst, hydrolysis agent, UV resistant agent and inorganic additive that each embodiment is used and polyester are produced
The primary quality measure of product is shown in Table 1, table 2 and table 3 respectively, and the consumption of all additives all obtains polyester based on polycondensation reaction
Theoretical yield meter.
Claims (9)
1. a kind of synthetic method of hydrolysis high-speed spinning spun-bonded non-woven polyester, it is characterised in that：Its with terephthalic acid (TPA) with
Ethylene glycol is raw material, first carries out esterification under the ethylene glycol solution effect of Titanium series catalyst, reacts and be at least to esterification yield
92%；Again in the presence of antimony-based catalyst ethylene glycol solution, hydrolysis monomer, inorganic additive and UV resistant agent, warp
Cross prepolymerization reaction and obtain the prepolymer that inherent viscosity is 0.3～0.5dl/g；Finally whole polycondensation reaction is carried out, obtain polyester and melt
Body, through Cast Strip, cooling and dicing, obtains hydrolysis high-speed spinning spun-bonded non-woven polyester after drying.
2. synthetic method according to claim 1, it is characterised in that：The hydrolysis monomer is selected from trimethyl phosphate, phosphorus
Triethylenetetraminehexaacetic acid ester, phosphonoacetate or double (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) calcium salt Irganox1330
In any one, its addition be 0.01-0.08%, in terms of polyester theoretical weight.
3. synthetic method according to claim 1, it is characterised in that：The inorganic additive selected from nano level barium sulfate,
One or more in titanium dioxide or silica, its addition are 0.25-0.45%, in terms of polyester theoretical weight.
4. synthetic method according to claim 1, it is characterised in that：The UV resistant agent is selected from 2- (2H- BTA -2-
Base) -4,6- two (1- methyl isophthalic acid-phenylethyl) phenol (UV-234), 2- (- 2 base of 4,6- diphenyl -1,3,5- triazine) -5- [(hexyl) epoxide] -
One or more in phenol (UV-1577) or double benzoxazoles talan, its addition are 0.01-0.08%, with poly-
Ester theoretical weight meter.
5. synthetic method according to claim 1, it is characterised in that：The mol ratio of the terephthalic acid (TPA) and ethylene glycol is 1：
1.05-1：2.5；One or more in titanium ethylene glycolate, butyl titanate or tetraisopropyl titanate of the Titanium series catalyst,
Titanium atom content in Titanium series catalyst is 0.00005-0.0005%, in terms of polyester theoretical weight；The antimony-based catalyst is selected from
Antimony glycol, at least one of antimony oxide or antimony acetate, the antimony atoms content of antimony-based catalyst is 0.01～0.03%,
Calculated with polyester theoretical weight.
6. synthetic method according to claim 1, it is characterised in that：During esterification, temperature is 220-280 DEG C, gauge pressure
For 0.05-0.15MPa；During prepolymerization reaction, absolute pressure is 2000～5000Pa, and temperature is 260～290 DEG C；Final minification gathers
During reaction, absolute pressure is 10～2000Pa, and temperature is 270～300 DEG C.
7. synthetic method according to claim 1 or 5, it is characterised in that：The terephthalic acid (TPA) with ethylene glycol mol ratio is
1:1.05-1:1.8.
8. the synthetic method according to claim 1 or 6, it is characterised in that：Esterification reaction temperature is 230～260 DEG C, table
Press as 0.08～0.12MPa；During the prepolymerization reaction, absolute pressure is 2000～5000Pa, and temperature is 265～285 DEG C；
During whole polycondensation reaction, absolute pressure is 10～2000Pa, and temperature is 275～288 DEG C.
9. the spunbond special polyester of synthetic method according to claim 1 is obtained hydrolysis high-speed spinning, it is characterised in which is special
Property viscosity be 0.68-0.72dl/g, content of carboxyl end group be 18-24mmol/t, DEG content be less than 0.8%, fusing point be more than 260
DEG C, moisture content is less than 0.1%, and ash content is less than 0.01% and suitable spin-drawing speed is the hydrolysis of 5000-6000m/min
High-speed spinning spun-bonded non-woven polyester.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111423566A (en) * | 2019-12-31 | 2020-07-17 | 浙江东太新材料有限公司 | Preparation method of titanium-based polyester composite material |
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| CN111423566A (en) * | 2019-12-31 | 2020-07-17 | 浙江东太新材料有限公司 | Preparation method of titanium-based polyester composite material |
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Application publication date: 20170308 |