CN105111423B - A kind of polymer waterborne polyester and preparation method thereof - Google Patents
A kind of polymer waterborne polyester and preparation method thereof Download PDFInfo
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- CN105111423B CN105111423B CN201510589134.6A CN201510589134A CN105111423B CN 105111423 B CN105111423 B CN 105111423B CN 201510589134 A CN201510589134 A CN 201510589134A CN 105111423 B CN105111423 B CN 105111423B
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- waterborne polyester
- polymer waterborne
- phthalic acid
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Abstract
The invention discloses a kind of polymer waterborne polyester, it as raw material and synthesizes obtained by terephthalic acid (TPA) (PTA), M-phthalic acid (IPA), ethylene glycol (BG), diethylene glycol (DEG), three monomers, catalyst and other auxiliary agents with mother liquor through over-churning, polycondensation, and its preparation method is：Slurry is made in phthalic acid (PTA), M-phthalic acid (IPA), ethylene glycol (BG), diethylene glycol (DEG), three monomers first, then esterifying kettle is equably sent into using measuring pump and adds catalyst progress esterification, the monomer of esterification generation adds after auxiliary agent and imports polycondensation vessel by filtering, carry out polycondensation reaction, after certain process value is reached, extruded with nitrogen, then through cooling, pelletizing, drying, screening, transparent polyester product is made.Polymer waterborne polyester of the present invention replaces traditional esters of acrylic acid, vinyl acetate esters product and Lauxite and melamine resin not environmentally, with series of advantages such as excellent adhesion strength, molecular weight height, good environmental protections, it can be widely used as textile hard agent.
Description
Technical field
The present invention relates to polyester art, daily chemical product especially textile material stiffening agent is mainly used in more particularly, to one kind
Polymer waterborne polyester and preparation method thereof.
Background technology
Hard finishing is one kind of fabric post-treatment, it by padding stiffening agent, make between the fiber in fabric yarn
Produce cementation under certain condition, stiffening agent is between fibrous inside, fiber or the surface of fiber forms film or produces crosslinking,
So that fabric produces stiffening, abundant, plentiful feel.It is widely used in during the Final finishing of drapery, especially window
Cord, suitcase cloth, the hard finishing of knitted fabric and lining cloth.
What existing stiffening agent was commonly used has polyacrylate, polyvinylacetate, Lauxite or melamine resin, existing
These classification stiffening agent quality are unstable, there is the defects such as molecular weight is low, chemical-resistance is poor, stiffening effect is really up to the mark, produce work
Not environmentally, especially Lauxite and melamine resin production cause the severe contamination to environment to skill, influence the life of people.
The content of the invention
In order to solve above-mentioned prior art problem, replace traditional esters of acrylic acid, acetic acid second the invention provides a kind of
Alkene esters product and Lauxite and melamine resin not environmentally, with excellent adhesion strength, molecular weight be high, good environmental protection
Etc. polymer waterborne polyester that series of advantages is used as stiffening agent and preparation method thereof.
The technical scheme is that：A kind of polymer waterborne polyester, it is characterised in that the polymer waterborne polyester by
40-50% p-phthalic acids (PTA), 1-2% M-phthalic acids (IPA), 20-25% ethylene glycol, 10-13% diethylene glycol (DEG)s, 8-
12% 3 monomer, 0.1-0.5% catalyst and the other auxiliary agents of 0.1-8% by weight percentage as raw material and pass through ester with mother liquor
Change, polycondensation synthesis is made.
The transparent shape of polymer waterborne resin.
The mother liquor is ethylene glycol terephthalate, and it is transparent liquid to ensure the liquid after esterification in the presence of mother liquor
Body, obtained polyester finished product is Transparent color.
Three monomer is 5-sodium sulfo isophthalate, and 5-sodium sulfo isophthalate is as modifying agent due to its sulphur
The ion characteristic that sour sodium gene expression goes out, imparts the water-soluble of polyester resin.
The catalyst uses antimony oxide, antimony glycol or Titanium series catalyst.
Other auxiliary agents include and are not limited to stabilizer, defoamer, dehydrating agent etc..
The polymer waterborne preparation process of polyester of the present invention, comprises the following steps：
Step S1：Mashing：Ethylene glycol is pumped to elevated dosing vessel into being beaten in kettle by conveying in proportion first, stirred
In the state of mixing, then p-phthalic acid (PTA), M-phthalic acid (IPA), three monomers, diethylene glycol (DEG) passed through into measuring pump respectively
In proportion in input mashing kettle, stir 1~2 hour, slurry is made；
Step S2：Esterification：Above-mentioned slurry slurry supply pump sends into slurry uniformly continuous the esterification with the presence of mother liquor
In kettle, stirred after adding quantitative catalyst, esterification is carried out at a temperature of esterification temperature is 180 DEG C~220 DEG C；
Esterification adds quantitative auxiliary agent after terminating, material is imported into polycondensation vessel again after being well mixed；
Step S3：Polycondensation reaction：Into the material of polycondensation vessel, under high vacuum environment, 240 DEG C of -280 DEG C of reactions one of heating
After fixing time, strand, which increases, reaches defined molecular weight, completes main reaction process, stops heating, stops vacuum, by polycondensation vessel
Interior material N2Extrude；
Step S4：Discharging, screening, packaging：In N2Under effect, polyester fondant is extruded, through underwater pelletizer pelletizing, dried
After screening, wind is sent to blending bunker, then metering packing.
The mother liquor is ethylene glycol terephthalate, accounts for the 40%-60% of slurry gross weight, can in the presence of mother liquor
To accelerate esterification, and ensure that the liquid after esterification is transparency liquid, obtained polyester finished product is Transparent color.
The high vacuum environment pressure is 600-1000Pa.
Molecular weight as defined in described is 8000-12000, and crossing HMW can cause complete water-soluble rate relatively low, it is impossible to reach
Water-soluble effect, too low molecular weight causes serous coat strength relatively low, influences the adhesion strength, surface tension, chemical-resistance of resin.
The EG that esterification and polycondensation reaction are generated in the inventive method can be extracted and be recycled as raw materials recovery, from
And reduce the expenditure of cost of material.
Preparation method process auxiliary of the present invention is controlled with computer (DCS or PLC computers) real-time parameter, eventually poly- product point
Son amount control becomes relatively easy, and operability is stronger in actual production, and final product quality just has guaranteed.
Beneficial effects of the present invention are：
1st, the polyester fondant obtained by polymer waterborne polyester of the invention has excellent adhesion strength, drying performance, leaching
Permeability, hygroscopicity, surface tension are moderate, and molecular weight is high, the series of advantages such as good environmental protection；And color is transparent, is suitable as
It is that stiffening agent is added on textile coating, does not interfere with the original color of textile；
2nd, the preparation method is that using copolymerization mode, by more than three kinds of modified monomer be terephthalic acid (TPA),
Phthalic acid, ethylene glycol, diethylene glycol (DEG), three monomers participate in multi-component copolymer by precise control by rational formula and chemically reacted, finished product
The indices of slurry can obtain reasonable embodiment, and whole synthetic reaction is divided to esterification to be completed with the step of polycondensation two, aided in computer
Real-time parameter is controlled, and whole accumulation control is relatively sharp strict, and finished product molecular weight is relatively easy to control between 8000-12000, obtained
Waterborne polyester steady quality；
3rd, entirely reaction be divided to esterification and the completion of polycondensation two to preparation method of the present invention, simplifies technique, energy-saving, is being esterified
It can be recycled with the EG that is generated in polycondensation reaction as raw materials recovery, save cost；Two-step method is raw compared with traditional preparation facilities
Production. art, variety variations are more flexible, and the smaller, risk of investment is relatively low, and finished product items physical index can reach weaving and use stiffening
Agent requirements；
4th, zero-emission environmental protection is realized in preparation method production process of the present invention, this is also traditional mode of production stiffening agent can not
Analogy.
Brief description of the drawings
Fig. 1 is preparation method schematic flow sheet of the present invention.
Embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples.
A kind of polymer waterborne polyester, its by 50% p-phthalic acid (PTA), 1.8% M-phthalic acid (IPA),
24% ethylene glycol (EG), 12.5% diethylene glycol (DEG), 10% 3 monomer, 0.3% catalyst and 1.4% other auxiliary agents percentage by weight are made
Through over-churning, polycondensation synthesize for raw material and with mother liquor and be made, wherein auxiliary agent uses stabilizer conventional on the market, defoamer, taken off
Aqua etc..
As shown in figure 1, its specific preparation method is as follows：
Step S1：Mashing
Weight is pumped to EG elevated dosing vessels by conveying than the EG for 24%, entered back into mashing kettle, in stirring
Under, PTA, IPA, three monomers, diethylene glycol (DEG) are equably put into mashing kettle by measuring pump respectively, stirs 1~2 hour, is made
Slurry, then slurry uniformly continuous is sent into esterifying kettle carry out esterification with slurry supply pump；
Step S2：Esterification
Slurry enters to be mixed in esterifying kettle with accounting for the mother liquor of slurry gross weight 50%, adds 0.3% catalyst, catalyst is adopted
With antimony oxide, under conditions of with the presence of mother liquor being ethylene glycol terephthalate, it is ensured that certain temperature is " clear
Esterification is carried out under point " (articulation point is that pulp solution keeps transparency), esterification temperature is 200 DEG C ± 5 DEG C, during reaction
Between 1 hour；The water of generation is esterified through esterification tower separation discharge reaction system, esterification adds after terminating and accounts for slurry gross weight
Other auxiliary agents than 1.4% are measured, material is imported into polycondensation vessel again after being well mixed；
Step S3：Polycondensation
Into the material of polycondensation vessel, vacuumized in heated condition, heating-up temperature is 260 DEG C ± 5 DEG C, and vacuum pressure is 800-
1000Pa, after reacting 1.5 hours, strand, which increases, reaches 8000-12000, then completes main reaction process, stops heating, stopping
Vacuum, by material N in polycondensation vessel2Extrude；
Step S4：Discharging screening, packaging
After the completion of polycondensation reaction, in N2Under effect, polyester fondant is extruded, through underwater pelletizer pelletizing, dried after screening,
Wind is sent to blending bunker, then metering packing.
Polymer waterborne polyester property test result such as following table made from preparation method of the present invention：
As seen from the above table, polymer waterborne polyester of the invention has excellent adhesion strength, and transparency is high, stability
Good, hygroscopicity is moderate, it is possible to resolve phenomenon is glued in moisture absorption again, and stiffening agent is done for yarn fabric, soft during fabric is hard, and almost without gas
Taste, is a excellent environmentally friendly weaving stiffening agent.
This preparation method mainly uses heating agent loop heating system heat supply, and heating agent uses conduction oil, sent into by oil pump
Heating furnace is heated to uniform temperature and is re-fed into main process system respectively to need heating equipment, and whole heat medium system uses closed cycle heat supply
Mode, safety is without leakage.
Preparation method main reaction system of the present invention is esterifying kettle and the EG of polycondensation vessel reaction generation or the EG of excess by reclaiming
Raw material again reuse is used as after distillation system purification；Thick EG is sent into rectifying still and heated, using principles of rectification in vacuum state
Under obtain high-purity EG from rectifying column.Rectifying is first carried out in vacuum state, EG boiling point can be reduced, the consumption of energy is reduced,
So as to reduce product cost.
Water-soluble copolyester molecular weight requirement of the present invention as weaving curing agent is less than general fibre, polyester for bottle,
Enzymatic synthesis condition is relatively mild, but due to introducing poly modified monomer, intermediate product is complex；The polymer waterborne of the present invention gathers
Ester finished product is obtained by improving the production technology of modified PET polyester.In the esterification stage, according to each modifying agent itself spy
Property and system in function difference, take the accurate feeding mode of stepwise site timing to feed intake；Polycondensation is due to three monomer modified doses
Participate in, its viscosity becomes more much bigger than conventional polyester, polycondensation is stirred to a certain extent becomes very difficult, to be designed compared with
HMW finished product, it is necessary to which special adjustment is made to condensation temperature, Stress control, through repeatedly it was verified that macromolecule of the present invention
Waterborne polyester preparation method, auxiliary is controlled with computer real-time parameter, and poly- molecular weight of product control eventually becomes relatively easy, actual
Operability is stronger in production, and final product quality is more guaranteed more stable.Preparation method two-step method of the present invention is raw compared with conventional apparatus
Production. art, variety variations are more flexible, while having the smaller, risk of investment relatively low, finished product items physical index can reach spinning
Knit and use stiffening agent requirements.
The above, only presently preferred embodiments of the present invention is not intended to limit the invention, every skill according to the present invention
Any trickle amendment, equivalent and improvement that art is substantially made to above example, should be included in technical solution of the present invention
Protection domain in.
Claims (7)
1. a kind of polymer waterborne polyester, it is characterised in that the polymer waterborne polyester is by 50% p-phthalic acid
(PTA), 1.8% M-phthalic acid (IPA), 24% ethylene glycol, 12.5% diethylene glycol (DEG), 10% 3 monomer, 0.3% catalyst and
1.4% other auxiliary agents by weight percentage as raw material and synthesize obtained with mother liquor through over-churning, polycondensation, between three monomer is
Phthalic acid -5- sodium sulfonates, the mother liquor is ethylene glycol terephthalate.
2. polymer waterborne polyester according to claim 1, it is characterised in that the polymer waterborne polyester is transparent
Shape.
3. polymer waterborne polyester according to claim 1, it is characterised in that the catalyst using antimony oxide,
Antimony glycol or Titanium series catalyst.
4. polymer waterborne polyester according to claim 1, it is characterised in that other auxiliary agents include stabilizer, disappeared
Infusion, dehydrating agent.
5. a kind of preparation method of polymer waterborne polyester as claimed in claim 1, it is characterised in that comprise the following steps：
Step S1：Mashing：Ethylene glycol is pumped to elevated dosing vessel into being beaten in kettle by conveying in proportion first, in stirring
Under state, then by p-phthalic acid (PTA), M-phthalic acid (IPA), three monomers, diethylene glycol (DEG) respectively by measuring pump press than
In example input mashing kettle, stir 1~2 hour, slurry is made；
Step S2：Esterification：Above-mentioned slurry slurry supply pump is sent into slurry uniformly continuous in the esterifying kettle with the presence of mother liquor,
Mother liquor is ethylene glycol terephthalate, accounts for the 40%-60% of slurry gross weight, is stirred after adding quantitative catalyst,
Esterification is carried out at a temperature of esterification temperature is 180 DEG C~220 DEG C；Esterification adds quantitative auxiliary agent after terminating, mix
Material is imported into polycondensation vessel again after closing uniformly；
Step S3：Polycondensation reaction：Into the material of polycondensation vessel, under high vacuum environment, 240 DEG C of -280 DEG C of timings of reaction one of heating
Between after, strand, which increases, reaches defined molecular weight, completes main reaction process, stops heating, stops vacuum, by thing in polycondensation vessel
Material uses N2Extrude；
Step S4：Discharging, screening, packaging：In N2Under effect, polyester fondant is extruded, through underwater pelletizer pelletizing, screening is dried
Afterwards, wind is sent to blending bunker, then metering packing；
Above-mentioned preparation process auxiliary is controlled with computer real-time parameter.
6. the preparation method of polymer waterborne polyester according to claim 5, it is characterised in that the high vacuum environment pressure
Power is 600-1000Pa.
7. the preparation method of polymer waterborne polyester according to claim 5, it is characterised in that molecular weight as defined in described
For 8000-12000.
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| CN105111423B true CN105111423B (en) | 2017-07-14 |
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| CN105949448A (en) * | 2016-06-17 | 2016-09-21 | 吴江市恒茂环保科技有限公司 | Process for preparing water-soluble polyester chip through regenerated bottle-grade chips and production system thereof |
| CN106046337B (en) * | 2016-08-12 | 2018-04-20 | 彭春海 | A kind of fabric conditioner and preparation method thereof |
| CN107177984A (en) * | 2017-05-30 | 2017-09-19 | 绍兴市柯桥区钱清通航轻纺辅料厂 | A kind of stiffening resin of environmental protection and preparation method thereof |
| EP4151673A4 (en) | 2020-05-12 | 2024-03-20 | Farm Rovi Lab Sa | Method for purifying biodegradable thermoplastic polymer particles for medical and/or pharmaceutical use |
| CN113279259A (en) * | 2021-06-21 | 2021-08-20 | 福州汇昌纺织有限公司 | Preparation method of 100% regenerated water-soluble polyester stiffening agent for non-woven fabric |
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| JP3775537B2 (en) * | 1997-09-10 | 2006-05-17 | 東洋紡績株式会社 | Copolyester resin, copolyester resin composition and multilayer molded article |
| TW550274B (en) * | 2000-03-24 | 2003-09-01 | Kanebo Ltd | Modified polyester and continuous process for manufacturing the same |
| CN100572417C (en) * | 2005-12-06 | 2009-12-23 | 中国石油天然气股份有限公司 | The preparation method of modified copolyester for non-fiber |
| CN103833994B (en) * | 2012-11-22 | 2016-12-28 | 东丽纤维研究所（中国）有限公司 | A kind of alkali soluble copolymer polyester and its production and use |
| CN104072738A (en) * | 2014-07-16 | 2014-10-01 | 珠海华润包装材料有限公司 | Novel PET (polyethylene terephthalate) chip and preparation method thereof |
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Effective date of registration: 20180717 Address after: 511300 Guangzhou, Zengcheng, Guangdong Guangzhou city Zengcheng Zengcheng Shi Tan Zhen Gang Village intersection 1 self compiled Patentee after: Guangzhou Honghao Textile Auxiliaries Co., Ltd. Address before: 510000 Guangzhou, Guangdong, Xintang, Zengcheng, Xintang Road West 8 new Kang Garden 5A103 new house Patentee before: Peng Chunhai |
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