CN105111423A - Polymer waterborne polyester and preparation method thereof - Google Patents
Polymer waterborne polyester and preparation method thereof Download PDFInfo
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- CN105111423A CN105111423A CN201510589134.6A CN201510589134A CN105111423A CN 105111423 A CN105111423 A CN 105111423A CN 201510589134 A CN201510589134 A CN 201510589134A CN 105111423 A CN105111423 A CN 105111423A
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- waterborne polyester
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Abstract
The invention discloses polymer waterborne polyester. The polymer waterborne polyester is prepared in the mode that terephthalic acid (PTA), isophthalic acid (IPA), ethylene glycol (BG), diethylene glycol, ternary monomers, a catalyst and other auxiliaries serve as raw materials, and the raw materials and mother liquid are subjected to esterification and condensation polymerization for synthesis. A preparation method of the polymer waterborne polyester includes the steps that firstly, terephthalic acid (PTA), isophthalic acid (IPA), ethylene glycol (BG), diethylene glycol and ternary monomers are made into paste and evenly fed into an esterification kettle through a metering pump, the catalyst is added for an esterification reaction, the auxiliaries are added to monomers generated by the esterification reaction, the mixture is filtered and guided into a condensation polymerization kettle for a condensation polymerization reaction, when a certain process value is reached, the mixture is extruded out through nitrogen, and the transparent polyester product is prepared after cooling, grain-sized dicing, drying and screening. The polymer waterborne polyester replaces traditional acrylic and vinyl acetate products, and urea resin and cyanamide resin which are not environmentally friendly, has a series of advantages of being excellent in adhesive force, high in molecular weight, good in environment friendliness and the like, and can serve as a textile hardening agent to be widely used.
Description
Technical field
The present invention relates to polyester art, especially relate to a kind of polymer waterborne polyester and preparation method thereof being mainly used in cosmetics of everyday use especially textile materials stiffening agent.
Background technology
Stiffening finish is the one of fabric post-treatment, it is by padding stiffening agent, make to produce cohesive action under certain condition between the fiber in fabric yarn, stiffening agent is between fibrous inside, fiber or the surface of fiber forms film or generation is crosslinked, thus it is stiffening to make fabric produce, abundant, plentiful feel.It is widely used in the Final finishing process of furnishing fabric, especially the stiffening finish of Curtains Fabrics, suitcase cloth, WARP-KNITTING and lining cloth.
What existing stiffening agent was conventional has polyacrylic ester, polyvinylacetate, urea-formaldehyde resin or melamine resin, these classification stiffening agent quality existing are unstable, there is the defects such as molecular weight is low, chemical resistance is poor, stiffening effect is really up to the mark, production technique not environmentally, especially urea-formaldehyde resin and melamine resin produce the severe contamination caused environment, affect the life of people.
Summary of the invention
In order to solve above-mentioned prior art problem, the invention provides and a kind ofly replace traditional esters of acrylic acid, vinyl acetate between to for plastic esters product and urea-formaldehyde resin not environmentally and melamine resin, there is series of advantages polymer waterborne polyester being used as stiffening agent such as excellent clinging power, molecular weight are high, good environmental protection and preparation method thereof.
Technical scheme of the present invention is: a kind of polymer waterborne polyester, it is characterized in that, described polymer waterborne polyester synthesizes obtained as raw material with mother liquor by 40-50% pure terephthalic acid (PTA), 1-2% m-phthalic acid (IPA), 20-25% ethylene glycol, 10-13% glycol ether, 8-12% tri-monomer, 0.1-0.5% catalyzer and other auxiliary agent of 0.1-8% by weight percentage through over-churning, polycondensation.
The transparent shape of described polymer waterborne resin.
Described mother liquor is ethylene glycol terephthalate, and the liquid ensure esterification under having mother liquor to exist after is transparent liquid, and obtained polyester finished product is transparent color.
Described three monomers are 5-sodium sulfo isophthalate, and the ion characteristic that 5-sodium sulfo isophthalate shows due to its sodium group as properties-correcting agent imparts the water-soluble of vibrin.
Described catalyzer adopts antimonous oxide, antimony glycol or Titanium series catalyst.
Other auxiliary agent described comprises and is not limited to stablizer, defoamer, dewatering agent etc.
Polymer waterborne preparation process of polyester of the present invention, comprises the following steps:
Step S1: making beating: first in proportion ethylene glycol is delivered to elevated dosing vessel by transferpump and enter in making beating still, under the state stirred, again pure terephthalic acid (PTA), m-phthalic acid (IPA), three monomers, glycol ether are dropped in making beating still respectively by volume pump in proportion, stir 1 ~ 2 hour, make slurry;
Step S2: esterification: slurry uniformly continous is sent in the esterifying kettle of mother liquor existence by above-mentioned slurry slurry supply pump, and stirring after adding quantitative catalyzer, is carry out esterification at the temperature of 180 DEG C ~ 220 DEG C at esterification temperature; Add quantitative auxiliary agent after esterification terminates, after mixing, again material is imported polycondensation vessel;
Step S3: polycondensation: the material entering polycondensation vessel, under high vacuum environment, after heating 240 DEG C-280 DEG C reaction certain hours, molecular chain increases the molecular weight reaching regulation, completes main reaction process, stops heating, stops vacuum, by material N in polycondensation vessel
2extrude;
Step S4: discharging, screening, packaging: at N
2under effect, extruded by polyester fondant, through underwater pelletizer pelletizing, after dry screening, wind delivers to blending bun, then metering packing.
Described mother liquor is ethylene glycol terephthalate, accounts for the 40%-60% of slurry gross weight, can enhance esterification under having mother liquor to exist, and ensures that the liquid after esterification is transparent liquid, and obtained polyester finished product is transparent color.
Described high vacuum environment pressure is 600-1000Pa.
The molecular weight of described regulation is 8000-12000, and cross high molecular and complete water-soluble rate can be caused lower, cannot reach water-soluble effect, too low molecular weight causes serous coat brute force on the low side, affects the clinging power of resin, surface tension, chemical resistance.
The EG that in the inventive method, esterification and polycondensation generate can be drawn out of as raw materials recovery recycling, thus reduces the expenditure of raw materials cost.
Preparation method's process of the present invention is auxiliary to be controlled with computer (DCS or PLC computer) real-time parameter, and poly-molecular weight of product controls to become relatively easy eventually, and in actual production, operability is stronger, and final product quality just has guaranteed.
Beneficial effect of the present invention is:
1, the polyester fondant that polymer waterborne polyester of the present invention obtains has excellent clinging power, drying performance, impregnability, and water absorbability, surface tension are moderate, the series of advantages such as molecular weight is high, good environmental protection; And color is transparent, is suitable as stiffening agent and is added on textile coating, the original color of textiles can not be affected;
2, preparation method of the present invention adopts copolymerization mode, the modified monomer of more than three kinds and terephthalic acid, m-phthalic acid, ethylene glycol, glycol ether, three monomers are pressed rational formula by accurate control and participate in multi-component copolymer chemical reaction, the indices of finished product slurry all can rationally be embodied, whole building-up reactions divides esterification and polycondensation two step to complete, assist and control with computer real-time parameter, it is more strictly clear that whole accumulation controls, finished product molecular weight is more easy to control between 8000-12000, obtained waterborne polyester steady quality;
3, the whole reaction of preparation method of the present invention divides esterification and polycondensation two to complete, Simplified flowsheet, energy-saving and cost-reducing, and the EG generated in esterification and polycondensation can be used as raw materials recovery and recycles, saving cost; Two-step approach is compared with traditional preparation facilities, and production technique, variety variations are more flexible, invest less, risk is lower, the every physical index of finished product all can reach weaving stiffening agent requirements;
4, realize zero release environmental protection in preparation method's production process of the present invention, this is also that traditional mode of production stiffening agent is incomparable.
Accompanying drawing explanation
Fig. 1 is preparation method's schematic flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further elaborated.
A kind of polymer waterborne polyester, its by 50% pure terephthalic acid (PTA), 1.8% m-phthalic acid (IPA), 24% ethylene glycol (EG), 12.5% glycol ether, 10% 3 monomer, 0.3% catalyzer and 1.4% other auxiliary agent by weight percentage synthesize obtained as raw material through over-churning, polycondensation with mother liquor, wherein auxiliary agent adopts conventional on the market stablizer, defoamer, dewatering agent etc.
As shown in Figure 1, its concrete preparation method is as follows:
Step S1: making beating
By weight ratio be 24% EG deliver to EG elevated dosing vessel by transferpump, enter in making beating still again, under whipped state, PTA, IPA, three monomers, glycol ether are dropped in making beating still respectively by volume pump equably, stir 1 ~ 2 hour, make slurry, then with slurry supply pump, slurry uniformly continous is sent into esterifying kettle and carried out esterification;
Step S2: esterification
Slurry enters in esterifying kettle and mixes with the mother liquor accounting for slurry gross weight 50%, add 0.3% catalyzer, catalyzer adopts antimonous oxide, having under mother liquor and ethylene glycol terephthalate existent condition, ensure that certain temperature carries out esterification under " articulation point " (described articulation point and pulp solution keep transparency), esterification temperature is 200 DEG C ± 5 DEG C, 1 hour reaction times; The water that esterification generates is separated through esterification tower and discharges reactive system, adds and accounts for slurry gross weight other auxiliary agent than 1.4%, again material is imported polycondensation vessel after mixing after esterification terminates;
Step S3: polycondensation
Enter the material of polycondensation vessel, vacuumize at heated condition, Heating temperature is 260 DEG C ± 5 DEG C, and vacuum pressure is 800-1000Pa, react after 1.5 hours, molecular chain growth reaches 8000-12000, then complete main reaction process, stop heating, stop vacuum, by material N in polycondensation vessel
2extrude;
Step S4: discharging screening, packaging
After polycondensation completes, at N
2under effect, extruded by polyester fondant, through underwater pelletizer pelletizing, after dry screening, wind delivers to blending bun, then metering packing.
The polymer waterborne polyester property test result that preparation method of the present invention obtains is as following table:
As seen from the above table, polymer waterborne polyester of the present invention has excellent clinging power, and transparency is high, good stability, water absorbability is moderate, can solve moisture absorption sticky phenomenon again, do stiffening agent for yarn fabric, soft during fabric is hard, and almost odorlessness, be the weaving stiffening agent of the environmental protection of a excellence.
This preparation method mainly adopts heating agent hydronics heat supply, heating agent adopts thermal oil, send into process furnace by oil pump to be heated to certain temperature and to send into main process system again and respectively need heating equipment, whole heat medium system adopts closed cycle heat-supplying mode, and safety is without revealing.
The EG that preparation method's main reaction system of the present invention and esterifying kettle and polycondensation vessel reaction generate or excessive EG by reclaim distillation system purify after as raw material again reuse; Thick EG is sent in rectifying still and heats, utilize principles of rectification to obtain high purity EG from rectifying tower under vacuum conditions.First carry out rectifying at vacuum state, the boiling point of EG can be reduced, fall low-energy consumption, thus reduce product cost.
The present invention is used as the water-soluble copolyester molecular weight requirement of weaving stiffening agent lower than general fibre, polyester for bottle, and enzymatic synthesis condition is relatively gentle, but owing to introducing poly modified monomer, intermediate product is comparatively complicated; Polymer waterborne polyester finished product of the present invention is that the production technique by improving modified PET polyester obtains.In the esterification stage, according to the difference of function in each properties-correcting agent self-characteristic and system, the accurate feeding mode of stepwise site timing is taked to feed intake; Polycondensation is due to the participation of three monomer modified doses, its viscosity becomes more much bigger than conventional polyester, be condensed to a certain degree to stir and become very difficult, the higher molecular weight finished product designed be obtained, special adjustment must be made to condensation temperature, pressure-controlling, through repeatedly facts have proved, polymer waterborne preparation process of polyester of the present invention, auxiliary with the control of computer real-time parameter, poly-molecular weight of product controls to become relatively easy eventually, in actual production, operability is stronger, and final product quality is more guaranteed more stable.Preparation method's two-step approach of the present invention is compared with conventional apparatus, and production technique, variety variations are more flexible, has that investment is less, risk is lower simultaneously, and the every physical index of finished product all can reach weaving stiffening agent requirements.
The above; be only preferred embodiment of the present invention; not in order to limit the present invention, every above embodiment is done according to technical spirit of the present invention any trickle amendment, equivalently replace and improve, all should be included in the protection domain of technical solution of the present invention.
Claims (10)
1. a polymer waterborne polyester, it is characterized in that, described polymer waterborne polyester synthesizes obtained as raw material with mother liquor by 40-50% pure terephthalic acid (PTA), 1-2% m-phthalic acid (IPA), 20-25% ethylene glycol, 10-13% glycol ether, 8-12% tri-monomer, 0.1-0.5% catalyzer and other auxiliary agent of 0.1-8% by weight percentage through over-churning, polycondensation.
2. polymer waterborne polyester according to claim 1, is characterized in that, the transparent shape of described polymer waterborne resin.
3. polymer waterborne polyester according to claim 1, is characterized in that, described mother liquor is ethylene glycol terephthalate.
4. polymer waterborne polyester according to claim 1, is characterized in that, described three monomers are 5-sodium sulfo isophthalate.
5. polymer waterborne polyester according to claim 1, is characterized in that, described catalyzer adopts antimonous oxide, antimony glycol or Titanium series catalyst.
6. polymer waterborne polyester according to claim 1, is characterized in that, other auxiliary agent described comprises and is not limited to stablizer, defoamer, dewatering agent.
7. a preparation method for polymer waterborne polyester as claimed in claim 1, is characterized in that, comprise the following steps:
Step S1: making beating: first in proportion ethylene glycol is delivered to elevated dosing vessel by transferpump and enter in making beating still, under the state stirred, again pure terephthalic acid (PTA), m-phthalic acid (IPA), three monomers, glycol ether are dropped in making beating still respectively by volume pump in proportion, stir 1 ~ 2 hour, make slurry;
Step S2: esterification: slurry uniformly continous is sent in the esterifying kettle of mother liquor existence by above-mentioned slurry slurry supply pump, and stirring after adding quantitative catalyzer, is carry out esterification at the temperature of 180 DEG C ~ 220 DEG C at esterification temperature; Add quantitative auxiliary agent after esterification terminates, after mixing, again material is imported polycondensation vessel;
Step S3: polycondensation: the material entering polycondensation vessel, under high vacuum environment, after heating 240 DEG C-280 DEG C reaction certain hours, molecular chain increases the molecular weight reaching regulation, completes main reaction process, stops heating, stops vacuum, by material N in polycondensation vessel
2extrude;
Step S4: discharging, screening, packaging: at N
2under effect, extruded by polyester fondant, through underwater pelletizer pelletizing, after dry screening, wind delivers to blending bun, then metering packing.
8. the preparation method of polymer waterborne polyester according to claim 7, is characterized in that, described mother liquor is ethylene glycol terephthalate, accounts for the 40%-60% of slurry gross weight.
9. the preparation method of polymer waterborne polyester according to claim 7, is characterized in that, described high vacuum environment pressure is 600-1000Pa.
10. the preparation method of polymer waterborne polyester according to claim 7, is characterized in that, the molecular weight of described regulation is 8000-12000.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN106046337A (en) * | 2016-08-12 | 2016-10-26 | 彭春海 | Fabric conditioning agent 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 |
| 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 |
| WO2021229111A1 (en) | 2020-05-12 | 2021-11-18 | Laboratorios Farmacéuticos Rovi, S.A. | Method for purifying biodegradable thermoplastic polymer particles for medical and/or pharmaceutical use |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN106046337A (en) * | 2016-08-12 | 2016-10-26 | 彭春海 | Fabric conditioning agent and preparation method thereof |
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| 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 |
| WO2021229111A1 (en) | 2020-05-12 | 2021-11-18 | Laboratorios Farmacéuticos Rovi, S.A. | 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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| CN105111423B (en) | 2017-07-14 |
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Effective date of registration: 20240607 Address after: Building 2, 4th Floor, No. 206 Mahai Road, Mashan Street, Yuecheng District, Shaoxing City, Zhejiang Province, 312086 Patentee after: Jinyu Zhehai (Shaoxing) New Materials Co.,Ltd. Country or region after: China Address before: 511300 Guangzhou, Zengcheng, Guangdong Guangzhou city Zengcheng Zengcheng Shi Tan Zhen Gang Village intersection 1 self compiled Patentee before: Guangzhou Honghao Textile Auxiliaries Co.,Ltd. Country or region before: China |