CN115651230B - PVC (polyvinyl chloride) coated polyester yarn and preparation method thereof - Google Patents
PVC (polyvinyl chloride) coated polyester yarn and preparation method thereof Download PDFInfo
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- CN115651230B CN115651230B CN202211382922.4A CN202211382922A CN115651230B CN 115651230 B CN115651230 B CN 115651230B CN 202211382922 A CN202211382922 A CN 202211382922A CN 115651230 B CN115651230 B CN 115651230B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229920000915 polyvinyl chloride Polymers 0.000 title description 91
- 239000004800 polyvinyl chloride Substances 0.000 title description 91
- 239000004014 plasticizer Substances 0.000 claims abstract description 69
- 125000005908 glyceryl ester group Chemical group 0.000 claims abstract description 67
- 239000011247 coating layer Substances 0.000 claims abstract description 53
- 125000003368 amide group Chemical group 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000002093 peripheral effect Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 54
- 238000004804 winding Methods 0.000 claims description 49
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 46
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000011187 glycerol Nutrition 0.000 claims description 17
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 16
- MROJXXOCABQVEF-UHFFFAOYSA-N Actarit Chemical compound CC(=O)NC1=CC=C(CC(O)=O)C=C1 MROJXXOCABQVEF-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- NJEKDCUDSORUJA-UHFFFAOYSA-N 8-[(2-hydroxybenzoyl)amino]octanoic acid Chemical compound OC(=O)CCCCCCCNC(=O)C1=CC=CC=C1O NJEKDCUDSORUJA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 229920004933 Terylene® Polymers 0.000 abstract description 13
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229960002446 octanoic acid Drugs 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229960005489 paracetamol Drugs 0.000 description 5
- 230000036541 health Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- -1 phthalic acid ester Chemical class 0.000 description 2
- 238000000678 plasma activation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UJAOSPFULOFZRR-UHFFFAOYSA-N (4-acetamidophenyl) acetate Chemical compound CC(=O)NC1=CC=C(OC(C)=O)C=C1 UJAOSPFULOFZRR-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000005473 octanoic acid group Chemical group 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application relates to the technical field of PVC/terylene composite fabrics, in particular to PVC coated terylene filaments and a preparation method thereof. The PVC coated polyester yarn comprises a modified polyester core wire and a PVC coating layer, wherein the PVC coating layer is arranged on the outer peripheral surface of the modified polyester core wire; the modified polyester core wire is formed by modifying the surface of polyester precursor through a glyceryl ester plasticizer, the PVC coating layer is formed by mixing PVC and the glyceryl ester plasticizer, and the glyceryl ester plasticizer contains an amide group. The terylene in the PVC coated terylene yarn and the PVC coating layer have the effect of being difficult to separate.
Description
Technical Field
The application relates to the technical field of PVC/terylene composite fabrics, in particular to PVC coated terylene filaments and a preparation method thereof.
Background
The PVC coated polyester yarn is a polyvinyl chloride flexible composite material taking polyester fabric as a reinforcement body, has higher strength and modulus, good dimensional stability, stronger bearing capacity and excellent fatigue resistance, and is further gradually applied to the fields of construction, automobiles, clothing and agriculture.
However, due to the characteristics of higher crystallinity, lack of polar groups on the surface, poor surface chemical activity and the like of the terylene, when the PVC is coated on the surface of the terylene, a stable and firm interface is not easy to form between the terylene and the PVC, so that the terylene and the PVC are easily separated.
Disclosure of Invention
In order to reduce the possibility of separation of terylene and PVC, the application provides a PVC coated terylene yarn and a preparation method thereof.
In a first aspect, the application provides a PVC coated polyester yarn, which adopts the following technical scheme:
the PVC coated polyester yarn comprises a modified polyester core wire and a PVC coating layer, wherein the PVC coating layer is arranged on the outer peripheral surface of the modified polyester core wire; the modified polyester core wire is formed by modifying the surface of polyester precursor through a glyceryl ester plasticizer, the PVC coating layer is formed by mixing PVC and the glyceryl ester plasticizer, and the glyceryl ester plasticizer contains an amide group.
Because the polyester yarn is surface modified by the glyceryl ester plasticizer, and the PVC coating layer is formed by mixing PVC and the glyceryl ester plasticizer, when the PVC coating layer is coated on the outer peripheral surface of the modified polyester core wire, the glyceryl ester plasticizer can effectively improve the intersolubility and wettability of the polyester yarn and the PVC, so that a quite large Van der Waals force is formed between the modified polyester core wire and the PVC coating layer, the interfacial binding force of the modified polyester core wire and the PVC coating layer is effectively improved, and the modified polyester core wire is promoted to be in close contact with the PVC coating layer.
In addition, phthalic acid plasticizers are generally selected as plasticizers applied to PVC at present, and although the phthalic acid plasticizers can also effectively improve the interfacial binding force between the modified polyester core wire and the PVC coating layer, the phthalic acid ester plasticizers have poor migration resistance, so the phthalic acid ester plasticizers are easy to migrate from the PVC matrix. The migrated phthalate plasticizer can act as secretion disrupters to poison the liver, heart, kidney, lung, testis and other organs of the human body, thereby affecting the health of people.
The glyceryl ester plasticizer has the advantages of small mobility, high temperature resistance and extraction resistance, and has relatively smaller toxicity, so that the glyceryl ester plasticizer can effectively improve the interfacial binding force between the modified polyester core wire and the PVC coating layer and reduce the influence on the health of people.
In addition, the glyceryl ester plasticizer contains amide groups, and the amide groups belong to polar groups and have quite good chemical activity, so that when the PVC coating layer is coated on the outer peripheral surface of the modified polyester core wire, the amide groups can further improve the interface binding force between the modified polyester core wire and the PVC coating layer.
Preferably, the glyceryl ester plasticizer is prepared from the following raw materials in parts by weight: 17-23 parts of glycerin, 90-130 parts of organic acid, 5-10 parts of cyclohexane and 0.3-1.0 part of tetra-n-butyl titanate, wherein the organic acid contains an amide group.
Since the glycerol (1, 2, 3-glycerol) contains three hydroxyl groups, the glycerol can be subjected to esterification reaction with organic acid to obtain the glyceryl ester plasticizer, so that the glyceryl ester plasticizer can be promoted to load the amide groups as much as possible and stably, and the interfacial binding force of the modified polyester core wire and the PVC coating layer is effectively improved.
Preferably, the organic acid is one of a mixture of octanoic acid and benzamide, 4-acetaminophenyl acetic acid, and 8- (2-hydroxybenzoylamino) octanoic acid.
Compared with the 4-acetamidophenylacetic acid which contains an amide group, the amide group in the mixture of the octanoic acid and the benzamide is derived from the benzamide, so that the amide group on the benzamide is difficult to stably load when the glyceryl ester plasticizer is prepared, and the interfacial bonding force between the modified polyester core wire and the PVC coating layer is relatively weak.
Compared with 4-acetamidophenylacetic acid, the 8- (2-hydroxybenzoylamino) caprylic acid contains hydroxyl in addition to amide groups, so that the abundance and the content of polar groups between the modified polyester core wire and the PVC coating layer are effectively increased, and the interfacial binding force of the modified polyester core wire and the PVC coating layer is further improved.
Preferably, the preparation method of the glyceryl ester plasticizer comprises the following steps:
esterification reaction: mixing glycerol, organic acid and cyclohexane, heating, adding tetrabutyl titanate, heating continuously, and reacting at constant temperature until the mixture is complete, thus obtaining the crude glyceryl ester plasticizer;
post-treatment: when the acid value of the crude glyceryl ester plasticizer is too high, firstly adding sodium hydroxide solution, carrying out deacidification reaction, then washing to be neutral, finally drying and centrifuging to remove water and cyclohexane in the glyceryl ester plasticizer, and finally obtaining the glyceryl ester plasticizer.
Since a large amount of water is generated when glycerin and organic acid are subjected to esterification reaction, the tetra-n-butyl titanate is very easy to dissolve in the water, so that the catalysis effect of the tetra-n-butyl titanate is affected. And the tetra-n-butyl titanate is added after the temperature is raised, and then the temperature is raised, so that the influence of water on the tetra-n-butyl titanate can be effectively reduced, and the preparation efficiency of the glyceryl ester plasticizer is indirectly improved.
In a second aspect, the application provides a preparation method of PVC coated polyester yarns, which adopts the following technical scheme: the preparation method of the PVC coated polyester yarn comprises the following steps:
preparing a modified polyester core wire: soaking polyester raw filaments in a glyceryl ester plasticizer-ethanol solution, taking out after full soaking, and heating and drying to obtain modified polyester core yarns;
preparing a PVC coating layer: mixing PVC with glyceryl ester plasticizer, extruding and granulating to obtain PVC master batch, extruding and coating the PVC master batch and modified polyester core wire, and finally cooling and solidifying to obtain PVC coated polyester yarn with PVC coating layer.
The preparation method is simple to operate, convenient to process and convenient for assembly line production.
Preferably, in the preparation of the modified polyester core wire, before the polyester precursor is soaked in the glyceryl ester plasticizer-ethanol solution, the alkali washing operation is performed on the polyester precursor through a sodium hydroxide aqueous solution.
The alkaline washing operation can promote the surface of the polyester yarn to present dot pits, so that the specific surface area of the polyester yarn is effectively increased, the contact area between the polyester yarn and the glyceryl ester plasticizer and the contact area between the polyester yarn and the PVC coating layer are effectively increased, the composite interface is increased, the contact point of polar groups is increased, and the interface binding force between the modified polyester core yarn and the PVC coating layer is further improved.
Preferably, the alkaline washing operation comprises the following steps:
s1, uniformly winding polyester raw filaments to form a polyester raw filament cylinder, and then preheating;
s2, spraying sodium hydroxide aqueous solution onto the polyester yarn cylinder in a spraying mode to perform alkali etching, wherein the polyester yarn cylinder keeps continuously rotating.
Compared with the method that the polyester precursor is directly soaked in the sodium hydroxide aqueous solution, the spray mode can promote alkali etching points on the surface of the polyester precursor to be more uniform and dense, effectively reduce the possibility of large-area holes on the surface of the polyester precursor, indirectly increase the specific surface area of the polyester precursor and further improve the interface binding force of the modified polyester core wire and the PVC coating while reducing the influence of alkali etching on the mechanical property of the polyester precursor.
Preferably, the alkaline washing operation is performed by an alkaline washing machine, the alkaline washing machine comprises an alkaline washing chamber and a winding device arranged in the alkaline washing chamber, a heater and an atomizer are arranged in the alkaline washing chamber, and the atomizer is used for spraying sodium hydroxide aqueous solution in a water mist form;
the winding device comprises a lifting assembly and a traversing winding assembly, wherein the traversing winding assembly is used for winding polyester yarns and forming polyester yarn bobbins, and the lifting assembly is used for conveying the polyester yarn bobbins into or out of the alkaline washing chamber;
the transverse moving winding assembly comprises a transverse moving air cylinder, a winding cage and a driving piece, wherein the winding cage is rotationally connected with a piston rod of the transverse moving air cylinder, the transverse moving air cylinder drives the winding cage to transversely move, and the driving piece drives the winding cage to continuously rotate;
the lifting assembly comprises a first lifting cylinder and a second lifting cylinder, the cylinder body of the transverse moving cylinder is arranged on the piston rod of the first lifting cylinder, and the driving piece is arranged on the piston rod of the second lifting cylinder.
When alkali washing operation is needed to be carried out on polyester yarns, a worker can firstly fix one end of the polyester yarns on one end of the winding cage close to the driving piece, then simultaneously start the driving piece and the traversing cylinder, the driving piece drives the winding cage to rotate and wind the polyester yarns, and the traversing cylinder drives the winding cage to translate, so that the polyester yarns are uniformly and non-overlapped wound on the winding cage, and finally the polyester yarn cylinder is formed. And then the lifting cylinder drives the polyester yarn cylinder to be transferred into the alkaline washing chamber, and then the heater and the sprayer can carry out spray type alkaline washing operation on the polyester yarn.
Preferably, the driving piece comprises a driving motor and a square column fixedly connected to the output end of the driving motor, and the driving motor is fixedly connected to a piston rod of the second lifting cylinder; the side wall of the winding cage is provided with a square groove, and the square column penetrates through the square groove;
the alkaline washing chamber comprises an alkaline washing chamber main body and a cover plate covered on the alkaline washing chamber main body, a first sliding groove and a second sliding groove are formed in the alkaline washing chamber main body, the square column is connected in the first sliding groove in a sliding mode, and a piston rod of the transverse moving cylinder is connected in the second sliding groove in a sliding mode.
When the transverse moving cylinder drives the winding cage to transversely move, the square column is always penetrated in the square groove, so that the driving motor is driven to continuously force the winding cage to rotate. After the polyester raw silk winding is completed, the lifting cylinder can promote the winding cage and the polyester raw silk cylinder to enter the alkaline washing machine, the inner traversing cylinder and the driving motor are still positioned outside the alkaline washing chamber, and the influence of high temperature and alkali liquor on the traversing cylinder and the driving motor is effectively reduced.
Preferably, in the preparation of the modified polyester core yarn, before the polyester precursor yarn is taken out of the glyceryl ester plasticizer-ethanol solution, the glyceryl ester plasticizer-ethanol solution is electrified.
The energizing operation can promote corona and plasma activation phenomena to be formed on the surface of the polyester precursor, so that the surface modification effect of the glyceryl ester plasticizer on the polyester precursor is effectively improved, and the interface binding force of the modified polyester core wire and the PVC coating layer is further improved.
In summary, the application has the following beneficial effects:
1. when the PVC coating layer is coated on the outer peripheral surface of the modified polyester core wire, the glyceryl ester plasticizer can effectively improve the intersolubility and wettability of the polyester precursor and PVC, so that a quite large Van der Waals force is formed between the modified polyester core wire and the PVC coating layer, the interfacial binding force of the modified polyester core wire and the PVC coating layer is effectively improved, and the modified polyester core wire and the PVC coating layer are promoted to be in close contact.
2. The glyceryl ester plasticizer has the advantages of small mobility, high temperature resistance and extraction resistance, and has relatively smaller toxicity, so that the glyceryl ester plasticizer can effectively improve the interfacial binding force between the modified polyester core wire and the PVC coating layer and reduce the influence on the health of people.
3. The glyceryl ester plasticizer contains amide groups, and the amide groups belong to polar groups and have quite good chemical activity, so that when the PVC coating layer is coated on the outer peripheral surface of the modified polyester core wire, the amide groups can further improve the interfacial binding force between the modified polyester core wire and the PVC coating layer.
Drawings
FIG. 1 is a cross-sectional view of a PVC coated polyester yarn;
FIG. 2 is a schematic structural view of an alkaline cleaner;
FIG. 3 is a schematic view of the structure of the winding device;
reference numerals: 1. modified polyester core wire; 2. a PVC coating layer; 3. an alkaline cleaner; 31. an alkaline washing chamber; 32. a winding device; 311. an alkaline washing chamber body; 312. a cover plate; 313. a heater; 314. a sprayer; 315. a first slip groove; 316. a second slip groove; 321. a lifting assembly; 322. traversing the winding assembly; 3141. an atomizing nozzle; 3142. a water pump; 3143. an alkali liquid pool; 3211. a first lifting cylinder; 3212. a second lifting cylinder; 3221. a traversing cylinder; 3222. a winding cage; 3223. a driving member; 32221. a square groove; 32231. a driving motor; 32232. square columns.
Detailed Description
The present application will be described in further detail with reference to the accompanying drawings, examples and comparative examples.
Raw materials
PVC CAS:9002-86-2; polyester yarn brand ZW100; glycerol CAS:56-81-5; cyclohexane CAS:110-82-7; tetra-n-butyl titanate CAS:5593-70-4; octanoic acid CAS:124-07-2; 4-acetaminophenyl acetate CAS:556-08-1;8- (2-hydroxybenzoylamino) octanoic acid CAS:183990-46-7; ethanol CAS:64-17-5; aqueous sodium hydroxide (15 wt%); DOP CAS 117-81-7.
Preparation example 1
A glyceryl ester plasticizer, the method of preparation comprising the steps of:
pre-preparation: 15g of glycerol and 150g of 4-acetaminophen acetic acid are filled into a three-necked flask, then 5g of cyclohexane is added into the three-necked flask as a water carrying agent, a snake-shaped condenser and a water separator are assembled on the three-necked flask, and 2g of cyclohexane is added into the water separator (the adding total amount of the cyclohexane can be optionally selected from 5-10 g);
esterification reaction: continuously stirring glycerol, 4-acetaminophenyl acetic acid and cyclohexane at a stirring speed of 400r/min through magnetic force, gradually heating, adding 0.5g of tetra-n-butyl titanate (the adding amount of the tetra-n-butyl titanate can be optionally selected between 0.3 and 1.0 g) when the temperature is raised to 140 ℃, continuously heating to 180 ℃ for constant temperature reaction, measuring the acid value of a reaction solution in the reaction process, observing the progress of the esterification reaction, and stopping the reaction when no water is generated in a water separator during the reaction to obtain a crude glyceryl ester plasticizer;
post-treatment: when the acid value of the crude glyceryl ester plasticizer is too high, firstly adding sodium hydroxide aqueous solution into the glyceryl ester plasticizer, and then carrying out deacidification reaction at 45 ℃ for 40min; washing the glyceryl ester plasticizer to be neutral by adding saturated saline water, removing cyclohexane and residual water by using a rotary evaporator, adding anhydrous sodium sulfate for drying, and finally centrifuging to obtain the glyceryl ester plasticizer;
in the post-treatment, the acid value change in the plasticizer synthesis process is measured by referring to the standard GB/T1668-2008 determination of acid value and acidity of the plasticizer, wherein the acid value is over-high and the acid value is smaller than 0.06 and is normal; and due to experimental errors, three parallel tests are performed at each measurement, and the average value is taken as the final acid value.
PREPARATION EXAMPLES 2 to 5
The difference from preparation example 1 is that the proportions of glycerin and 4-acetaminophenylacetic acid in the glyceryl ester plasticizer are different, as shown in Table 1.
TABLE 1 proportion Table (g) of the components in preparation examples 1 to 5
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | |
| Glycerol | 15 | 17 | 20 | 23 | 25 |
| 4-Acetaminophen acetic acid | 150 | 130 | 120 | 90 | 70 |
Preparation example 6
The difference from preparation example 3 is that 4-acetamidophenylacetic acid is replaced with a mixture of octanoic acid and benzamide in the same addition amount, and the weight ratio of octanoic acid to benzamide is 1:1.
Preparation example 7
The difference from preparation example 3 is that 4-acetaminophen acetic acid is replaced with octanoic acid of the same addition amount.
Preparation example 8
The difference from preparation example 3 is that 4-acetaminophenylacetic acid is replaced with the same added amount of 8- (2-hydroxybenzoylamino) octanoic acid.
Preparation example 9
The difference from preparation example 3 is that 4-acetamidophenylacetic acid was replaced with DOP in the same addition amount.
Examples
Example 1
Referring to fig. 1, a PVC coated polyester yarn includes a modified polyester core wire 1 and a PVC coating layer 2, the PVC coating layer 2 being coated on an outer circumferential surface of the modified polyester core wire 1.
The preparation method of the PVC coated polyester yarn comprises the following steps:
preparing a modified polyester core wire 1:
s1, uniformly winding polyester raw filaments to form a polyester raw filament cylinder, and then preheating for 2 hours at 60 ℃;
s2, spraying a sodium hydroxide aqueous solution onto the polyester yarn cylinder in a spraying manner, and then carrying out alkaline etching for 2 hours at 80 ℃ while the polyester yarn cylinder keeps continuously rotating;
s3, after alkali corrosion is finished, washing the polyester yarn cylinder through saturated saline, washing and drying, soaking the polyester yarn cylinder in a glyceryl ester plasticizer-ethanol solution for 3 hours, wherein the content of the glyceryl ester plasticizer in the glyceryl ester plasticizer-ethanol solution is 30wt%, preparing example 1 is selected as the glyceryl ester plasticizer, after the polyester yarn cylinder is fully soaked, switching on 220V alternating current for conducting treatment for 20 minutes, and finally taking out and drying at 60 ℃ to obtain the modified polyester core yarn 1.
In this embodiment, the alkaline etching operation of the polyester yarn is performed by the alkaline cleaner 3, and the structure of the alkaline cleaner 3 is specifically as follows:
referring to fig. 2, the alkaline washing machine 3 includes an alkaline washing chamber 31 and a winding device 32 installed outside the alkaline washing chamber 31, wherein the alkaline washing chamber 31 includes an alkaline washing chamber body 311 and a cover plate 312 hinged to the top of the alkaline washing chamber body 311, and the cover plate 312 covers and seals the alkaline washing chamber body 311.
The heater 313 is installed to the bottom of alkaline washing chamber main part 311, and eight atomizer 314 are installed to the inner wall circumference of alkaline washing chamber main part 311 evenly spaced. In this embodiment, the heater 313 is a commercially available conventional resistance wire heater 313, the sprayer 314 includes an atomizing nozzle 3141, a water pump 3142, and a lye tank 3143, the liquid inlet of the atomizing nozzle 3141 is communicated with the lye tank 3143, the water pump 3142 transfers the sodium hydroxide aqueous solution in the lye tank 3143 to the atomizing nozzle 3141, and the atomizing nozzle 3141 sprays the sodium hydroxide aqueous solution in the form of water mist.
Referring to fig. 2 and 3, the winding device 32 includes a lifting assembly 321 and a traversing winding assembly 322, wherein the traversing winding assembly 322 is used for winding the polyester yarn and forming a polyester yarn cylinder, and the lifting assembly 321 is used for feeding the polyester yarn cylinder into or out of the alkaline washing chamber main body 311.
The traversing winding assembly 322 comprises a traversing cylinder 3221, a winding cage 3222 and a driving piece 3223, wherein the driving piece 3223 comprises a driving motor 32231 and a square column 32232 fixedly connected to the output end of the driving motor 32231, a square groove 32221 is formed in one end of the winding cage 3222, the square column 32232 is always arranged in the square groove 32221 in a penetrating mode, and one end, far away from the driving motor 32231, of the winding cage 3222 is connected with a piston rod of the traversing cylinder 3221 in a rotating mode.
The lifting assembly 321 comprises a first lifting cylinder 3211 and a second lifting cylinder 3212, wherein a cylinder body of the traversing cylinder 3221 is fixedly connected to a piston rod of the first lifting cylinder 3211, and the driving motor 32231 is fixedly connected to a piston rod of the second lifting cylinder 3212.
The sidewall of the alkaline washing chamber body 311 is provided with a first sliding groove 315 and a second sliding groove 316. Square column 32232 is slidably connected to first sliding groove 315, and the piston rod of sideslip cylinder 3221 is slidably connected to second sliding groove 316. In the present embodiment, the first sliding groove 315 and the second sliding groove 316 are filled with sealing elastic rubber strips, so as to seal the alkaline washing chamber 31.
When alkali washing operation is required to be carried out on the polyester yarn, a worker can fix one end of the polyester yarn on one end of the winding cage 3222 close to the transverse moving cylinder 3221, then simultaneously start the driving motor 32231 and the transverse moving cylinder 3221, and then the polyester yarn can be uniformly and non-overlapped wound on the winding cage 3222, and finally the polyester yarn cylinder is formed. Then, the lifting cylinder can transfer the polyester yarn cylinder into the alkaline washing chamber main body 311, and after the cover plate 312 is covered, the heater 313 and the sprayer 314 can be sequentially started, so that the atomization alkaline washing operation is realized.
In addition, the fixed connection can be realized by adopting a conventional fixed connection mode such as welding fixation, bolt fixation and the like according to actual selection, and the rotary connection can be realized by adopting a conventional rotary connection mode such as pin shaft fixation, bearing connection and the like according to actual selection.
PVC coating layer 2 preparation:
PVC master batch preparation: PVC and glyceryl ester plasticizer-preparation example 1 are mixed according to the mass ratio of 5:1, then heated and extruded by a double screw extruder, and finally cooled and granulated to obtain PVC master batch;
twin screw extrusion granulation parameters: the rotation speed of the screw of the main machine is 200rpm, the rotation speed of the screw of the feeder is 25rpm, the temperature of the I area is 150 ℃, the temperature of the II area is 70 ℃, the temperature of the III area is 170 ℃, the temperature of the IV area is 170 ℃, the temperature of the V area is 170 ℃, the temperature of the VI area is 170 ℃, the temperature of the VII area is 170 ℃, the temperature of the VIII area is 170 ℃, and the temperature of the IX area is 170 ℃. And cooling the extruded product by a water tank, and directly granulating.
And extruding and coating the PVC master batch and the modified polyester core wire 1 by a single screw extruder, and finally cooling and solidifying the PVC master batch and the modified polyester core wire by a water tank to obtain the PVC coated polyester yarn with the PVC coating layer 2.
Single screw extrusion coating parameters: the screw speed was 90rpm, the winding speed was 1500rpm, the zone I temperature was 140 ℃, the zone II temperature was I50 ℃, and the zone III temperature was 150 ℃. Examples 2 to 8
Except that preparation example 1 was replaced with preparation examples 2 to 8 having the same addition amount as that of example 1.
Example 9
The difference from example 8 is that in the modified polyester core wire preparation-S2, the polyester yarn cylinder is directly immersed in an aqueous sodium hydroxide solution for 2 hours, thereby completing the alkali etching operation.
Example 10
The difference from example 8 is that in the modified polyester core wire preparation-S3, after the polyester yarn cylinder is fully impregnated, the polyester yarn is directly taken out and dried at 60 ℃ to obtain the modified polyester core wire.
Comparative example
Comparative example 1
The difference from example 1 is that the modified polyester core yarn is replaced with polyester yarn, and the PVC coating is formed by extrusion molding of PVC only.
Comparative example 2
Except that preparation example 1 was replaced with preparation example 9 having the same addition amount as that of example 1.
Performance test
Detection method
1. Peel strength test
5 samples were taken from examples 1-10 and comparative examples 1-2, respectively, and the samples were then tested for peel strength using a Songton WDW-10 universal material testing machine and averaged according to FZ/T01010-2012 determination of peel strength of coated fabrics.
The test temperature was (21.+ -. 2) DEG C, the relative humidity was (65.+ -. 5)%, the clamping gauge was 30mm, and the rate was 100mm/min.
Detection result: the results of the tests of examples 1-10 and comparative examples 1-2 are shown in Table 2.
TABLE 2 Peel Strength test results Table for examples 1-10 and comparative examples 1-2
As can be seen from the combination of comparative examples 1 to 2 and table 2, the peel strength of comparative example 2 is significantly increased relative to comparative example 1, thereby demonstrating that the interfacial bonding force between the polyester core wire and the PVC coating 2 can be significantly enhanced by modifying the polyester yarn with a plasticizer and blending with PVC.
The reason is that the polyester yarn is modified on the surface by the plasticizer, and the PVC coating layer 2 is formed by mixing PVC and the plasticizer, so when the PVC coating layer 2 is coated on the outer peripheral surface of the modified polyester core wire 1, the plasticizer can effectively improve the intersolubility and wettability of the polyester yarn and the PVC, so that a quite large Van der Waals force is formed between the modified polyester core wire 1 and the PVC coating layer 2, the interfacial bonding force between the modified polyester core wire 1 and the PVC coating layer 2 is effectively improved, and the modified polyester core wire 1 is promoted to be in close contact with the PVC coating layer 2.
It can be seen from the combination of comparative example 2 and example 1 and the combination of table 2 that the peel strength of example 1 is further improved relative to comparative example 2. Therefore, compared with DOP used as a plasticizer, the glyceryl ester plasticizer prepared by using 4-acetamidophenylacetic acid can further improve the interfacial binding force between the modified polyester core wire 1 and the PVC coating layer 2.
The reason is that the glyceryl ester plasticizer prepared from the 4-acetamidophenylacetic acid contains amide groups, the amide groups belong to polar groups, the glyceryl ester plasticizer has quite good chemical activity, and the amide groups can further improve the interfacial binding force between the modified polyester core wire 1 and the PVC cladding layer 2. Compared with DOP, the glyceryl ester plasticizer has weak toxicity and strong extraction resistance, and effectively reduces the influence of the plasticizer on the health of people.
It can be seen from the combination of examples 1 to 5 and Table 2 that the peel strength between the modified polyester core yarn 1 and the PVC cladding layer 2 was gradually improved as the amount of the added glycerin was increased, but when the amount of the added glycerin reached 20g and the amount of the added 4-acetaminophen acetic acid reached 120g, the peel strength between the modified polyester core yarn 1 and the PVC cladding layer 2 was rather reduced if the amount of the added glycerin was further increased and the amount of the added 4-acetaminophen acetic acid was further decreased.
The reason for this is probably that when the amount of glycerol added reaches 20g and the amount of 4-acetaminophenylacetic acid added reaches 120g, the hydroxyl group in glycerol and the carboxyl group on 4-acetaminophenylacetic acid can undergo esterification reaction as quickly as possible, and more glyceryl ester plasticizers are formed, so that the content of the active ingredients in the glyceryl ester plasticizers is effectively increased.
It can be seen from the combination of examples 3 and examples 6 to 8 and Table 5 that the peel strength of example 6 is greatly reduced compared with example 3, because the amide group in the mixture of octanoic acid and benzamide is derived from benzamide compared with 4-acetamidophenylacetic acid itself, and thus the amide group on benzamide is difficult to stably load when the glyceryl ester plasticizer is prepared, and thus the interfacial bonding force between the modified polyester core 1 and the PVC coating layer 2 is relatively weak.
Compared with example 6, the peel strength of example 7 is further reduced, thereby further proving that the amide group can effectively improve the interfacial bonding force between the modified terylene core 1 and the PVC coating layer 2.
Compared with example 3, the peel strength of example 8 is significantly improved, however, the reason is that, compared with 4-acetamidophenylacetic acid, 8- (2-hydroxybenzoylamino) octanoic acid contains hydroxyl groups in addition to amide groups, so that the abundance and content of polar groups between the modified polyester core wire 1 and the PVC coating layer 2 are effectively increased, and the interfacial bonding force between the modified polyester core wire 1 and the PVC coating layer 2 is further improved.
As can be seen from the combination of examples 8 to 10 and table 2, the peel strength of example 9 is significantly reduced compared with example 8, which is because, compared with the case of directly immersing the polyester yarn in the aqueous solution of sodium hydroxide, the spray method can promote the alkali etching points on the surface of the polyester yarn to be more uniform and dense, indirectly increase the specific surface area of the polyester yarn, and further increase the interfacial bonding force between the modified polyester core yarn 1 and the PVC coating layer 2.
Compared with the example 8, the peeling strength of the example 10 is also obviously reduced, and the reason is that the electrified operation can promote the corona and plasma activation phenomena on the surface of the polyester precursor, so that the surface modification effect of the glyceryl ester plasticizer on the polyester precursor is effectively improved, and the interface binding force of the modified polyester core wire 1 and the PVC coating layer 2 is further improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. The PVC coated polyester yarn is characterized by comprising a modified polyester core wire (1) and a PVC coating layer (2), wherein the PVC coating layer (2) is arranged on the outer peripheral surface of the modified polyester core wire (1); the modified polyester core wire (1) is formed by surface modification of polyester precursor through a glyceryl ester plasticizer, the PVC coating layer (2) is formed by mixing PVC and the glyceryl ester plasticizer, the glyceryl ester plasticizer contains an amide group, and the glyceryl ester plasticizer is prepared from the following raw materials in parts by weight: 17-23 parts of glycerin, 90-130 parts of organic acid, 5-10 parts of cyclohexane and 0.3-1.0 part of tetra-n-butyl titanate, wherein the organic acid contains amide groups, and the preparation method of the glyceryl ester plasticizer comprises the following steps of: esterification reaction: mixing glycerol, organic acid and cyclohexane, heating, adding tetrabutyl titanate, heating continuously, and reacting at constant temperature until the mixture is complete, thus obtaining the crude glyceryl ester plasticizer;
post-treatment: when the acid value of the crude glyceryl ester plasticizer is too high, firstly adding sodium hydroxide solution, carrying out deacidification reaction, then washing to be neutral, finally drying and centrifuging to remove water and cyclohexane in the glyceryl ester plasticizer, and finally obtaining the glyceryl ester plasticizer.
2. The PVC coated polyester yarn according to claim 1, wherein: the organic acid is one of a mixture of octanoic acid and benzamide, 4-acetaminophenyl acetic acid and 8- (2-hydroxybenzoylamino) octanoic acid.
3. A method for preparing the PVC coated polyester yarn as in any one of claims 1-2, comprising the steps of:
preparing a modified polyester core wire (1): soaking polyester raw filaments in a glyceryl ester plasticizer-ethanol solution, taking out after full soaking, and heating and drying to obtain a modified polyester core wire (1);
PVC coating (2) preparation: mixing PVC with glyceryl ester plasticizer, extruding and granulating to obtain PVC master batch, extruding and coating the PVC master batch and the modified polyester core wire (1), and finally cooling and solidifying to obtain the PVC coated polyester yarn with the PVC coating layer (2).
4. The method for preparing the PVC-coated polyester yarn according to claim 3, wherein the method comprises the following steps: in the preparation of the modified polyester core wire (1), before the polyester precursor is soaked in the glyceryl ester plasticizer-ethanol solution, the alkali washing operation is carried out on the polyester precursor through the sodium hydroxide aqueous solution.
5. The method for preparing the PVC coated polyester yarn according to claim 4, wherein the alkali washing operation comprises the steps of:
s1, uniformly winding polyester raw filaments to form a polyester raw filament cylinder, and then preheating;
s2, spraying sodium hydroxide aqueous solution onto the polyester yarn cylinder in a spraying mode to perform alkali etching, wherein the polyester yarn cylinder keeps continuously rotating.
6. The method for preparing the PVC-coated polyester yarn according to claim 5, wherein the method comprises the following steps: the alkaline washing operation is carried out by an alkaline washing machine (3), the alkaline washing machine (3) comprises an alkaline washing chamber (31) and a winding device (32) arranged in the alkaline washing chamber (31), a heater (313) and an atomizer (314) are arranged in the alkaline washing chamber (31), and the atomizer is used for spraying sodium hydroxide aqueous solution in a water mist form;
the winding device (32) comprises a lifting assembly (321) and a traversing winding assembly (322), the traversing winding assembly (322) is used for winding polyester yarns and forming polyester yarn cylinders, and the lifting assembly (321) is used for conveying the polyester yarn cylinders into or out of the alkaline washing chamber (31);
the transverse moving winding assembly (322) comprises a transverse moving air cylinder (3221), a winding cage (3222) and a driving piece (3223), wherein the winding cage (3222) is rotatably connected with a piston rod of the transverse moving air cylinder (3221), the transverse moving air cylinder (3221) drives the winding cage (3222) to transversely translate, and the driving piece (3223) drives the winding cage (3222) to continuously rotate;
the lifting assembly (321) comprises a first lifting cylinder (3211) and a second lifting cylinder (3212), a cylinder body of the transverse moving cylinder (3221) is arranged on a piston rod of the first lifting cylinder (3211), and the driving piece (3223) is arranged on a piston rod of the second lifting cylinder (3212).
7. The method for preparing the PVC-coated polyester yarn according to claim 6, wherein the method comprises the following steps: the driving piece (3223) comprises a driving motor (32231) and a square column (32232) fixedly connected to the output end of the driving motor (32231), and the driving motor (32231) is fixedly connected to a piston rod of the second lifting cylinder (3212); a square groove (32221) is formed in the side wall of the winding cage (3222), and the square column (32232) is arranged in the square groove (32221) in a penetrating mode;
the alkaline washing chamber (31) comprises an alkaline washing chamber main body (311) and a cover plate (312) covered on the alkaline washing chamber main body (311), a first sliding groove (315) and a second sliding groove (316) are formed in the alkaline washing chamber main body (311), the square column (32232) is connected in the first sliding groove (315) in a sliding mode, and a piston rod of the transverse moving cylinder (3221) is connected in the second sliding groove (316) in a sliding mode.
8. The method for preparing the PVC-coated polyester yarn according to claim 3, wherein the method comprises the following steps: in the preparation of the modified polyester core wire (1), before the polyester precursor is taken out of the glyceryl ester plasticizer-ethanol solution, the glyceryl ester plasticizer-ethanol solution is electrified.
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| CN103242516A (en) * | 2013-05-23 | 2013-08-14 | 江南大学 | Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer |
| CN110106707A (en) * | 2019-05-05 | 2019-08-09 | 上海康贡新材料科技有限公司 | PVC coating modification dacron thread and its production method |
| CN112981962A (en) * | 2021-02-07 | 2021-06-18 | 杭州易川塑业有限公司 | Polyester covered yarn, preparation method thereof and high-fatigue-resistance mesh cloth |
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| CN103242516A (en) * | 2013-05-23 | 2013-08-14 | 江南大学 | Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer |
| CN110106707A (en) * | 2019-05-05 | 2019-08-09 | 上海康贡新材料科技有限公司 | PVC coating modification dacron thread and its production method |
| CN112981962A (en) * | 2021-02-07 | 2021-06-18 | 杭州易川塑业有限公司 | Polyester covered yarn, preparation method thereof and high-fatigue-resistance mesh cloth |
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