CN118290788A - Polyvinyl chloride plasticizing film and preparation method thereof - Google Patents
Polyvinyl chloride plasticizing film and preparation method thereof Download PDFInfo
- Publication number
- CN118290788A CN118290788A CN202410402043.6A CN202410402043A CN118290788A CN 118290788 A CN118290788 A CN 118290788A CN 202410402043 A CN202410402043 A CN 202410402043A CN 118290788 A CN118290788 A CN 118290788A
- Authority
- CN
- China
- Prior art keywords
- hexanediol
- oleate
- polyvinyl chloride
- epoxy
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 88
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 88
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229940049964 oleate Drugs 0.000 claims abstract description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000004593 Epoxy Substances 0.000 claims abstract description 33
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005642 Oleic acid Substances 0.000 claims abstract description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000019253 formic acid Nutrition 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003755 preservative agent Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000005012 migration Effects 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000003200 Adenoma Diseases 0.000 description 1
- 206010001233 Adenoma benign Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010477 Prilezhaev reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a polyvinyl chloride plasticizing film and a preparation method thereof, wherein the preparation method comprises the following steps: step one, preparation of 1, 6-hexanediol oleate: the oleic acid and the 1, 6-hexanediol are reacted under the catalysis of concentrated sulfuric acid, sodium hydroxide is added to neutralize residual oleic acid, residual sodium hydroxide and 1, 6-hexanediol are removed by washing, standing and liquid separation are carried out, residual water is removed by rotary evaporation, and 1, 6-hexanediol oleate is obtained; step two, preparing epoxy 1, 6-hexanediol oleate: using hydrogen peroxide as an oxidant, and formic acid and concentrated sulfuric acid as catalysts, and reacting 1, 6-hexanediol oleate to obtain epoxy 1, 6-hexanediol oleate; preparing a polyvinyl chloride plasticizing film: and (3) blending SG5 polyvinyl chloride resin with epoxy 1, 6-hexanediol oleate, standing, evaporating and drying to obtain the polyvinyl chloride plasticizing film. The polyvinyl chloride plasticizing film provided by the application has the characteristics of readily available raw materials, simple and convenient process, environment friendliness and excellent performance.
Description
Technical Field
The invention relates to the field of materials, in particular to a polyvinyl chloride plasticizing film and a preparation method thereof.
Background
Polyvinyl chloride (PVC) has been beneficial in various respects to modern civilization. PVC is one of the most consumed plastics for balls. In recent years, the market demand for global PVC materials continues to increase from 3830 ten thousand tons in 2013 to 5431 ten thousand tons in 2020, and at present, the global demand for PVC is still rising, with the asia-tai being the region with the highest global consumption. PVC is widely used in various fields with its excellent properties and low price. People can see them almost in various fields of production and life. Soft PVC products include wallpaper, toys, boots, sleeves, window screens, gloves, curtains, etc., wherein PVC cables are increasingly demanded. But problems such as poor mechanical properties, cold resistance, thermal stability and the like remain during use. Therefore, the product use effect can be further improved by adding a plasticizer to the PVC resin.
Plasticizers have been used to date as the most important additive in flexible PVC products, with global plasticizer usage on the order of billions of yuan for 2023. Despite the variety of plasticizers and their low cost, there are still many problems. More than half of the world's countries have winter temperatures below 0 ℃, however, in low temperature environments, the choice of plasticizers is extremely limited, thus severely restricting the use of plasticizers in cold environments. The most commonly used cold-resistant plasticizers on the market at present are di (2-ethylhexyl) adipate (DOA) and di (2-ethylhexyl) sebacate (DOS), but the defects are obvious, and the migration resistance is too poor, so that the cold-resistant plasticizers are easy to migrate out of PVC products, and influence the properties of the PVC products, therefore, the cold-resistant plasticizers are used as auxiliary plasticizers in most cases, and the addition amount is generally not more than 20 weight percent, so that the problems of hardening and use safety of the products are caused. In addition, in the study of oral DOA of mice, all mice suffer from adenoma and liver cancer with different degrees, so DOA is easy to migrate out of PVC matrix, and thus the DOA is a threat to human health. Meanwhile, the DOA production process is complex, the control condition is strict, the product efficiency is low, and the phenomena of high cost and waste of raw materials are caused.
Oleic acid, the main component in vegetable oils, has two major chemical characteristics: (1) The long fatty chains generally contain unsaturated double bonds, the double bonds are easy to oxidize, the flexibility of molecules can be greatly reduced due to the existence of the double bonds, the long fatty chains can be inserted between the molecular chains of the polymer according to an internal plasticizing mechanism, and the activity space between the molecular chains is increased, so that the long fatty chains are easier to move; (2) The contained ester bond can generate strong interaction with a polymer molecular chain, so that the compatibility between the plasticizer and the polymer is improved, and the synthetic process principle is simple, so that the plasticizer is a natural raw material for preparing the industrial cold-resistant plasticizer. However, the pure use of oleic acid can reduce various properties of PVC, such as mechanical properties, migration resistance and the like, so that the PVC does not have actual conditions of industrial production.
The 1, 6-hexanediol has two hydroxyl groups at the end positions of a carbon chain, has higher activity, and can react with organic acid, isocyanate and anhydride to form different types of derivatives. The 1, 6-hexanediol is an emerging fine chemical raw material, and has wider and wider application in the fields of ultraviolet curing paint, polyurethane, polyester, plasticizer, pesticide, medicine, dye and the like, and is mainly used for improving the mechanical strength of products and improving the performances of hydrolysis resistance, heat resistance, chemical corrosion resistance and the like of the products.
Disclosure of Invention
The application aims at the defects that the conventional cold-resistant plasticizer DOA has poor migration resistance and is harmful to human health and pollutes the environment. The environment-friendly material oleic acid and the industrialized material 1, 6-hexanediol are used for esterification and epoxidation modification, the epoxy 1, 6-hexanediol oleate plasticizer is synthesized and applied to the SG soft 5-type PVC material, so that the mechanical property, migration resistance and cold resistance of the SG soft 5-type PVC film are obviously improved, and the comprehensive performance of the PVC material is effectively improved.
The application provides a preparation method of a polyvinyl chloride plasticizing film, which comprises the following steps:
Step one, preparation of 1, 6-hexanediol oleate: the oleic acid and the 1, 6-hexanediol are reacted under the catalysis of concentrated sulfuric acid, sodium hydroxide is added to neutralize residual oleic acid, residual sodium hydroxide and 1, 6-hexanediol are removed by washing, standing and liquid separation are carried out, residual water is removed by rotary evaporation, and 1, 6-hexanediol oleate is obtained;
Step two, preparing epoxy 1, 6-hexanediol oleate: using hydrogen peroxide as an oxidant, and formic acid and concentrated sulfuric acid as catalysts, and reacting 1, 6-hexanediol oleate to obtain epoxy 1, 6-hexanediol oleate;
preparing a polyvinyl chloride plasticizing film: and (3) blending SG5 polyvinyl chloride resin with epoxy 1, 6-hexanediol oleate, standing, evaporating and drying to obtain the polyvinyl chloride plasticizing film.
In some embodiments, step one comprises:
Adding 0.6383mol of oleic acid and 0.3192mol of 1, 6-hexanediol into a reaction vessel, adding 0.0276mol of 98wt% concentrated sulfuric acid, stirring and heating to 130-150 ℃ under nitrogen atmosphere to perform reaction, adding 5.33g of 15-20wt% sodium hydroxide solution after the reaction is finished to neutralize excessive oleic acid, removing excessive 1, 6-hexanediol and sodium hydroxide through water washing, standing and separating liquid, and removing residual water in the mixture through rotary evaporation to obtain 1, 6-hexanediol oleate.
In some embodiments, step two comprises:
adding 1, 6-hexanediol oleate into a reaction container, adding hydrogen peroxide, formic acid and 89wt% concentrated sulfuric acid, stirring at 55-65 ℃ for reaction for 8-10 hours, washing to remove excessive hydrogen peroxide, formic acid and concentrated sulfuric acid, and removing residual water by rotary evaporation to obtain epoxy 1, 6-hexanediol oleate.
In some embodiments, the mass ratio of 1, 6-hexanediol oleate, hydrogen peroxide, formic acid, and concentrated sulfuric acid is 100 (70-75): 15-20): 1-3.
In some embodiments, step three comprises:
Adding SG soft 5-type polyvinyl chloride resin and tetrahydrofuran into a reaction container, stirring until the solution is clear and transparent, then adding epoxy 1, 6-hexanediol oleate, pouring the reaction solution into a culture dish after stirring for 24-30h, covering a preservative film with holes to prevent solvent from volatilizing too fast, standing for 24h, turning over the polyvinyl chloride film, evaporating for 2-3d at the ambient temperature, and drying for 3d at the temperature of 50-80 ℃ to remove tetrahydrofuran, thereby obtaining the polyvinyl chloride plasticizing film.
In some embodiments, the mass ratio of SG soft 5-type polyvinyl chloride resin to epoxy 1, 6-hexanediol oleate is 10 (3-5).
The application also provides the polyvinyl chloride plasticized film obtained by the preparation method.
Compared with the prior art, the application has the following advantages:
1. Oleic acid is derived from rapeseed oil of Qinghai, is a biomass material, and has the advantages of green environmental protection and low price.
2. The preparation process for synthesizing the epoxy 1, 6-hexanediol oleate is simple and convenient, and the experimental flow is safe.
3. The synthetic epoxy 1, 6-hexanediol oleate plasticizer realizes the unified compromise of superior mechanical property, excellent migration resistance and stable cold resistance of the SG soft 5 type PVC material.
4. Compared with commercial dioctyl adipate (DOA) plasticizer, the synthetic epoxy 1, 6-hexanediol oleate plasticizer has similar cold resistance, but better mechanical property, greatly improved migration resistance and better commercial competitiveness.
Drawings
Fig. 1 shows Dynamic Mechanical Analysis (DMA) curves of the SG soft 5 PVC, the PVC plasticized films prepared in example 1, example 2 and example 3.
Detailed Description
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
The application firstly extracts environment-friendly biomass oleic acid from rapeseed oil, then carries out esterification reaction with 1, 6-hexanediol to synthesize a1, 6-hexanediol oleate plasticizer, and then carries out epoxidation reaction on carbon-carbon double bonds in the 1, 6-hexanediol oleate to finally prepare the epoxy 1, 6-hexanediol oleate plasticizer. On one hand, the synthetic epoxy 1, 6-hexanediol oleate plasticizer realizes that the PVC plasticizing film with excellent mechanical property, excellent migration resistance and stable and unified cold resistance is prepared from SG soft 5 type PVC. On the other hand, the reaction flow in the epoxy 1, 6-hexanediol oleate is simple and safe. In conclusion, the epoxy 1, 6-hexanediol oleate plasticizer provides a new direction for the diversification and functional development of cold-resistant plasticizers while meeting the requirements of alpine regions, and further expands the applicability of the plasticizer in the aspect of industrial production of PVC.
The preparation method of the application is mainly divided into three parts: (1) preparation of 1, 6-hexanediol oleate: synthesizing high-purity 1, 6-hexanediol oleate by using methods of oil bath, rotary evaporation, centrifugation, extraction and the like; (2) preparation of epoxy 1, 6-hexanediol oleate: using hydrogen peroxide as an oxidant, and formic acid and concentrated sulfuric acid as catalysts, and synthesizing epoxy 1, 6-hexanediol oleate by a Prilezhaev reaction; (3) preparation of SG soft 5 type PVC plastic film: and (3) blending the SG soft 5-type PVC resin with epoxy 1, 6-hexanediol oleate by using an in-situ grafting polymerization method, and standing, evaporating and drying to obtain the SG soft 5-type PVC plasticizing film.
The preparation specific process of the application comprises the following steps:
Preparation of 1, 6-hexanediol oleate: to a 250ml three-necked flask, 0.6383mol of oleic acid and 0.3192mol of 1, 6-hexanediol were added, and to the mixture was added 0.0276mol (1.5% by mass of oleic acid) of concentrated sulfuric acid (98% by weight) as a catalyst, and the three-necked flask was placed in an oil bath under a nitrogen atmosphere with magnetic stirring and heated to 130℃to 150℃to conduct a reaction for 7.5 to 8.5 (e.g., 8) hours. After the reaction is finished, 5.33g of sodium hydroxide solution with the concentration of 15-20wt% is added to neutralize and react excessive oleic acid, excessive 1, 6-hexanediol and sodium hydroxide are removed by water washing, the mixture is stood for liquid separation, and residual water is removed by rotary evaporation, so that a product with higher purity is obtained.
Preparation of epoxy 1, 6-hexanediol oleate: first, 0.15mol of 1, 6-hexanediol oleate was added to a three-necked flask, followed by 1.23mol (70-75% by mass of 1, 6-hexanediol oleate) of hydrogen peroxide, 0.196mol (15-20% by mass of 1, 6-hexanediol oleate) of formic acid and 0.006mol (1-3% by mass of 1, 6-hexanediol oleate) of concentrated sulfuric acid. Placing the mixture into a water bath kettle, setting the temperature to 60 ℃ and stirring the mixture for reaction for 8 to 10 hours. After the ester is completely converted, removing excessive acid and oxidant by washing with water, and removing residual water by rotary evaporation to obtain the epoxy 1, 6-hexanediol oleate.
Preparation of SG5 type PVC plasticizing film: 12g SG soft 5 PVC resin and 150ml tetrahydrofuran were added to a 250ml beaker and magnetically stirred until the solution was clear and transparent. Then adding 30-50wt% of epoxy 1, 6-hexanediol oleate plasticizer, stirring for 24-30h, pouring the mixture into a culture dish with 150mm, covering a preservative film with small holes to prevent solvent from volatilizing too fast, standing for 24h, turning over a PVC film, evaporating for 2-3d at ambient temperature, drying for 3d in a constant temperature box with 50-80 ℃ to remove tetrahydrofuran, and finally cutting into strips for later use.
Example 1
Preparation of SG5 type PVC plasticizing film: 12g SG soft 5 PVC resin and 150ml tetrahydrofuran were added to a 250ml beaker and magnetically stirred until the solution was clear and transparent. Then adding dioctyl adipate (DOA) plasticizer which is 50% of the mass of SG soft 5 type PVC resin, stirring for 24 hours, pouring the mixture into a culture dish with 150mm, covering a preservative film with small holes to prevent solvent from volatilizing too fast, standing for 24 hours, turning over the PVC film, evaporating for 2 days at the ambient temperature, drying for 3 days in a constant temperature box with the temperature of 50 ℃ to remove tetrahydrofuran, and finally cutting into strips for later use.
Example 2
Preparation of 1, 6-hexanediol oleate: to a 250ml three-necked flask, 0.6383mol of oleic acid and 0.3192mol of 1, 6-hexanediol were added, and to the mixture was added 0.0276mol (1.5% of the mass of oleic acid) of concentrated sulfuric acid catalyst, and the three-necked flask was placed in an oil bath under magnetic stirring under nitrogen atmosphere and heated to 130℃to effect a reaction. After the reaction is finished, 5.33g of 15wt% sodium hydroxide solution is added to neutralize and react excessive oleic acid, excessive 1, 6-hexanediol and sodium hydroxide are removed by water washing, the mixture is stood for liquid separation, and residual water is removed by rotary evaporation, so that a product with higher purity is obtained.
Preparation of SG soft 5 type PVC plasticizing film: 12g SG soft 5 PVC resin and 150ml tetrahydrofuran were added to a 250ml beaker and magnetically stirred until the solution was clear and transparent. Then adding 1, 6-hexanediol oleate plasticizer which is 50% of the mass of the SG soft 5 type PVC resin, stirring for 24 hours, pouring the mixture into a 150mm culture dish, covering a preservative film with small holes to prevent solvent from volatilizing too fast, standing for 24 hours, turning over the PVC film, evaporating for 2 days at the ambient temperature, drying for 3 days in a constant temperature box at 50 ℃ to remove tetrahydrofuran, and finally cutting into strips for later use.
Example 3
Preparation of 1, 6-hexanediol oleate: to a 250ml three-necked flask, 0.6383mol of oleic acid and 0.3192mol of 1, 6-hexanediol were added, and to the mixture was added 0.0276mol (1.5% of the mass of oleic acid) of concentrated sulfuric acid catalyst, and the three-necked flask was placed in an oil bath under magnetic stirring under nitrogen atmosphere and heated to 130℃to effect a reaction. After the reaction is finished, 5.33g of 15wt% sodium hydroxide solution is added to neutralize and react excessive oleic acid, excessive 1, 6-hexanediol and sodium hydroxide are removed by water washing, the mixture is stood for liquid separation, and residual water is removed by rotary evaporation, so that a product with higher purity is obtained.
Preparation of epoxy 1, 6-hexanediol oleate: first, 0.15mol of 1, 6-hexanediol oleate was added to the three-necked flask, followed by 1.23mol (70% by mass of 1, 6-hexanediol oleate) of hydrogen peroxide, 0.196mol (15% by mass of 1, 6-hexanediol oleate) of formic acid and 0.006mol (1% by mass of 1, 6-hexanediol oleate) of concentrated sulfuric acid. Placing the mixture into a water bath kettle, setting the temperature to be 60 ℃, and stirring the mixture for reaction for 8 hours. After the ester is completely converted, the excessive acid and oxidant in the ester are removed by washing with water, and then the residual water in the ester is removed by rotary evaporation, so that the purified product epoxy 1, 6-hexanediol oleate is finally obtained.
Preparation of SG soft 5 type PVC plasticizing film: 12gSG soft 5 PVC resin and 150ml tetrahydrofuran were added to a 250ml beaker and magnetically stirred until the solution was clear and transparent. Then adding epoxy 1, 6-hexanediol oleate plasticizer which is 50% of the mass of the SG soft 5 type PVC resin, stirring for 24 hours, pouring the mixture into a culture dish with 150mm, covering a preservative film with small holes to prevent solvent from volatilizing too fast, standing for 24 hours, turning over the PVC film, evaporating for 2 days at the ambient temperature, drying for 3 days in an incubator with the temperature of 50 ℃ to remove tetrahydrofuran, and finally cutting into strips for later use.
And (3) testing material performance: mechanical properties (elongation at break, tensile strength) were measured according to GB/T13022-91 at a tensile rate of 50mm/min using an electronic tensile tester under ambient conditions, dumbbell-shaped bars were cut by using a specific die, the test length of each bar was 25mm (L) ×3.5mm (W) ×0.2mm (H), and during the test, the average of five test results was taken for each bar as the final test result.
Dynamic Mechanical Analysis (DMA) PVC films were tested using a dynamic thermo-mechanical analyzer. Rectangular specimens (30 mm x 5mm x 1 mm) were tested in tensile mode at a fixed frequency of 1Hz and heated from-40 ℃ to 80 ℃ at a rate of 10 ℃/min. Table 1 shows the effect of different plasticizers on PVC composite properties.
TABLE 1
As can be seen from the data in table 1: SG soft 5 PVC is hard and brittle in the texture of pure PVC materials due to the difficulty of free movement of the internal molecular chains. The PVC after plasticization of example 2 has a lower elongation at break than the PVC of example 1, but is higher than pure PVC, giving rise to a certain plasticization effect. Example 3 the plasticization effect was better for example 3 compared to the tensile strength and elongation at break of the PVC in example 1. The epoxy 1, 6-hexanediol oleate plasticizer can effectively improve the mechanical properties of a plasticized film, and a larger movable space is formed between PVC chains after the plasticizer is added, so that the mechanical properties of the material are enhanced.
FIG. 1 shows DMA curves of SG5 PVC, example 1, example 2, and example 3. Whether PVC articles are normally used in a low temperature environment depends on whether the plasticizer has good plasticizing effect in that environment. The cold resistance of PVC test pieces can be evaluated by the glass transition temperature (Tg), and generally, the lower the Tg of the plasticized PVC test piece, the better the flexibility at low temperature, i.e., the better the cold resistance. Tg of different test pieces can be accurately tested through DMA, so that Tan delta curves of four PVC test pieces have only one peak value, and the compatibility between the four plasticizers and PVC is good. As can be seen from Table 1, the PVC film plasticized in example 2 had a Tg of only 58.37 ℃and showed that the plasticizing effect was impaired by the presence of carbon-carbon double bonds in the plasticizer. Example 3 the plasticized PVC film Tg is much less than neat PVC, indicating that the plasticizer of example 3 can improve the cold resistance of PVC, mainly because: the epoxy group can form strong dipole-dipole interaction with PVC and prevent entanglement of PVC molecular chains, so that the free volume among polymer molecules is increased, the movement of the PVC molecular chains is promoted, and the Tg of PVC is reduced. Although example 3 had a slightly higher Tg than example 1, the lower the temperature such as the loss factor of example 3 was than example 1, which means that the lower the loss factor was, the better the elasticity of the material was, and the lower the loss rate was at low temperature, so that example 3 still had a better plasticizing effect at low temperature and had better cold resistance.
It should be understood by those skilled in the art that the above embodiments are exemplary embodiments only and that various changes, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (7)
1. A method for preparing a polyvinyl chloride plasticized film, comprising:
Step one, preparation of 1, 6-hexanediol oleate: the oleic acid and the 1, 6-hexanediol are reacted under the catalysis of concentrated sulfuric acid, sodium hydroxide is added to neutralize residual oleic acid, residual sodium hydroxide and 1, 6-hexanediol are removed by washing, standing and liquid separation are carried out, residual water is removed by rotary evaporation, and 1, 6-hexanediol oleate is obtained;
Step two, preparing epoxy 1, 6-hexanediol oleate: using hydrogen peroxide as an oxidant, and formic acid and concentrated sulfuric acid as catalysts, and reacting 1, 6-hexanediol oleate to obtain epoxy 1, 6-hexanediol oleate;
preparing a polyvinyl chloride plasticizing film: and (3) blending SG5 polyvinyl chloride resin with epoxy 1, 6-hexanediol oleate, standing, evaporating and drying to obtain the polyvinyl chloride plasticizing film.
2. The method of claim 1, wherein step one comprises:
Adding 0.6383mol of oleic acid and 0.3192mol of 1, 6-hexanediol into a reaction vessel, adding 0.0276mol of 98wt% concentrated sulfuric acid, stirring and heating to 130-150 ℃ under nitrogen atmosphere to perform reaction, adding 5.33g of 15-20wt% sodium hydroxide solution after the reaction is finished to neutralize excessive oleic acid, removing excessive 1, 6-hexanediol and sodium hydroxide through water washing, standing and separating liquid, and removing residual water in the mixture through rotary evaporation to obtain 1, 6-hexanediol oleate.
3. The method of claim 1, wherein step two comprises:
adding 1, 6-hexanediol oleate into a reaction container, adding hydrogen peroxide, formic acid and 89wt% concentrated sulfuric acid, stirring at 55-65 ℃ for reaction for 8-10 hours, washing to remove excessive hydrogen peroxide, formic acid and concentrated sulfuric acid, and removing residual water by rotary evaporation to obtain epoxy 1, 6-hexanediol oleate.
4. The preparation method according to claim 3, wherein the mass ratio of 1, 6-hexanediol oleate to hydrogen peroxide to formic acid to concentrated sulfuric acid is 100 (70-75): 15-20): 1-3.
5. The method of claim 1, wherein step three comprises:
Adding SG soft 5-type polyvinyl chloride resin and tetrahydrofuran into a reaction container, stirring until the solution is clear and transparent, then adding epoxy 1, 6-hexanediol oleate, pouring the reaction solution into a culture dish after stirring for 24-30h, covering a preservative film with holes to prevent solvent from volatilizing too fast, standing for 24h, turning over the polyvinyl chloride film, evaporating for 2-3d at the ambient temperature, and drying for 3d at the temperature of 50-80 ℃ to remove tetrahydrofuran, thereby obtaining the polyvinyl chloride plasticizing film.
6. The preparation method according to claim 5, wherein the mass ratio of the SG soft 5-type polyvinyl chloride resin to the epoxy 1, 6-hexanediol oleate is 10 (3-5).
7. A polyvinyl chloride plasticized film obtained by the production method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410402043.6A CN118290788A (en) | 2024-04-03 | 2024-04-03 | Polyvinyl chloride plasticizing film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410402043.6A CN118290788A (en) | 2024-04-03 | 2024-04-03 | Polyvinyl chloride plasticizing film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118290788A true CN118290788A (en) | 2024-07-05 |
Family
ID=91685231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410402043.6A Pending CN118290788A (en) | 2024-04-03 | 2024-04-03 | Polyvinyl chloride plasticizing film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118290788A (en) |
-
2024
- 2024-04-03 CN CN202410402043.6A patent/CN118290788A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108752506B (en) | Sulfydryl biomass-based monomer internal plasticization PVC material and preparation method thereof | |
| CN115058216B (en) | High-strength oil-stain-resistant aging-resistant UV moisture dual-curing adhesive and preparation method thereof | |
| CN108250422B (en) | Preparation method of organic silicon modified polyester plasticizer | |
| CN110642719A (en) | Preparation method and application of malic acid-based environment-friendly plasticizer | |
| CN111777510A (en) | Preparation method and application of plant oil-based environment-friendly plasticizer with high thermal stability | |
| CN116425766A (en) | Epoxy isosorbide plasticizer and preparation method thereof | |
| CN110964332B (en) | Hyperbranched polyester toughened and reinforced high-strength recyclable soybean protein film and preparation method thereof | |
| CN113817143A (en) | Acetylated polyester plasticizer and preparation method thereof | |
| CN111718314B (en) | Preparation method and application of plant oil-based cold-resistant plasticizer | |
| CN105837812A (en) | Aliphatic-aromatic-copolymerization-type carborane polyester and preparing method thereof | |
| CN118290788A (en) | Polyvinyl chloride plasticizing film and preparation method thereof | |
| CN108948338B (en) | End-capped unsaturated polyester resin and synthesis process thereof | |
| CN111892702A (en) | Terephthalic acid type unsaturated polyester resin and preparation method thereof | |
| CN112920394B (en) | Preparation method and application of lactic acid-based environment-friendly plasticizer | |
| CN112409557B (en) | Vegetable oil-based polyurethane film and preparation thereof | |
| CN116102702A (en) | Method for preparing castor oil-based polyurethane without solvent and catalyst and application thereof | |
| CN110092910A (en) | A method of promoting silicone materials resilience performance | |
| CN114394896A (en) | Glyceryl ester plasticizer, preparation method thereof and nontoxic environment-friendly polyvinyl chloride | |
| CN110387069B (en) | Epoxy soybean oil rosin-cellulose-based polymer blend membrane and preparation method and application thereof | |
| CN108530640B (en) | Rosin propiolic ester internal plasticization PVC material and preparation method thereof | |
| CN112225712B (en) | Epoxidized soybean oil propylene pimaric acid ester and preparation method and application thereof | |
| CN114805786B (en) | Tannin extract-based polyether polyol fatty acid ester plasticizer and preparation method and application thereof | |
| CN103450446A (en) | Synthesis method of modified bisphenol A epoxy acrylate | |
| CN116693471B (en) | Bio-based epoxy chain extender, and preparation method and application thereof | |
| CN103524712A (en) | Synthetic method of modified bisphenol A epoxy acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |