CN116082761A - Low-odor PVC modified material and preparation method thereof - Google Patents

Low-odor PVC modified material and preparation method thereof Download PDF

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Publication number
CN116082761A
CN116082761A CN202211472421.5A CN202211472421A CN116082761A CN 116082761 A CN116082761 A CN 116082761A CN 202211472421 A CN202211472421 A CN 202211472421A CN 116082761 A CN116082761 A CN 116082761A
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modified material
pvc
plasticizer
stabilizer
pvc modified
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Inventor
路中伟
吴维新
马吉卫
朱勇兴
戴晓峰
王静雅
苏青青
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Zhejiang Tianyuan Medical Mat Co ltd
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Zhejiang Tianyuan Medical Mat Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a low-odor PVC modified material, which is prepared from the following raw materials in parts by mass: 50-65 parts of PVC resin powder, 40-50 parts of plasticizer, 0.1-1 part of stabilizer and 0.2-1 part of lubricant. The invention adopts the formula of a non-o-benzene plasticizing system, strictly follows the European Union RoHS environmental protection instruction, has no toxic effect on human bodies, ensures that the modified material has good wear resistance and toughness, and can be applied to medical granules to prepare blood bags and other articles.

Description

Low-odor PVC modified material and preparation method thereof
Technical Field
The invention relates to the technical field of polymers, in particular to a low-odor PVC modified material and a preparation method thereof, belonging to the field of C08L 27/06.
Background
PVC material has the advantages of fire resistance, chemical corrosion resistance, strong weather resistance and the like, is the universal plastic with the largest yield in the world, and has very wide application. The product has wide application in building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like. However, with the continuous improvement of environmental protection requirements of various industries on materials, the problem of the sporadic property of the PVC materials influences the popularization and the application of products.
CN114854148A discloses a polyvinyl chloride composite material, its preparation method and use, comprising: polyvinyl chloride resin, o-benzene plasticizer, epoxidized soybean oil, heavy calcium stabilizer, ammonia-resistant auxiliary agent and inorganic flame retardant. The polyvinyl chloride composite material provided by the invention has low odor, excellent heat resistance and light resistance. But its odor score rating is only 3.0, still requiring further optimization.
CN107286512a discloses a low-odor environment-friendly polyvinyl chloride composite material comprising: polyvinyl chloride resin, chlorinated polyethylene, butyl etherified urea resin, plasticizer, phenylhydrazide derivative, lubricant, flame retardant, vermiculite powder and montmorillonite. The odor grading grade of the low-odor environment-friendly polyvinyl chloride composite material disclosed by the patent reaches 2.5, the amount of volatile gas generated in the polymer is reduced, pollution is reduced, but the formula is complex, and further optimization is still needed.
Disclosure of Invention
Aiming at the problems, the invention discloses a low-odor PVC modified material, which comprises the following raw materials in parts by mass: 50-65 parts of PVC resin powder, 40-50 parts of plasticizer, 0.1-1 part of stabilizer and 0.2-1 part of lubricant.
Preferably, the preparation raw materials comprise: 55.14 parts of PVC resin powder, 44.15 parts of plasticizer, 0.28 part of stabilizer and 0.45 part of lubricant.
In one embodiment, the PVC resin powder has an average degree of polymerization of 2000 to 4000.
Preferably, the PVC resin powder has an average degree of polymerization of 2500-3500, such as obtained from Xinjiang, model number: TYH-2500, the average degree of polymerization was 2500.
In one embodiment, the plasticizer is selected from one or more of modified polyester, triethyl citrate, tributyl citrate, epoxidized soybean oil, epoxidized peanut oil, epoxidized cottonseed oil, epoxidized corn oil, and epoxidized sunflower oil.
Preferably, the plasticizer is a compound of modified polyester and epoxidized soybean oil, and the mass ratio is (10-30): 1.
further preferably, the mass ratio of the modified polyester to the epoxidized soybean oil is 20:1.
the modified polyester was purchased from Yu Xintai g chemical (chinese) limited under the model number plasticizer MPN.
The epoxidized soybean oil, CAS number: 8013-07-8, all of which are commercially available.
PVC is white powder with an amorphous structure, starts to decompose at about 170 ℃, has poor light and heat stability, can decompose to generate hydrogen chloride after being exposed to sunlight at more than 100 ℃ or for a long time, and further automatically catalyzes the decomposition to cause discoloration. The average polymerization degree of the PVC resin powder used in the invention is 2000-4000, and the PVC resin powder with high polymerization degree is characterized in that the crystallization phase of PVC molecular chain groups is greatly improved, the winding points among random molecular chains are increased due to the increase of molecular weight, and the macromolecular chains are difficult to slide, so that the PVC resin powder has high tensile strength and high elongation, and has excellent fatigue resistance, weather resistance, oil resistance, cold resistance, ozone resistance, heat resistance and solvent resistance, but also has larger brittleness, no abrasion resistance and poor toughness, therefore, the plasticizer is needed to be added, the toughness is improved, and the breaking elongation of plastic products is enhanced. Among the plasticizers commonly used, phthalate plasticizers are most widely used, and researches show that phthalate plasticizers are endocrine disruptors which act as female hormones and volatilize, and the phthalate plasticizers can be absorbed by human bodies through skin, digestive tracts and respiratory tracts, so that damage to reproductive systems can be caused by long-term contact. Therefore, the applicant has found through a great deal of researches that the modified polyester is selected, and the Epoxidized Soybean Oil (ESO) is used as an auxiliary plasticizer, so that the modified material has no toxic or harmful effect on human body, and the problems of high molecular viscosity, poor fluidity and uneven mixing in PVC resin processing, especially high molecular weight PVC processing, are solved unexpectedly while good wear resistance of the modified material is ensured. The inventors believe that the possible reasons are: the modified polyester contains a large amount of polar groups which can form hydrogen bonds with PVC, so that acting force of the modified polyester and the PVC is improved, epoxy groups in the epoxidized soybean oil can capture Cl on the PVC to a certain extent, thereby effectively stopping free radical reaction, reducing degradation rate, reducing material odor, simultaneously, the epoxidized soybean oil has good compatibility with the PVC, and the modified polyester overcomes inter-chain resistance and is uniformly mixed under the action of a small amount of epoxidized soybean oil, so that the toughness of the PVC is improved.
In one embodiment, the stabilizer is selected from one or more of a barium zinc composite heat stabilizer, a calcium zinc composite heat stabilizer, a magnesium aluminum zinc composite heat stabilizer, and an organotin-based stabilizer.
Preferably, the stabilizer is a calcium-zinc composite heat stabilizer.
The stabilizer is a calcium-zinc composite heat stabilizer, and is fully and thermally mixed and modified at 60-125 ℃, so that the migration and precipitation of the plasticizer under the conditions of heating and solvent are effectively reduced, and the stability of the PVC granules is ensured.
In one embodiment, the lubricant is selected from one or more of silane polymers, solid paraffin, liquid paraffin, fatty acid salts, calcium stearate, zinc stearate, fatty amides, methylene bis-stearamide, oleamide, stearamide.
Preferably, the lubricant is a compound of zinc stearate and oleamide, and the mass ratio is (3-10): 1.
the invention also discloses a preparation method of the low-odor PVC modified material, which comprises the following steps:
(1) Blending materials, namely blending the materials to form jelly;
(2) Mixing at high speed, and putting the jelly into a high-speed blender to form a mixed jelly;
(3) Screw extrusion, namely putting the mixed jelly into an extruder for screw extrusion;
(4) Granulating, and air-cooling to obtain the high-quality PVC granular product.
In one embodiment, the high speed mixing process is carried out at temperatures of 60-70 ℃, 115-120 ℃, 80-90 ℃, 115-120 ℃, 120-125 ℃ for five stages, each temperature being subjected to 1-3 minutes to form a mixed gum.
Preferably, the high speed mixing process is carried out at a temperature of 60 ℃, 115 ℃, 80 ℃, 115 ℃, 125 ℃ for 2 minutes each to form a mixed gum.
In one embodiment, the screw extrusion temperature is 120-130 ℃.
Preferably, the screw extrusion temperature is 125 ℃.
Advantageous effects
1. The average polymerization degree of the PVC resin powder used in the invention is 2000-4000, so that the modified material has excellent fatigue resistance, weather resistance, oil resistance, cold resistance, ozone resistance, heat resistance and solvent resistance.
2. The formula of the non-o-benzene plasticizing system is adopted, the environmental protection instruction of RoHS of European Union is strictly followed, no toxic or harmful effect is caused to human bodies, meanwhile, the modified material is guaranteed to have good wear resistance and toughness, and the modified material can be applied to medical granules to prepare blood bags and other articles.
3. The modified polyester is compounded with the epoxidized soybean oil, so that the problems of high viscosity, poor fluidity and uneven mixing during processing of the PVC resin are solved.
4. The stabilizer is a calcium-zinc composite heat stabilizer, and is fully and thermally mixed and modified at 60-125 ℃, so that the migration and precipitation of the plasticizer under the conditions of heating and solvent are effectively reduced, and the stability of the PVC granules is ensured.
Detailed Description
Example 1
The embodiment 1 discloses a low-odor PVC modified material, which is prepared from the following raw materials in parts by mass: 50 parts of PVC resin powder, 49 parts of plasticizer, 0.1 part of stabilizer and 1 part of lubricant.
The PVC resin powder is purchased from Xinjiang, and the model is as follows: TYH-2500, the average degree of polymerization was 2500.
The plasticizer is a compound of modified polyester and epoxidized soybean oil, and the mass ratio is 10:1.
the modified polyester was purchased from Yu Xintai g chemical (chinese) limited under the model MPN.
The epoxidized soybean oil, CAS number: 8013-07-8, all of which are commercially available.
The stabilizer is a calcium-zinc composite heat stabilizer, and is purchased from Galala Chemicals, model: CZ-11.
The lubricant is a compound of zinc stearate and oleamide, and the mass ratio is 3:1.
the embodiment 1 on the other hand discloses a preparation method of the low-odor PVC modified material, which comprises the following steps:
(1) Blending materials, namely blending the materials to form jelly;
(2) Mixing at high speed, and feeding the jelly into a high speed blender, and subjecting to temperature of 60 deg.C, 115 deg.C, 80 deg.C, 115 deg.C and 125 deg.C for 2 min to obtain mixed jelly.
(3) Screw extrusion, namely putting the mixed jelly into an extruder for screw extrusion; the extrusion temperature was 125 ℃;
(4) Granulating, and air-cooling to obtain the high-quality PVC granular product.
Example 2
The embodiment 2 discloses a low-odor PVC modified material, which is prepared from the following raw materials in parts by mass: 65 parts of PVC resin powder, 40 parts of plasticizer, 1 part of stabilizer and 0.2 part of lubricant.
The PVC resin powder is purchased from Xinjiang, and the model is as follows: TYH-2500, the average degree of polymerization was 2500.
The plasticizer is a compound of modified polyester and epoxidized soybean oil, and the mass ratio is 30:1.
the modified polyester was purchased from Yu Xintai g chemical (chinese) limited under the model MPN.
The epoxidized soybean oil, CAS number: 8013-07-8, all of which are commercially available.
The stabilizer is a calcium-zinc composite heat stabilizer, and is purchased from Galala Chemicals, model: CZ-11.
The lubricant is a compound of zinc stearate and oleamide, and the mass ratio is 10:1.
the preparation method is the same as in example 1.
Example 3
The embodiment 3 discloses a low-odor PVC modified material, which is prepared from the following raw materials in parts by mass: 55.14 parts of PVC resin powder, 44.15 parts of plasticizer, 0.28 part of stabilizer and 0.45 part of lubricant.
The PVC resin powder is purchased from Xinjiang, and the model is as follows: TYH-2500, the average degree of polymerization was 2500.
The plasticizer is a compound of modified polyester and epoxidized soybean oil, and the mass ratio is 20:1.
the modified polyester was purchased from Yu Xintai g chemical (chinese) limited under the model MPN.
The epoxidized soybean oil, CAS number: 8013-07-8, all of which are commercially available.
The stabilizer is a calcium-zinc composite heat stabilizer, and is purchased from Galala Chemicals, model: CZ-11.
The lubricant is a compound of zinc stearate and oleamide, and the mass ratio is 6:1.
the preparation method is the same as in example 1.
Example 4
The difference between this example 4 and example 3 is that the PVC resin powder, purchased from zilutarition, has the model: polyvinyl chloride S-700, the average degree of polymerization was 700.
Example 5
This example 5 differs from example 3 in that the plasticizer is a modified polyester.
Example 6
The difference between the present example 7 and the example 3 is that the plasticizer is a compound of acetyl tributyl citrate and epoxidized soybean oil, and the mass ratio is 20:1.
performance testing
1. Odor rating: odor grading tests were performed according to the popular automobile odor detection Enterprise Standard of PV 3900-2000. Placing (10+/-1) g of the sample to be detected into a 100ml wide-mouth bottle, placing the bottle into a constant-temperature oven at 80 ℃, and detecting odor score after 2 hours. The higher the rating, the greater the odor, the rating is rated on a scale of 1 to 6.
2. Tensile strength and elongation at break: sample preparation and appearance inspection were carried out according to GB1039, and tensile strength and elongation at break were tested according to GB/T1040-1992 test method for tensile Property of plastics; the test was carried out with a SANS electronic universal tester CMT7503 at a speed of 10 mm/min.
3. Thermal stability: the thermal stability is characterized according to the national standard GB/T2917.1-2002 "determination of the evolution of hydrogen chloride and any other acidic products at 180℃for blends based on homopolymers and copolymers of vinyl chloride". The test paper is discolored by degrading the test sample to release hydrogen chloride gas, and the test sample is discolored by degrading double bond components such as tert-butyl chloride and the like, so that the thermal stability of the test sample can be represented by the test paper discoloration time and the test sample discoloration time in an experiment.
TABLE 1
Figure BDA0003958937330000061
4. The materials obtained in example 3 were tested according to the test method of GB T14233.1-2008 medical infusion, blood transfusion and injection apparatus, and the results are shown in Table 2 below. (report number ZJTY-ZB-JL-249-A)
Figure BDA0003958937330000062
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Claims (10)

1. The low-odor PVC modified material is characterized by comprising the following preparation raw materials in parts by mass: 50-65 parts of PVC resin powder, 40-50 parts of plasticizer, 0.1-1 part of stabilizer and 0.2-1 part of lubricant.
2. The PVC modified material according to claim 1, wherein the PVC resin powder has an average degree of polymerization of 2000 to 4000.
3. The PVC modified material of claim 1, wherein the plasticizer is selected from one or more of plasticizer MPN, triethyl citrate, tributyl citrate, epoxidized soybean oil, epoxidized peanut oil, epoxidized cottonseed oil, epoxidized corn oil, epoxidized sunflower oil.
4. The PVC modified material according to claim 3, wherein the plasticizer is a compound of plasticizer MPN and epoxidized soybean oil, and the mass ratio is (10-30): 1.
5. the PVC modified material according to claim 1, wherein the stabilizer is one or more selected from the group consisting of a barium-zinc composite heat stabilizer, a calcium-zinc composite heat stabilizer, a magnesium-aluminum-zinc composite heat stabilizer, and an organotin-based stabilizer.
6. The PVC modified material of claim 1, wherein the lubricant is selected from one or more of silane polymers, paraffin wax, liquid paraffin, fatty acid salts, calcium stearate, zinc stearate, fatty amides, methylene bis-stearic acid amide, oleic acid amide, stearic acid amide.
7. The PVC modified material according to claim 6, wherein the lubricant is a combination of zinc stearate and oleamide, and the mass ratio is (3-10): 1.
8. a method for preparing a PVC modified material according to any one of claims 1 to 7, comprising the steps of:
(1) Blending materials, namely blending the materials to form jelly;
(2) Mixing at high speed, and putting the jelly into a high-speed blender to form a mixed jelly;
(3) Screw extrusion, namely putting the mixed jelly into an extruder for screw extrusion;
(4) Granulating, and air-cooling to obtain the high-quality PVC granular product.
9. The method of claim 8, wherein the high speed mixing is performed at a temperature of 60-70 ℃, 115-120 ℃, 80-90 ℃, 115-120 ℃, 120-125 ℃ for about 1-3 minutes each to form a mixed gum.
10. The PVC modified material of claim 8, wherein the screw extrusion temperature is 120-130 ℃.
CN202211472421.5A 2022-11-23 2022-11-23 Low-odor PVC modified material and preparation method thereof Pending CN116082761A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101555337A (en) * 2008-04-09 2009-10-14 上海天原集团胜德塑料有限公司 Low-precipitation type environmentally-friendly transparent soft polyvinyl chloride granules
RU2013106696A (en) * 2013-02-15 2014-08-20 Общество с ограниченной ответственностью "МЕД-ИСТ" PLASTICIZED COMPOSITION BASED ON POLYVINYL CHLORIDE FOR MEDICAL PURPOSES
CN104109323A (en) * 2014-07-31 2014-10-22 东莞市祺龙电业有限公司 Migration-resistant environment-friendly PVC (Polyvinyl Chloride) modified material and preparation method thereof
CN105778338A (en) * 2016-03-25 2016-07-20 上海天原集团胜德塑料有限公司 Environment-friendly soft polyvinyl chloride granules

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101555337A (en) * 2008-04-09 2009-10-14 上海天原集团胜德塑料有限公司 Low-precipitation type environmentally-friendly transparent soft polyvinyl chloride granules
RU2013106696A (en) * 2013-02-15 2014-08-20 Общество с ограниченной ответственностью "МЕД-ИСТ" PLASTICIZED COMPOSITION BASED ON POLYVINYL CHLORIDE FOR MEDICAL PURPOSES
CN104109323A (en) * 2014-07-31 2014-10-22 东莞市祺龙电业有限公司 Migration-resistant environment-friendly PVC (Polyvinyl Chloride) modified material and preparation method thereof
CN105778338A (en) * 2016-03-25 2016-07-20 上海天原集团胜德塑料有限公司 Environment-friendly soft polyvinyl chloride granules

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孔萍，刘青山: "《塑料挤出工（中、高级）培训教程》", vol. 1, 广州：广东高等教育出版社, pages: 46 - 47 *

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