CN113185786B - Low-temperature weather-resistant PVC composition and preparation method and application thereof - Google Patents
Low-temperature weather-resistant PVC composition and preparation method and application thereof Download PDFInfo
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- CN113185786B CN113185786B CN202110396198.XA CN202110396198A CN113185786B CN 113185786 B CN113185786 B CN 113185786B CN 202110396198 A CN202110396198 A CN 202110396198A CN 113185786 B CN113185786 B CN 113185786B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a low-temperature weather-resistant PVC composition, a preparation method and application thereof, wherein the composition comprises the following components in parts by weight: 80-100 parts of polyvinyl chloride resin; 10-20 parts of PMMA; 1-2 parts of MBS toughening agent; 0.1-0.5 part of lubricant; 1-4 parts of a weather-resistant agent; 1-4 parts of a stabilizer; 0.5-2 parts of ethylene-vinyl acetate copolymer; the content of vinyl acetate in the ethylene-vinyl acetate copolymer is more than or equal to 10wt%. The composition has low-temperature weather resistance and high bending strength, and can be applied to the field of electrical sleeves.
Description
Technical Field
The invention relates to the technical field of PVC material modification, and more particularly relates to a low-temperature weather-resistant PVC composition, and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is a high molecular compound polymerized from vinyl chloride monomer, and is one of the general plastic varieties with large output; the corrosion-resistant water-based paint has excellent corrosion resistance due to excellent chemical stability, acid resistance and alkali resistance, and is widely applied to the fields of industry, agriculture, municipal engineering, building water supply and drainage and the like. However, PVC has many disadvantages, such as greater brittleness, poorer thermal stability, easy thermal degradation during processing, poor processing fluidity, etc., which greatly limit the popularization and use of PVC materials.
Therefore, polyvinyl chloride products on the market are modified at present, and a toughening agent, a plasticizer, a heat stabilizer and the like are generally added into PVC resin to improve other properties, for example, chinese patent (CN 108219326A) discloses a formula of a high-impact-resistant PVC pipe and a preparation method thereof, but the defects of a PVC resin + MBS + calcium carbonate system are obvious, particularly in northeast China, because the temperature is below zero DEG C for a long time every year, on one hand, MBS improves the low-temperature toughness of PVC resin, but the weather resistance of the system is reduced after MBS resin is added, and on the other hand, filler calcium carbonate is separated from PVC materials at low temperature, and the phenomenon of calcium carbonate falling off is caused, so that the defects of other properties are reduced.
In the prior art, PMMA and MBS are also added into a PVC system, for example, a master thesis (Zhang Qian. PVC/PMMA blending material modification and performance research [ D ]. Tianjin science and technology university, 2014.) researches an MBS, PVC, PMMA ternary mixing system, wherein PMMA and MBS only improve the toughness of PVC resin. The above system cannot be directly applied to the field of electrical casing pipes because the current electrical casing pipes need a certain bending strength for convenient installation, and MBS and PMMA are added to cause the bending strength to be reduced, so that the application in the electrical casing pipes cannot be met.
Disclosure of Invention
The invention provides a low-temperature weather-resistant PVC composition for overcoming the defects of reduced bending strength and poor low-temperature weather resistance of the system.
The invention also aims to provide a preparation method of the low-temperature weather-resistant PVC composition.
The invention also aims to provide application of the low-temperature weather-resistant PVC composition.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low-temperature weather-resistant PVC composition comprises the following components in parts by weight:
the content of vinyl acetate in the ethylene-vinyl acetate copolymer is more than or equal to 10wt%.
Generally, the MBS toughening agent and PMMA are added into a PVC system to respectively improve the toughness and rigidity of PVC resin, but after the PVC product is used for a long time, the impact resistance and the toughness of the PVC product are greatly reduced, and particularly in a low-temperature area, the weather resistance of the PVC product is sharply reduced. The inventor finds that PMMA can improve the low-temperature weather resistance and the impact resistance, because the PMMA has higher fusion degree with PVC, is uniformly inserted into a net structure formed by PVC, is not easy to shrink and fall off in a low-temperature environment, and can support the net structure formed by PVC/MBS to improve the low-temperature weather resistance and the impact resistance.
For the application in the field of electrical casing, certain bending strength needs to be satisfied, but the addition of PMMA to PVC resin can reduce the bending strength of the resin and cannot be applied in the field of electrical casing, and the inventors found that the addition of ethylene-vinyl acetate copolymer to the system can improve the bending strength of the resin, and if the vinyl acetate content in the ethylene-vinyl acetate copolymer is less than 10wt%, the mixture is not sufficiently softened and the bending strength cannot be improved.
After the ethylene-vinyl acetate copolymer is added into the PVC/PMMA blend, the softening degree of the blend can be effectively improved, and the poor flexibility of the product caused by the hardness of the PVC/PMMA can be reduced, so that the bending elasticity and the toughness of the product can be improved, and the pressure resistance and the impact resistance of the product can not be influenced.
On the other hand, the added PMMA can replace calcium carbonate in PVC resin, so that the structural shrinkage of the product at low temperature is prevented from damaging the fusion structure of PVC/calcium carbonate particles, and the performance of the PVC product is prevented from being reduced; this is probably because PMMA can replace the function of calcium carbonate, and PMMA and PVC/MBS have better compatibility, also can keep certain shock resistance under the condition of extremely low temperature.
The low temperature means that the outdoor temperature is below minus 25 ℃.
Preferably, the vinyl acetate in the ethylene-vinyl acetate copolymer is less than or equal to 20wt%.
If the content of vinyl acetate in the ethylene-vinyl acetate copolymer is more than 18wt%, the fusibility of the ethylene-vinyl acetate copolymer and other materials is poor.
Preferably, the MBS toughening agent is a methyl methacrylate-butadiene-styrene copolymer.
Preferably, the weight average molecular weight of the polyvinyl chloride resin is 35000-65000.
If the molecular weight is smaller, the resin is difficult to process, and the fusion plasticizing effect is poor, so that the product has poor toughness; if the molecular weight is too large, the resin has an excessively good fusion plasticizing effect and is easily decomposed at high temperature.
Preferably, the weather-resistant agent is rutile type titanium dioxide and/or an ultraviolet absorber.
Preferably, the lubricant is one or more of paraffin, stearic acid or polyethylene wax.
Preferably, the stabilizer is a calcium zinc stabilizer.
The preparation method of the low-temperature weather-resistant PVC composition comprises the following steps:
s1, weighing polyvinyl chloride resin, PMMA (polymethyl methacrylate), MBS (methyl methacrylate) flexibilizer, lubricant, weather-resistant agent, stabilizer and ethylene-vinyl acetate copolymer in proportion, and blending uniformly to obtain premix;
and S2, extruding, molding and cutting the premix obtained in the step S1 to obtain the low-temperature weather-resistant PVC composition.
Preferably, the extrusion processing temperature of the step S2 is 180 to 220 ℃.
A PVC electrical bushing made from the low temperature weather resistant PVC composition.
The electrician's sleeve pipe has low temperature weatherability and bending strength is higher, facilitates the installation and uses.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low-temperature weather-resistant PVC composition, which improves the low-temperature weather resistance and the shock resistance by adding PMMA, because the PMMA has higher fusion degree with PVC, is uniformly inserted into a net structure formed by PVC, is not easy to shrink and fall off in a low-temperature environment, can support the net structure formed by PVC/MBS to improve the low-temperature weather resistance, and in addition, the ethylene-vinyl acetate copolymer is added into a system to prevent the defect of reduced bending strength caused by adding PMMA into the system.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
polyvinyl chloride resin a: the weight average molecular weight is 35000; zhongtai group, SG-4
Polyvinyl chloride resin B: the weight average molecular weight is 55000; zhongtai group, SG-5
Polyvinyl chloride resin C: the weight average molecular weight is 65000; zhongtai group, SG-7
PMMA: winning Chuangdegusai, PQ61-400L
Ethylene-vinyl acetate copolymer a: a vinyl acetate content of 10wt% U.S. dupont EVA 3135;
ethylene-vinyl acetate copolymer B: EVA 550 of 15wt% of vinyl acetate;
ethylene-vinyl acetate copolymer C: a vinyl acetate content of 18wt% U.S. dupont EVA 450;
ethylene-vinyl acetate copolymer D: a vinyl acetate content of 28wt% U.S. dupont EVA 210;
ethylene-vinyl acetate copolymer E: a vinyl acetate content of 9wt% U.S. dupont EVA 750;
MBS flexibilizer: japanese Brillouin B-564;
lubricant: qingdao Bangni chemical, BN108;
weather-resistant agent: nanjing titanium dioxide, NR950;
a stabilizer: a calcium zinc stabilizer;
examples and comparative examples the low temperature weather resistant PVC compositions were prepared by the following process comprising the steps of:
s1, weighing polyvinyl chloride resin, PMMA, MBS toughening agent, lubricant, weather resisting agent, stabilizer and ethylene-vinyl acetate copolymer according to a proportion, and blending uniformly to obtain a premix;
s2, extruding and molding the premix obtained in the step S1 to obtain the low-temperature weather-resistant PVC composition, wherein the extrusion processing temperature is 180-220 ℃.
Examples 1 to 5
The examples provide a series of low temperature weatherable PVC compositions, the specific formulations are shown in table 1;
TABLE 1 formulations (parts) of examples 1 to 5
Examples 6 to 9 and comparative examples 1 to 3
This comparative example provides a series of PVC compositions, the specific formulations of which are given in Table 3
TABLE 3 formulations (parts) of examples 6 to 9 and comparative examples 1 to 3
The pipes prepared from the PVC low temperature weather resistant compositions obtained in the above examples and comparative examples were tested for their properties by the following test methods:
low-temperature weather resistance: referring to JG/T25-1999 method for measuring freeze-thaw cycle resistance of architectural coating, the coating is placed at-25 +/-2 ℃ for 90 days, and is contrastively checked for phenomena of chalking, cracking, peeling, foaming, discoloration and the like.
Detection standard: JG 3050-1998 insulating electrical sleeve and fitting for construction. And placed outdoors at a low temperature of-15 ℃ to-30 ℃ for one month, and then the following experiment is carried out:
impact strength: according to the method for measuring the impact resistance of the 6.5 sleeve in the standard requirement of JG 3050-1998 insulating electrical sleeve and fitting for buildings, the number of damage/total number of the impact strength is more than or equal to 10/12, otherwise, the sleeve is not qualified.
Bending strength: the method accords with the method for measuring the bending performance of 6.6 sleeves in the standard requirements of JG 3050-1998 insulating electrical sleeves and accessories for buildings.
Dropping: the method for measuring the falling performance of the sleeve and the fitting meets the standard requirement of 'JG 3050-1998 insulating electrical sleeve and fitting for building' 6.8 sleeve and fitting.
From comparative examples 1 to 3, it can be seen that the flexural strength cannot be improved without adding the ethylene-vinyl acetate copolymer or with a vinyl acetate content of less than 10% by weight, and the low-temperature weather resistance cannot be satisfied with the calcium carbonate system.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The low-temperature weather-resistant PVC composition is characterized by comprising the following components in parts by weight:
the content of vinyl acetate in the ethylene-vinyl acetate copolymer is more than or equal to 10wt% and less than 18wt%;
the weight average molecular weight of the polyvinyl chloride resin is 35000-65000.
2. The low temperature, weather-resistant PVC composition according to claim 1, wherein the weather-resistant agent is rutile type titanium dioxide.
3. The low temperature, weatherable PVC composition of claim 1, wherein the lubricant is one or more of paraffin wax, stearic acid, or polyethylene wax.
4. The low temperature weatherable PVC composition of claim 1, wherein the stabilizer is a calcium zinc stabilizer.
5. The process for the preparation of a low temperature weatherable PVC composition according to any one of claims 1 to 4, characterized in that it comprises the following steps:
s1, weighing polyvinyl chloride resin, PMMA (polymethyl methacrylate), MBS (methyl methacrylate) flexibilizer, lubricant, weather-resistant agent, stabilizer and ethylene-vinyl acetate copolymer in proportion, and blending uniformly to obtain premix;
and S2, extruding and molding the premix obtained in the step S1 to obtain the low-temperature weather-resistant PVC composition.
6. The method for preparing a low temperature weather-resistant PVC composition according to claim 5, wherein the extrusion processing temperature of step S2 is 180-220 ℃.
7. A PVC electrical bushing, characterized in that it is made of a low-temperature weather-resistant PVC composition according to any of claims 1 to 4.
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Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185048A (en) * | 1974-05-07 | 1980-01-22 | Dynamit Nobel Aktiengesellschaft | Polyvinyl chloride of high impact strength prepared on the basis of ethylene-vinyl acetate or ethylene-alkylacrylate copolymers |
| US5017659A (en) * | 1987-03-13 | 1991-05-21 | Groep L A V D | Polymer composition, a process for its manufacture, and a thermoplastic moulding composition |
| DE3927777A1 (en) * | 1989-08-23 | 1991-02-28 | Solvay Werke Gmbh | SOFTENER-FREE MOLDING MATERIAL BASED ON POLYVINYL CHLORIDE, METHOD FOR THE PRODUCTION AND USE THEREOF |
| JP2003061486A (en) * | 2001-08-30 | 2003-03-04 | Achilles Corp | Agricultural vinyl chloride-based resin film |
| CN101451007A (en) * | 2007-11-29 | 2009-06-10 | 福建亚通新材料科技股份有限公司 | High impact polychloroethylene pressure tube |
| CN101948596B (en) * | 2010-10-27 | 2012-07-25 | 康泰塑胶科技集团有限公司 | Polyvinyl chloride composite material and preparation method thereof |
| CN103087437A (en) * | 2011-10-27 | 2013-05-08 | 山东远洋塑胶工业有限公司 | Methyl methacrylate polymer modified polyvinyl chloride pipe composition |
| CN105237909A (en) * | 2015-10-26 | 2016-01-13 | 宜宾天原集团股份有限公司 | PVC-M impact-resistant low-temperature-resistant pipe and preparation method thereof |
| CN107474430A (en) * | 2017-08-16 | 2017-12-15 | 山东霞光实业有限公司 | A kind of PVC Modified wood plastic section bars of door and window and preparation method thereof |
| CN108219326B (en) * | 2018-04-03 | 2021-02-05 | 马鞍山顾地塑胶有限公司 | Formula and preparation method of high-impact-resistance PVC (polyvinyl chloride) pipe |
| CN111793297A (en) * | 2020-06-10 | 2020-10-20 | 福建澳工塑胶电器有限公司 | Low-temperature brittleness resistant PVC-U flame-retardant electrical casing and preparation method thereof |
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