CN111234409B - Auxiliary agent master batch for polyvinyl chloride modification and preparation method thereof - Google Patents
Auxiliary agent master batch for polyvinyl chloride modification and preparation method thereof Download PDFInfo
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- C08J3/20—Compounding polymers with additives, e.g. colouring
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- 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
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- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the field of high polymer materials, and discloses an auxiliary master batch for polyvinyl chloride modification and a preparation method thereof, wherein the auxiliary master batch comprises the following raw materials in parts by weight: 30-45 parts of ABS high rubber powder; 25-35 parts of general-purpose ABS; 1-10 parts of nano particles; 5-10 parts of a heat stabilizer; 1.5-5 parts of a lubricant; 1-20 parts of a processing aid. The auxiliary agent master batch is prepared by stirring and mixing the components in a high-speed mixer. According to the invention, the impact toughness of PVC is obviously improved by using ABS high-rubber powder, the thermal stability and mechanical property of the material are improved by using general-grade ABS, and the heat stabilizer, the lubricant and the processing aid are cooperated, so that the obtained aid master batch can simultaneously improve the impact toughness and the thermal stability of the PVC material, and the obtained modified PVC material has excellent comprehensive performance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an auxiliary agent master batch for polyvinyl chloride modification and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of the main varieties of general plastics, has the characteristics of flame retardance, corrosion resistance, good electrical insulation, low cost, wide application and the like, can be prepared into soft or hard products with different performances and suitable for different occasions by adding various additives and using various forming methods, and is applied to the fields of building materials, packaging materials, electronic materials, daily consumer goods materials and the like. However, the non-plasticized polyvinyl chloride material has the disadvantages of high brittleness, poor thermal stability, low thermal deformation temperature and the like, and the application range of the non-plasticized polyvinyl chloride material is greatly limited.
In the blending modification of polyvinyl chloride, inorganic powder materials are commonly added to reduce the cost and improve the hardness of a system, and in order to meet the use requirement, the addition amount of the general inorganic powder materials is larger, so that the rigidity and the heat resistance of PVC can be improved, and the toughness and the processing flow property of the materials are also reduced.
The blending method adopted in the prior art is a simple and effective way for improving the heat resistance and the toughness of the polyvinyl chloride. Chinese patent CN109517313A discloses a high-toughness plasticized PVC (polyvinyl chloride) wall panel and a preparation method thereof, wherein vinyl acetate and acrylonitrile are grafted to a polyvinyl chloride main chain, and the vinyl acetate and the acrylonitrile are matched with the use of modified nano-silica and nano-styrene butadiene rubber particles, so that good plasticity, impact strength, tensile strength and other mechanical properties are obtained, and the application range of the polyvinyl chloride composite wall panel is expanded.
Chinese patent CN102321313A discloses a composition of calcium carbonate, rubber and polyvinyl chloride and a preparation method thereof, wherein a filler is prepared into suspension by adopting a coagulation coprecipitation method, the suspension is blended with latex to prepare filled powder rubber, and the filled powder rubber is blended with a polyvinyl chloride base body, dried and dehydrated to obtain a composite alloy which has good toughness and strength and is easy to process.
Chinese patent CN104312047A discloses a heat-resistant and impact-resistant polyvinyl chloride-poly-1-butene compound and a preparation method thereof, wherein polyvinyl chloride, poly-1-butene, a compatibilizer, an internal and external lubricant, rigid nano particles and rare earth-epoxy composite stabilizer are uniformly mixed according to a certain sequence, and the heat resistance of the polyvinyl chloride is improved by the compatibilization of the poly-1-butene and the synergistic toughening of the rigid particles.
Although there have been many studies on the improvement of impact resistance, thermal stability, etc. of polyvinyl chloride in the prior art, the contradiction between toughness and thermal stability of polyvinyl chloride still exists. Generally, the compatibility of the heat-resistant modifier and a system is poor, so that the processability and the mechanical property of the system are reduced; acrylonitrile-butadiene-styrene (ABS) is often used to improve the toughness of pvc materials, but at the same time reduces the material stiffness and heat resistance; the inorganic rigid particles are used for improving the mechanical property of the polyvinyl chloride material and reducing the cost, but simultaneously cause higher viscosity and poor flow processability; therefore, how to prepare polyvinyl chloride with all the properties is still a problem to be continuously researched.
Meanwhile, in the production process of polyvinyl chloride products in the prior art, various additives need to be added in a plurality of times, and the problems of complex process, easy generation of dust, uneven mixing of the additives with small addition amount in a system and the like exist.
Disclosure of Invention
The invention aims to solve the problem that the impact toughness and the heat resistance of a polyvinyl chloride product cannot be obtained simultaneously in the prior art, and provides an auxiliary master batch for polyvinyl chloride modification.
In order to achieve the purpose, the invention adopts the technical scheme that:
the auxiliary master batch for modifying polyvinyl chloride comprises the following raw material components in parts by weight:
ABS is one of the main modification aids of polyvinyl chloride and is used for improving the defects of toughness and heat resistance of the polyvinyl chloride, and an acrylonitrile block in the ABS can have good compatibility with the polyvinyl chloride and is easy to disperse in the polyvinyl chloride efficiently. The invention utilizes the core-shell type ABS high-rubber powder, wherein the polybutadiene composition microspheres are surrounded by the polyacrylonitrile-polystyrene composition, thus greatly improving the impact toughness of PVC; the universal ABS has low polybutadiene content, can improve the heat resistance of the polyvinyl chloride, properly increases the mechanical strength, and can synergistically improve the processing performance and the heat stability of the PVC with a heat stabilizer, a processing aid and the like. The two ABS materials are used in combination, so that the impact toughness and the heat resistance of the PVC are both considered, and the comprehensive performance is optimal.
The rubber content of the ABS high rubber powder is 65-70%; the rubber content of the general ABS is 40-60%. The ABS high rubber powder with the rubber content of 65-70% can obviously improve the impact toughness of the polyvinyl chloride blend, and ensure that a Polybutylene (PB) phase and an acrylonitrile-styrene copolymer (SAN) phase in the ABS have good interface binding force; the general ABS with the gel content of 40-60% can improve the heat resistance of the polyvinyl chloride substrate on the premise of not damaging the mechanical properties of the blend. The proportion of the components can play a good synergistic effect in the rubber phase and SAN phase in the blend and PVC matrix under the conditions of impact, stretching, temperature rise and the like, thereby ensuring the improvement of the comprehensive performance.
The nano particles comprise any one or more of nano white carbon black, nano calcium carbonate, nano graphene, nano montmorillonite and nano bimetallic oxide particles.
The heat stabilizer is a composite stabilizer of organic rare earth and organic tin, wherein the weight ratio of the organic rare earth to the organic tin is 3: 1-1: 2. The PVC hot melt adhesive is mainly used for inhibiting PVC thermal decomposition and discoloration in the high-temperature blending process. The composite stabilizer is safe and environment-friendly, wherein the organic rare earth can promote PVC plasticization, improve the processing fluidity of PVC, improve the short-term thermal stability of PVC, and the organic tin can improve the long-term thermal stability of PVC.
The organic rare earth comprises any one or more of lanthanum laurate, lanthanum citrate, lanthanum itaconate, lanthanum ricinoleate, lanthanum octoate, lanthanum isooctanoate, lanthanum naphthenate, lanthanum oxalate, lanthanum maleamate, lanthanum 2-ethylhexanoate, cerium laurate, cerium citrate, cerium itaconate, cerium ricinoleate, cerium octoate, cerium isooctanoate, cerium naphthenate, cerium oxalate, cerium maleamate and cerium 2-ethylhexanoate.
The organic tin comprises any one or more of coordination methyl tin mercaptide, dimethyl tin oxide, methyl tin maleate, dimethyl tin dineodecanoate, dibutyl tin oxide, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin laurate maleate, dibutyl tin bis (monobutyl maleate), dibutyl tin bis (monooctyl maleate), dioctyl tin oxide, dioctyl tin dilaurate, dioctyl tin maleate, dioctyl tin bis (monooctyl maleate) and dioctyl tin bis (2-ethylhexyl thioglycolate).
The lubricant comprises any one or more of ethylene glycol monostearate, ethylene glycol distearate, glycerol monostearate, acetylated monoglyceride, pentaerythritol, dipentaerythritol and pentaerythritol stearic acid.
The processing aid is a mixture of a styrene-acrylonitrile copolymer (SAN) and an Acrylate Copolymer (ACR), and the mass ratio of the styrene-acrylonitrile copolymer to the acrylate copolymer is 1: 1-1: 4. The function of the PVC modifier is to reduce the viscosity of the blend, improve the fluidity, improve the processability of PVC and ensure the uniform dispersion of all components.
The intrinsic viscosity of the styrene-acrylonitrile copolymer is 10-14 mL/g; the intrinsic viscosity of the acrylate copolymer is 0.5-1.5 mL/g. The matching between the intrinsic viscosity numbers of the selected styrene-acrylonitrile copolymer and the acrylate copolymer can obviously improve the processing fluidity of PVC.
The preparation method of the auxiliary agent master batch for polyvinyl chloride modification provided by the invention comprises the following steps: weighing 30-45 parts by weight of ABS high-rubber powder; 25-35 parts of general-purpose ABS; 1-10 parts of nano particles, 5-10 parts of heat stabilizer, 1.5-5.0 parts of lubricant and 1-20 parts of processing aid by weight are added into a high-speed stirrer to be mixed for 10-20 minutes, and the mixture is discharged when the mixing temperature reaches 60-85 ℃, and cooled to obtain the aid master batch. Various modification aids are mixed at high speed to form a whole, and when the modifier is used for modifying polyvinyl chloride, the defects of multiple addition of the aids, complex process and easy generation of dust are avoided.
The invention provides an application of an auxiliary master batch in polyvinyl chloride modification, which is to blend the auxiliary master batch with 100 parts by weight of polyvinyl chloride to obtain modified polyvinyl chloride. The blending method can be directly mixed with the auxiliary agent master batch in a high-speed stirrer, and can also be a banbury mixer, an extruder and other blending methods commonly used by people in the field. The polyvinyl chloride modified by the assistant master batch has excellent thermal stability, impact toughness and comprehensive performance.
Compared with the prior art, the invention has the following beneficial effects:
the impact toughness of PVC is obviously improved by using ABS high-rubber powder, the thermal stability and mechanical property of the material are maintained by using general-purpose ABS, a heat stabilizer, a lubricant and a processing aid are cooperatively used, the obtained aid master batch can simultaneously improve the impact toughness and the thermal stability of the PVC material, and the obtained modified PVC material has excellent comprehensive performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiment are all purchased from commercial places, and the ABS high-rubber powder adopts HR-181 of Korea Jinhu, and the rubber content is 70%; the rubber content of the universal ABS is 40%, and the material has various performance test standards: notched impact strength ASTM-D256; tensile strength and elongation at break ASTM-D638.
Example 1
100 g of PVC, 2 g of ABS high-rubber powder, 1 g of nano white carbon black, 4 g of lanthanum laurate, 1 g of coordination methyl tin mercaptide, 1.5 g of ethylene glycol monostearate, 0.5 g of SAN with the intrinsic viscosity of 10ml/g and 0.5 g of ACR with the intrinsic viscosity of 0.5ml/g are weighed, added into a high-speed stirrer and mixed for 10 minutes, and the mixture is discharged when the mixing temperature reaches 60 ℃ to obtain a mixture.
And putting the obtained mixture into a mold on a flat vulcanizing machine at 175 ℃ for preheating for 3 minutes, then carrying out hot pressing at 10MPa for 10 minutes, taking out, and carrying out cold pressing on a normal-temperature flat vulcanizing machine for 2 minutes to obtain the modified PVC material. The mechanical properties and vicat softening temperature were measured and the results are shown in table 1.
Examples 2 to 6
A compound was prepared according to the procedure of example 1, in which the amounts of ABS high-rubber powder were replaced by 8 g, 14 g, 20 g, 26 g, 40 g, respectively, and the masses of the other components were unchanged. Modified PVC materials were prepared according to the procedure of example 1 and tested for mechanical properties and Vicat softening temperature, the results of which are shown in Table 1.
As shown in Table 1, it can be seen from the experimental results of examples 1 to 6 that, when only ABS high-rubber powder is added, the impact strength of the modified PVC material is steadily improved from 4.7kJ/m as the addition amount of the ABS high-rubber powder is increased2Is raised to 41.2kJ/m2(ii) a The elongation at break of the material is also clearObviously improves the impact toughness of the PVC material by the ABS high rubber powder.
However, as the addition amount of the high-rubber ABS powder increases, the Vicat softening temperature of the modified PVC material is reduced, which shows that the temperature resistance of the material is reduced, and the tensile strength of the material is also reduced, which shows that a large amount of high-rubber ABS powder can cause the heat resistance and the tensile strength of the modified PVC material to be reduced.
Table 1 mechanical properties and Vicat softening temperature of modified PVC materials of examples 1-6
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Impact Strength (kJ/m)2) | 4.7 | 6.1 | 13.2 | 21.0 | 34.5 | 41.2 |
| Vicat softening temperature (. degree. C.) | 78.6 | 76.5 | 77.2 | 77.6 | 74.7 | 73.8 |
| Tensile Strength (MPa) | 55.3 | 40.9 | 42.2 | 40.1 | 37.9 | 39.4 |
| Elongation at Break (%) | 18.1 | 19.8 | 26.5 | 29.7 | 36.2 | 39.8 |
Example 7
According to the experimental results of the embodiments 1 to 6, the amount of the ABS high-rubber powder is 30 g calculated by 100 g of PVC, and various performances of the modified PVC material after the universal ABS is added are further tested.
100 g of PVC, 30 g of ABS high-rubber powder, 10 g of general-grade ABS, 1 g of nano white carbon black, 4 g of lanthanum laurate, 1 g of coordination methyl tin mercaptide, 1.5 g of ethylene glycol monostearate, 2 g of SAN with the intrinsic viscosity of 10ml/g and 2 g of ACR with the intrinsic viscosity of 0.5ml/g are weighed, added into a high-speed stirrer and mixed for 10 minutes, and the mixture is discharged when the mixing temperature reaches 60 ℃ to obtain a mixture.
And putting the obtained mixture into a mold on a flat vulcanizing machine at 175 ℃ for preheating for 3 minutes, then carrying out hot pressing at 10MPa for 10 minutes, taking out, and carrying out cold pressing on a normal-temperature flat vulcanizing machine for 2 minutes to obtain the modified PVC material. The mechanical properties and vicat softening temperature were measured and the results are shown in table 2.
Examples 8 to 12
A blend was prepared according to the procedure of example 7, wherein the amounts of universal grade ABS were replaced with 20 g, 25 g, 30 g, 35 g, 40 g, respectively, and the other components were unchanged in mass. Modified PVC materials were prepared according to the procedure of example 7 and tested for mechanical properties and Vicat softening temperature, the results of which are shown in Table 2.
It can be seen that under the condition that the addition amount of the ABS high rubber powder is not changed, the impact strength of the modified PVC material is reduced with the increase of the addition amount of the general-purpose ABS, but still kept at 20kJ/m2The above;
meanwhile, the Vicat softening temperature of the modified PVC material is slightly improved, the tensile strength can be kept above 40MPa, the elongation at break can be kept above 28%, and therefore the PVC material has good tensile strength and temperature resistance under the condition of keeping higher impact toughness by matching ABS high rubber powder and general-purpose ABS.
Table 2 mechanical properties and Vicat softening temperature of modified PVC materials of examples 7-12
| Performance of | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Impact Strength (kJ/m)2) | 36.5 | 33.0 | 28.9 | 24.5 | 23.3 | 21.6 |
| Vicat softening temperature (. degree. C.) | 76.1 | 79.0 | 81.1 | 80.7 | 81.4 | 85.0 |
| Tensile Strength (MPa) | 57.9 | 45.1 | 43.3 | 45.8 | 41.9 | 40.2 |
| Elongation at Break (%) | 33.8 | 35.2 | 28.5 | 33.7 | 32.2 | 35.4 |
Claims (2)
1. The application of the auxiliary master batch for polyvinyl chloride modification in polyvinyl chloride modification comprises the following raw material components in parts by weight:
the rubber content of the ABS high rubber powder is 65-70%; the gel content of the general ABS is 40-60%;
the nano particles are nano white carbon black;
the heat stabilizer is a composite stabilizer of organic rare earth and organic tin, wherein the weight ratio of the organic rare earth to the organic tin is 3: 1-1: 2;
the organic rare earth is lanthanum laurate;
the organic tin is coordination methyl tin mercaptide;
the lubricant is ethylene glycol monostearate;
the processing aid is a mixture of a styrene-acrylonitrile copolymer and an acrylate copolymer, wherein the mass ratio of the styrene-acrylonitrile copolymer to the acrylate copolymer is 1: 1-1: 4;
the intrinsic viscosity of the styrene-acrylonitrile copolymer is 10 mL/g; the intrinsic viscosity of the acrylate copolymer is 0.5 mL/g;
and blending the auxiliary master batch with 100 parts by weight of polyvinyl chloride to obtain the modified polyvinyl chloride.
2. The use of the adjuvant masterbatch for polyvinyl chloride modification according to claim 1 in polyvinyl chloride modification, wherein the preparation method of the adjuvant masterbatch comprises: weighing 30-45 parts of ABS high-rubber powder; 25-35 parts of general-purpose ABS; 1-10 parts of nano particles, 5-10 parts of heat stabilizer, 1.5-5.0 parts of lubricant and 1-20 parts of processing aid by weight are added into a high-speed stirrer to be mixed for 10-20 minutes, and the mixture is discharged when the mixing temperature reaches 60-85 ℃, and cooled to obtain the aid master batch.
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|---|---|---|---|---|
| CN102040786A (en) * | 2010-12-30 | 2011-05-04 | 佛山市顺德区圆融新材料有限公司 | Antiflaming PVC (poly vinyl chloride)/ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN106700389A (en) * | 2016-11-14 | 2017-05-24 | 中山市亮彩染料实业有限公司 | Super tough ABS masterbatch composite material |
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