CN112126170A - PVC tray and preparation method thereof - Google Patents

PVC tray and preparation method thereof Download PDF

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Publication number
CN112126170A
CN112126170A CN202010887199.XA CN202010887199A CN112126170A CN 112126170 A CN112126170 A CN 112126170A CN 202010887199 A CN202010887199 A CN 202010887199A CN 112126170 A CN112126170 A CN 112126170A
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Prior art keywords
pvc
tray
filler
type
parts
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Inventor
郭俊凡
顾丽丽
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Shandong Xindidan Environmental Protection Technology Co ltd
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Shandong Xindidan Environmental Protection Technology Co ltd
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Priority to CN202010887199.XA priority Critical patent/CN112126170A/en
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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    • C08J2203/00—Foams characterized by the expanding agent
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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
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    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
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    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

The invention belongs to the technical field of PVC materials, and particularly relates to a PVC tray and a preparation method thereof. The material comprises, by mass, 70-80 parts of polyvinyl chloride resin, 20-30 parts of PCV scrap, 3.5-4.0 parts of ethylene-octene copolymer, 0.5-0.8 part of foaming agent, 4.0-6.0 parts of foaming regulator, 0.5-1.0 part of impact modifier, 0.1-0.5 part of initiator, 3.0-4.5 parts of filler, 1.0-3.0 parts of antioxidant, 0.5-1.5 parts of lubricant, 2.0-3.0 parts of coupling agent and 1.5-3.0 parts of heat stabilizer. The PVC tray provided by the invention adopts the synergistic cooperation of the ethylene-octene copolymer and the impact modifier, the impact resistance of the tray is enhanced, the filler is modified by using the coupling agent, the compatibility of the filler and PVC resin is increased, and the service life of the tray is prolonged by adding the antioxidant and the heat stabilizer.

Description

PVC tray and preparation method thereof
Technical Field
The invention belongs to the technical field of PVC materials, and particularly relates to a PVC tray and a preparation method thereof.
Background
Polyvinyl chloride (PVC) section bar is produced by adopting a polyvinyl chloride material, and is produced by taking polyvinyl chloride and copolymer resin thereof as main raw materials, adding auxiliary materials such as a filler, a plasticizer, a stabilizer and the like, and coating or rolling, extruding or extruding on a flaky continuous base material. Because of the advantages of water resistance, flame resistance, acid and alkali resistance, moth resistance, light weight, smooth and flat surface, no deformation, easy processing, recyclability and the like, the PVC section becomes a common thermal forming material, can replace part of stainless steel and other corrosion-resistant synthetic materials, and is widely applied to the fields of building engineering, municipal engineering, chemical engineering, industrial production and the like.
The pallet is an indispensable carrying tool in chemical and industrial production, is a medium for converting static goods into dynamic goods, is a carrying platform, and is a movable platform or a movable ground. Even if the goods are put on the ground and lose flexibility, the goods can be immediately moved after being loaded with the pallets, and the goods become flexible and mobile goods. At present, the types of the trays classified according to the materials mainly include: wooden pallets, bamboo pallets, multi-ply board pallets, plastic pallets, steel pallets, paper pallets, plastic-wood pallets, molded pallets, etc., but all suffer from some drawbacks. The wooden tray is not fireproof and waterproof, is easy to damp, is easy to grow insects and decay, is easy to generate burrs at corners and has low bearing capacity. The plastic tray has the advantages of no water absorption, high turnover rate, convenient recycling and the like as a substitute of the traditional tray, plays a bigger and bigger role in the field of warehouse logistics, but has the defects of low strength, poor impact resistance, easy occurrence of scratches on the surface when placing some heavier objects and the like.
Disclosure of Invention
The purpose of the invention is: a PVC pallet is provided. The PVC tray has the advantages of high strength, strong impact resistance, no scratch after long-term use and the like; the invention also provides a preparation method thereof.
The PVC tray comprises the following raw materials in parts by weight:
Figure BDA0002655920510000011
Figure BDA0002655920510000021
wherein:
the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 3.5-5.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
The foaming agent is at least two of p-toluenesulfonyl azide, 4' -oxybis-benzenesulfonyl hydrazide, azobisisobutyronitrile or azodicarbonamide.
The foaming regulator is one or more of methyl methacrylate, methyl acrylate or butyl acrylate.
The impact modifier is a composition of trifluoroethyl methacrylate, nitrile rubber and n-octyl acrylate.
The initiator is peroxide, and the peroxide is one or more of diisopropyl peroxydicarbonate, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, lauroyl peroxide, diphenoxyethyl peroxydicarbonate or bis (2-ethyl) hexyl peroxydicarbonate.
The filler is one or two of red mud, gold tailings or bacterial cellulose, preferably a mixture of the red mud and the gold tailings, and the weight ratio of the red mud to the gold tailings is 1: 1.
The antioxidant is one or more of octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, triphenyl phosphite, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or dilauryl thiodipropionate.
The lubricant is one or more of pentaerythritol stearate, stearic acid, polyethylene wax or Fischer-Tropsch wax.
The coupling agent is one or more of 3-glycidyl ether oxypropyl triethoxysilane, gamma-glycidyl propyl methyldimethoxysilane, sodium dodecyl benzene sulfonate, polyether silicone oil or polyvinyl alcohol.
The heat stabilizer is a calcium-zinc composite stabilizer.
The preparation method of the PVC tray comprises the following steps:
(1) carrying out polymerization reaction on the ethylene-octene copolymer, the impact modifier and the initiator at the temperature of 140 ℃ and 150 ℃;
(2) adding the filler into the coupling agent and mixing at the temperature of 100-120 ℃;
(3) putting the products obtained in the step (1) and the step (2), polyvinyl chloride resin, PCV scrap, a foaming agent, a foaming regulator, a filler, an antioxidant, a lubricant and a heat stabilizer into a mixer according to a ratio for mixing, wherein the mixing temperature is kept at 190 ℃ and the mixing time is 20-30 min;
(4) and taking out the mixture for extrusion molding, obtaining a molten material through an extruder, carrying out vacuum negative pressure cooling and shaping on the molten material, cooling and molding the molten material through a cooling system to obtain a tray, and carrying out post-treatment on the molded tray to obtain the PVC tray.
Compared with the prior art, the invention has the following beneficial effects:
(1) the PVC tray provided by the invention adopts the synergistic cooperation of the ethylene-octene copolymer and the impact modifier, the impact resistance of the tray is enhanced, the filler is modified by using the coupling agent, the compatibility of the filler and PVC resin is increased, and the service life of the tray is prolonged by adding the antioxidant and the heat stabilizer.
(2) The PVC tray provided by the invention has the advantages of high surface hardness, strong scratch resistance, excellent impact resistance, and high tensile strength and bending strength.
(3) The preparation method of the PVC tray has the advantages of easily available raw materials, simple process, easy realization of industrial production, good performance of the prepared tray and long service life.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The PVC tray described in this embodiment 1 comprises the following raw materials in parts by mass:
Figure BDA0002655920510000031
wherein:
the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 4.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
The foaming agent is a mixture of p-toluenesulfonyl azide and azobisisobutyronitrile.
The foaming regulator is methyl methacrylate.
The impact modifier is a composition of trifluoroethyl methacrylate, nitrile rubber and n-octyl acrylate.
The initiator is peroxide, and the peroxide is a mixture of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
The filler is red mud, and the chemical composition of the red mud is SiO2 12.3％、Al2O3 33.5％、Fe2O3 7.6％、CaO 21.3％、MgO 1.2％、TiO2 3.5％、K2O 0.5％、Na23.7% of O and 16.4% of loss on ignition.
The antioxidant is octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
The lubricant is a mixture of pentaerythritol stearate and Fischer-Tropsch wax.
The coupling agent is 3-glycidyl ether oxypropyl triethoxysilane.
The heat stabilizer is a calcium-zinc composite stabilizer.
The preparation method of the PVC tray described in this embodiment 1 comprises the following steps:
(1) polymerizing the ethylene-octene copolymer, the impact modifier and the initiator at 145 ℃;
(2) adding the filler into the coupling agent and mixing at 110 ℃;
(3) putting the products obtained in the steps (1) and (2), polyvinyl chloride resin, PCV scrap, a foaming agent, a foaming regulator, a filler, an antioxidant, a lubricant and a heat stabilizer into a mixer according to a ratio for mixing, wherein the mixing temperature is kept at 170 ℃, and the mixing time is 25 min;
(4) and taking out the mixture for extrusion molding, obtaining a molten material through an extruder, carrying out vacuum negative pressure cooling and shaping on the molten material, cooling and molding the molten material through a cooling system to obtain a tray, and carrying out post-treatment on the molded tray to obtain the PVC tray.
Example 2
The PVC tray described in this embodiment 2 is composed of the following raw materials in parts by mass:
Figure BDA0002655920510000041
wherein:
the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 5.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
The foaming agent is a mixture of 4, 4' -oxybis-benzenesulfonyl hydrazide, azodiisobutyronitrile and azodicarbonamide.
The foaming regulator is a mixture of methyl methacrylate and butyl acrylate.
The impact modifier is a composition of trifluoroethyl methacrylate, nitrile rubber and n-octyl acrylate.
The initiator is peroxide, and the peroxide is bis (2-ethyl) hexyl peroxydicarbonate.
The filler is a mixture of red mud and gold tailings, and the weight ratio of the red mud to the gold tailings is 1: 1; the chemical composition of the red mud is SiO2 12.3％、Al2O3 33.5％、Fe2O3 7.6％、CaO 21.3％、MgO 1.2％、TiO23.5％、K2O0.5％、Na23.7 percent of O and 16.4 percent of loss on ignition; the chemical composition of the gold tailings is SiO270.5％、Al2O3 17％、K2O 3％、Na2O 3％、CaO 2％、MgO 0.2％、Fe2O3 1％、TiO20.1% and traces of zirconium dioxide, zinc oxide and barium oxide.
The antioxidant is triphenyl phosphite.
The lubricant is stearic acid.
The coupling agent is a mixture of gamma-glycidylpropylmethyldimethoxysilane and polyvinyl alcohol.
The heat stabilizer is a calcium-zinc composite stabilizer.
The preparation method of the PVC tray described in this embodiment 2 comprises the following steps:
(1) carrying out polymerization reaction on the ethylene-octene copolymer, the impact modifier and the initiator at 150 ℃;
(2) adding the filler into the coupling agent and mixing at 120 ℃;
(3) putting the products obtained in the steps (1) and (2), polyvinyl chloride resin, PCV scrap, a foaming agent, a foaming regulator, a filler, an antioxidant, a lubricant and a heat stabilizer into a mixer according to a ratio for mixing, wherein the mixing temperature is kept at 190 ℃ and the mixing time is 30 min;
(4) and taking out the mixture for extrusion molding, obtaining a molten material through an extruder, carrying out vacuum negative pressure cooling and shaping on the molten material, cooling and molding the molten material through a cooling system to obtain a tray, and carrying out post-treatment on the molded tray to obtain the PVC tray.
Example 3
The PVC tray described in this embodiment 3 is composed of the following raw materials in parts by mass:
Figure BDA0002655920510000051
Figure BDA0002655920510000061
wherein:
the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 3.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
The foaming agent is a mixture of azodiisobutyronitrile and azodicarbonamide.
The foaming regulator is butyl acrylate.
The impact modifier is a composition of trifluoroethyl methacrylate, nitrile rubber and n-octyl acrylate.
The initiator is peroxide, and the peroxide is lauroyl peroxide.
The filler is bacterial cellulose.
The antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The lubricant is a mixture of stearic acid and polyethylene wax.
The coupling agent is sodium dodecyl benzene sulfonate.
The heat stabilizer is a calcium-zinc composite stabilizer.
The preparation method of the PVC tray described in this embodiment 3 comprises the following steps:
(1) carrying out polymerization reaction on the ethylene-octene copolymer, the impact modifier and the initiator at 140 ℃;
(2) adding the filler into the coupling agent and mixing at 10 ℃;
(3) putting the products obtained in the steps (1) and (2), polyvinyl chloride resin, PCV scrap, a foaming agent, a foaming regulator, a filler, an antioxidant, a lubricant and a heat stabilizer into a mixer according to a ratio for mixing, wherein the mixing temperature is kept at 180 ℃, and the mixing time is 30 min;
(4) and taking out the mixture for extrusion molding, obtaining a molten material through an extruder, carrying out vacuum negative pressure cooling and shaping on the molten material, cooling and molding the molten material through a cooling system to obtain a tray, and carrying out post-treatment on the molded tray to obtain the PVC tray.
Comparative example 1
The PVC tray of comparative example 1 comprises the following raw materials in parts by mass:
Figure BDA0002655920510000062
Figure BDA0002655920510000071
wherein:
the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 5.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
The foaming agent is a mixture of 4, 4' -oxybis-benzenesulfonyl hydrazide, azodiisobutyronitrile and azodicarbonamide.
The foaming regulator is a mixture of methyl methacrylate and butyl acrylate.
The impact modifier is a composition of trifluoroethyl methacrylate, nitrile rubber and n-octyl acrylate.
The initiator is peroxide, and the peroxide is bis (2-ethyl) hexyl peroxydicarbonate.
The filler is a mixture of red mud and gold tailings, and the weight ratio of the red mud to the gold tailings is 1: 1; the chemical composition of the red mud is SiO2 12.3％、Al2O3 33.5％、Fe2O3 7.6％、CaO 21.3％、MgO 1.2％、TiO23.5％、K2O0.5％、Na23.7 percent of O and 16.4 percent of loss on ignition; the chemistry of the gold tailingsHas the composition of SiO270.5％、Al2O3 17％、K2O 3％、Na2O 3％、CaO 2％、MgO 0.2％、Fe2O3 1％、TiO20.1% and traces of zirconium dioxide, zinc oxide and barium oxide.
The antioxidant is triphenyl phosphite.
The lubricant is stearic acid.
The coupling agent is a mixture of gamma-glycidylpropylmethyldimethoxysilane and polyvinyl alcohol.
The heat stabilizer is a calcium-zinc composite stabilizer.
The preparation method described in this comparative example 1 is the same as that of example 2.
Comparative example 2
The PVC tray of comparative example 2 comprises the following raw materials in parts by mass:
Figure BDA0002655920510000072
Figure BDA0002655920510000081
wherein:
the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 5.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
The foaming agent is a mixture of 4, 4' -oxybis-benzenesulfonyl hydrazide, azodiisobutyronitrile and azodicarbonamide.
The foaming regulator is a mixture of methyl methacrylate and butyl acrylate.
The impact modifier is a composition of trifluoroethyl methacrylate and nitrile rubber.
The initiator is peroxide, and the peroxide is bis (2-ethyl) hexyl peroxydicarbonate.
The filler is red mud and gold tailThe weight ratio of the red mud to the gold tailings is 1: 1; the chemical composition of the red mud is SiO2 12.3％、Al2O3 33.5％、Fe2O3 7.6％、CaO 21.3％、MgO 1.2％、TiO23.5％、K2O0.5％、Na23.7 percent of O and 16.4 percent of loss on ignition; the chemical composition of the gold tailings is SiO270.5％、Al2O3 17％、K2O 3％、Na2O 3％、CaO 2％、MgO 0.2％、Fe2O3 1％、TiO20.1% and traces of zirconium dioxide, zinc oxide and barium oxide.
The antioxidant is triphenyl phosphite.
The lubricant is stearic acid.
The coupling agent is a mixture of gamma-glycidylpropylmethyldimethoxysilane and polyvinyl alcohol.
The heat stabilizer is a calcium-zinc composite stabilizer.
The preparation method described in this comparative example 2 is the same as that of example 2.
Comparative example 3
The raw materials for the PVC pallet and the preparation method thereof described in comparative example 3 are the same as those of comparative example 2, except that the impact modifier is a combination of nitrile rubber and n-octyl acrylate.
Comparative example 4
The raw materials for the PVC pallet and the preparation method thereof described in comparative example 4 are the same as those of comparative example 2, except that the impact modifier is a combination of trifluoroethyl methacrylate and n-octyl acrylate.
The PVC trays prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, and the results are shown in table 1 below:
Figure BDA0002655920510000091

Claims (10)

1. a PVC tray, its characterized in that: the raw materials comprise the following components in parts by mass:
Figure FDA0002655920500000011
2. the PVC tray of claim 1, wherein: the polyvinyl chloride resin is a compound of SG-5 and SG-8, the mass ratio of SG-8 type PVC resin powder to SG-5 type PVC resin powder is 3.5-5.5:1, the average polymerization degree of SG-5 type PVC resin powder is 1000-type 1100, and the average polymerization degree of SG-8 type PVC resin powder is 700-type 750.
3. The PVC tray of claim 1, wherein: the foaming agent is at least two of p-toluenesulfonyl azide, 4' -oxybis-benzenesulfonyl hydrazide, azodiisobutyronitrile or azodicarbonamide; the foaming regulator is one or more of methyl methacrylate, methyl acrylate or butyl acrylate.
4. The PVC tray of claim 1, wherein: the impact modifier is a composition of trifluoroethyl methacrylate, nitrile rubber and n-octyl acrylate.
5. The PVC tray of claim 1, wherein: the initiator is peroxide, and the peroxide is one or more of diisopropyl peroxydicarbonate, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, lauroyl peroxide, diphenoxyethyl peroxydicarbonate or bis (2-ethyl) hexyl peroxydicarbonate.
6. The PVC tray of claim 1, wherein: the filler is one or two of red mud, gold tailings, bacterial cellulose or expanded perlite powder.
7. The PVC tray of claim 6, wherein: the filler is a mixture of red mud and gold tailings, and the weight ratio of the red mud to the gold tailings is 1: 1.
8. The PVC tray of claim 1, wherein: the antioxidant is one or more of octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, triphenyl phosphite, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or dilauryl thiodipropionate; the heat stabilizer is a calcium-zinc composite stabilizer.
9. The PVC tray of claim 1, wherein: the lubricant is one or more of pentaerythritol stearate, stearic acid, polyethylene wax or Fischer-Tropsch wax; the coupling agent is one or more of 3-glycidyl ether oxypropyl triethoxysilane, gamma-glycidyl propyl methyldimethoxysilane, sodium dodecyl benzene sulfonate, polyether silicone oil or polyvinyl alcohol.
10. A method for preparing the PVC tray of claim 1, characterized in that: the method comprises the following steps:
(1) carrying out polymerization reaction on the ethylene-octene copolymer, the impact modifier and the initiator at the temperature of 140 ℃ and 150 ℃;
(2) adding the filler into the coupling agent and mixing at the temperature of 100-120 ℃;
(3) putting the products obtained in the step (1) and the step (2), polyvinyl chloride resin, PCV scrap, a foaming agent, a foaming regulator, a filler, an antioxidant, a lubricant and a heat stabilizer into a mixer according to a ratio for mixing, wherein the mixing temperature is kept at 190 ℃ and the mixing time is 20-30 min;
(4) and taking out the mixture for extrusion molding, obtaining a molten material through an extruder, carrying out vacuum negative pressure cooling and shaping on the molten material, cooling and molding the molten material through a cooling system to obtain a tray, and carrying out post-treatment on the molded tray to obtain the PVC tray.
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CN109810429A (en) * 2019-01-22 2019-05-28 青岛海诺瓦型材制造有限公司 A kind of plastic-aluminum co-extrusion section bar weather-proof foamed plastic and preparation method thereof

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EP0288723A1 (en) * 1987-04-29 1988-11-02 Alkor Gmbh Kunststoffe Flexible, deep-drawnable plastic resin film for automobiles formed of several layers
CN102224192A (en) * 2008-11-28 2011-10-19 三菱丽阳株式会社 Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body
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Application publication date: 20201225