CN114456284A - Low-temperature toughened polyion polymer, PVC heat stabilizer and PVC livestock plate - Google Patents

Low-temperature toughened polyion polymer, PVC heat stabilizer and PVC livestock plate Download PDF

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CN114456284A
CN114456284A CN202111471477.4A CN202111471477A CN114456284A CN 114456284 A CN114456284 A CN 114456284A CN 202111471477 A CN202111471477 A CN 202111471477A CN 114456284 A CN114456284 A CN 114456284A
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pvc
polymer
parts
heat stabilizer
antioxidant
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CN114456284B (en
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施燕琴
张伟民
王旭
朱小云
陈路凯
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Zhejiang Hongtian New Material Technology Co ltd
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Abstract

The invention relates to the field of PVC heat stabilizers, and discloses a low-temperature toughened polyion polymer, a PVC heat stabilizer and a PVC livestock plate. The preparation method of the polyion polymer comprises the following steps: (1) carrying out polymerization reaction on a monomer A containing carbon-carbon double bonds and carboxylic acid groups, an olefin monomer B and an initiator to obtain a copolymer; (2) regulating the pH value of the copolymer to be 5.0-6.0 by using a counter ion compound A; (3) and (3) regulating the pH value of the obtained single-ion copolymer to 6.2-7.5 by using a counter ion compound B to obtain the multi-ion polymer. The invention firstly adopts the copolymerization method to prepare the polyion polymer as the main component of the PVC heat stabilizer, which can effectively improve the low-temperature impact resistance of PVC; on the basis, calcium stearate, zinc stearate and other components are compounded, so that the thermal stability of PVC can meet the requirement, and the PVC livestock-raising board with low-temperature impact resistance can be prepared.

Description

Low-temperature toughened polyion polymer, PVC heat stabilizer and PVC livestock plate
Technical Field
The invention relates to the field of PVC heat stabilizers, in particular to a low-temperature toughened polyion polymer, a PVC heat stabilizer and a PVC livestock plate.
Background
The development speed of livestock raising is high in recent years, and the use amount of farm building materials is gradually increased, wherein the livestock raising boards are an indispensable part of the farm building materials. The traditional wooden livestock boards cannot meet the current agricultural requirements because of the problems of easy mildew and rot, low strength, environment damage and the like. PVC, which is the second most common plastic, has a variety of excellent properties and has been widely used in various fields. Wherein in animal husbandry, PVC poultry board is as a novel material, owing to can recycle, accords with the big trend of replacing wood with moulding, replaces steel with moulding, consequently can replace the use of wooden poultry board better. Specifically, PVC poultry board mainly used animal breeding baffle designs into hollow form, compares in other materials, and the hollow board advantage is obvious in the PVC: the material is light, sturdy and durable, and is pleasing to the eye comfortable, nontoxic difficult fire, and dampproofing and waterproofing is prevented the worm and is eaten and need not maintain, washs the equipment convenience, and weatherability is strong, long service life, and shock resistance is corrosion-resistant, can not be because of the temperature variation fracture deformation. However, the PVC material also has a certain defect that the impact resistance at low temperature is poor, and a modifier is required to be added for modification.
At present, many researchers have developed and studied ionic polymers, and there are two methods known for synthesizing ionic polymers, the first being a copolymerization method in which a monomer having a polymerizable ionizing functional group is copolymerized with an olefin monomer, and then the copolymer is neutralized with a hydroxide or an alkaline salt to form an ionic polymer; the second method is to functionalize the polymer molecule, for example, by sulfonating the polymer with a sulfonating agent, and then neutralizing the polymer with a hydroxide or basic salt. The low-temperature impact resistance of the composite material can be improved by adding a proper amount of ionic polymer into the composite material, so that the material has better flexural toughness and impact toughness in a low-temperature environment. Meanwhile, the ionic polymer has a non-polar long chain, so that the ionic polymer has good compatibility with a resin matrix and can be well dispersed in the resin matrix. However, most of the ionic polymers obtained by the current research are single ions, namely, single ionic polymers, and the improvement of the low-temperature impact resistance of the PVC is limited, so that the requirements of high-performance PVC products cannot be met.
Because of the charge effect, ions of the same charge can be repulsive, which can hinder the preparation of polyionic polymers after the preparation of a unimonic polymer. Meanwhile, the enhancement action mode of the single-ion polymer is single, for example, monovalent ions mainly improve the mechanical property of the material in an ion aggregation mode; the divalent ions realize the improvement of mechanical properties through the cross-linking effect of ionic bonds. Therefore, the single ion polymer has limited improvement on the low-temperature impact resistance of PVC, and cannot meet the requirement of high-performance PVC products. Therefore, the invention adopts a copolymerization method, uses acrylic acid and olefin monomers to prepare the polyion polymer, so that a nonpolar chain has univalent cations and divalent cations at the same time, the polyion polymer can improve the mechanical property of the material through the crosslinking action of ionic bonds, can improve the mechanical property of the material through an ion aggregation mode, can be successfully prepared by regulating and controlling the pH value, and then can be used as the main component of a PVC heat stabilizer, and compared with the monoaon polymer, the low-temperature impact resistance of PVC can be further effectively improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low-temperature toughened polyion polymer, a PVC heat stabilizer and a PVC livestock plate. The invention firstly adopts the copolymerization method to prepare the polyion polymer as the main component of the PVC heat stabilizer, which can effectively improve the low-temperature impact resistance of PVC; on the basis, calcium stearate, zinc stearate and other components are compounded, so that the requirement of a PVC thermal stability composite product is met, and the PVC livestock board with low-temperature impact resistance is prepared.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a low-temperature toughened polyion polymer, and a preparation method thereof comprises the following steps:
(1) carrying out polymerization reaction on a monomer A containing carbon-carbon double bonds and carboxylic acid groups, an olefin monomer B and an initiator to obtain a copolymer.
(2) Regulating the pH value of the copolymer to 5.0-6.0 by using a counter ion compound A to obtain a single ion polymer; the counter ion compound A comprises one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate and sodium acetate.
(3) Adjusting the pH value of the single ion polymer to 6.2-7.5 by using a compound B of counter ions to obtain a multi-ion polymer; the counter ion compound B comprises one or more of calcium hydroxide, sodium calcium bicarbonate, calcium carbonate, calcium acetate, zinc hydroxide and zinc acetate.
As described in the technical section of the application, most of ionic polymers reported in the prior art for improving the low-temperature impact resistance of PVC are single ionic polymers, but the enhancement mode of the single ionic polymers is single, for example, monovalent ions mainly improve the mechanical properties of the material by means of ion aggregation; the divalent ions realize the improvement of mechanical properties through the cross-linking effect of ionic bonds. Therefore, the single ion polymer has limited improvement on the low-temperature impact resistance of PVC, and cannot meet the requirement of high-performance PVC products. Therefore, the polyion polymer is prepared by adopting a copolymerization method, so that a nonpolar chain simultaneously contains univalent cations and divalent cations, and the polyion polymer can improve the mechanical property of the material through the crosslinking action of ionic bonds and can improve the mechanical property of the material through an ion aggregation mode. However, the group of the present invention found that when preparing polyionic polymers, due to the charge effect, ions with the same charge would have repulsion, which easily causes obstacles to be encountered when further preparing polyionic polymers after preparing single ionic polymers. Therefore, the team of the invention discovers that the regulation and control of the pH value in the preparation process are crucial through further research, finally obtains that the pH value of each step is controlled in the specific range, can successfully prepare the polyion polymer containing reasonable monovalent/divalent cation proportion, and can further effectively improve the low-temperature impact resistance of PVC by taking the polyion polymer as the main component of the PVC heat stabilizer compared with the uniionic polymer.
Preferably, in step (1): the monomer A containing the carbon-carbon double bond and the carboxylic acid group is one or more of acrylic acid and methacrylic acid; the addition amount is 5-15 parts by weight. The olefin monomer B is one or more of ethylene, butadiene, styrene and propylene; the addition amount is 20 to 50 parts by weight. The initiator is one or more of azodiisobutyronitrile, dibenzoyl peroxide, tert-butyl hydroperoxide and dicumyl peroxide; the addition amount is 1 to 5 parts by weight.
More preferably, the amount of the monomer A containing a carbon-carbon double bond and a carboxylic acid group is 10 parts by weight; the addition amount of the olefin monomer B is 35 parts by weight; the addition amount of the initiator is 3 parts by weight.
Preferably, in step (1): the reaction temperature is 50-80 ℃, and the preferable reaction temperature is 65 ℃; the reaction time is 3-5 h, and the preferable reaction time is 4 h; the stirring speed is 30-50 r/min, preferably 40 r/min.
Preferably, in step (2), the pH of the copolymer is adjusted to 6.0 with the counter ion compound A to give a mono-ionic polymer.
Preferably, in step (3), the nonionic polymer is adjusted to a pH of 7.0 with a compound B as a counter ion to give a polyionic polymer.
In a second aspect, the invention provides a PVC heat stabilizer, which comprises the following components in parts by weight: 5-15 parts of low-temperature toughened polyion polymer, 1-30 parts of zinc stearate, 1-40 parts of calcium stearate, 5-50 parts of triphenyl phosphate, 5-20 parts of antioxidant and 1-5 parts of lubricant.
According to the invention, the low-temperature toughened polyion polymer is compounded with calcium stearate, zinc stearate and other components, so that the thermal stability of PVC can meet the requirements, and the PVC livestock-raising plate with low-temperature impact resistance can be prepared.
Preferably, the PVC heat stabilizer comprises the following components in parts by weight: 10 parts of low-temperature toughened polyion polymer, 20 parts of zinc stearate, 30 parts of calcium stearate, 20 parts of triphenyl phosphate, 10 parts of antioxidant and 4 parts of lubricant.
Preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168 and antioxidant 215; further preferably, the antioxidant 1010 and the antioxidant 168 are mixed at a mass ratio of 3: 1.
Preferably, the lubricant is selected from one or more of stearic acid, polyethylene wax, glyceryl stearate and oxidized polyethylene wax; further preferred is a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1.5.
In a third aspect, the present invention provides a PVC livestock board, comprising 100phr of PVC powder, 1 to 5phr of PVC heat stabilizer as defined in any one of claims 5 to 7.
Preferably, the PVC livestock-raising plate comprises 100phr of PVC powder, 1-5 phr of PVC heat stabilizer and 2-15 phr of epoxidized soybean oil.
Most preferably, the PVC livestock board comprises 100phr of PVC powder, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil.
Preferably, the preparation method of the PVC livestock board comprises the following steps: uniformly stirring the PVC powder, the PVC heat stabilizer and the epoxy soybean oil, mixing for 2-5 min at the temperature of 170-185 ℃, and then hot-pressing for 0.5-2min at the temperature of 170-185 ℃ and at the pressure of 100-110bar to obtain the PVC livestock-raising plate.
Preferably, the mixing temperature is 180 ℃, and the mixing time is 3 min; n; the hot-pressing temperature is 180 ℃ and the hot-pressing pressure is 110 bar.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention realizes the increase of the low-temperature impact resistance of the PVC material by using the polyion polymer and by means of the crosslinking action and the aggregation action of ionic bonds in the polyion polymer, thereby meeting the use requirement of the PVC composite material in animal husbandry.
(2) The preparation method successfully prepares the polyion polymer containing reasonable monovalent/divalent cation ratio by strictly controlling the pH of each step, and is simple to operate, green, environment-friendly and easy to industrialize.
(3) The polyion polymer, calcium salt, zinc salt and the like are compounded and then can be used as a PVC heat stabilizer to be applied to PVC products, and the obtained products have excellent initial whiteness and long-term heat stability.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A low-temperature toughened polyion polymer is prepared by the following steps:
(1) 5-15 parts by weight (preferably 10 parts by weight) of monomer A (one or more of acrylic acid and methacrylic acid) containing carbon-carbon double bonds and carboxylic acid groups, 20-50 parts by weight (preferably 35 parts by weight) of olefin monomer B (one or more of ethylene, butadiene, styrene and propylene) and 1-5 parts by weight (preferably 3 parts by weight) of initiator (one or more of azodiisobutyronitrile, dibenzoyl peroxide, tert-butyl hydroperoxide and dicumyl peroxide) are subjected to polymerization reaction at 50-80 ℃ (preferably 65 ℃) and 30-50 r/min (preferably 40r/min) for 3-5 h (preferably 4h) to obtain the copolymer.
(2) Adjusting the pH value of the copolymer to be 5.0-6.0 (preferably 6.0) by using a counter ion compound A (one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate and sodium acetate) to obtain a single ion polymer; the counter ion compound A comprises one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate and sodium acetate.
(3) And (3) adjusting the pH value of the single ionic polymer to 6.2-7.5 (preferably 7.0) by using a compound B (one or more of calcium hydroxide, sodium calcium bicarbonate, calcium carbonate, calcium acetate, zinc hydroxide and zinc acetate) of counter ions to obtain the multi-ionic polymer.
A PVC heat stabilizer comprises the following components in parts by weight: 5-15 parts of low-temperature toughened polyion polymer, 1-30 parts of zinc stearate, 1-40 parts of calcium stearate, 5-50 parts of triphenyl phosphate, 5-20 parts of antioxidant and 1-5 parts of lubricant.
The preferable formula is as follows: 10 parts of low-temperature toughened polyion polymer, 20 parts of zinc stearate, 30 parts of calcium stearate, 20 parts of triphenyl phosphate, 10 parts of antioxidant and 4 parts of lubricant.
Preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168 and antioxidant 215; further preferably, the antioxidant 1010 and the antioxidant 168 are mixed at a mass ratio of 3: 1. The lubricant is selected from one or more of stearic acid, polyethylene wax, glyceryl stearate and oxidized polyethylene wax; further preferred is a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1.5.
A PVC livestock-raising board comprises 100phr of PVC powder and 1-5 phr of PVC heat stabilizer. Preferably, the composition also comprises 2 to 15phr of epoxidized soybean oil. Most preferably, 100phr of PVC powder, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are included.
The preparation method of the PVC livestock-raising board comprises the following steps: uniformly stirring PVC powder, a PVC heat stabilizer and epoxy soybean oil, mixing for 2-5 min (3min) at 185 ℃ at 170-.
Example 1
Preparation of polyion polymer:
(1) methacrylic acid (5phr), ethylene (20phr) and azobisisobutyronitrile (1phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 50 ℃ for 3 hours under magnetic stirring at 30r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 5.0 by using NaOH solution (0.1mol/L) to obtain the single ion polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 6.2 with calcium hydroxide solution (0.1mol/L) to obtain the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 10phr of polyion polymer, 20phr of zinc stearate, 20phr of triphenyl phosphate, 10phr of antioxidant (a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 3: 1) and 4phr of lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain the compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 170 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 170 ℃ to be pressed for 1min at 100bar to obtain the PVC livestock-raising plate.
Example 2
Preparation of polyion polymer:
(1) acrylic acid (15phr), butadiene (50phr) and dibenzoyl peroxide (5phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 80 ℃ for 5 hours under magnetic stirring at 50r/min to give a copolymer.
(2) The pH of the copolymer obtained in step (1) was adjusted to 6.0 with sodium bicarbonate solution (0.1mol/L) to obtain a monoanionic polymer.
(3) And (3) adjusting the pH value of the single ion polymer obtained in the step (2) to 7.5 by using a calcium bicarbonate solution (0.1mol/L) to obtain a final multi-ion polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock-raising plate:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a double-roll mill at 185 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 185 ℃ to be pressed for 1min under 100bar to obtain the PVC livestock-raising plate.
Example 3
Preparation of polyion polymer:
(1) acrylic acid (10phr), styrene (35phr) and tert-butyl hydroperoxide (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4 hours under magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 6.0 by using a sodium carbonate solution (0.1mol/L) to obtain a single ionic polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 7.0 with 0.1mol of calcium carbonate to give the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Example 4
Preparation of polyion polymer:
(1) acrylic acid (10phr), propylene (35phr) and dicumyl peroxide (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4 hours under magnetic stirring at 40r/min to obtain a copolymer.
(2) Adjusting the pH value of the copolymer obtained in the step (1) to 6.0 by using a sodium acetate solution (0.1mol/L) to obtain a single ion polymer;
(3) the pH of the monoionic polymer obtained in step (2) was adjusted to 7.0 with zinc hydroxide solution (0.1mol/L) to obtain the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Example 5
Preparation of polyion polymer:
(1) methacrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4h with magnetic stirring at 40r/min to obtain a copolymer.
(2) The pH of the copolymer obtained in step (1) was adjusted to 6.0 with sodium hydroxide solution (0.1mol/L) to obtain a monoanionic polymer.
(3) And (3) adjusting the pH value of the monoionic polymer obtained in the step (2) to 7.0 by using a zinc acetate solution (0.1mol/L) to obtain a final polyionic polymer.
Preparation of PVC heat stabilizer:
and (2) uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Example 6
Preparation of polyion polymer:
(1) methacrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4h with magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 6.0 by using a sodium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 7.0 with calcium hydroxide solution (0.1mol/L) to obtain the final polyionic polymer.
Preparing a PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 1
Preparation of a Monoionic Polymer:
(1) acrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4 hours under magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 6.0 by using a sodium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
Preparation of PVC heat stabilizer:
uniformly mixing 20g of the single ion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 2
Preparation of a Monoionic Polymer:
(1) acrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4 hours under magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 7.0 by using a calcium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
Preparation of PVC heat stabilizer:
and (2) uniformly mixing 20g of the monoanionic polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 3
Preparation of PVC heat stabilizer:
and uniformly mixing 30g of zinc stearate, 20g of triphenyl phosphate, 10g of antioxidant (a mixture of the antioxidant 1010 and the antioxidant 168 in a mass ratio of 3: 1) and 4g of lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer, 8phr of epoxidized soybean oil and 30phr of DIOP are stirred uniformly and then placed on a two-roll mill at 180 ℃ to be mixed for 2min, and a PVC sheet is obtained. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 4:
preparation of polyion polymer:
(1) methacrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4h with magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 4.0 by using a sodium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 7.0 with calcium hydroxide solution (0.1mol/L) to obtain the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
after 100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly, the mixture is placed on a double-roll mill at 180 ℃ to be mixed for 2min, and a PVC sheet is obtained. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 5:
preparation of polyion polymer:
(1) methacrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4h with magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 6.5 by using a sodium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 7.0 with calcium hydroxide solution (0.1mol/L) to obtain the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 6:
preparation of polyion polymer:
(1) methacrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4h with magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 5.5 by using a sodium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 6.0 with calcium hydroxide solution (0.1mol/L) to the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly and then placed on a two-roll mill at 180 ℃ for mixing for 2min to obtain a PVC sheet. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Comparative example 7:
preparation of polyion polymer:
(1) methacrylic acid (10phr), ethylene (35phr) and azobisisobutyronitrile (3phr) were placed in a 500mL three-necked flask equipped with a reflux apparatus and reacted at 65 ℃ for 4h with magnetic stirring at 40r/min to obtain a copolymer.
(2) And (3) adjusting the pH value of the copolymer obtained in the step (1) to 6.0 by using a sodium hydroxide solution (0.1mol/L) to obtain a single ionic polymer.
(3) The pH of the monoionic polymer obtained in step (2) was adjusted to 8.0 with calcium hydroxide solution (0.1mol/L) to obtain the final polyionic polymer.
Preparation of PVC heat stabilizer:
and uniformly mixing 20g of the polyion polymer, 30g of zinc stearate, 20g of triphenyl phosphate, 10g of an antioxidant (a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3: 1) and 4g of a lubricant (a mixture of polyethylene wax and glyceryl stearate in a mass ratio of 1: 1) in a high-speed mixer to obtain a compound heat stabilizer of the polyion polymer, namely the PVC heat stabilizer.
Preparing the PVC livestock board:
after 100phr of PVC, 3phr of PVC heat stabilizer and 8phr of epoxidized soybean oil are stirred uniformly, the mixture is placed on a double-roll mill at 180 ℃ to be mixed for 2min, and a PVC sheet is obtained. And (3) placing the PVC sheet on a tabletting machine at 180 ℃ and pressing for 1min at 110bar to obtain the PVC livestock-raising plate.
Performance testing
Testing thermal stability:
thermal stability time of congo red: the congo red test method was performed according to the GB 2917-82 standard. 100phr of PVC powder and 2phr of PVC heat stabilizer prepared in each example and comparative example are prepared into a 2mm sample slice by a two-roll mill mixing method, the sample slice is cut into small particles with the side length of about 2mm, and PVC material particles are filled into a glass test tube with the diameter of 17mm and the length of 150mm, so that the PVC material is ensured to be about 5cm high in the test tube. And inserting a hollow glass tube with a rubber plug into the test tube, wherein the hollow glass tube is communicated with the inside of the test tube and the atmosphere. And rolling the Congo red test paper and plugging the coiled Congo red test paper into an opening at the lower part of the hollow glass tube, so that the distance between the lower end of the Congo red test paper and the upper end of the PVC particles is 2 cm. The device is placed in an oil bath pan at 180 ℃, and the liquid level of the oil bath pan is ensured to be parallel and level with the upper end of the PVC particles in the test tube. And (3) putting the test tube into an oil bath pan to start timing, stopping timing when the Congo red test paper is changed into blue, and recording the time as the static thermal stability time of the stabilizer. Three experiments were performed for each formulation and the average was taken.
Oven static thermal stabilization time: scanning the prepared PVC sample on a HP laser jet Pro MFP M227fdw black-white laser multifunctional all-in-one machine of Hewlett-packard company to record the original color, then placing the sample on a copper net, placing the sample in a 180 ℃ oven, taking out the sample piece every 10min for scanning, and recording the color change until the sample piece is completely black. The test results are shown in Table 1.
TABLE 1 measurement results of examples 1 to 6 and comparative examples 1 to 7
Figure BDA0003386989930000121
As can be seen from the table:
first, the low temperature impact performance of the PVC coupons (comparative example 3) was not ideal without the addition of polyionic polymers or monoanionic polymers, and the low temperature impact performance of the PVC coupons (examples 1-6 and comparative examples 1-2) was significantly improved after the addition. While comparing the low temperature impact properties between the mono-ionic polymers (comparative examples 1-2) and the multi-ionic polymers (examples 1-6), it was found that the multi-ionic polymers were better at enhancing the low temperature impact properties of the PVC plaques (example 6 is a single factor control as compared to comparative examples 1-2).
Secondly, the introduction of the polyion polymer can better improve the long-term thermal stability (static thermal stability time) of the PVC sample wafer, and the polyion polymer containing zinc ions or calcium ions can play a role in complexing unstable chloride ions in a PVC chain.
Furthermore, the effect of pH on the polyionic polymer (example 6 and comparative examples 4-7) was compared to find that the PVC sample has poor low temperature impact properties and poor thermal stability, because the pH value can affect the proportion of cations in the polyionic polymer, and if the pH value is too low (comparative examples 4 and 6), the content of monovalent cations or divalent cations is reduced, so that the crosslinking effect or aggregation effect of ionic bonds is weakened, and the low temperature impact properties and the thermal stability of the material are reduced; if the pH is too high (comparative examples 5, 7) the content of divalent cations may be decreased or increased, for example, if the pH in step (2) is too high (comparative example 5) the divalent cation introduction process may be affected by the charge effect to decrease the content thereof, and on the other hand, if the pH in step (3) is too high (comparative example 7) the ratio between monovalent cations and divalent cations may be destroyed to limit the low temperature impact properties of the material.
In conclusion, the polyion polymer has great significance for improving the low-temperature impact performance of the PVC material, and the PVC material can be better applied to animal husbandry.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. A low temperature toughened polyion polymer is characterized in that: the preparation method comprises the following steps:
(1) carrying out polymerization reaction on a monomer A containing carbon-carbon double bonds and carboxylic acid groups, an olefin monomer B and an initiator to obtain a copolymer;
(2) regulating the pH value of the copolymer to 5.0-6.0 by using a counter ion compound A to obtain a single ion polymer; the counter ion compound A comprises one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate and sodium acetate;
(3) regulating the pH value of the single ion polymer to be 6.2-7.5 by using a counter ion compound B to obtain a multi-ion polymer; the counter ion compound B comprises one or more of calcium hydroxide, sodium calcium bicarbonate, calcium carbonate, calcium acetate, zinc hydroxide and zinc acetate.
2. The low temperature toughened polyionic polymer of claim 1 wherein: in the step (1):
the monomer A containing the carbon-carbon double bond and the carboxylic acid group is one or more of acrylic acid and methacrylic acid; the addition amount is 5-15 parts by weight;
the olefin monomer B is one or more of ethylene, butadiene, styrene and propylene; the addition amount is 20-50 parts by weight;
the initiator is one or more of azodiisobutyronitrile, dibenzoyl peroxide, tert-butyl hydroperoxide and dicumyl peroxide; the addition amount is 1 to 5 parts by weight.
3. The low temperature toughened polyionic polymer of claim 1 wherein: in the step (1): the reaction temperature is 50-80 ℃; the reaction time is 3-5 h; the stirring speed is 30-50 r/min.
4. The low temperature toughened polyionic polymer of claim 1 wherein:
in the step (2), a counter ion compound A is used for adjusting the pH value of the copolymer to 6.0, so as to obtain a single ion polymer;
in the step (3), the pH value of the single ion polymer is adjusted to 7.0 by using a compound B of a counter ion, so as to obtain a multi-ion polymer.
5. A PVC heat stabilizer is characterized in that: the paint comprises the following components in parts by weight: 5-15 parts of the low-temperature toughened polyion polymer as claimed in any one of claims 1-4, 1-30 parts of zinc stearate, 1-40 parts of calcium stearate, 5-50 parts of triphenyl phosphate, 5-20 parts of an antioxidant and 1-5 parts of a lubricant.
6. The PVC thermal stabilizer of claim 5, wherein: the paint comprises the following components in parts by weight: 10 parts of low-temperature toughened polyion polymer, 20 parts of zinc stearate, 30 parts of calcium stearate, 20 parts of triphenyl phosphate, 10 parts of antioxidant and 4 parts of lubricant.
7. The PVC thermal stabilizer of claim 5, wherein:
the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168 and antioxidant 215;
the lubricant is selected from one or more of stearic acid, polyethylene wax, glyceryl stearate and oxidized polyethylene wax.
8. The utility model provides a PVC poultry board which characterized in that: comprising 100phr of PVC powder, 1 to 5phr of a PVC heat stabilizer according to one of claims 5 to 7.
9. The PVC animal husbandry plate of claim 8, wherein: comprises 100phr of PVC powder, 1 to 5phr of PVC heat stabilizer and 2 to 15phr of epoxidized soybean oil.
10. The PVC animal husbandry plate of claim 9, wherein: the preparation method comprises the following steps: uniformly stirring the PVC powder, the PVC heat stabilizer and the epoxy soybean oil, mixing for 2-5 min at the temperature of 170-185 ℃, and then hot-pressing for 0.5-2min at the temperature of 170-185 ℃ and at the pressure of 100-110bar to obtain the PVC livestock-raising plate.
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Citations (6)

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Publication number Priority date Publication date Assignee Title
GB1142364A (en) * 1965-08-25 1969-02-05 Rohm & Haas Modifiers for vinyl halide polymers
US5194498A (en) * 1991-09-09 1993-03-16 Rohm And Haas Company Poly(vinyl chloride) blends and additives therefor
CN102603989A (en) * 2010-12-15 2012-07-25 阿肯马法国公司 Process for core shell impact modifiers and impact modified thermoplastic composition with enhanced hydrolytic resistance
CN108892631A (en) * 2018-08-09 2018-11-27 广州臻莱迈新材料科技有限公司 A kind of heat stabilizer and its synthetic method for PVC
CN113061291A (en) * 2021-03-24 2021-07-02 浙江工业大学 Polyanion metal salt, preparation method thereof and heat stabilizer
CN113337054A (en) * 2021-06-30 2021-09-03 汪知信 High-strength heat-resistant PVC (polyvinyl chloride) foamed sheet and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1142364A (en) * 1965-08-25 1969-02-05 Rohm & Haas Modifiers for vinyl halide polymers
US5194498A (en) * 1991-09-09 1993-03-16 Rohm And Haas Company Poly(vinyl chloride) blends and additives therefor
CN102603989A (en) * 2010-12-15 2012-07-25 阿肯马法国公司 Process for core shell impact modifiers and impact modified thermoplastic composition with enhanced hydrolytic resistance
CN108892631A (en) * 2018-08-09 2018-11-27 广州臻莱迈新材料科技有限公司 A kind of heat stabilizer and its synthetic method for PVC
CN113061291A (en) * 2021-03-24 2021-07-02 浙江工业大学 Polyanion metal salt, preparation method thereof and heat stabilizer
CN113337054A (en) * 2021-06-30 2021-09-03 汪知信 High-strength heat-resistant PVC (polyvinyl chloride) foamed sheet and preparation method thereof

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