CN115583913B - Zinc burning inhibitor and preparation method and application thereof - Google Patents
Zinc burning inhibitor and preparation method and application thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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- C08K5/3435—Piperidines
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Abstract
The invention discloses a zinc burning inhibitor and a preparation method and application thereof, belonging to the technical field of fine chemical engineering. The carbamido compound containing piperidine amine is used as a zinc burning inhibitor, wherein the contained piperidine amine is an organic amine compound (hindered amine) with steric hindrance, and has good inhibition effect on free radical degradation reaction of high polymer (such as PVC); the urea chain segment in the structure can complex metal zinc ions and the like, so that the phenomenon of zinc burning is greatly relieved, HCl gas can be absorbed by the urea-containing chain segment, the catalytic degradation of PVC is effectively inhibited, unstable Cl atoms in PVC can be replaced, and the unstable structure of PVC is reduced.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, and particularly relates to a zinc burning inhibitor, and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is one of five common plastics in the world, but has poor thermal stability and obvious decomposition below the processing temperature, which greatly limits the application of the PVC in various fields. Therefore, a large amount of zinc-containing composite heat stabilizer is required to be added in the processing, forming and application processes.
However, when a zinc-containing compound is used as a heat stabilizer component, the PVC material can be subjected to catastrophic sudden color change degradation at a certain high temperature period, the phenomenon is called zinc burning in the PVC processing field, and the existence of the zinc burning phenomenon not only seriously affects the service performance of a PVC product, but also damages the appearance of the PVC product and directly affects the user experience. In order to suppress the adverse effects of "zinc burn" on PVC stabilizers, solutions have been sought.
At present, the effective method is to use zinc soap and calcium stearate to compound, namely the so-called calcium-zinc composite stabilizer. The calcium soap can capture HCl, and the generated metal chloride has no catalytic action on the HCl removal reaction, but can effectively replace the chloride generated by the zinc soap to regenerate the zinc soap. The zinc soap and the calcium soap complement each other in the aspects of stability and initial coloring property, and an obvious effect is achieved on solving the zinc burning phenomenon. However, this method still has drawbacks such as the dosage of the formulation is not easy to control, and the effect is to be improved. The Clarian company patent US5969014-A discloses a nylon multifunctional stabilizer Nylostab S-EED containing hindered amine group and its preparation method, which uses isophthaloyl dichloride and tetraalkyl piperidine amine as raw materials, and water as solvent for the reaction, but the yield of the method is limited because the raw materials are hydrolyzed in the reaction stage, and in order to reach acceptable yield, excessive tetraalkyl piperidine amine component must be used, which causes waste of resources. At present, HALS have been reported to be effective in stabilizing systems for PVC, but the current research is not as intensive. The Chinese patent with the publication number of CN113604027A discloses the influence of a polymer containing carbamide groups on the thermal stability of PVC, and the phenomenon of zinc burning can be effectively delayed when the polymer is compounded with calcium/zinc. The ureido-containing polymer is a single-function auxiliary additive, and the effects of inhibiting 'zinc burn' and improving stability are still in room for improvement.
Disclosure of Invention
The invention aims to provide a zinc burning inhibitor and a preparation method and application thereof. The carbamido compound containing piperidine amine is used as a zinc burning inhibitor, wherein the contained piperidine amine is an organic amine compound (hindered amine) with steric hindrance, and has good inhibition effect on free radical degradation reaction of high polymer (such as PVC); the urea chain segment in the structure can complex metal zinc ions and the like, so that the phenomenon of zinc burning is greatly relieved, HCl gas can be absorbed by the urea-containing chain segment, the catalytic degradation of PVC is effectively inhibited, unstable Cl atoms in PVC can be replaced, and the unstable structure of PVC is reduced.
In order to realize the purpose, the invention provides the following technical scheme:
the invention adopts one of the technical schemes: provides a zinc burning inhibitor, the structural formula is shown as the formula (Z):
wherein R is 1 Is any one of structures shown in formulas I-XII:
formula I:
formula II:
formula III:
formula IV:
formula V:
formula VI:
formula VII:
formula VIII:
formula IX:
formula X:
formula XI:
formula XII:
；
R 2 is H or alkyl containing 1~5 carbons;
R 3 h or an alkyl group having 1 to 20 carbon atoms.
Preferably, the zinc burning inhibitor is powder, and if the zinc burning inhibitor is not powder, grinding treatment is required before use so as to increase the dispersibility of the piperidine amine urea-based compound in the PVC products prepared subsequently.
Preferably, when R is in the structure of the zinc burning inhibitor 1 When the base is selected to be the structure shown in the formula V, the static stabilization time reaches 2224s in a Congo red test, and the color change degree is small and the change is slow in a heat aging test.
The second technical scheme of the invention is as follows: the preparation method of the zinc burning inhibitor comprises the following steps:
(1) Preparing compounds of the general formula (X) and the general formula (Y) according to the reaction equation of the zinc burning inhibitor;
(2) Dissolving a compound of a general formula (Y) in an organic solvent to obtain a mixed solution A, and dissolving a compound of a general formula (X) in an organic solvent to obtain a mixed solution B;
(3) Adding the mixed solution B into the preheated mixed solution A, reacting, and removing the solvent after the reaction is finished to prepare the zinc burning inhibitor;
the reaction equation of the zinc burning inhibitor is as follows:
r in the above reaction equation 1 、R 2 、R 3 And R in the formula (Z) 1 、R 2 、R 3 The same is true.
Preferably, the molar ratio of the compound of the general formula (X) to the compound of the general formula (Y) is 1 (2.0 to 2.5), and more preferably 1 (2.1 to 2.2).
Preferably, the organic solvents in step (2) are one or more of acetonitrile, N-dimethylformamide, ethanol, hexane, toluene, tetrahydrofuran and acetone, and most preferably acetonitrile; the mass ratio of the compound of the general formula (X) to the organic solvent is 1 (8 to 30), more preferably 1 (10 to 20), and most preferably 1; the mass ratio of the compound of the general formula (Y) to the organic solvent is 1 (8 to 30), more preferably 1 (10 to 20), and most preferably 1.
Preferably, the temperature of the preheated mixed solution A in the step (3) is 20 to 60 ℃, and the most preferred temperature is 30 ℃; the mixed liquid B is added dropwise for 10 to 60min, and more preferably 20 to 40min; the temperature of the reaction is 20 to 60 ℃, and the time is 30 to 80min, more preferably 40 to 60min.
The third technical scheme of the invention is as follows: the PVC product prepared based on the zinc burning inhibitor is provided, and comprises the following raw materials in parts by weight: 100 parts of rigid polyvinyl chloride, 0.1 to 2 parts of the above mentioned zinc burning inhibitor, 0.1 to 1 part of calcium soap and 0.1 to 1 part of zinc soap.
Preferably, the raw material of the PVC product also comprises 10 parts of a plasticizer.
The plasticizer can improve the performance of PVC products and reduce the production cost, and is mainly used for weakening the secondary valence bonds among resin molecules, increasing the mobility of the resin molecular bonds, reducing the crystallinity of the resin molecules, increasing the plasticity of the resin molecules, increasing the flexibility of the resin molecules and facilitating the processing.
Preferably, the calcium soap is at least one of calcium stearate, calcium cinnamate, calcium palmitate, and calcium linoleate; the zinc soap is at least one of zinc stearate, zinc cinnamate, zinc palmitate and zinc linoleate; the plasticizer is dioctyl phthalate.
More preferably, the calcium soap is calcium stearate; the zinc soap is zinc stearate.
Calcium stearate and zinc stearate are used as calcium soap and zinc soap, and when the calcium stearate and the zinc stearate are plasticated in an open mill, the calcium stearate and the zinc stearate are compounded for use, so that the initial whiteness of PVC can be improved, the long-term thermal stability of the PVC can also be improved, and the calcium stearate and the zinc stearate are efficient, low in cost and convenient for large-scale industrial application.
The fourth technical scheme of the invention is as follows: the preparation method of the PVC product comprises the following steps: and uniformly mixing the components, mixing and plasticizing, and tabletting to obtain the PVC product.
The PVC product is compounded by the zinc burning inhibitor, the calcium stearate and the zinc stearate, so that a better effect can be achieved, a zinc burning phenomenon can be relieved, the defect of poor stability of the calcium stearate in the early stage is overcome, the catalytic degradation effect of HCl gas on the PVC product is inhibited, the aging speed of PVC is slowed down, the thermal stability of PVC is improved, the initial whiteness of PVC is improved, the long-term stability is improved, and the thermal degradation of PVC is delayed.
Preferably, the mixing is carried out on a two-roll open mill, the roll temperature of the open mill is 160-180 ℃, the roll distance is 0.3-0.5 mm, the roll speed is 40-60r/min, the roll passing amount is 60-100g each time, the sheet is folded in half for the first time 2~3 times, the roll passing time is 5-10 times, and the open mill time is 3-5min; the tabletting is carried out on a flat plate vulcanizing machine, the temperature is 140-180 ℃, the pressure is 1-5T, and the tabletting time is 3-5 min.
More preferably, the roll temperature of the open mill is 168 ℃, the roll spacing is 0.3mm, the roll speed is 40r/min, the roll passing amount is 65g each time, the mixture is folded in half 2 times after being subjected to primary sheeting and passed through the roll 8 times, the open milling time is 4min, the temperature of the vulcanizing press is 170 ℃, the pressure is 1T, and the sheeting time is 3min.
The beneficial technical effects of the invention are as follows:
the invention adopts the carbamido compound containing piperidine amine as the zinc burning inhibitor, wherein the contained piperidine amine is an organic amine compound (hindered amine) with space obstruction, and has good inhibition effect on the free radical degradation reaction of high polymer (such as PVC); the urea chain segment in the structure can complex metal zinc ions and the like, so that the phenomenon of zinc burning is greatly relieved, HCl gas can be absorbed by the urea-containing chain segment, the catalytic degradation of PVC is effectively inhibited, unstable Cl atoms in PVC can be replaced, and the unstable structure of PVC is reduced. The compound containing piperidine amine carbamido belongs to a multifunctional hard PVC auxiliary additive.
The zinc burning inhibitor obtained by adopting the technical scheme of the invention can relieve the phenomenon of zinc burning, inhibit the catalytic degradation of HCl gas on PVC products, slow down the aging speed of PVC, improve the thermal stability of PVC, improve the initial whiteness of PVC, improve the long-term stability and delay the thermal degradation of PVC.
The invention also provides a PVC product, and the synergistic effect is generated by the compound use of the zinc burning inhibitor and the calcium soap/zinc soap, so that the defect of the calcium soap/zinc soap as a heat stabilizer can be overcome, and the stability of the product when the zinc burning inhibitor is singly used as the stabilizer can be improved.
The preparation process of the zinc burning inhibitor and the PVC product provided by the invention is simple, the used raw materials are cheap and easy to obtain, the overall preparation process is simple and easy to operate, the equipment requirement is low, the post-treatment process is simple, and the environment-friendly and efficient green concept is met.
Drawings
FIG. 1 is a graph of the degradation of PVC articles prepared in example 1~5 and comparative example 1~3 cut into 20mm by 20mm square coupons in a heat aging oven over time.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Preparation of zinc burning inhibitor
(a) 3.125g (0.020 mol) of tetramethylpiperidinamine were dissolved in 50g of dry acetonitrile to obtain a solution A, and 2.502g (0) was taken.010 mol) 4,4' -diphenylmethane diisocyanate was dissolved in 50g of dry acetonitrile to give a solution B; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed for 10min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, continuously stirring for 30min, and stopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The base is shown as formula IV.
(2) Preparation of composite materials
Taking 100 parts of hard PVC, 1 part of the zinc burning inhibitor prepared in the step (1), 0.8 part of zinc stearate, 0.2 part of calcium stearate and 10 parts of dioctyl phthalate, uniformly stirring by using a high-speed stirrer, and then mixing and plasticizing into a sheet by using a double-roll open mill, wherein the set temperature of a roller of the double-roll open mill is 168 ℃, the roller distance is 0.3mm, the roller speed is 40r/min, the open time is 4min, and the roll passing amount is 65g; after the initial plasticizing and sheeting, the plasticized PVC test piece is folded for 2 times, passes through a roller for 8 times, and is placed in a flat vulcanizing machine for sheeting treatment after the open milling time, wherein the temperature of the flat vulcanizing machine is 170 ℃, the pressure is 1T, and the sheeting time is 3min. And finally, slicing according to the test requirement to obtain a sample 1.
Example 2
(1) Preparation of zinc burning inhibitor
(a) Dissolving 3.125g (0.020 mol) of tetramethylpiperidine amine in 50g of dry acetonitrile to obtain a solution A, and dissolving 2.223g (0.010 mol) of isophorone diisocyanate in 50g of dry acetonitrile to obtain a solution B; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed to finish dropwise adding for 10min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, continuously stirring for 30min, and stopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The group is shown as the formula V.
(2) Preparation of composite materials
See example 1 for the preparation of composite material to obtain sample 2.
Example 3
(1) Preparation of zinc burn inhibitor
Two portions of 50g of dry acetonitrile were taken in a beaker, and 3.125g (0.020 mol) of tetramethylpiperidinamine was dissolved in one portion of acetonitrile and poured into a three-necked flask. And then 2.223g (0.01 mol) of isophorone diisocyanate is taken and dissolved in another part of acetonitrile, and then the acetonitrile solution of isophorone diisocyanate is gradually dripped into a three-neck flask, the dripping is finished for 10min, the reaction is stirred at normal temperature, and the acetonitrile solvent is supplemented along with the increase of the reaction progress. Keeping the temperature at 30 ℃, continuing stirring for 50 minutes after the system becomes white, and after the reaction is completed, carrying out suction filtration, washing, drying and grinding on the product to obtain light yellow powder. The obtained powder is the inhibitor of zinc burning, wherein R in the structure of the inhibitor of zinc burning 1 The group is shown as the formula V.
(a) Dissolving 3.125g (0.020 mol) of tetramethylpiperidine amine in 50g of dry acetonitrile to obtain a solution A, and dissolving 2.223g (0.010 mol) of isophorone diisocyanate in 50g of dry acetonitrile to obtain a solution B; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed for 10min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, continuously stirring for 50min, and stopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The group is shown as formula V.
(2) Preparation of composite materials
See example 1 for the preparation of composite material to obtain sample 3.
Example 4
(1) Preparation of zinc burn inhibitor
(a) 3.125g (0.020 mol) of tetramethylpiperidinamine were dissolved in 50g of dry acetonitrile to give solution A, 2.223g (0.010 mol) of isophorone diisocyanate were dissolved in 50g of dry acetonitrile to give solution BLiquid; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed to finish dropping for 20min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, continuously stirring for 50min, and stopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The group is shown as formula V.
(2) Preparation of composite materials
See example 1 for the preparation of the composite material to obtain sample 4.
Example 5
(1) Preparation of zinc burning inhibitor
(a) Dissolving 3.281g (0.021 mol) of tetramethylpiperidine amine in 50g of dried acetonitrile to obtain a solution A, and dissolving 2.223g (0.010 mol) of isophorone diisocyanate in 50g of dried acetonitrile to obtain a solution B; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed to finish dropwise adding for 20min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, continuously stirring for 50min, and stopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The group is shown as formula V.
(2) Preparation of composite materials
See example 1 for the preparation of the composite material to obtain sample 5.
Example 6
(1) Preparation of zinc burn inhibitor
(a) Dissolving 3.281g (0.021 mol) of tetramethyl piperidine amine in 50g of dry acetonitrile to obtain a solution A, and dissolving 1.628g (0.010 mol) of hexamethylene diisocyanate in 50g of dry acetonitrile to obtain a solution B; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed to finish dropping for 20min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, stirring is continued for 50minStopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The base is shown as a formula II.
(2) Preparation of composite materials
See example 1 for the preparation of the composite material to provide sample 6.
Example 7
(1) Preparation of zinc burn inhibitor
(a) Dissolving 3.281g (0.021 mol) of tetramethylpiperidine amine in 50g of dried acetonitrile to obtain a solution A, and dissolving 1.742g (0.010 mol) of toluene diisocyanate in 50g of dried acetonitrile to obtain a solution B; (b) Pouring the solution A into a three-neck flask, gradually dropwise adding the solution B into the three-neck flask, controlling the dropwise adding speed to finish dropping for 20min, and stirring at 30 ℃ for reaction. After white suspended particles appear in the system, continuously stirring for 50min, and stopping the reaction to obtain a product C; (c) And carrying out suction filtration, washing, drying and grinding on the product C to obtain light yellow powder D. The obtained powder D is the zinc burning inhibitor, wherein R in the structure of the zinc burning inhibitor 1 The group is shown in formula VI.
(2) Preparation of composite materials
See example 1 for the preparation of the composite material to obtain sample 7.
Comparative example 1
(1) Preparation of composite materials
100 parts of hard PVC and 10 parts of dioctyl phthalate are taken, uniformly stirred by a high-speed stirrer and then mixed and plasticized into sheets by a double-roll open mill, wherein the set temperature of a roller of the double-roll open mill is 168 ℃, the roller spacing is 0.3mm, the roller speed is 40r/min, the open milling time is 4min, and the roll passing amount is 65g; after the initial plasticizing and sheet forming, folding the plasticized PVC sample sheet for 2 times, passing through a roller for 8 times, after the open milling time is reached, placing the sample sheet in a flat vulcanizing machine for pressing and processing, wherein the temperature of the flat vulcanizing machine is 170 ℃, the pressure is 1T, the sheet forming time is 3min, and slicing to obtain a comparison sample 1.
Comparative example 2
(1) Preparation of composite materials
100 parts of hard PVC, 2 parts of zinc stearate and 10 parts of dioctyl phthalate are taken, uniformly stirred by a high-speed stirrer and then mixed and molded into sheets by a double-roll open mill, wherein the roll of the double-roll open mill is set to have the temperature of 168 ℃, the roll spacing of 0.3mm, the roll speed of 40r/min, the open milling time of 4min and the roll passing amount of 65g; after the initial plasticizing and sheet forming, folding the plasticized PVC sample sheet for 2 times, passing through a roller for 8 times, after the open milling time is reached, placing the sample sheet in a flat vulcanizing machine for pressing and processing, wherein the temperature of the flat vulcanizing machine is 170 ℃, the pressure is 1T, the sheet forming time is 3min, and slicing to obtain a comparative sample 2.
Comparative example 3
(1) Preparation of composite materials
100 parts of hard PVC, 1.6 parts of zinc stearate, 0.4 part of calcium stearate and 10 parts of dioctyl phthalate are taken, uniformly stirred by a high-speed stirrer and then mixed and molded into sheets by a double-roll open mill, wherein the roll of the double-roll open mill is set to have the temperature of 168 ℃, the roll distance of 0.3mm, the roll speed of 40r/min, the open time of 4min and the roll passing amount of 65g; after the initial plasticizing and sheet forming, folding the plasticized PVC sample sheet for 2 times, passing through a roller for 8 times, after the open milling time is reached, placing the sample sheet in a flat vulcanizing machine for pressing and processing, wherein the temperature of the flat vulcanizing machine is 170 ℃, the pressure is 1T, the sheet forming time is 3min, and slicing to obtain a comparison sample 3.
Examples of effects
And (3) stability testing: respectively testing the static thermal stability performance of the sample at 180 ℃ by adopting a Congo red test method and a thermal aging box discoloration method, observing the discoloration time of Congo red test paper and the thermal degradation discoloration condition of the sample, and observing the static color change condition of the PVC sheet; the longer the time interval from the beginning of the Congo red test to the generation of color change of the Congo red test paper is, the better the static thermal stability of the sample is; in the thermal aging test, the slower the color change of the sample is, which shows that the thermal aging effect of the sample is good and the static thermal stability is good.
1. Congo red test method: the mixture of the PVC products samples 1 to 7 and the comparative samples 1 to 3 prepared in the above examples 1 to 7 and comparative examples 1 to 3 was put into a glass test tube of 150mm x 150mm, the mixture was closed with a rubber stopper having a hollow glass tube, congo red test paper was fixed with a hollow glass tube, each test tube to which the sample was put in an oil bath pan, and the time of discoloration of the Congo red test paper was observed and recorded after the start of the measurement, as shown in Table 1, wherein the distance between the Congo red test paper and the mixture was 23 to 25mm and the oil bath temperature was 180 to 185 ℃.
TABLE 1 static thermal stability time of test and reference samples using Congo red test paper test method
The later the time for the congo red test paper to discolor shows that the better the effect of the thermal stabilizer in the sample for absorbing HCl is, the better the static thermal stability can be.
As can be seen from Table 1, the static thermal stability time of samples 1-7 is much longer than that of comparative samples 1-3, indicating that the thermal stability improvement effect of the complex of the zinc burning inhibitor, zinc stearate and calcium stearate on PVC is better than that of the complex of zinc stearate and zinc stearate. The zinc burning inhibitor has a synergistic effect with the compounding of calcium stearate and zinc stearate.
2. Thermal aging test method: the PVC product samples 1-7 and the comparative samples 1-3 prepared in the above examples 1-7 and comparative examples 1-3 were cut into PVC square pieces of 20mm x 20mm, the PVC square pieces were placed on a stainless steel tray, the PVC square pieces were respectively numbered, and uniformly arranged at a certain interval, and then placed in a thermal aging box for constant temperature heating, wherein the temperature of the thermal aging box was 180 ℃, a fan and a turntable were kept simultaneously on, the PVC sample pieces were taken out every 10min, and photographed for recording, and then after the temperature of the thermal aging box was increased to 185 ℃, the temperature was kept constant, the thermal aging box was opened and the PVC sample pieces were placed, and the test results are shown in FIG. 1.
The heat aging method judges the heat stability by observing the degree and speed of color change of the sample in a heat aging box. Groups such as conjugated double bonds and the like can be generated when PVC is degraded, the conjugated double bonds are chromophoric groups, the color of the PVC is darker along with the increase of the number of the chromophoric groups, the PVC is completely degraded when the PVC is completely blackened, the deepening of the color is delayed by delaying the thermal degradation of a sample, and the degradation aging of the PVC can be improved by prolonging the thermal degradation time.
Generally, the phenomenon of delaying the thermal degradation discoloration of PVC is mainly shown by reducing the number of conjugated double bonds, namely reducing the number of chromophoric groups, and the PVC discoloration degree is visually reduced along with the change of time. From sample 5 and comparative sample 3, the initial whiteness of the PVC samples with the addition of the scorch inhibitor was better than that of the PVC samples without the addition of the scorch inhibitor.
The data in table 1 and fig. 1 show that when the piperidine-containing amine compound is added into PVC as a zinc burning inhibitor, the initial whiteness is better, and the effect of delaying the thermal degradation process of PVC is better. The zinc burning inhibitor is added into the calcium stearate/zinc stearate compound heat stabilizer, so that the zinc burning phenomenon of PVC can be effectively inhibited or weakened. The comparison of samples 1-7 with comparative sample 3 shows that the scorch inhibitor is very effective in inhibiting or reducing the "scorch" phenomenon of PVC.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. A PVC product is characterized by comprising the following raw materials in parts by mass: 100 parts of hard polyvinyl chloride, 0.1 to 2 parts of a zinc burning inhibitor, 0.1 to 1 part of calcium soap and 0.1 to 1 part of zinc soap;
the structural formula of the zinc burning inhibitor is shown as the formula (Z):
Wherein R is 1 Is any one of structures shown in formulas II-V and VIII-X:
formula II:
formula III:
formula IV:
formula V:
formula VIII:
formula IX:
formula X:
；
R 2 is H or alkyl containing 1~5 carbons;
R 3 h or an alkyl group having 1 to 20 carbon atoms.
2. The PVC article of claim 1 wherein the preparation of the zinc burn inhibitor comprises the steps of:
(1) Preparing compounds of the general formula (X) and the general formula (Y) according to the reaction equation of the zinc burning inhibitor;
(2) Dissolving a compound of a general formula (Y) in an organic solvent to obtain a mixed solution A, and dissolving a compound of a general formula (X) in an organic solvent to obtain a mixed solution B;
(3) Adding the mixed solution B into the preheated mixed solution A, reacting, and removing the solvent after the reaction is finished to prepare the zinc burning inhibitor;
the reaction equation of the zinc burning inhibitor is as follows:
r in the above reaction equation 1 、R 2 、R 3 The same as in claim 1.
3. The PVC product according to claim 2, wherein the molar ratio of the compound of the general formula (X) to the compound of the general formula (Y) is 1 (2.0 to 2.5).
4. The PVC article of claim 2, wherein in step (2) the organic solvents are all one or more of acetonitrile, N-dimethylformamide, ethanol, hexane, toluene, tetrahydrofuran, and acetone; the mass ratio of the compound of the general formula (X) to the organic solvent is 1 (8 to 30); the mass ratio of the compound of the general formula (Y) to the organic solvent is 1 (8 to 30).
5. The PVC product according to claim 2, wherein the temperature of the preheated mixed solution A in the step (3) is 20 to 60 ℃; the mixed solution B is added dropwise for 10 to 60min; the temperature of the reaction is 20 to 60 ℃, and the time is 30 to 80min.
6. The PVC product according to claim 1, wherein the raw materials further comprise 10 parts by mass of a plasticizer.
7. The PVC article of any one of claims 1~6 wherein the calcium soap is at least one of calcium stearate, calcium cinnamate, calcium palmitate, and calcium linoleate; the zinc soap is at least one of zinc stearate, zinc cinnamate, zinc palmitate and zinc linoleate.
8. The PVC article of claim 6, wherein the plasticizer is dioctyl phthalate.
9. A method of making the PVC article of any one of claims 1~8 comprising the steps of: and uniformly mixing the components, mixing and plasticizing, and tabletting to obtain the PVC product.
10. The preparation method of the rubber composition, according to claim 9, is characterized in that the mixing is carried out on a two-roll open mill, the roll temperature of the open mill is 160-180 ℃, the roll spacing is 0.3-0.5 mm, the roll speed is 40-60r/min, the roll passing amount is 60-100g each time, the initial sheet folding is 2~3 times, the roll passing is 5-10 times, and the open milling time is 3-5min; the tabletting is carried out on a flat plate vulcanizing machine, the temperature is 140-180 ℃, the pressure is 1-5T, and the tabletting time is 3-5 min.
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