WO2023116870A1 - Polyvinyl chloride polymer heat stabilizer, preparation method therefor and use thereof, composite stabilizer, and method for preparing polyvinyl chloride sheet - Google Patents

Abstract

The present invention discloses the preparation of an ultrasonic radiation calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer and the use thereof in a soft product, wherein the ultrasonic radiation calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer takes calcium/lanthanum-based metal oxide as a component to be activated, and is enhanced after ultrasonic radiation by blending modification and bonding with PVC, such that the ultrasonic radiation calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer is prepared; the calcium/lanthanum-based metal oxide is one or more of calcium oxide and lanthanum oxide. The ultrasonic radiation calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer of the present invention can improve both the heat stability of the polymer and the compatibility of the blend with the PVC system; and the polymer heat stabilizer and a product thereof prepared by the present patent are simple in process, low in cost, non-toxic and harmless, and have potential economic and environmental benefits.

Description

Polyvinyl chloride polymer heat stabilizer and its preparation method and application, composite stabilizer, preparation method of polyvinyl chloride sheet

This application is required to be submitted to the Chinese Patent Office on December 24, 2021. The application number is CN202111597141.2, and the title of the invention is "A preparation of ultrasonic radiation calcium, lanthanum-based polyvinyl chloride polymer heat stabilizer and its application in soft products." The priority of the Chinese patent application ", the entire content of which is incorporated in this application by reference.

technical field

The invention belongs to the field of processing aids for polymer materials, and in particular relates to a polyvinyl chloride polymer heat stabilizer, a preparation method and application thereof, a composite stabilizer, and a preparation method of polyvinyl chloride flakes.

Background technique

With the improvement of production technology, the heat resistance of polyvinyl chloride resin has been greatly improved, but it is still necessary to add heat stabilizers. The common bulk heat stabilizers include calcium zinc, organic tin, rare earth, organic Compounds and lead salts, etc. With the increase of user demands, the selection of additives or groups to carry out blending modification, grafting reaction or formation of chemical bonds on PVC resin has attracted widespread attention. Most of the metal oxides are in an inert state, with good stability, and it is difficult to graft reaction with PVC or form chemical bonds. However, in view of the non-toxic, safe and low-cost characteristics of calcium, magnesium, zinc, lanthanum and cerium oxides, if Grafting it to the PVC polymer chain will improve the heat-resistant stability of the PVC chain on the one hand, and greatly enhance the compatibility with PVC on the other hand. This will significantly improve the stability efficiency of PVC products, reduce the production cost of polymers, and improve economic, environmental and social benefits.

Regarding the effect of metal oxides on PVC, the current literature discloses that different metal oxides CaO, ZnO, CuO, MgO, Fe ₂ O ₃ and Al ₂ O ₃ have effects on PVC (chlorine: oxygen = 1:1 mol ratio) at low temperature in a nitrogen atmosphere. The effect of decomposition at 310°C (J. Anal. Appl. Pyrolysis, 2021, 159: 105312). Reported the pyrolysis performance of transition metal oxides TiO ₂ , V ₂ O ₅ , MoO ₃ , MnO ₂ , CuO, Fe ₂ O ₃ and ZnO on PVC (Process Saf.Environ.Prot.2020,140:211-220) . The modification of PVC films by ultrasonic waves was studied. Ultrasonic waves can stimulate PVC films to cause structural changes in the polymer matrix, showing that the concentration of some parts of PVC isomers increases, such as carbonyl groups, polyenes, and carboxylic acids appearing in the polymer matrix. New species (Ultrason. Sonochem. 2002, 9: 139-141). In addition, there are literature reports on the pyrolysis of polyvinyl chloride-metal oxide mixtures: quantitative product analysis and chlorine fixation ability of metal oxides (J.Anal.Appl.Pyrolysis, 200677:159-168) and so on.

However, the currently obtained polyvinyl chloride still has the defect of insufficient thermal stability, and the production cost of the thermal stabilizer is relatively high.

Contents of the invention

In order to solve the lack of thermal stability of the current PVC resin, reduce the cost of heat stabilizers, and improve economic and social benefits, the present invention provides a preparation of ultrasonic radiation calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer and its application in Applications in soft products.

The ultrasonic radiation calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer of the present invention uses calcium-lanthanum-based metal oxide as the component to be activated, and through the bonding between blending modified grinding and PVC, after ultrasonic radiation It has been strengthened, so that the ultrasonic radiation calcium/lanthanum based polyvinyl chloride polymer heat stabilizer can be prepared.

The calcium-lanthanum-based metal oxide is one or more of calcium oxide and lanthanum oxide.

Specifically include the following steps:

At room temperature, weigh the dried PVC resin and calcium-lanthanum-based metal oxide, mix and grind at high speed for 6 hours to obtain a calcium/lanthanum-based metal oxide-PVC blend, then place it in an ultrasonic oscillator, heat at 45°C for 4- After 8 hours, a calcium/lanthanum-based metal oxide-PVC activated blend was obtained, that is, a calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer irradiated by ultrasonic waves.

Each component is composed as follows in parts by mass: 5 parts of PVC resin, 1-2 parts of calcium/lanthanum-based metal oxide (preferably 1 part).

The application of the calcium/lanthanum-based polyvinyl chloride polymer thermal stabilizer of the present invention is to compound it with organic tin and dipentaerythritol to form a composite stabilizer, which is applied to PVC resin materials to improve the thermal stability of composite materials.

Specifically include the following steps:

Step 1: Mix dioctyl terephthalate (DOTP), calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer, dipentaerythritol, and organotin heat stabilizer, ultrasonically oscillate, stir, mix and dissolve for 30 minutes, and obtain a uniform co- mixture heat stabilizer precursor;

Step 2: Mix and grind the blend heat stabilizer precursor obtained in step 1 with the PVC base material, stir at a high speed to obtain a premix, and then place it in an internal mixer for internal mixing, with a melt temperature of 170-175°C and a screw speed of 40r/min, internal mixing time 4-5min, after the torque rises sharply and then decreases, and remains unchanged, after the completion, take out the mixed material, use a flat vulcanizer to press at 100°C for 40 seconds, and the thickness is l. 0mm PVC sheet for subsequent performance testing.

In steps 1 and 2, each raw material component constitutes as follows by mass parts:

50 parts of dioctyl terephthalate, 0.5-5.0 parts of calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer, 0.5-2.0 parts of dipentaerythritol, 0.1-2.0 parts of organotin heat stabilizer; 100 parts of PVC base material.

More preferably: 50 parts of dioctyl terephthalate, 3.0 parts of calcium/lanthanum-based polyvinyl chloride polymer heat stabilizer, 1.0 part of dipentaerythritol, 0.5 parts of organotin heat stabilizer; 100 parts of PVC base material.

Adding dioctyl terephthalate (DOTP) in the above-mentioned preparation process is the plasticizer of PVC material, and in the process of M-PVC blend complex thermal stabilizer preparation, adding DOTP in advance is to use it as dissolved Solvent use.

The organotin heat stabilizer is one or more of methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide, etc.

According to modern electronic theory, the positively charged calcium, zinc and lanthanum in the central atoms of calcium oxide, zinc oxide, and lanthanum oxide are all acids, while the negatively charged chlorine atoms in polyvinyl chloride or the chlorine free radicals generated by heating are A kind of base, when subjected to grinding and ultrasonic radiation, calcium/lanthanum is prone to acid-base neutralization reaction with active chlorine to form a (Ca-Cl, La-Cl) coordination complex centered on acid metal, When in the transition state, due to the high energy, chlorine donates electrons, and the acid metal obtains electrons, forming a relatively stable metal-based-PVC activated blend. The calcium/lanthanum oxide-PVC activated blend involved in the present invention has a polyvinyl chloride chain structure, and contains metal-Cl coordination groups on the main chain. On the one hand, it has better compatibility with PVC polymers, on the other hand The heat resistance of the blend is significantly improved.

Under the conditions of grinding and ultrasonic radiation, the present invention adopts metal oxide to carry out chemical action to PVC resin surface, and described metal oxide is calcium oxide, calcium oxide/zinc oxide and lanthanum oxide as modifier, after grinding and ultrasonic radiation, calcium , calcium zinc and lanthanum-PVC blends have significant chemical bonding, which can effectively improve the heat resistance stability of PVC products and greatly improve the compatibility with polymers.

The present invention uses metal oxides for surface modification, adopts grinding and ultrasonic radiation technology as a green and rapid preparation method, and prepares calcium, magnesium, zinc, lanthanum and cerium doped modified PVC blends and Corresponding film, and the 180 ℃ Congo red method was used to measure the Congo red discoloration rate of different blends. Among them, calcium, calcium zinc and lanthanum have a strong bond with PVC resin, the thermal stability is significantly improved, and it is non-toxic and has good environmental compatibility.

The method for evaluating the thermal stability of PVC among the present invention is the Congo red test, and the test device refers to the GB-T 2917-1982 standard; 2.2g PVC/metal oxide powder is weighed and placed in a test tube, and the Congo red test paper wetted with distilled water and Insert the thermometer into the test tube and keep it at a constant temperature of 180°C. During the experiment, record the time for the initial and complete bluening of the Congo red test paper. The quality of the thermal stability of the sample can be judged by the length of the initial and complete blue-turning time of Congo red.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

1. The modifiers used in the present invention are calcium oxide and lanthanum oxide, which have the advantages of good environmental compatibility, non-toxic and harmless, and easy degradation;

2. Calcium oxide and lanthanum oxide can promote the generation of electrostatic attraction and chemical bond between calcium/lanthanum and chlorine atoms in polyvinyl chloride molecules under grinding and ultrasonic radiation;

3. The blend produced by calcium, lanthanum and PVC can improve the thermal stability of the polymer on the one hand, and improve the compatibility of the blend with the PVC system on the other hand;

4. Calcium/lanthanum-based polymer blends fully meet the development requirements for environmental protection at home and abroad, with low cost and potential application prospects;

5. Calcium/lanthanum-based polymer blend complex, organotin and dipentaerythritol composite stabilizer, which can enhance the thermal stability with PVC polymer.

Detailed ways

The present invention uses calcium, magnesium, zinc, lanthanum, cerium metal oxides as electrophilic reagents, and electrophilic addition reaction occurs with chlorine anions ^Cl- or chlorine free radicals in the C-Cl bond in PVC; the specific usage amount is per 100 Add 5-40 parts of metal oxide to 1 part of PVC, and use grinding method and ultrasonic radiation method to induce electrophilic addition reaction between metal and chlorine in the oxide, the purpose is to improve the heat resistance stability of PVC resin.

There are two main methods for the interface contact between PVC resin and metal oxide M _x O _y : 1. PVC and M _x O _y are prepared by grinding the reaction complex; 2. PVC and M _x O _y are ground by grinding and ultrasonic radiation Preparation of reaction complexes.

The M-PVC blend prepared by grinding method, grinding method plus ultrasonic radiation method is used as heat stabilizer, and the dosage is 0.5-20 parts per 100 parts of PVC, preferably 3.0 parts.

(1) Metal oxide-PVC blend complex

M _x O _y -PVC blend, where x=1-2, y=1-3, M=one or more of calcium, magnesium, zinc, lanthanum, cerium, the PVC used in the sample preparation has been dehydrated After drying, carry out at room temperature.

Weigh 5.0 parts of PVC resin, 1.0 parts of CaO, mix and grind at high speed for 6 hours to obtain 6.0 parts of calcium oxide-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of MgO, mix and grind at high speed for 6 hours to obtain 6.0 parts of magnesium oxide-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of ZnO, mix and grind at high speed for 6 hours to obtain 6.0 parts of zinc oxide-PVC blend;

Weigh 10 parts of PVC resin, 1.0 parts of CaO, 1.0 parts of ZnO, mix and grind at high speed for 6 hours, and obtain 12 parts of calcium oxide, zinc oxide-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of La ₂ O ₃ , mix and grind at high speed for 6 hours to obtain 6.0 parts of lanthanum oxide-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of Ce ₂ O ₃ , mix and grind at high speed for 6 hours to obtain 6.0 parts of cerium oxide-PVC blend.

(2) Metal oxide-PVC activated blend (ultrasonic radiation)

M = one or more of calcium, magnesium, zinc, lanthanum, and cerium. The polymer used in sample preparation is PVC resin, which is dried and dehydrated at room temperature.

Weigh 5.0 parts of PVC resin, 1.0 parts of CaO, mix and grind at high speed for 6 hours, and irradiate with ultrasonic waves to obtain 6.0 parts of radiated calcium-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of MgO, mix and grind at high speed for 6 hours, and irradiate with ultrasonic waves to obtain 6.0 parts of irradiated magnesium-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of ZnO, high-speed mixing and grinding for 6 hours, and ultrasonic radiation to obtain 6.0 parts of irradiated zinc-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of CaO, and 1.0 parts of ZnO, mix and grind at high speed for 6 hours, and irradiate with ultrasonic waves to obtain 6.0 parts of calcium oxide, zinc oxide-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of La ₂ O ₃ , high-speed mixing and grinding for 6 hours, and ultrasonic radiation to obtain 6.0 parts of irradiated lanthanum-PVC blend;

Weigh 5.0 parts of PVC resin, 1.0 parts of Ce ₂ O ₃ , mix and grind at high speed for 6 hours, and irradiate with ultrasonic to obtain 6.0 parts of irradiated cerium-PVC blend.

Embodiment 1:

Weigh 5.0 parts by mass of PVC and 1.0 parts by mass of calcium oxide, stir and grind at high speed for 6 hours, and mix evenly to obtain 6 g of calcium oxide-PVC blend.

Example 2:

Weigh 5.0 parts by mass of PVC, 1.0 parts by mass of calcium oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat and radiate for 240 minutes to obtain 6 g of radiated calcium-PVC blend.

Example 3:

Weigh 5.0 parts by mass of PVC and 2.0 parts by mass of calcium oxide, stir and grind at high speed for 6 hours, and mix evenly to obtain 7 g of magnesium oxide-PVC blend.

Example 4:

Weigh 5.0 parts by mass of PVC, 2.0 parts by mass of calcium oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat and radiate for 240 minutes to obtain 7g of radiated magnesium oxide-PVC blend.

Example 5:

Weigh 5.0 parts by mass of PVC and 1.0 parts by mass of zinc oxide, stir and grind at high speed for 6 hours, and mix evenly to obtain 6 g of zinc oxide-PVC blend.

Embodiment 6:

Weigh 5.0 parts by mass of PVC, 1.0 parts by mass of zinc oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat and radiate for 240 minutes to obtain 6 g of irradiated zinc-PVC blend.

Embodiment 7:

Weigh 5.0 parts by mass of PVC and 1.0 parts by mass of magnesium oxide, stir and grind at high speed for 6 hours, and mix evenly to obtain 6 g of magnesium oxide-PVC blend.

Embodiment 8:

Weigh 5.0 parts by mass of PVC, 1.0 parts by mass of magnesium oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat and radiate for 240 minutes to obtain 6 g of radiated magnesium-PVC blend.

Embodiment 9:

Weigh 5.0 parts by mass of PVC, 0.5 parts by mass of calcium oxide, and 0.5 parts by mass of zinc oxide, stir and grind at high speed for 6 hours, and mix evenly to obtain 6 g of calcium oxide/zinc oxide-PVC blend.

Example 10:

Weigh 5.0 parts by mass of PVC, 0.5 parts by mass of calcium oxide, and 0.5 parts by mass of zinc oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C for 240 minutes of heating and radiation, and obtain 6 g of radiated calcium-zinc-PVC blend .

Example 11:

Weigh 5.0 parts by mass of PVC and 1.0 parts by mass of lanthanum oxide, stir and grind at high speed for 6 hours, and mix well to obtain 6 g of lanthanum oxide-PVC blend.

Example 12:

Weigh 5.0 parts by mass of PVC, 1.0 parts by mass of lanthanum oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C for 240 minutes of heating and radiation, and obtain 6 g of irradiated lanthanum-PVC blend.

Example 13:

Weigh 5.0 parts by mass of PVC, 1.0 parts by mass of lanthanum oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat and radiate for 480 minutes to obtain 6 g of irradiated lanthanum-PVC blend.

Example 14:

Weigh 5.0 parts by mass of PVC, 2.0 parts by mass of lanthanum oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C for 240 minutes of heating and radiation, and obtain 6 g of irradiated lanthanum-PVC blend.

Example 15:

Weigh 5.0 parts by mass of PVC, 2.0 parts by mass of lanthanum oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat for 480 minutes of radiation to obtain 6 g of irradiated cerium-PVC blend.

Example 16:

Weigh 5.0 parts by mass of PVC and 1.0 parts by mass of cerium oxide, stir and grind at high speed for 6 hours, and mix evenly to obtain 6 g of cerium oxide-PVC blend.

Example 17:

Weigh 5.0 parts by mass of PVC, 1.0 parts by mass of cerium oxide, stir and grind at high speed for 6 hours, mix well, place in an ultrasonic oscillator at 45°C and heat and radiate for 240 minutes to obtain 6 g of irradiated cerium-PVC blend.

Comparative example pure PVC resin powder

The Congo red test results of the above different embodiments are shown in Table 1 below.

Table 1 Congo red experiment (metal matrix-polyvinyl chloride polymer blend)

(Note: τi/min is the initial blue-turning time; τc/min is the complete blue-turning time; *ultrasonic oscillator power 120w, frequency 40 Hz, water temperature 45°C; Congo red test temperature 180°C; Examples 1 and 3 , 5, 7, 9, 11 and 16 were prepared by mixing and grinding for 6 hours; Examples 2, 4, 6, 8, 10, 12, 13, 14, 15 and 17 were prepared by mixing and grinding for 6 hours first, and then ultrasonic radiation. a is prepared by stirring and mixing PVC and oxide powder for 30 minutes without grinding or ultrasonic radiation.)

Table 1 is the Congo red experiment of metal-based-polymer blends; when the experimental temperature was constant at 180°C, it can be seen from the table that before ultrasonic radiation, Example 1, PVC/CaO (5/1) (at this time, the calcium oxide content is 16.7%) when high-speed mixing and grinding for 6 hours, the initial discoloration time of Congo red was 84min, and the complete discoloration time was 91min; and after 240min of ultrasonic radiation, the initial discoloration time of Congo red was 119min, and the complete discoloration time was 140min; After that, the initial discoloration time (induction period) was prolonged by 41.7%, and the complete discoloration time was prolonged by 53.8%.

And when embodiment 3PVC/CaO (5/2) (this moment calcium oxide content is 28.6%) high-speed mixed grinding 6h before ultrasonic radiation, Congo red initial discoloration time is 307min, and complete discoloration time is 551min; And through ultrasonic radiation after 240min In Example 4, the initial discoloration time of Congo Red was 286min, and the complete discoloration time was 316min; after visible radiation, the initial discoloration time (induction period) decreased by 6.84%, and the complete discoloration time decreased by 42.6%. It can be seen that when the calcium oxide increases to 28.6%, the ultrasonic radiation will cause the PVC polymer to be unstable. At this time, the calcium content increases, and the ultrasonic radiation calcium-chlorine reaction will partially remove the hydrogen chloride reaction to generate calcium chloride. It can be seen that the calcium content should be less than 28.6%.

As can be seen from Example 5 and Example 6, after ultrasonic radiation for 240min, both the initial discoloration and complete discoloration time of the zinc oxide-PVC blend were 20min, and the induction period of the hydrogen chloride removal reaction was not extended or reduced, as can be seen The "zinc burning" phenomenon of zinc oxide in the blend is very obvious.

From Example 7 and Example 8, it can be seen that after ultrasonic radiation for 240min, the initial discoloration and complete discoloration time for the magnesium oxide-PVC blend were respectively 25min and 73min, which were respectively 8.70% and 87.2% longer than before the radiation. It can be seen that the magnesium oxide in the blend has no significant effect on the induction period of ultrasonic radiation, but it can significantly inhibit the complete discoloration (removal of hydrogen chloride) reaction.

Example 9 before ultrasonic radiation, when PVC/CaO/ZnO (5/0.5/0.5) (calcium oxide and zinc oxide contents were 8.33% respectively) were mixed and ground at high speed for 6 hours, the initial discoloration time of Congo red was 62min, and the complete discoloration time And through the embodiment 10 after ultrasonic radiation 240min, Congo red initial discoloration time is 53min, and complete discoloration time is 62min; After visible radiation, initial discoloration time (induction period) shortens 14.5%, complete discoloration time shortens 8.82%. It can be seen that the thermal stability decreases slightly after ultrasonic radiation under the conditions of this ratio.

Example 11 before ultrasonic radiation, when PVC/lanthanum oxide (5/1) (at this time, the content of lanthanum oxide is 16.7%) was mixed and ground at high speed for 6 hours, the initial discoloration time of Congo red was 20min, and the complete discoloration time was 35min; In Example 12 after 240min, the initial discoloration time of Congo red was 37min, and the complete discoloration time was 45min; after visible radiation, the initial discoloration time (induction period) was prolonged by 85%, and the complete discoloration time was prolonged by 28.6%. This indicates that ultrasonic irradiation can significantly improve the induction period and thermal stability of the polymeric blends, and inhibit the dehydrochlorination reaction.

Example 13 after ultrasonic radiation, when PVC/lanthanum oxide (5/1) (at this time, the content of lanthanum oxide is 16.7%) was mixed and ground at high speed for 6 hours, after 480 min of ultrasonic radiation, the initial discoloration time of Congo red was 39 min, and the complete discoloration time was 59min; after visible radiation, the initial discoloration was prolonged by 5.41% compared with (240min), and the complete discoloration time was prolonged by 31.1%. This indicates that prolonging the irradiation time has little effect on the induction period, but can significantly prolong the complete discoloration time of the blend and inhibit the dehydrochlorination reaction.

Example 14 after ultrasonic radiation, when PVC/lanthanum oxide (5/2) (at this time, the content of lanthanum oxide is 28.6%) was mixed and ground for 6 hours at high speed, after 240 min of ultrasonic radiation, the initial discoloration time of Congo red was 30 min, and the complete discoloration time was 46min; in Example 15 where the irradiation time was extended to 480min, the initial discoloration time was 30min, and the complete discoloration time was 47min. When the lanthanum oxide content is 28.6%, prolonging the irradiation time has almost no effect on the initial discoloration time (induction period) and complete discoloration time of dehydrogenation, which shows that the lanthanum oxide content is extremely important.

Before radiation, comparative example 1, when PVC/cerium oxide (5/1) (this moment cerium oxide content is 16.7%) high-speed mixed grinding 6h, through ultrasonic radiation 240min after comparative example 2, Congo red initial discoloration time is 8min, complete The discoloration time is 11min; after visible radiation, the initial discoloration time is 1.0min, and the complete discoloration time decreases by 1.0min. This shows that cerium oxide has poor activity and high inertness, and has no effect on ultrasonic waves and carbon-chlorine bonds. This shows that cerium oxide is relatively stable before and after irradiation, and there is almost no interaction between cerium oxide and PVC in the cerium oxide-PVC blend, which is equivalent to the Congo red discoloration result of pure PVC resin in Comparative Example 3.

Comparative examples 4, 5 and 6 are all only mixing and stirring, without grinding and radiation, the initial bluish and complete bluish time of Congo red all decreased, and the most obvious decrease was lanthanum oxide and calcium oxide/zinc oxide compound, which Grinding is shown to be critical for Example 9 and slightly reduced for Control 5.

Under the action of ultrasonic waves, metal oxides are used as surface modifiers for the blending reaction with PVC. During the experiment, it was found that PVC/ZnO is prone to "zinc burning" as the temperature increases. And increasing the ultrasonic radiation has no effect on the initial bluing time and the complete bluing time. Comparing PVC/CaO, PVC/La ₂ O ₃ , PVC/MgO samples, it can be seen that increasing the radiation can prolong the sample's blue-turning time, and the irradiation can maximize the initial and complete blue-turning time of the sample.

(3) Metal-based-polymer blends, organotin and dipentaerythritol composite heat stabilizers to prepare PVC films

Using calcium-PVC and lanthanum-PVC blends as heat stabilizers

Take 100 parts of PVC resin model S-65, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 3.0 parts of calcium-PVC blend (PVC:calcium oxide=2.5:0.5 parts), 1.0 part of dipentaerythritol.

Take 100 parts of PVC resin model S-65, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 3.0 parts of lanthanum-PVC blend (PVC: lanthanum oxide=2.5:0.5 parts), 1.0 part of dipentaerythritol.

Ultrasonic radiation calcium-PVC, lanthanum-PVC blends were used as heat stabilizers

Take 100 parts of PVC resin model S-65, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 3.0 parts of ultrasonic radiation calcium-PVC blend (PVC: calcium oxide=2.5:0.5 parts), 1.0 part of dipentaerythritol.

Take 100 parts of PVC resin model S-65, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 3.0 parts of ultrasonically irradiated lanthanum-PVC blend (PVC: lanthanum oxide=5.0:1.0 parts), and 1.0 part of dipentaerythritol.

Example 18: No ultrasonic radiation

Preparation of PVC/DOTP/OT/calcium-PVC blend/dipentaerythritol composite film: get 50 parts by mass of DOTP, 1 part by mass of dipentaerythritol, calcium-PVC blend (PVC:calcium oxide=2.5:0.5 part)3 Parts by mass and 0.5 parts by mass of organic tin stabilizer were mixed and dissolved, and ultrasonic vibration was started for 30 minutes to obtain a uniform precursor; the obtained precursor was added to 100 parts by mass of PVC, stirred at high speed to obtain a premix, and placed in a small internal mixer Medium mixing, melt temperature 170-175°C, screw speed 40r/min, mixing time 4-5min, wait for the torque to rise sharply and then decrease, and then keep the same, when finished, take out the mixing material and use a flat vulcanizer Press at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0mm.

Example 19: Ultrasonic radiation

Preparation of PVC/DOTP/OT/radiation calcium-PVC blend/dipentaerythritol composite film: take DOTP50 mass parts, dipentaerythritol 1 mass part, radiation calcium-PVC blend (PVC:calcium oxide=2.5:0.5 parts) 3 parts by mass and 0.5 parts by mass of organotin stabilizer were mixed and dissolved, and ultrasonic vibration was started for 30 minutes to obtain a uniform precursor; the obtained precursor was added to 100 parts by mass of PVC, stirred at high speed to obtain a premix, and placed in a small mixer Mixing in the machine, the melt temperature is 170-175℃, the screw speed is 40r/min, the mixing time is 4-5min, after the torque rises sharply and then decreases, and when it remains the same, when it is finished, take out the mixed material and use a flat plate for vulcanization Press the machine at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0mm.

Example 20: Ultrasonic radiation

Preparation of PVC/DOTP/OT/radiation calcium-PVC blend/dipentaerythritol composite film: take DOTP50 mass parts, dipentaerythritol 1.0 mass parts, radiation calcium-PVC blend (PVC: calcium oxide = 15:3 parts) 18 parts by mass and 0.5 parts by mass of organic tin stabilizer were mixed and dissolved, and ultrasonic vibration was started for 30 minutes to obtain a uniform precursor; the obtained precursor was added to 100 parts by mass of PVC, stirred at high speed to obtain a premix, and placed in a small mixer Mixing in the machine, the melt temperature is 170-175℃, the screw speed is 40r/min, the mixing time is 4-5min, after the torque rises sharply and then decreases, and when it remains the same, when it is finished, take out the mixed material and use a flat plate for vulcanization Press the machine at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0mm.

Example 21: No ultrasonic radiation

Preparation of PVC/DOTP/OT/lanthanum-PVC blend/dipentaerythritol composite film: get DOTP 50 mass parts, dipentaerythritol 1.0 mass part, lanthanum-PVC blend (PVC: lanthanum oxide=2.5/0.5 part) 3.0 Parts by mass and 0.5 parts by mass of organic tin stabilizer were mixed and dissolved, and ultrasonic vibration was started for 30 minutes to obtain a uniform precursor; the obtained precursor was added to 100 parts by mass of PVC, stirred at high speed to obtain a premix, and placed in a small internal mixer For banburying, the melt temperature is 170-1750°C, the screw speed is 40r/min, and the banburying time is 4-5min. After the torque rises sharply and then falls, and remains unchanged, when it is finished, take out the mixed material and use a flat vulcanizer to Press at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0 mm.

Example 22: Ultrasonic radiation

Preparation of PVC/DOTP/OT/radiation lanthanum-PVC blend/dipentaerythritol composite film: take DOTP50 mass parts, dipentaerythritol 1.0 mass parts, radiation lanthanum-PVC blend (PVC: lanthanum oxide=2.5:0.5 part) 3.0 parts by mass and 0.5 parts by mass of organic tin stabilizer were mixed and dissolved, and mixed with ultrasonic vibration for 15 minutes to obtain a uniform precursor; the obtained precursor was added to 100 parts by mass of PVC, stirred at high speed to obtain a premix, and placed in a small mixer Mixing in the machine, the melt temperature is 170-175℃, the screw speed is 40r/min, the mixing time is 4-5min, after the torque rises sharply and then decreases, and when it remains the same, when it is finished, take out the mixed material and use a flat plate for vulcanization Press the machine at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0mm.

Example 23: Ultrasonic radiation (lanthanum-PVC blend increased from 0.5 to 3.0 parts)

Preparation of PVC/DOTP/OT/radiation lanthanum-PVC blend/dipentaerythritol composite film: get DOTP50 mass parts, dipentaerythritol 1.0 mass parts, radiation lanthanum-PVC blend (PVC: lanthanum oxide=15:3.0 parts ) 18 parts by mass and 0.5 parts by mass of organotin stabilizer were mixed and dissolved, and mixed with ultrasonic vibration for 15 minutes to obtain a uniform precursor; the obtained precursor was added to 100 parts by mass of PVC, stirred at high speed to obtain a premix, and placed in a small banburying Mixing in the machine, the melt temperature is 170-175℃, the screw speed is 40r/min, the mixing time is 4-5min, after the torque rises sharply and then decreases, and when it remains the same, when it is finished, take out the mixed material and use a flat plate for vulcanization Press the machine at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0mm.

Comparative example 1: 0.5 parts of irradiated lanthanum-PVC blend + 0.5 parts of cerium stearate

Preparation of PVC/DOTP/OT/radiation lanthanum-PVC blend/dipentaerythritol composite film: get 50 mass parts of DOTP, 0.5 part of cerium stearate, 1.0 mass part of dipentaerythritol, radiation lanthanum-PVC blend (PVC: oxidation Lanthanum=2.5:0.5 parts) 3.0 parts by mass and 0.5 parts by mass of organic tin stabilizer are mixed and dissolved, and mixed for 15 minutes in ultrasonic vibration to obtain a uniform precursor; the precursor is added to 100 parts by mass of PVC, and stirred at a high speed to obtain a premixed Put the material in a small internal mixer for internal mixing, the melt temperature is 170-175°C, the screw speed is 40r/min, and the internal mixing time is 4-5min. After the torque rises sharply and then decreases, and remains unchanged, it is finished and taken out For the mixed material, use a flat vulcanizing machine to press at 100°C for 40 seconds to obtain a PVC sheet with a thickness of 1.0mm.

Comparative example 2:

Preparation of PVC/DOTP film: Take 50 parts by mass of DOTP and 100 parts by mass of PVC, stir and dissolve at high speed to obtain a premix, put it in a small internal mixer for internal mixing, the melt temperature is 170-175°C, and the screw speed is 40r/min , the mixing time is 4-5min. After the torque rises sharply and then decreases, and remains the same, after the completion, take out the mixed material, and use a flat vulcanizer to press at 100°C for 40 seconds, and then a PVC with a thickness of 1.0mm is obtained. Flakes.

Table 2 below shows the results of the Congo red experiment. Different PVC films prepared with calcium/lanthanum metal-PVC polymer blends, organotin and dipentaerythritol composite stabilizers were used as the investigation objects. (PVC-CaO) in embodiment 18 and (PVC-CaO)* in embodiment 19 are prepared by embodiment 1 and embodiment 2 respectively; (PVC-CaO) in embodiment 20* and (PVC in embodiment 21 -La ₂ O ₃ ) were prepared from Example 4 and Example 11, respectively. (PVC-La ₂ O ₃ )* in Example 22 and (PVC-La ₂ O ₃ )* in Example 23 were prepared from Example 12 and Example 14, respectively. Comparative Example 1 was prepared from (PVC-La ₂ O ₃ )* in Example 12 and adding 0.5 parts of LaSt ₃ .

Table 2 Congo red experiment (preparation of PVC film by compound stabilizer)

(Note: τi/min is the initial blue-turning time; τc/min is the complete blue-turning time. Embodiments 19, 20, 22, 23 and 24* are prepared by grinding 6h plus ultrasonic radiation (ultrasonic oscillator power 120W, frequency 40 Hz), the initial water temperature is 45°C; Examples 18 and 21 are prepared by grinding for 6h; Congo red test temperature is 180°C)

As can be seen from Table 2, after ultrasonic radiation, Example 19 is 31min and 29min longer than Example 18 Congo Red's initial blue and complete blue, which shows that the composite stabilizer formed by OT, (PVC-CaO)* and Dip The heat resistance of PVC film is significantly enhanced. Compared with Example 19, the initial and complete bluening of Congo red in Example 20 was prolonged by 12min and 54min respectively, which indicated that increasing the usage of polymer calcium-based stabilizer (PVC-CaO)* could improve the heat resistance of the film. Compared with Example 21, the initial and complete bluening of Congo red in Example 22 was prolonged by 9 minutes and 28 minutes respectively, which indicates that the polymer lanthanum-based stabilizer (PVC-La ₂ O ₃ )* can improve the heat resistance of the composite film material. Example 22 compared with Example 23 Congo red initially turned blue and completely turned blue by 4min and 17min respectively, which showed that the usage amount of polymer lanthanum-based stabilizer (PVC-La ₂ O ₃ )* was increased from 0.5 parts to 3.0 parts It will weaken the heat resistance of the composite film material and reduce the thermal stability of the film.

Compared with Example 22 in Comparative Example 1, when 0.5 part of lanthanum stearate was added, the initial blue and complete blue were reduced by 12min and 23min respectively, which indicated that 3.0 parts of (PVC-La ₂ O ₃ )* and 0.5 parts of The lanthanum stearate produced an antagonistic effect on the heat resistance of the composite film. The control example 2 is a blank sample, and the initial and complete bluening times are 6 and 12 minutes respectively.

Can draw following conclusion by above-mentioned result, macromolecule calcium-based stabilizer (PVC-CaO) * can significantly improve the heat-resistant stability of PVC film; CaO)* can continue to increase the induction period of the film, and the time to completely turn blue is significantly increased. Polymer lanthanum-based stabilizer (PVC-La ₂ O ₃ )* can improve the heat resistance of PVC film, and the initial blue-turning time of PVC film is as follows:

(PVC-CaO)*(15-3.0 parts)>(PVC-CaO)*(2.5-0.5 parts)>(PVC-CaO)(2.5-0.5 parts)>(PVC-La ₂ O ₃ )*(2.5- 0.5 parts)>(PVC-La ₂ O ₃ )*(15-3.0 parts)>(PVC-La ₂ O ₃ )(2.5-0.5 parts)>(PVC-La ₂ O ₃ )*(2.5-0.5 parts) +LaSt ₃ (0.5 parts)>Blank

Polymer heat stabilizers composed of different metal oxides-PVC, their stability (bonding force) strengths are as follows:

CaO>CaO-ZnO>La ₂ O ₃ >MgO>ZnO>Ce ₂ O ₃

The binding force of Ca-Cl is much greater than that of Zn-Cl; Zn-Cl produces a strong "zinc burning"; due to the inertness of cerium oxide (Ce ₂ O ₃ ), there is almost no binding force between Ce-Cl.

Performance Testing

test case 1

Carry out TG-FTIR analysis to the PVC sheet that embodiment 18 and embodiment 19 obtain, the test figure that obtains is as shown in Figure 1 and Figure 2, and Figure 1 is embodiment 18, and Figure 2 is embodiment 19, and wherein X-axis is time , the Y axis is the absorbance, and the Z axis is the peak time;

It can be seen from Figure 1 and Figure 2 that the vibration peaks of all the characteristic groups of the gas phase products in Figure 1 are higher than those in Figure 2, which indicates that under the action of ultrasonic radiation, a strong intermolecular force occurs between PVC and metal M.

test case 2

The PVC sheet obtained in Example 18 and Example 19 is subjected to heat aging surface discoloration experiment, and the test results obtained are as shown in Figure 3, wherein A is Example 18, and B is Example 19; it can be seen from Figure 3 that A is ultrasonically Before, the surface was almost completely carbonized and blackened at 180 minutes, indicating that the heat resistance of A was poor; while after ultrasonic treatment of B, there was almost no significant change in the surface at 300 minutes, which indicated that the heat resistance of B was significantly improved.

Test case 3

The PVC sheet that embodiment 18 and embodiment 19 obtains is carried out thermogravimetric analysis, and the test chart that obtains is as shown in Figure 4, and wherein A is embodiment 19, and B is embodiment 18;

It can be seen from Figure 4 that after ultrasonic radiation, the heat resistance of the PVC sheet is improved.

The above content is a further detailed description of the present invention in conjunction with specific embodiments, but the embodiments of the present invention are not limited by the above examples, and any other changes that do not deviate from the spirit or principle of the present invention , replacement, modification, combination and simplification are all within the protection scope of the present invention.

Claims (12)

1. A preparation method of polyvinyl chloride polymer heat stabilizer, is characterized in that, comprises the following steps:

   Calcium/lanthanum-based metal oxide is used as the component to be activated, blended with PVC, modified and ground to produce a bonding effect between the component to be activated and PVC, and then ultrasonic radiation is performed, and the bonding effect is in the Obtained strengthening after ultrasonic radiation, obtain described polyvinyl chloride polymer thermal stabilizer;

   The calcium/lanthanum-based metal oxide is one or more of calcium oxide and lanthanum oxide.
2. The preparation method according to claim 1, comprising the steps of:

   At room temperature, weigh the dried polyvinyl chloride and calcium/lanthanum-based metal oxide, mix and grind at high speed for 6 hours to obtain a calcium/lanthanum-based metal oxide-polyvinyl chloride blend;

   The calcium/lanthanum-based metal oxide-polyvinyl chloride blend is placed in an ultrasonic oscillator and heated at 45°C for 4-8 hours to obtain the polyvinyl chloride polymer heat stabilizer.
3. The preparation method according to claim 1 or 2, characterized in that each component is composed as follows in parts by mass: 5 parts of polyvinyl chloride, 1-2 parts of calcium/lanthanum-based metal oxide.
4. The polyvinyl chloride polymer thermal stabilizer prepared by the preparation method described in any one of claims 1 to 3 is characterized in that the polyvinyl chloride polymer thermal stabilizer is calcium/lanthanum-based metal oxide and polyvinyl chloride The formed coordination complex has a polyvinyl chloride chain structure, and the main chain contains metal-Cl coordination groups.
5. The application of the polyvinyl chloride polymer heat stabilizer described in claim 4 or the polyvinyl chloride polymer heat stabilizer prepared by the preparation method described in any one of claims 1 to 3 in polyvinyl chloride resin materials.
6. A composite stabilizer, characterized in that it comprises the polyvinyl chloride polymer heat stabilizer according to claim 4 or the polyvinyl chloride polymer heat stabilizer prepared by the preparation method described in any one of claims 1 to 3, Organotin heat stabilizers and dipentaerythritol.
7. The composite stabilizer according to claim 6, characterized in that, each component comprises in parts by mass: 0.5-5.0 parts of polyvinyl chloride polymer heat stabilizer, 0.5-2.0 parts of dipentaerythritol, organotin heat stabilizer 0.1-2.0 parts.
8. The composite stabilizer according to claim 7, characterized in that it comprises 3.0 parts of polyvinyl chloride polymer heat stabilizer, 1.0 part of dipentaerythritol, and 0.5 part of organotin heat stabilizer.
9. The composite stabilizer according to any one of claims 6 to 8, characterized in that the organotin heat stabilizer is one or more of methyltin mercaptide, octyltin mercaptide and butyltin mercaptide.
10. A preparation method of polyvinyl chloride sheet, is characterized in that, comprises the following steps:

    Step 1: Mix dioctyl terephthalate, polyvinyl chloride polymer heat stabilizer, dipentaerythritol, and organotin heat stabilizer, ultrasonically oscillate, stir, mix and dissolve for 30 minutes, and obtain a uniform blend heat stabilizer precursor The polyvinyl chloride polymer thermal stabilizer is the polyvinyl chloride polymer thermal stabilizer according to claim 4 or the polyvinyl chloride polymer thermal stabilizer prepared by the preparation method described in any one of claims 1 to 3 ;

    Step 2: Mix the blend heat stabilizer precursor described in step 1 with the polyvinyl chloride base material, stir at a high speed to obtain a premix, and then put it in an internal mixer for internal mixing, the melt temperature is 170-175°C, and the screw The rotation speed is 40r/min, and the mixing time is 5-7min. After the torque rises sharply and then falls, and remains unchanged, when it is finished, take out the mixed material while it is hot, and use a flat vulcanizer to press it at 100°C for 40 seconds, and the thickness will be obtained. It is a polyvinyl chloride sheet of l.0mm.
11. The preparation method according to claim 10, characterized in that, in the steps 1 and 2, each raw material component is constituted as follows in parts by mass:

    50 parts of dioctyl terephthalate, 0.5-5.0 parts of polyvinyl chloride polymer heat stabilizer, 0.5-2.0 parts of dipentaerythritol, 0.1-2.0 parts of organotin heat stabilizer, and 100 parts of polyvinyl chloride matrix material.
12. The preparation method according to claim 11, wherein each raw material component constitutes as follows in parts by mass:

    50 parts of dioctyl terephthalate, 3.0 parts of polyvinyl chloride polymer heat stabilizer, 1.0 part of dipentaerythritol, 0.5 parts of organotin heat stabilizer, and 100 parts of polyvinyl chloride matrix material.

Images