阅读说明：本技术 一种氧化锌高聚物的制备方法及其应用 (Preparation method and application of zinc oxide high polymer ) 是由 曹兰 郑雷 臧晓燕 王志晔 荣先超 蒲诚勇 于 2021-01-26 设计创作，主要内容包括：本发明公开了一种氧化锌高聚物的制备方法及其应用,所述制备方法包括以下步骤：1)制备表面较多缺陷纳米氧化锌载体；2)制备烯烃聚合催化剂：在氮气环境下将纳米氧化锌载体和氯化镁加入球磨罐,注入钛金属化合物,把球磨罐放入湿法球磨机中研磨,制得烯烃聚合催化剂；3)制备氧化锌高聚物。本发明制备的氧化锌高聚物具有氧化锌活性组分,且氧化锌含量可达到80%以上,可作为氧化锌载体应用降低普通氧化锌使用量,也可以直接应用于牙胶尖、医用夹板等领域。(The invention discloses a preparation method and application of a zinc oxide high polymer, wherein the preparation method comprises the following steps: 1) preparing a nano zinc oxide carrier with more defects on the surface; 2) preparation of olefin polymerization catalyst: adding a nano zinc oxide carrier and magnesium chloride into a ball-milling tank in a nitrogen environment, injecting a titanium metal compound, and putting the ball-milling tank into a wet ball mill for grinding to prepare an olefin polymerization catalyst; 3) preparing the zinc oxide high polymer. The zinc oxide high polymer prepared by the invention has zinc oxide active components, the content of zinc oxide can reach more than 80%, and the zinc oxide high polymer can be used as a zinc oxide carrier to reduce the using amount of common zinc oxide, and can also be directly applied to the fields of gutta-percha tips, medical splints and the like.)

1. A preparation method of a zinc oxide high polymer is characterized by comprising the following steps:

1) preparing a nano zinc oxide carrier: mixing zinc salt or zinc hydrate salt with a first additive, a second additive and an aliphatic alcohol solvent, fully stirring, heating to 100-220 ℃ after stirring, keeping for 5-15h, then heating to 220-300 ℃ and keeping for 2-10 h, then centrifuging, collecting gray powder, burning the gray powder in a muffle furnace, and carrying out stage heating to prepare the nano zinc oxide carrier with more defects on the surface;

the first additive is an alcohol containing phenyl;

the second additive is one or a combination of more of urea, urea derivatives, thiourea and thiourea derivatives;

the aliphatic alcohol solvent is an aliphatic alcohol solvent with 1-3 carbon atoms;

2) preparation of olefin polymerization catalyst: adding the nano zinc oxide carrier prepared in the step 1) and magnesium chloride into a ball milling tank in a nitrogen environment, injecting a titanium metal compound, and putting the ball milling tank into a wet ball mill for grinding to prepare an olefin polymerization catalyst;

3) preparing a zinc oxide high polymer: under the vacuum state, adding a diene monomer into a reaction kettle, sequentially adding a cocatalyst and the olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization for 10-50min at 0 ℃, then carrying out polymerization for 5-20h at the polymerization temperature of 10-30 ℃, adding acidified ethanol to terminate the polymerization after the polymerization is finished, and carrying out vacuum drying to obtain the zinc oxide high polymer.

2. The method for producing a zinc oxide polymer according to claim 1, wherein: the nano zinc oxide carrier in the step 2) is pretreated before being added into a ball milling tank, and the pretreatment method comprises the following steps: vacuum drying the nano zinc oxide carrier, adding the nano zinc oxide carrier into a polymerization flask, adding an organic solvent and a pretreatment medium into the polymerization flask in a nitrogen environment, stirring or soaking for 1-50h at 40-60 ℃, and after the reaction is finished, evaporating the solvent under a reduced pressure condition to obtain a nano zinc oxide carrier pretreatment substance;

the pretreatment medium is titanium tetrahalide OR an aluminum-containing compound Al (OR ') nR3-n, n is more than OR equal to 0 and less than OR equal to 3, and R' are alkyl groups with 2-10 carbon atoms.

3. The method for producing a zinc oxide polymer according to claim 1, wherein: the first additive in the step 1) is benzyl alcohol; the aliphatic alcohol solvent is absolute methanol.

4. The method for producing a zinc oxide polymer according to claim 1, wherein: in the step 1), the mass concentration of the zinc salt or the hydrated zinc salt in the aliphatic alcohol solvent is 60-100g/L, the mass concentration of the first additive in the aliphatic alcohol solvent is 100-300g/L, and the mass concentration of the second additive in the aliphatic alcohol solvent is 1-10 g/L.

5. The method for producing a zinc oxide polymer according to claim 1, wherein: the mass ratio of the nano zinc oxide carrier to the magnesium chloride in the step 2) is 4-24: 1.

6. The method for producing a zinc oxide polymer according to claim 1, wherein: the titanium metal compound in the step 2) is titanium tetrachloride.

7. The method for producing a zinc oxide polymer according to claim 2, wherein: the organic solvent is alkane with 5-10 carbon atoms, cycloalkane with 5-10 carbon atoms, ether with 2-12 carbon atoms and/or tetrahydrofuran.

8. The method for producing a zinc oxide polymer according to claim 2, wherein: the organic solvent is hexane, the pretreatment medium is titanium tetrachloride, and the mass volume ratio of the nano zinc oxide carrier to the organic solvent to the pretreatment medium is 10g to (5-20) mL to (0.5-3) mL.

9. The method for producing a zinc oxide polymer according to claim 1, wherein: in the step 3), the diene monomer is isoprene, butadiene or farnesene, and the cocatalyst is triisobutylaluminum; the volume ratio of the diene monomer to the cocatalyst is 20-30: 4, and the mass volume ratio of the olefin polymerization catalyst to the cocatalyst is (1-120) g: 3 mL.

10. The zinc oxide polymer as defined in claim 1 or 2, which is applicable to the fields of composite rubber materials for shock-absorbing mounts, composite materials for gutta-percha points, medical splints, etc.

Technical Field

The invention relates to the technical field of fine chemical engineering, in particular to a preparation method and application of a zinc oxide high polymer.

Background

In recent years, zinc oxide nanoparticles have unique photocatalytic performance, high broad-spectrum antibacterial activity and long-term stability under extreme conditions due to unique physical and chemical characteristics of optics, catalysis, piezoelectricity and the like, and have great development prospects in the biomedical fields of biosensing and detection, drug delivery, bioimaging, antibiosis, tumor cell targeted killing and the like. However, the zinc oxide nanoparticles have strong van der waals force and high surface energy caused by high reactivity of the zinc oxide nanoparticles, so that the zinc oxide nanoparticles are easy to agglomerate, the dispersion stability of the nanoparticles is greatly reduced, and the application of the zinc oxide nanoparticles in various fields is greatly limited.

Meanwhile, the nano zinc oxide is an essential component in the rubber vulcanization process as an activating agent for accelerating vulcanization, is applied more and more in rubber composite materials, can be used as a vulcanization accelerator, and has a certain reinforcing effect on rubber. However, due to their high surface energy and growth characteristics along specific crystal planes, nano-ZnO is extremely prone to agglomeration, which severely hampers its utility in rubber composites [ Journal of the American Chemical Society,2005,127(38): 13331-; journal of Applied Polymer Science,2012,124(4):3099 and 3107.

In order to solve the problems, the preparation of the nano zinc oxide-based composite particles is an effective means, and the nano zinc oxide-based composite particles not only can improve the dispersion stability of the zinc oxide nano particles, but also can be combined with other materials to endow other functional attributes. The preparation method comprises the steps of mixing zinc ions with polyethylene glycol to obtain a precursor solution, coating the zinc ions with the polyethylene glycol in the precursor solution to generate a steric hindrance effect, and thus obtaining the nano-scale zinc oxide composite material, wherein the zinc oxide composite material has certain organic compatibility and is beneficial to application in the field of solar cells (CN 103972395B). The preparation method comprises the steps of generating a zinc oxide nano-film on a substrate by adopting an electrostatic spinning method, calcining, and growing zinc oxide nano-columns on the surface of the generated zinc oxide nano-film with hexagonal wurtzite crystal phase by taking each zinc oxide nano-wire as an axis to form a zinc oxide nano-column array, wherein the obtained zinc oxide can be used for LEDs, solar cells or photocatalytic surfaces (CN 104671277B).

The invention provides a method for preparing a zinc oxide high polymer by anchoring a titanium metal compound serving as an active component of a Ziegler-natta catalyst on defect surfaces of nano zinc oxide and magnesium chloride by using nano zinc oxide as a carrier. The zinc oxide high polymer prepared by the invention can be used as a zinc oxide carrier to reduce the using amount of common zinc oxide, and can also be directly applied to the fields of gutta-percha tips, medical splints and the like.

Disclosure of Invention

The invention aims to provide a preparation method of a zinc oxide high polymer.

In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a zinc oxide high polymer is characterized by comprising the following steps:

1) preparing a nano zinc oxide carrier: mixing zinc salt or zinc hydrate salt with a first additive, a second additive and an aliphatic alcohol solvent, fully stirring, heating to 100-220 ℃ after stirring, keeping for 5-15h, then heating to 220-300 ℃ and keeping for 2-10 h, then centrifuging, collecting gray powder, burning the gray powder in a muffle furnace, and carrying out stage heating to prepare the nano zinc oxide carrier with more defects on the surface;

the first additive is an alcohol containing phenyl;

the second additive is one or a combination of more of urea, urea derivatives, thiourea and thiourea derivatives;

the aliphatic alcohol solvent is an aliphatic alcohol solvent with 1-3 carbon atoms;

2) preparation of olefin polymerization catalyst: adding the nano zinc oxide carrier prepared in the step 1) and magnesium chloride into a ball milling tank in a nitrogen environment, injecting a titanium metal compound, and putting the ball milling tank into a wet ball mill for grinding to prepare an olefin polymerization catalyst;

3) preparing a zinc oxide high polymer: under the vacuum state, adding a diene monomer into a reaction kettle, sequentially adding a cocatalyst and the olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization for 10-50min at 0 ℃, then carrying out polymerization for 5-20h at the polymerization temperature of 10-30 ℃, adding acidified ethanol to terminate the polymerization after the polymerization is finished, and carrying out vacuum drying to obtain the zinc oxide high polymer.

Further, the method comprises the following steps of; the nano zinc oxide carrier in the step 2) is pretreated before being added into a ball milling tank, and the pretreatment method comprises the following steps: vacuum drying the nano zinc oxide carrier, adding the nano zinc oxide carrier into a polymerization flask, adding an organic solvent and a pretreatment medium into the polymerization flask in a nitrogen environment, stirring or soaking for 1-50h at 40-60 ℃, and after the reaction is finished, evaporating the solvent under a reduced pressure condition to obtain a nano zinc oxide carrier pretreatment substance;

the pretreatment medium is titanium tetrahalide OR an aluminum-containing compound Al (OR ') nR3-n, n is more than OR equal to 0 and less than OR equal to 3, and the carbon atoms of R and R' are alkyl groups of 2-10;

further, the method comprises the following steps of; the first additive in the step 1) is benzyl alcohol; the aliphatic alcohol solvent is absolute methanol.

Further, the method comprises the following steps of; in the step 1), the mass concentration of the zinc salt or the hydrated zinc salt in the aliphatic alcohol solvent is 60-100g/L, the mass concentration of the first additive in the aliphatic alcohol solvent is 100-300g/L, and the mass concentration of the second additive in the aliphatic alcohol solvent is 1-10 g/L.

Further, the method comprises the following steps of; the mass ratio of the nano zinc oxide carrier to the magnesium chloride in the step 2) is 4-24: 1.

Further, the method comprises the following steps of; the titanium metal compound in the step 2) is titanium tetrachloride.

Further, the method comprises the following steps of; the organic solvent is alkane with 5-10 carbon atoms, cycloalkane with 5-10 carbon atoms, ether with 2-12 carbon atoms and/or tetrahydrofuran.

Further, the method comprises the following steps of; the organic solvent is hexane, the pretreatment medium is titanium tetrachloride, and the mass volume ratio of the nano zinc oxide carrier to the organic solvent to the pretreatment medium is 10g to (5-20) mL to (0.5-3) mL.

Further, the method comprises the following steps of; in the step 3), the diene monomer is isoprene, butadiene or farnesene, and the cocatalyst is triisobutylaluminum; the volume ratio of the diene monomer to the cocatalyst is 20-30: 4, and the mass volume ratio of the olefin polymerization catalyst to the cocatalyst is (1-120) g: 3mL

The invention also provides the application of the zinc oxide high polymer in preparing a damping support composite rubber material, a gutta-percha point composite material and a medical splint.

The invention has the beneficial effects that: the intermediate product olefin polymerization catalyst particles prepared by the preparation method have the appearance form of light yellow powder or light yellow flowing liquid, contain rod-shaped nano zinc oxide carriers and are uniform without agglomeration; the titanium metal compound can be stably distributed at crystal defects on the surface of magnesium chloride and crystal defects of nano zinc oxide. The finally prepared zinc oxide high polymer has zinc oxide active components, the content of zinc oxide can reach more than 80%, the zinc oxide high polymer can be used as a zinc oxide carrier to reduce the using amount of common zinc oxide, and can also be directly applied to the fields of gutta-percha tips, medical splints and the like.

Detailed Description

The following specific examples are explained in detail with respect to the method for producing the zinc oxide polymer of the invention. These examples are not intended to limit the scope of the invention and should not be construed as limiting the invention to only the conditions, parameters or values set forth in the specification.

Example 1:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) 4000g of the nano zinc oxide carrier particles prepared in the step 1) and 1000g of anhydrous magnesium chloride are added into a ball milling tank which is dried and sealed after being replaced by high-purity nitrogen for three times, then 15mL of analytically pure titanium tetrachloride is injected, after the charging is finished, the ball milling tank is placed into a planetary ball mill and is milled for 10 hours, and the olefin polymerization catalyst is prepared. In the catalyst, the mass percentage of the titanium element is 0.13 wt%, and the mass percentage of the zinc element is 64.17 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutyl aluminum and 40g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization at 0 ℃ for 30min, then carrying out polymerization reaction for 10h, wherein the polymerization reaction temperature is 22 ℃, adding acidified ethanol to terminate the polymerization reaction after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain about 2510g of zinc oxide high polymer, wherein the content of nano zinc oxide is about 1.8%.

Example 2:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) 4000g of the nano zinc oxide carrier particles prepared in the step 1) and 1000g of anhydrous magnesium chloride are added into a ball milling tank which is dried and sealed after being replaced by high-purity nitrogen for three times, then 15mL of analytically pure titanium tetrachloride is injected, after the charging is finished, the ball milling tank is placed into a planetary ball mill and is milled for 10 hours, and the olefin polymerization catalyst is prepared. In the catalyst, the mass percentage of the titanium element is 0.13 wt%, and the mass percentage of the zinc element is 64.17 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutylaluminum and 500g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization at 0 ℃ for 30min, then carrying out polymerization reaction for 6h, wherein the polymerization reaction temperature is 22 ℃, adding acidified ethanol to terminate the polymerization reaction after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain about 2590g of zinc oxide high polymer, wherein the content of nano zinc oxide is about 16%.

Example 3:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) 4000g of the nano zinc oxide carrier particles prepared in the step 1) and 1000g of anhydrous magnesium chloride are added into a ball milling tank which is dried and sealed after being replaced by high-purity nitrogen for three times, then 15mL of analytically pure titanium tetrachloride is injected, after the charging is finished, the ball milling tank is placed into a planetary ball mill and is milled for 10 hours, and the olefin polymerization catalyst is prepared. In the catalyst, the mass percentage of the titanium element is 0.13 wt%, and the mass percentage of the zinc element is 64.17 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutylaluminum and 4000g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization at 0 ℃ for 30min, then carrying out polymerization reaction for 1.2h, wherein the polymerization reaction temperature is 22 ℃, adding acidified ethanol to terminate the polymerization reaction after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain 4800g of zinc oxide high polymer, wherein the content of nano zinc oxide is about 67%.

Example 4:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) Adding 4800g of the nano zinc oxide carrier particles prepared in the step 1) and 200g of anhydrous magnesium chloride into a dry and sealed ball-milling tank after three times of replacement by high-purity nitrogen in a nitrogen environment, then injecting 15mL of analytically pure titanium tetrachloride, after the addition is finished, putting the ball-milling tank into a planetary ball mill, and grinding for 10 hours to prepare the olefin polymerization catalyst. In the catalyst, the mass percentage of the titanium element is 0.13 wt%, and the mass percentage of the zinc element is 77.01 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutylaluminum and 2000g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization at 0 ℃ for 30min, then carrying out polymerization reaction for 2.5h, wherein the polymerization reaction temperature is 22 ℃, adding acidified ethanol to terminate the polymerization reaction after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain 5500g of zinc oxide polymer, wherein the content of nano zinc oxide is about 77%.

Example 5:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) Adding 4800g of the nano zinc oxide carrier particles prepared in the step 1) and 200g of anhydrous magnesium chloride into a dry and sealed ball-milling tank after three times of replacement by high-purity nitrogen in a nitrogen environment, then injecting 15mL of analytically pure titanium tetrachloride, after the addition is finished, putting the ball-milling tank into a planetary ball mill, and grinding for 10 hours to prepare the olefin polymerization catalyst. In the catalyst, the mass percentage of the titanium element is 0.13 wt%, and the mass percentage of the zinc element is 77.01 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutylaluminum and 4000g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization at 0 ℃ for 30min, then carrying out polymerization reaction for 0.5h, wherein the polymerization reaction temperature is 22 ℃, adding acidified ethanol to terminate the polymerization reaction after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain 4600g of zinc oxide polymer, wherein the content of nano zinc oxide is about 83%.

Example 6:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) Adding 4800g of the nano zinc oxide carrier particles prepared in the step 1) and 200g of anhydrous magnesium chloride into a dry and sealed ball-milling tank after three times of replacement by high-purity nitrogen in a nitrogen environment, then injecting 0.5mL of analytically pure titanium tetrachloride, after the addition is finished, putting the ball-milling tank into a planetary ball mill, and grinding for 10 hours to obtain the olefin polymerization catalyst. In the catalyst, the mass percentage of titanium element is 0.004 wt%, and the mass percentage of zinc element is 77.3 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutyl aluminum and 2030g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization for 30min at 0 ℃, then carrying out polymerization for 8h, wherein the polymerization temperature is 22 ℃, adding acidified ethanol to terminate the polymerization after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain about 5825g of zinc oxide high polymer, wherein the content of nano zinc oxide is about 33.6%.

Example 7:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dried gray powder, calcining at a temperature rise rate of 5 deg.C/min to 600 deg.C, and maintaining at 600 deg.C for 6 hr to obtain the final productObtaining the nano zinc oxide carrier particles with more defects on the surface.

2) Adding 4800g of the nano zinc oxide carrier particles prepared in the step 1) and 200g of anhydrous magnesium chloride into a dry and sealed ball-milling tank after three times of replacement by high-purity nitrogen in a nitrogen environment, then injecting 0.5mL of analytically pure titanium tetrachloride, after the addition is finished, putting the ball-milling tank into a planetary ball mill, and grinding for 10 hours to obtain the olefin polymerization catalyst. In the catalyst, the mass percentage of titanium element is 0.004 wt%, and the mass percentage of zinc element is 77.3 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutyl aluminum and 4068g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization for 30min at 0 ℃, then carrying out polymerization for 2.5h, wherein the polymerization temperature is 22 ℃, adding acidified ethanol to terminate the polymerization after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain about 4780g of zinc oxide high polymer, wherein the content of nano zinc oxide is about 81.7%.

Example 8:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) Adding 5000g of the nano zinc oxide carrier particles prepared in the step 1) into a polymerization flask after vacuum treatment, adding 5000mL of hexane and 500mL of titanium tetrachloride into the polymerization flask under a nitrogen environment, soaking and standing for 30h at 40 ℃ in an anhydrous and oxygen-free manner, decompressing and evaporating a solvent after the reaction is finished, and performing vacuum drying to obtain a nano zinc oxide carrier pretreatment substance; 4800g of nano zinc oxide carrier pretreatment and 200g of anhydrous magnesium chloride are added into a ball milling tank which is dried and sealed after being replaced by high-purity nitrogen for three times under the nitrogen environment, then 0.5mL of analytically pure titanium tetrachloride is injected, after the charging is finished, the ball milling tank is placed into a planetary ball mill and is milled for 10 hours, and the olefin polymerization catalyst is prepared. In the catalyst, the mass percentage of the titanium element is 0.005 wt%, and the mass percentage of the zinc element is 76.8 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutyl aluminum and 4068g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization for 30min at 0 ℃, then carrying out polymerization for 2.5h, wherein the polymerization temperature is 22 ℃, adding acidified ethanol to terminate the polymerization after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain 4986g of zinc oxide high polymer, wherein the content of the nano zinc oxide is about 78.3%.

Example 9:

a preparation method of a zinc oxide high polymer comprises the following steps:

1) in the anhydrous and oxygen-free environment, 18Kg of Zn (NO) is added₃)₂·6H₂O was dissolved in 200L of anhydrous methanol. After complete dissolution, 0.9Kg of urea and 39Kg of benzyl alcohol were added to the mixture. Stirring in an autoclave for 6 hours under a nitrogen environment, heating to 200 ℃ for reaction for 10 hours, heating to 280 ℃ for reaction for 5 hours, and removing internal low-boiling-point substances. Centrifuging, collecting dry gray powder, calcining to 600 ℃ at the heating rate of 5 ℃/min, and then keeping at 600 ℃ for 6h to prepare the nano zinc oxide carrier particles with more defects on the surface.

2) Adding 5000g of the nano zinc oxide carrier particles prepared in the step 1) into a polymerization flask after vacuum treatment, adding 5000mL of hexane and 500mL of titanium tetrachloride into the polymerization flask under a nitrogen environment, stirring for 24h at 40 ℃ in an anhydrous and oxygen-free manner, decompressing and evaporating a solvent after the reaction is finished, and performing vacuum drying to obtain a nano zinc oxide carrier pretreatment substance; 4800g of nano zinc oxide carrier pretreatment and 200g of anhydrous magnesium chloride are added into a ball milling tank which is dried and sealed after being replaced by high-purity nitrogen for three times under the nitrogen environment, then 0.5mL of analytically pure titanium tetrachloride is injected, after the charging is finished, the ball milling tank is placed into a planetary ball mill and is milled for 10 hours, and the olefin polymerization catalyst is prepared. In the catalyst, the mass percentage of the titanium element is 0.005 wt%, and the mass percentage of the zinc element is 75.2 wt%; the apparent form of the catalyst is light gray powder; wherein, the content of titanium and zinc elements in the catalyst is measured by an ultraviolet spectrophotometry.

3) Adding 7500mL of isoprene monomer into a reaction kettle in a vacuum state, sequentially adding 120mL of triisobutyl aluminum and 4068g of olefin polymerization catalyst prepared in the step 2), carrying out prepolymerization for 30min at 0 ℃, then carrying out polymerization for 2.5h, wherein the polymerization temperature is 22 ℃, adding acidified ethanol to terminate the polymerization after the polymerization is finished, and carrying out vacuum drying at 30 ℃ to obtain about 5135g of zinc oxide high polymer, wherein the content of nano zinc oxide is about 76.0%.

Performance test experiments:

1. the zinc oxide polymers prepared in examples 1 to 7 were applied to the formulation for preparing a vibration damping mount composite material for performance testing.

Table 1 shows the formulation of the composite material for the damping mount No. 1 to No. 8, wherein No. 1 is a comparative formulation and the detailed weight ratio of each component in the raw materials is shown in table 1.

The preparation method of the damping support comprises the following steps:

weighing the components according to the proportion of the formula No. 1 to the formula No. 8 in the table 1 (parts by weight), mixing the plasticated natural rubber, carbon black N330, nano titanium dioxide, microcrystalline wax, an anti-aging agent 4020, an anti-ultraviolet agent, tackifying resin, C5 petroleum resin, 3mm long chopped carbon fiber, aromatic oil, zinc oxide or zinc oxide high polymer and stearic acid by an internal mixer for 5 minutes at 40 revolutions per minute and 80 ℃, uniformly mixing, and discharging and standing for later use; then mixing the mixed rubber and vulcanizing agents (sulfur and N-cyclohexyl-2-benzothiazole sulfonamide) in an internal mixer uniformly at 40 r/min and 80 ℃ for 3 min, and then discharging. Cutting the rubber compound added with the vulcanizing agent into rubber sheets, and alternately stacking the rubber sheets according to the steel plates, wherein n layers of steel plates and n +1 layers of rubber sheets are counted to obtain blanks; and putting the blank into a preheated mold, and vulcanizing the blank for T90+100min at the temperature of 145 ℃ and under the pressure of 14.5MPa to obtain the rubber support.

A5 gram sample of the rubber mount was weighed into a vulkameter to determine the scorch time T10 and the positive craft cure time T90. The rubber support samples were vulcanized on a flat vulcanizing machine at 160 ℃ x T90, vulcanization pressure: 14.5MPa, preparing a strength sheet and a peeling strength sample. The performance of the strength sheet and the peel strength test piece were tested, and the material properties are shown in Table 2.

Table 11-8 damping support composite material formula

The test method and the standard are as follows:

1) the first part of the GB/T531.1-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method is a Shore durometer method;

2) determining the tensile stress strain performance of GB/T528-2009 vulcanized rubber or thermoplastic rubber;

3) GB/T3512-;

4) GB/T7759.1-2015 determination of compression set of vulcanized rubber or thermoplastic rubber;

5) GB/T7762- -2014 vulcanized rubber or thermoplastic rubber resists ozone crack static tensile test.

TABLE 21-8 damping support composite material performance test data

The data in table 2 show that, for the damping support composite material, after the zinc oxide high polymer prepared by the invention is used, the low-temperature brittleness, the tensile fatigue and the six-grade flexion and deflection performance of the composite material are greatly improved. For example, in the formula No. 4, after 5 parts of zinc oxide high polymer with the nano zinc oxide content of about 76.0% is added, compared with the formula No. 1, the dosage of zinc oxide is reduced by 33%, the physical and mechanical properties are well maintained, in the low-temperature resistance, the low-temperature brittleness is reduced by 4 ℃, the extension fatigue life is improved by 60%, and the six-level flexion fatigue is improved by 168%. Therefore, when the zinc oxide high polymer prepared by the invention is applied to a damping support composite material, the zinc oxide dosage can be effectively reduced, the good physical and mechanical properties can be kept, and the dynamic fatigue performance can be greatly improved.

2. The zinc oxide polymers prepared in examples 5, 8 and 9 were applied to the formulation for preparing a gutta-percha point composite for performance testing.

Table 3 shows the formulation of the gum tip composite No. 11 to 14, wherein No. 11 is a comparative formulation and the detailed weight ratios of the components in the raw materials are shown in table 3.

Formula of gum tip composite material for No. 311-14 teeth

The preparation method of the No. 11 comparative gutta-percha point composite material comprises the following steps:

weighing the components according to the formula No. 11 (in parts by weight) in the table 3, weighing the plasticated trans-polyisoprene at 70 r/min, heating to 100 ℃, adding 1/3 filler components, mixing for 4 min by using an internal mixer to mix uniformly, adding the rest of the filler, and mixing for 4 min by using the internal mixer to mix uniformly. After mixing, a little of powdered filler which is not completely and uniformly dispersed is arranged on the surface, a sheet with the thickness of about 1mm is quickly pressed by an open mill at the temperature of 105 ℃, then a Mooney sample and a melt index are quickly cut, and the material properties are shown in Table 4.

No. 12-14 gutta-percha point composite material taking the zinc oxide high polymer prepared by the embodiment of the invention as a main base material comprises the following steps:

weighing the components according to the formula (weight parts) No. 12-14 in the table 3, weighing the plasticated zinc oxide polymer, heating to 100 ℃ at 70 r/min, adding all the filler components, and mixing by using an internal mixer for 3 min to uniformly mix. After mixing, the samples are all free of powdery filler, the samples are quickly pressed into slices of about 1mm at 105 ℃ by an open mill, and then the Mooney samples and the melt index are quickly sheared, wherein the material properties are shown in Table 4.

TABLE 4 gutta-percha point composite mechanical properties

The data in table 4 show that, for the gutta-percha point composite material, the preparation processability and the use performance of the gutta-percha point composite material are obviously improved by using the zinc oxide high polymer prepared by the embodiment of the invention compared with the comparative example.