阅读说明：本技术 一种碳酸钙高填充pp聚乙烯材料的增强韧性及强度配方 (Formula for enhancing toughness and strength of calcium carbonate high-filling PP (polypropylene) polyethylene material ) 是由 田亚林 毛彩荣 于 2021-08-11 设计创作，主要内容包括：本发明涉及聚乙烯材料生产技术领域,公开了一种碳酸钙高填充PP聚乙烯材料的增强韧性及强度配方,包括以下组成部分：乙烯、聚乙烯催化剂、丙烯、聚丙烯催化剂和碳酸钙,每种组成部分按重量份组成如下：50～55份乙烯、5～10份聚乙烯催化剂、10～15份丙烯、1～2份聚丙烯催化剂和1～2份碳酸钙,本发明通过使用JL-G02型改性剂、苯二酚和六亚甲基四胺改良的碳酸钙填充聚乙烯,用此改良后的碳酸钙填充生产出来的聚乙烯材料区别于用普通改性剂改良碳酸钙填充生产出来的聚乙烯材料,本发明的聚乙烯材料的拉伸性能、断裂伸张率、杨氏模量和缺口冲击强度都得到了极大的提高,拥有极高的韧性和极大的强度。(The invention relates to the technical field of polyethylene material production, and discloses a formula for enhancing toughness and strength of a calcium carbonate high-filling PP polyethylene material, which comprises the following components: ethylene, a polyethylene catalyst, propylene, a polypropylene catalyst and calcium carbonate, wherein each component comprises the following components in parts by weight: 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate, JL-G02 type modifier, dihydroxybenzene and hexamethylenetetramine modified calcium carbonate are used for filling polyethylene, and the polyethylene material filled and produced by the modified calcium carbonate is different from the polyethylene material filled and produced by the modified calcium carbonate by using common modifier.)

1. The formula for enhancing toughness and strength of the calcium carbonate high-filling PP polyethylene material comprises the following components: the catalyst comprises ethylene, a polyethylene catalyst, propylene, a polypropylene catalyst and calcium carbonate, and is characterized in that each component comprises the following components in parts by weight: 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate.

2. The formula for enhancing toughness and strength of the calcium carbonate highly-filled PP polyethylene material is characterized in that the polyethylene catalyst comprises a U-J catalyst and a cocatalyst, the U-J catalyst is composed of tetrahydrofuran, magnesium chloride, titanium trichloride, tri-n-hexyl aluminum mineral oil and diethyl aluminum chloride, and the cocatalyst is triethyl aluminum, wherein the content ratio of the tetrahydrofuran, the magnesium chloride, the titanium trichloride, the tri-n-hexyl aluminum mineral oil, the diethyl aluminum chloride and the triethyl aluminum is 3:2:2:2:3: 1.

3. The formula for enhancing toughness and strength of the calcium carbonate highly-filled PP polyethylene material as claimed in claim 1, wherein the polypropylene catalyst is a spherical ZN catalyst, the spherical ZN catalyst is composed of titanium chloride, n-hexane and spherical magnesium chloride, and the content ratio of the titanium chloride, the n-hexane and the spherical magnesium chloride is 3:1: 1.

4. The formulation of claim 1, wherein the calcium carbonate is modified by a modifier, and the preparation method of the modified calcium carbonate comprises the following steps:

s1, taking out the common calcium carbonate, and drying the common calcium carbonate in an industrial dryer to ensure that the moisture in the common calcium carbonate is reduced to be below 0.5 percent;

s2, putting the dried common calcium carbonate into a high-speed mixer, and adding a JL-G02 type modifier, benzenediol and hexamethylenetetramine according to the amount of 1.5 percent of the weight of the common calcium carbonate;

and S3, raising the temperature in the high-speed mixer to 100 ℃, starting a stirring device in the high-speed mixer to stir uniformly, and taking out the finished product, namely the improved calcium carbonate for later use after stirring for 10 min.

5. The formula for enhancing toughness and strength of the calcium carbonate highly-filled PP polyethylene material as claimed in claim 1, wherein the preparation method comprises the following steps:

s4, preparing an initiator in advance, and dissolving organic peroxide in paraffin to prepare the initiator with the mass of 1% of that of the ethylene;

s5, simultaneously putting 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate into a polymerization kettle for high-pressure polymerization reaction, and pumping the prepared initiator into the polymerization kettle through a pump;

s6, enabling polyethylene granules and unreacted ethylene generated after high-pressure polymerization to enter a condenser through a pressure reducing valve at the bottom of a polymerization kettle for cooling, discharging the polyethylene granules and the unreacted ethylene into a high-pressure separator for separation when the polyethylene granules and the unreacted ethylene are cooled to a certain temperature, separating the oligomer from most of the separated unreacted ethylene and the polymer through an oligomer separator, wherein the unreacted ethylene can be collected for reuse, and the oligomer is directly discharged;

s7, discharging the polyethylene material in the high-pressure separator into a low-pressure separator for decompression, separating residual ethylene and discharging the residual ethylene for reuse;

s8, adding an antioxidant and an antistatic agent into the low-pressure separator, feeding the mixture and polyethylene in a molten state into a granulator after passing through a gear pump for underwater granulation, putting the granules into a cyclone separator for gas-solid separation after passing through a vibrating screen, and discharging the granules into a magnetic separator to remove metal particles mixed with the granules for use.

6. The formulation for enhancing toughness and strength of PP-PE material with calcium carbonate highly filled in claim 5, wherein the pressure of high pressure polymerization in S5 is controlled to be 110-200 MPa, the pressure of separation in the high pressure separator in S6 is controlled to be 25-30 MPa, and the pressure of decompression in the low pressure separator in S7 is controlled to be 40-50 MPa.

Technical Field

The invention relates to the technical field of polyethylene material production, in particular to a formula for enhancing toughness and strength of a calcium carbonate high-filling PP polyethylene material.

Background

The polyethylene material is usually produced by adding calcium carbonate into the ethylene raw material to enhance the toughness and strength of the polyethylene material.

The patent technology of the linear low-density polyethylene film filled and modified by calcium carbonate and the preparation method thereof (with the publication number of CN 104530554) disclosed by Chinese patent uses a mixture of potassium perfluorobutylsulfonate and octyl phthalate to improve the calcium carbonate, so that the toughness and the strength of the produced polyethylene material are improved to a certain extent, but the method for improving the calcium carbonate is more conventional, and the toughness and the strength of the produced polyethylene material are only improved a little and cannot be greatly improved. Therefore, the skilled person provides a formulation for enhancing toughness and strength of calcium carbonate high-filled PP polyethylene material to solve the above problems in the background art.

Disclosure of Invention

The invention aims to provide a formula for enhancing toughness and strength of a calcium carbonate high-filling PP polyethylene material so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

the formula for enhancing toughness and strength of the calcium carbonate high-filling PP polyethylene material comprises the following components: ethylene, a polyethylene catalyst, propylene, a polypropylene catalyst and calcium carbonate, wherein each component comprises the following components in parts by weight: 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate.

As a still further scheme of the invention: the polyethylene catalyst comprises a U-J catalyst and a cocatalyst, wherein the U-J catalyst is composed of tetrahydrofuran, magnesium chloride, titanium trichloride, tri-n-hexyl aluminum mineral oil and diethyl aluminum chloride, and the cocatalyst is triethyl aluminum, wherein the content ratio of the tetrahydrofuran, the magnesium chloride, the titanium trichloride, the tri-n-hexyl aluminum mineral oil, the diethyl aluminum chloride and the triethyl aluminum is 3:2:2:2:3: 1.

As a still further scheme of the invention: the polypropylene catalyst is a spherical ZN catalyst, the spherical ZN catalyst is composed of titanium chloride, n-hexane and spherical magnesium chloride, and the content ratio of the titanium chloride to the n-hexane to the spherical magnesium chloride is 3:1: 1.

As a still further scheme of the invention: the calcium carbonate is modified by a modifier, and the preparation method of the modified calcium carbonate comprises the following steps:

s1, taking out the common calcium carbonate, and drying the common calcium carbonate in an industrial dryer to ensure that the moisture in the common calcium carbonate is reduced to be below 0.5 percent;

s2, putting the dried common calcium carbonate into a high-speed mixer, and adding a JL-G02 type modifier, benzenediol and hexamethylenetetramine according to the amount of 1.5 percent of the weight of the common calcium carbonate;

and S3, raising the temperature in the high-speed mixer to 100 ℃, starting a stirring device in the high-speed mixer to stir uniformly, and taking out the finished product, namely the improved calcium carbonate for later use after stirring for 10 min.

The formula for enhancing toughness and strength of the calcium carbonate high-filling PP polyethylene material comprises the following steps:

s4, preparing an initiator in advance, and dissolving organic peroxide in paraffin to prepare the initiator with the mass of 1% of that of the ethylene;

s5, simultaneously putting 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate into a polymerization kettle for high-pressure polymerization reaction, and pumping the prepared initiator into the polymerization kettle through a pump;

s6, enabling polyethylene granules and unreacted ethylene generated after high-pressure polymerization to enter a condenser through a pressure reducing valve at the bottom of a polymerization kettle for cooling, discharging the polyethylene granules and the unreacted ethylene into a high-pressure separator for separation when the polyethylene granules and the unreacted ethylene are cooled to a certain temperature, separating the oligomer from most of the separated unreacted ethylene and the polymer through an oligomer separator, wherein the unreacted ethylene can be collected for reuse, and the oligomer is directly discharged;

s7, discharging the polyethylene material in the high-pressure separator into a low-pressure separator for decompression, separating residual ethylene and discharging the residual ethylene for reuse;

s8, adding an antioxidant and an antistatic agent into the low-pressure separator, feeding the mixture and polyethylene in a molten state into a granulator after passing through a gear pump for underwater granulation, putting the granules into a cyclone separator for gas-solid separation after passing through a vibrating screen, and discharging the granules into a magnetic separator to remove metal particles mixed with the granules for use.

As a still further scheme of the invention: the pressure control of the high-pressure polymerization reaction in the S5 is 110-200 Mpa, the pressure control of the separation in the high-pressure separator in the S6 is 25-30 Mpa, and the pressure control of the decompression in the low-pressure separator in the S7 is 40-50 Mpa.

Compared with the prior art, the invention has the beneficial effects that:

the invention uses JL-G02 type modifier, dihydroxybenzene and hexamethylenetetramine modified calcium carbonate to fill polyethylene, the polyethylene material filled by the modified calcium carbonate is different from the polyethylene material filled by the conventional modified calcium carbonate with common modifier, the tensile property, the breaking elongation, the Young modulus and the notch impact strength of the polyethylene material are greatly improved, and the polyethylene material has extremely high toughness and strength.

Detailed Description

In the embodiment of the invention, the formula for enhancing toughness and strength of the calcium carbonate high-filling PP polyethylene material comprises the following components: ethylene, a polyethylene catalyst, propylene, a polypropylene catalyst and calcium carbonate, wherein each component comprises the following components in parts by weight: 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate.

Preferably, the polyethylene catalyst comprises a U-J catalyst and a cocatalyst, the U-J catalyst consists of tetrahydrofuran, magnesium chloride, titanium trichloride, tri-n-hexyl aluminum mineral oil and diethyl aluminum chloride, and the cocatalyst is triethyl aluminum, wherein the content ratio of the tetrahydrofuran, the magnesium chloride, the titanium trichloride, the tri-n-hexyl aluminum mineral oil, the diethyl aluminum chloride and the triethyl aluminum is 3:2:2:2:3: 1.

Preferably, the polypropylene catalyst is a spherical ZN catalyst, and the spherical ZN catalyst is composed of titanium chloride, n-hexane and spherical magnesium chloride, wherein the content ratio of the titanium chloride to the n-hexane to the spherical magnesium chloride is 3:1: 1.

Preferably, the calcium carbonate is modified by a modifier, and the preparation method of the modified calcium carbonate comprises the following steps:

s1, taking out the common calcium carbonate, and drying the common calcium carbonate in an industrial dryer to ensure that the moisture in the common calcium carbonate is reduced to be below 0.5 percent;

s2, putting the dried common calcium carbonate into a high-speed mixer, and adding a JL-G02 type modifier, benzenediol and hexamethylenetetramine according to the amount of 1.5 percent of the weight of the common calcium carbonate;

and S3, raising the temperature in the high-speed mixer to 100 ℃, starting a stirring device in the high-speed mixer to stir uniformly, and taking out the finished product, namely the improved calcium carbonate for later use after stirring for 10 min.

The formula for enhancing toughness and strength of the calcium carbonate high-filling PP polyethylene material comprises the following steps:

s4, preparing an initiator in advance, and dissolving organic peroxide in paraffin to prepare the initiator with the mass of 1% of that of the ethylene;

s5, simultaneously putting 50-55 parts of ethylene, 5-10 parts of polyethylene catalyst, 10-15 parts of propylene, 1-2 parts of polypropylene catalyst and 1-2 parts of calcium carbonate into a polymerization kettle for high-pressure polymerization reaction, and pumping the prepared initiator into the polymerization kettle through a pump;

s6, enabling polyethylene granules and unreacted ethylene generated after high-pressure polymerization to enter a condenser through a pressure reducing valve at the bottom of a polymerization kettle for cooling, discharging the polyethylene granules and the unreacted ethylene into a high-pressure separator for separation when the polyethylene granules and the unreacted ethylene are cooled to a certain temperature, separating the oligomer from most of the separated unreacted ethylene and the polymer through an oligomer separator, wherein the unreacted ethylene can be collected for reuse, and the oligomer is directly discharged;

s7, discharging the polyethylene material in the high-pressure separator into a low-pressure separator for decompression, separating residual ethylene and discharging the residual ethylene for reuse;

s8, adding an antioxidant and an antistatic agent into the low-pressure separator, feeding the mixture and polyethylene in a molten state into a granulator after passing through a gear pump for underwater granulation, putting the granules into a cyclone separator for gas-solid separation after passing through a vibrating screen, and discharging the granules into a magnetic separator to remove metal particles mixed with the granules for use.

Preferably, the pressure of the high-pressure polymerization reaction in S5 is controlled to 110 to 200MPa, the pressure of the high-pressure separator in S6 is controlled to 25 to 30MPa, and the pressure of the low-pressure separator in S7 is controlled to 40 to 50 MPa.

To better illustrate the technical effect of the present invention, it is illustrated by the following tests:

the invention is selected as the embodiment;

the method comprises the following steps of selecting a calcium carbonate filled and modified linear low-density polyethylene film disclosed in Chinese patent and a preparation method thereof (No. CN 104530554) as a first comparative example;

selecting a preparation method (No. CN 112480713A) of nano calcium carbonate for filling a polyethylene transparent film disclosed by Chinese patent as a comparative example II;

a data analysis table was prepared as follows:

from the above table it can be analyzed that:

1. comparative example one a mixture of potassium perfluorobutylsulfonate and octyl phthalate was used to modify calcium carbonate to produce a polyethylene material having a transverse tensile strength of 23Mpa and a longitudinal tensile strength of 4 Mpa; in the second comparative example, monolaurate reaction and aluminate coupling agent are used to modify calcium carbonate, and the transverse tensile strength and the longitudinal tensile strength of the polyethylene material prepared by the calcium carbonate are respectively 49.7Mpa and 8.5 Mpa; examples JL-G02 type modifier, benzenediol and hexamethylenetetramine modified calcium carbonate were used to prepare polyethylene material having transverse tensile strength of 50.2MPa and longitudinal tensile strength of 15.6 MPa;

2. the polyethylene material of comparative example one had an elongation at break in the transverse direction of 1145% and an elongation at break in the machine direction of 730%; comparative example two has no data presentation; the polyethylene material of the example had a transverse elongation at break of 1744% and a longitudinal elongation at break of 1175%;

3. we measured the polyethylene material of comparative example I by actual operation, and measured that its Young's modulus is 1874 MPa; the Young modulus of the polyethylene material of the comparative example II is measured to be 2376Mpa by actual operation; the Young's modulus of the polyethylene material of the example was 2940 MPa;

4. we measured the polyethylene material of comparative example I by actual operation and found that its notched impact strength was 254J/M; the notched impact strength of the polyethylene material of comparative example II was measured to be 354J/M by actual operation; the polyethylene material of the example had a notched impact strength of 443J/M;

from this it can be analytically derived: the polyethylene material produced by filling the modifier of JL-G02 type, benzenediol and hexamethylenetetramine modified calcium carbonate has transverse tensile strength, longitudinal tensile strength, transverse flow breaking elongation, longitudinal breaking elongation, Young modulus and notched impact strength far higher than those of the polyethylene materials of the first comparative example and the second comparative example.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.