阅读说明：本技术 一种电工膜用聚丙烯树脂添加剂及其制备方法 (Polypropylene resin additive for electrical film and preparation method thereof ) 是由 谭魁龙 焦凤鸣 王彦荣 于 2020-03-12 设计创作，主要内容包括：本发明实施例公开了一种电工膜用聚丙烯树脂添加剂及其制备方法,包括自由基捕捉剂、过氧化物分解剂和酸吸收剂；自由基捕捉剂选自含受阻酚类化合物；过氧化物分解剂选自含亚磷酸酯类化合物和/或含有机硫类化合物；酸吸收剂选自含硬脂酸盐类化合物和/或含插层结构的水滑石类化合物。制备方法包括将自由基捕捉剂、过氧化物分解剂和酸吸收剂加入有机溶剂中混合后,脱除有机溶剂。本发明通过采用特定的自由基捕捉剂、过氧化物分解剂和酸吸收剂,并在有机溶剂中充分溶解和析出后,使三者之间形成了十分良好的络合力,添加到聚丙烯粉料中,分散均匀,不会发生迁移,进而解决灰分含量高以及灰分分布不均等问题,进一步提高了电工膜的性能和应用领域。(The embodiment of the invention discloses a polypropylene resin additive for an electrical film and a preparation method thereof, wherein the polypropylene resin additive comprises a free radical trapping agent, a peroxide decomposing agent and an acid absorbent; the free radical scavenger is selected from hindered phenol compounds; the peroxide decomposer is selected from phosphite ester-containing compounds and/or organic sulfur-containing compounds; the acid absorbent is selected from stearate-containing compounds and/or hydrotalcite-like compounds with intercalation structure. The preparation method comprises the steps of adding the free radical trapping agent, the peroxide decomposing agent and the acid absorbent into the organic solvent, mixing, and removing the organic solvent. According to the invention, specific free radical trapping agent, peroxide decomposer and acid absorbent are adopted, and after the three are fully dissolved and separated out in the organic solvent, a very good complexing force is formed among the three, and the free radical trapping agent, the peroxide decomposer and the acid absorbent are added into polypropylene powder, so that the polypropylene powder is uniformly dispersed and cannot migrate, the problems of high ash content, uneven ash distribution and the like are further solved, and the performance and the application field of the electrical film are further improved.)

1. An additive for polypropylene resin for electrical films, which is characterized by comprising a free radical scavenger, a peroxide decomposer and an acid absorbent; and the number of the first and second electrodes,

the free radical scavenger is selected from hindered phenol compounds;

the peroxide decomposer is selected from phosphite ester-containing compounds and/or organic sulfur-containing compounds;

the acid absorbent is selected from a compound containing stearate and/or a hydrotalcite compound containing an intercalation structure.

2. The polypropylene resin additive for electrical engineering films as claimed in claim 1, wherein the radical scavenger is selected from at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate;

preferably, the radical scavenger is selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene;

the peroxide decomposer is at least one selected from phenyl trisnonylphenyl phosphite, dioctadecyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dilauryl thiodipropionate and dioctadecyl thiodipropionate;

preferably, the peroxide decomposer is selected from tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite;

the acid absorbent is at least one selected from calcium stearate, zinc stearate, sodium stearate, magnesium stearate and magnesium aluminum hydrotalcite;

preferably, the magnalium hydrotalcite is at least one selected from DHT-4A, Hycite713, HT-P and C L C-120;

more preferably, the acid absorbent is selected from at least one of calcium stearate, magnesium aluminum hydrotalcite with a grade of DHT-4A and magnesium aluminum hydrotalcite with a grade of Hycite 713.

3. The polypropylene resin additive for electrical engineering films as claimed in claim 1 or 2, wherein the content of the radical scavenger, the peroxide decomposer and the acid absorbent is 1: 0.01-50: 0.0001-1;

preferably, the mass ratio of the content of the free radical scavenger to the content of the peroxide decomposer is 1: 0.05-10: 0.001-0.1;

more preferably, the mass ratio of the content of the radical scavenger to the content of the peroxide decomposer is 1:0.5 to 5:0.01 to 0.05.

4. A method for preparing the polypropylene resin additive for electrical film according to any one of claims 1 to 3, comprising: adding the free radical trapping agent, the peroxide decomposer and the acid absorbent into an organic solvent, mixing, and removing the organic solvent to obtain the polypropylene resin additive for the electrical film.

5. The preparation method of the polypropylene resin additive for electrical films as claimed in claim 4, wherein the mixing process is carried out by using an atomized jet stirring device, the atomized jet stirring device comprises a blowing jet structure (1) and a stock solution mixing structure (2) which are sequentially arranged from top to bottom, and the blowing jet structure (1) and the stock solution mixing structure (2) are connected through a sieve plate assembly (3); and the number of the first and second electrodes,

the blowing jet structure (1) at least comprises a cavity (11), a drainage tube (13) which is communicated with the liquid storage mixing structure (2) and the cavity (11) through a pump body (12), an atomizing injection piece (14) which is arranged in the drainage tube (13) and connected to one end of the cavity (11) and a nozzle (141) extends to the inside of the cavity (11), and a powder adding component (15) which is arranged in the cavity (11) and is positioned above the atomizing injection piece (14) and used for adding powder, wherein a fan (151) for blowing off the powder is arranged in the powder adding component (15);

the liquid storage and mixing structure (2) at least comprises a liquid storage cavity (21) for storing an organic solvent and a heating and stirring assembly (22) at least partially arranged in the liquid storage cavity (21).

6. The method for preparing polypropylene resin additive for electrical engineering films as claimed in claim 5, wherein the drainage tube (13) comprises a main tube (131) and a plurality of secondary tubes (132) sequentially communicated from the liquid storage and mixing structure (2) to the cavity (11), each secondary tube (132) is connected with an atomizing injection member (14), and the injection direction of the nozzle (141) of the atomizing injection member (14) extends along the radial direction of the cavity (11).

7. The method for preparing polypropylene resin additive for electrical film according to claim 5 or 6, wherein the powder adding assembly (15) comprises a feeding tube (152) having an axis direction extending in a vertical direction, and a bottom end of the feeding tube (152) is located above the nozzle (141), the blower (151) is disposed outside the feeding tube (152), and a blowing direction of the blower (151) is inclined downward and toward an extending direction of the axis of the feeding tube (152).

8. The method for preparing polypropylene resin additive for electrical engineering films as claimed in claim 5, wherein the screen plate assembly (3) comprises at least a first screen plate (31) and a second screen plate (32) sequentially arranged from top to bottom, the screen opening of the first screen plate (31) is larger than that of the second screen plate (32), the first screen plate (31) and the second screen plate (32) are relatively moved in the horizontal direction, and the opposite sides of the first screen plate (31) and the second screen plate (32) are respectively formed with grinding protrusions (33) in matching arrangement.

9. The preparation method of the polypropylene resin additive for electrical engineering films as claimed in claim 4, wherein the organic solvent is one or more selected from alkanes, aromatic hydrocarbons, ketone compounds and alcohol compounds, wherein the number of carbon atoms of the alkanes is 5-20;

preferably, the alkane is selected from at least one of n-pentane, isopentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane and n-decane, the aromatic hydrocarbon is selected from at least one of toluene, ethylbenzene, xylene and trimethylbenzene, the ketone compound is selected from aliphatic and/or aromatic ketone compounds with 3-10 carbon atoms, and the alcohol compound is selected from aliphatic and/or aromatic ketone compounds with 3-10 carbon atoms;

more preferably, the ketone compound is at least one of acetone, butanone and propiophenone, and the alcohol compound is at least one of ethanol, 1-butanol, 1-pentanol and 1-hexanol.

10. The method for preparing the polypropylene resin additive for electrical films according to claim 4, wherein the temperature of the mixing process is 0-200 ℃, and the stirring rate is 0-1000 r/min;

the organic solvent is removed by at least one of normal pressure drying, vacuum drying, spray drying and fluidized drying.

Technical Field

The embodiment of the invention relates to the field of production and preparation of polypropylene resin additives, and particularly relates to a polypropylene resin additive for an electrical film and a preparation method thereof.

Background

Polypropylene electrical films are used in a large number of capacitor applications, such as power capacitors, telecommunications capacitors, composite film capacitors, and the like, due to their outstanding electrical, mechanical, chemical resistance, good gloss, low shrinkage, and relatively low cost.

At present, due to the increasing performance requirements, the production and application of electrical films impose very strict requirements on the ash content of polypropylene resins, which usually require that the ash content of the resins is less than 50ppm, preferably less than 30 ppm. In addition, the electrical film has higher requirements on the distribution uniformity of ash in the polypropylene resin, and the more uniform the distribution of ash, the stronger the electrical film has the capability of resisting high-voltage electric breakdown.

Patent CN101421318B relates to a polymerization process for the manufacture of propylene polymers with low ash content using ziegler-natta catalysts with diethers as internal electron donor. CN101896511A relates to a process for making polypropylene with reduced ash of homo-and copolymers of polypropylene, and the propylene polymers involved can be used to make films, such as capacitor films, and fibers and non-wovens, such as staple fibers, spunbond non-wovens or meltblown non-wovens. CN104558814B discloses a synthetic method of special resin for low-ash polypropylene wire drawing materials. Under the action of a main catalyst and a cocatalyst and with or without addition of an external electron donor, propylene is subjected to polymerization reaction in a two-section loop reactor to generate a polypropylene resin base material, the polypropylene resin base material and an antioxidant are used to obtain a low-ash polypropylene resin product, the main catalyst is mainly prepared from HA-DQ and oleyl ester, and the low-ash polypropylene drawing special resin HAs the advantages that the ash content of the synthesized polypropylene drawing special resin is less than 0.01%, and the mechanical property and the processing stability of the special material are improved. Northern european chemical company, patent CN104136469A, discloses a process for preparing polypropylene having a low ash content in a polymerization reactor comprising at least three polymerization reactors connected in series. However, the specific type of the additive is not specified, and more internal electron donor and external electron donor are often added, so that ash content is reduced to a certain extent, but the polypropylene resin is prone to cause a problem of uneven impurity distribution in the production process of an electrical film, thereby reducing the high-voltage breakdown resistance of the electrical film and influencing the use of the electrical film.

Disclosure of Invention

Therefore, the embodiment of the invention provides a polypropylene resin additive for an electrical film and a preparation method thereof, wherein the specific free radical scavenger, peroxide decomposer and acid absorbent are fully mixed in an organic solvent and then the organic solvent is removed, so that the obtained additive can effectively reduce ash content, improve the uniformity of ash content distribution and further improve the performance and application field of the obtained electrical film when being applied to the polypropylene resin for the electrical film.

In order to achieve the above object, an embodiment of the present invention provides the following:

in one aspect of an embodiment of the present invention, there is provided a polypropylene resin additive for electrical film, including a radical scavenger, a peroxide decomposer, and an acid absorbent; and the number of the first and second electrodes,

the free radical scavenger is selected from hindered phenol compounds;

the peroxide decomposer is selected from phosphite ester-containing compounds and/or organic sulfur-containing compounds;

the acid absorbent is selected from a compound containing stearate and/or a hydrotalcite compound containing an intercalation structure.

In a preferred embodiment of the present invention, the radical scavenger is at least one selected from the group consisting of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate.

In a preferred embodiment of the present invention, the radical scavenger is selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene;

the peroxide decomposer is at least one selected from phenyl trisnonylphenyl phosphite, dioctadecyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dilauryl thiodipropionate and dioctadecyl thiodipropionate.

As a preferred embodiment of the present invention, the peroxide decomposer is selected from tris (2, 4-di-t-butylphenyl) phosphite and/or bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite;

the acid absorbent is at least one selected from calcium stearate, zinc stearate, sodium stearate, magnesium stearate and magnesium aluminum hydrotalcite.

As a preferable embodiment of the invention, the magnalium hydrotalcite is at least one selected from DHT-4A, Hycite713, HT-P and C L C-120.

In a preferred embodiment of the present invention, the acid absorbent is at least one selected from the group consisting of calcium stearate, magnesium aluminum hydrotalcite having a trade name of DHT-4A, and magnesium aluminum hydrotalcite having a trade name of Hycite 713.

In a preferred embodiment of the present invention, the content ratio by mass of the radical scavenger, the peroxide decomposer and the acid absorbent is 1:0.01 to 50:0.0001 to 1.

In a preferred embodiment of the present invention, the mass ratio of the content of the radical scavenger to the content of the peroxide decomposer is 1:0.05 to 10:0.001 to 0.1.

In a preferred embodiment of the present invention, the mass ratio of the content of the radical scavenger to the content of the peroxide decomposer is 1:0.5 to 5:0.01 to 0.05.

In another aspect of an embodiment of the present invention, there is also provided a method for preparing the polypropylene resin additive for electrical film according to the above, including: adding the free radical trapping agent, the peroxide decomposer and the acid absorbent into an organic solvent, mixing, and removing the organic solvent to obtain the polypropylene resin additive for the electrical film.

As a preferred scheme of the invention, an atomization jet stirring device is adopted for mixing in the mixing process, the atomization jet stirring device comprises a blowing jet structure and a liquid storage mixing structure which are sequentially arranged from top to bottom, and the blowing jet structure is connected with the liquid storage mixing structure through a sieve plate component; and the number of the first and second electrodes,

the blowing jet structure at least comprises a cavity, a drainage tube, an atomizing jet part and a powder adding assembly, wherein the drainage tube is communicated with the liquid storage mixing structure and the cavity through a pump body;

stock solution mixed structure includes the stock solution chamber that is used for saving organic solvent at least to and at least part set up in the heating stirring subassembly in the stock solution chamber.

As a preferable scheme of the present invention, the drainage tube includes a main tube and a plurality of sub-tubes, which are sequentially communicated with each other from the liquid storage mixing structure to the cavity, each sub-tube is connected to an atomizing injection member, and an injection direction of a nozzle of the atomizing injection member extends along a radial direction of the cavity.

As a preferable scheme of the invention, the powder adding assembly comprises a feeding pipe, the axis direction of which extends along the vertical direction, the bottom end of the feeding pipe is positioned above the nozzle, the blower is arranged on the outer side of the feeding pipe, and the blowing direction of the blower is inclined downwards and faces the extension direction of the axis of the feeding pipe.

As a preferable scheme of the present invention, the screen plate assembly at least includes a first screen plate and a second screen plate sequentially arranged from top to bottom, a screen aperture of the first screen plate is larger than a screen aperture of the second screen plate, the first screen plate and the second screen plate relatively move along a horizontal direction, and grinding protrusions are respectively formed on opposite side surfaces of the first screen plate and the second screen plate in a matching arrangement.

As a preferable scheme of the invention, the organic solvent is one or more selected from alkane, aromatic hydrocarbon, ketone compounds and alcohol compounds, wherein the carbon atom number of the alkane is 5-20.

In a preferred embodiment of the present invention, the alkane is at least one selected from n-pentane, isopentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane and n-decane, the aromatic hydrocarbon is at least one selected from toluene, ethylbenzene, xylene and trimethylbenzene, the ketone compound is an aliphatic and/or aromatic ketone compound having 3 to 10 carbon atoms, and the alcohol compound is an aliphatic and/or aromatic ketone compound having 3 to 10 carbon atoms.

In a preferred embodiment of the present invention, the ketone compound is at least one of acetone, butanone and propiophenone, and the alcohol compound is at least one of ethanol, 1-butanol, 1-pentanol and 1-hexanol.

As a preferred scheme of the invention, the temperature in the mixing process is 0-200 ℃, and the stirring speed is 0-1000 r/min;

the organic solvent is removed by at least one of normal pressure drying, vacuum drying, spray drying and fluidized drying.

The embodiment of the invention has the following advantages:

the ash content of the polypropylene resin can be effectively reduced and the distribution uniformity of the ash content is improved when the polypropylene resin is applied to the polypropylene resin by mixing the specific free radical scavenger, the peroxide decomposer and the acid absorbent; meanwhile, the raw materials are mixed and dissolved by taking an organic solvent as a medium and then the organic solvent is removed, so that the dispersion degree of the obtained additive is further improved, the improvement on the dispersion uniformity of ash content in the polypropylene resin for the electrical film is further improved,

drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.

The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.

FIG. 1 is a schematic structural diagram of an atomizing jet stirring device provided in an embodiment of the present invention;

FIG. 2 is a schematic view of a portion of an atomizing spray member provided in accordance with an embodiment of the present invention;

fig. 3 is a schematic view of a partial structure of a screen deck assembly provided in an embodiment of the present invention;

FIG. 4 is a graph comparing the results of the tests of example 1, example 2, example 4, example 8 and comparative example 1 of the present invention.

In the figure:

1-a blowing jet structure; 2-liquid storage mixed structure; 3-a screen deck assembly;

11-a cavity; 12-a pump body; 13-a drainage tube; 14-atomizing spray member; 15-powder feeding component;

131-main tube; 132-secondary tube;

141-a nozzle;

151-a fan; 152-a feed tube;

21-a liquid storage cavity; 22-heating the stirring assembly;

31-a first screen deck; 32-a second screen deck; 33-grinding the bumps.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a polypropylene resin additive for an electrical film, which comprises a free radical trapping agent, a peroxide decomposer and an acid absorbent; and the number of the first and second electrodes,

the free radical scavenger is selected from hindered phenol compounds;

the peroxide decomposer is selected from phosphite ester-containing compounds and/or organic sulfur-containing compounds;

the acid absorbent is selected from a compound containing stearate and/or a hydrotalcite compound containing an intercalation structure.

Specifically, in a preferred embodiment of the present invention, the radical scavenger is selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, the peroxide decomposer is selected from tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, and the acid absorbent is selected from at least one of calcium stearate, magnesium aluminum hydrotalcite of brand DHT-4A, and magnesium aluminum hydrotalcite of brand Hycite 713.

In a further preferred embodiment, the content ratio by mass of the radical scavenger, the peroxide decomposer and the acid absorbent is 1:0.01 to 50:0.0001 to 1. Certainly, in order to achieve better effects of reducing ash content and improving the dispersion uniformity of ash content, the mass ratio of the content of the radical scavenger to the content of the peroxide decomposer is 1: 0.5-5: 0.01-0.05.

The invention also provides a preparation method of the polypropylene resin additive for the electrical film, which comprises the following steps: adding the free radical trapping agent, the peroxide decomposer and the acid absorbent into an organic solvent, mixing, and removing the organic solvent to obtain the polypropylene resin additive for the electrical film. Of course, it should be further noted that, the feeding sequence of the free radical scavenger, the peroxide decomposer and the acid absorbent can be selected according to the actual situation, and the feeding environment is to stir and mix the materials under a certain temperature and stirring speed, and the organic solvent is removed after the powder is fully dissolved in the organic solvent and stabilized for a period of time. Further, the temperature in the mixing process is 15-150 ℃; more preferably, the temperature of the mixing process is 30-80 ℃. The stirring speed is 10-500 r/min; more preferably, the stirring speed is 25-100 r/min.

In a preferred embodiment, as shown in fig. 1-3, an atomizing jet stirring device is used for mixing, specifically, in the mixing process, an organic solvent is placed in the liquid storage mixing structure 2, pumped into the drainage tube 13 through the pump body 12 and sprayed into the cavity 11 through the nozzle 141 of the atomizing spray member 14 along the horizontal direction in fig. 1, then the feeding is performed through the feeding tube 152, the blower 151 is started to blow air, so that the powder is uniformly dispersed in the cavity 11, meanwhile, the sprayed organic solvent is uniformly deposited on the sieve plate assembly 3, the small-particle deposit directly falls into the liquid storage mixing structure 2 to be mixed, the larger particles can further realize the grinding of the small-particle deposit by the grinding protrusions 33 through the relative movement between the first sieve plate 31 and the second sieve plate 32, and further falls into the liquid storage mixing structure 2 to be further stirred after being ground to small particles, therefore, the obtained additive has better uniform dispersion, and the distribution uniformity of the ash content of the prepared polypropylene resin for the electrical film is further improved on the premise of reducing the ash content of the polypropylene resin, so that the electrical service performance of the polypropylene resin is improved.

In the following, the details are given by way of example, 1010 corresponds to the radical scavenger pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 330 corresponds to the radical scavenger 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 168 corresponds to the peroxide decomposer tris (2, 4-di-tert-butylphenyl) phosphite, and 626 corresponds to the peroxide decomposer bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.