Antistatic agent and preparation method and application thereof

文档序号：562092 发布日期：2021-05-18 浏览：4次中文

阅读说明：本技术 一种抗静电剂及其制备方法和应用 (Antistatic agent and preparation method and application thereof ) 是由沈佳兴宋唯立吕浩东于 2021-02-07 设计创作，主要内容包括：本发明涉及抗静电剂技术领域,更具体地,本发明涉及一种抗静电剂及其制备方法和应用。所述抗静电剂的制备原料包括酸酐接枝聚醚和聚丙烯。通过化学反应的方式将酸酐接枝聚醚接枝到聚丙烯上,与传统的物理共混的方式相比,聚醚不容易析出,增加抗静电作用的时长,接枝后的抗静电剂在聚丙烯中的分布更佳均匀,抗静电效果更好。选择合适链长的聚醚和聚丙烯接枝,促进抗静电剂在聚烯烃加工过程分散的同时,保持一定的分散相结构,进一步促进抗静电性的提高。使用二酸酐和乙烯基聚醚接枝,增加酸酐接枝聚醚上双键含量,促进共混挤出过程中,在较低温度和时间和聚丙烯接枝的可能性,提高抗静电剂的稳定性和加工效率,促进大规模生产和应用。(The invention relates to the technical field of antistatic agents, in particular to an antistatic agent and a preparation method and application thereof. The preparation raw materials of the antistatic agent comprise anhydride grafted polyether and polypropylene. The anhydride grafted polyether is grafted to the polypropylene in a chemical reaction mode, compared with the traditional physical blending mode, the polyether is not easy to separate out, the antistatic effect is prolonged, the distribution of the grafted antistatic agent in the polypropylene is better and uniform, and the antistatic effect is better. Polyether and polypropylene with proper chain length are selected for grafting, so that the dispersion of the antistatic agent in the polyolefin processing process is promoted, a certain dispersed phase structure is kept, and the improvement of the antistatic property is further promoted. The dianhydride and vinyl polyether are used for grafting, so that the double bond content of the anhydride grafted polyether is increased, the possibility of polypropylene grafting at lower temperature and time in the blending extrusion process is promoted, the stability and the processing efficiency of the antistatic agent are improved, and the large-scale production and application are promoted.)

1. The antistatic agent is characterized in that the preparation raw materials of the antistatic agent comprise anhydride grafted polyether and polypropylene, and the weight ratio of the anhydride grafted polyether to the polypropylene is (1-2): (2-3).

2. The antistatic agent of claim 1 wherein the anhydride grafted polyether is prepared from a vinyl polyether and an anhydride.

3. The antistatic agent according to claim 2, wherein the vinyl polyether and the acid anhydride are present in a molar ratio of (1 to 2.5): 1.

4. the antistatic agent according to claim 2, wherein the vinyl polyether has a number average molecular weight of 1000 to 4000.

5. Antistatic agent according to claim 2, characterized in that the anhydride is a mono-and/or a di-anhydride.

6. The antistatic agent of claim 5 wherein the mono anhydride is selected from one or more of acetic anhydride, phthalic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.

7. Antistatic agent according to claim 5, characterized in that the dianhydride is selected from one or more of pyromellitic anhydride, hydrogenated pyromellitic anhydride, 1,2,3, 4-butanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride.

8. The antistatic agent according to any one of claims 1 to 7, wherein the polypropylene is homo-polypropylene or co-polypropylene.

9. A method for preparing an antistatic agent according to any one of claims 1 to 8, comprising: blending and extruding preparation raw materials of the antistatic agent to obtain the antistatic agent.

10. Use of an antistatic agent according to any one of claims 1 to 9 for polyolefin processing.

Technical Field

The invention relates to the technical field of antistatic agents, in particular to an antistatic agent and a preparation method and application thereof.

Background

Polypropylene, PP for short, is a thermoplastic resin with no toxicity, no color, no odor and excellent performance, and is colorless translucent thermoplastic general-purpose plastic. Since the advent, the development of the technology has been rapidly advanced in many fields. However, the resistivity of PP is too high due to the excellent insulating property, charges are easy to accumulate in the production process or the use process, and the injection molding sample is difficult to remove, so that dust is easy to adhere to the injection molding sample, and great inconvenience is brought to production, processing and life. In order to solve the static problem of PP, PEG, carbon black, graphite, metal filler and the like are mostly added to achieve the corresponding antistatic purpose, the method has certain effect, but the problems of uneven filler distribution, poor compatibility, easy precipitation, short antistatic effect and the like still exist, and the use of the material is influenced.

Compared with the traditional antistatic agent, the antistatic effect is durable, no induction period exists, the antistatic performance of the antistatic agent is not achieved by a water layer, so that the dependence on the relative humidity of air is small, the conventional polymeric antistatic agent is generally grafted with carboxylic acid on polypropylene and then reacted with PEG to obtain a grafted product serving as the antistatic agent, but the problems of high preparation temperature, complex preparation process and the like exist, and the long-term antistatic performance of the processed plastic is influenced due to poor thermal stability of the PEG.

Disclosure of Invention

In order to solve the problems, the invention provides an antistatic agent in a first aspect, and the antistatic agent is prepared from the following raw materials in parts by weight (1-2): (2-3).

As a preferred technical scheme, the anhydride grafted polyether is prepared from vinyl polyether and anhydride.

As a preferable technical scheme of the invention, the molar ratio of the vinyl polyether to the acid anhydride is (1-2.5): 1.

as a preferable technical scheme of the invention, the number average molecular weight of the vinyl polyether is 1000-4000.

In a preferred embodiment of the present invention, the acid anhydride is a mono-anhydride and/or a di-anhydride.

In a preferred embodiment of the present invention, the mono-anhydride is selected from one or more of acetic anhydride, phthalic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

In a preferred embodiment of the present invention, the dianhydride is selected from one or more of pyromellitic anhydride, hydrogenated pyromellitic anhydride, 1,2,3, 4-butanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, and cyclopentanetetracarboxylic dianhydride.

As a preferable technical scheme of the invention, the polypropylene is homo-polypropylene or co-polypropylene.

The second aspect of the present invention provides a method for preparing the antistatic agent, comprising: blending and extruding preparation raw materials of the antistatic agent to obtain the antistatic agent.

The third aspect of the invention provides the application of the antistatic agent in polyolefin processing.

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

(1) the anhydride grafted polyether is grafted to the polypropylene in a chemical reaction mode, compared with the traditional physical blending mode, the polyether is not easy to separate out, the antistatic effect is prolonged, the distribution of the grafted antistatic agent in the polypropylene is better and uniform, and the antistatic effect is better.

(2) Polyether and polypropylene with proper chain length are selected for grafting, so that the dispersion of the antistatic agent in the polyolefin processing process is promoted, a certain dispersed phase structure is kept, and the improvement of the antistatic property is further promoted.

(3) The dianhydride and vinyl polyether are used for grafting, so that the double bond content of the anhydride grafted polyether is increased, the possibility of polypropylene grafting at lower temperature and time in the blending extrusion process is promoted, the stability and the processing efficiency of the antistatic agent are improved, and the large-scale production and application are promoted.

(4) Compared with the copolymerized polypropylene containing a small amount of ethylene copolymerization, the homopolymerized polypropylene is more beneficial to improving the grafting efficiency, reduces the falling of the antistatic agent and a finished product prepared by polyolefin processing under the action of water and the like, causes the reduction of the antistatic property and prolongs the service life of the antistatic agent.

(5) By using the antistatic agent provided by the invention, the decomposition at higher temperature can be reduced, the stability in the application process is improved, and the service life is prolonged.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.

The invention provides an antistatic agent, which is prepared from the following raw materials in parts by weight (1-2): (2 to 3), there may be mentioned, 1: 2. 1: 3. 2: 2. 2: 3.

anhydride grafted polyethers

In one embodiment, the anhydride grafted polyether of the present invention is prepared from a vinyl polyether and an anhydride.

The vinyl polyether is a polymer grafted at one end of the polyether and containing a vinyl group, and the other end of the polyether is a hydroxyl group, wherein the vinyl group can be isopentenol, methallyl alcohol, allyl alcohol, butenol, hexenol and the like, is not particularly limited, and is preferably vinyl polyoxyethylene ether.

As examples of the vinyl polyoxyethylene ether, mention may be made of prenol polyoxyethylene ethers such as TPEG-2400 (number average molecular weight of 2400) by Shaanxi Chang Long chemical Co., Ltd, methallyl alcohol polyoxyethylene ethers such as HPEG-2400 (number average molecular weight of 2400) by Hainan petrochemical of Jiangsu province, SPEG-2400 (number average molecular weight of 2400) by optimization chemical (Nongo) Co., Ltd, allyl alcohol polyoxyethylene ethers such as APEG-700 (number average molecular weight of 700) by Chengtai Fine chemical Co., Ltd, APEG-1000 (number average molecular weight of 1000), APEG-2000 (number average molecular weight of 2000), APEG-2500 (number average molecular weight of 2500), APEG-3000 (number average molecular weight of 3000), and APEG-4000 (number average molecular weight of 4000). The statistical average by number of molecules is referred to as the number average molecular weight.

The vinyl polyether of the present invention preferably has a number average molecular weight of 1000 to 4000, for example, 1000, 1500, 2000, 2500, 3000, 3500, 4000, preferably 1500 to 3500, more preferably 2000 to 3000.

The applicant finds that the antistatic agent obtained by using the anhydride grafted polyether with a certain chain length and polypropylene to perform grafting reaction can be used in the processing of a polyolefin matrix, can be uniformly dispersed in a finished product, and improves the compatibility, wherein part of the antistatic agent migrates to the surface of the finished product, and forms a conductive network by using the action of oxygen atoms in the polyether chain, acid radicals remained in the anhydride and the like to transfer static charges in and on the surface of the finished product, so that the resistivity is reduced. The applicant has found that when the polyether chain is relatively long, the interfacial action between the antistatic agent dispersed phase and the polyolefin continuous phase is weak, which is not favorable for the dispersion of the antistatic agent, and when the polyether chain is relatively short and the compatibility is too high, the dispersed phase is relatively small, which is not favorable for the improvement of the electrostatic performance.

In addition, the applicant finds that polyether is difficult to graft on polypropylene, when vinyl polyether and polypropylene are used for grafting independently, more polyether and polypropylene are physically blended without participating in reaction, the improvement of dispersibility and the like is not facilitated, the antistatic property is low, and the polyethylene is easy to fall off, break and the like under the action of water, heat and the like or in the long-term use process, the long-term antistatic property is reduced, the service life is not facilitated to be prolonged.

More preferably, the anhydride of the present invention is a mono-anhydride and/or a di-anhydride. Further preferably, the monoanhydride of the present invention is selected from one or more of acetic anhydride, phthalic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Still more preferably, the dianhydride according to the invention is selected from one or more of pyromellitic anhydride, hydrogenated pyromellitic anhydride, 1,2,3, 4-butanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride. Preferred are dianhydrides, more preferred are pyromellitic anhydride, hydrogenated pyromellitic anhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride.

And the applicant finds that when dianhydride, especially cyclic dianhydride is used, in the polyolefin processing process, on one hand, flexible polyether grafted polypropylene and a polyolefin chain in the antistatic agent are entangled to form an elastic interface layer to promote the adhesion of a dispersed phase and a continuous phase and reduce the falling off, and on the other hand, the existence of a cyclic structure in the dispersed phase is also beneficial to the stability of the dispersed phase, promotes the long-term antistatic performance and has good antistatic stability in water and heat environments.

The anhydride grafted polyether of the present invention can be prepared by esterification of vinyl polyether and anhydride, and in one embodiment, the anhydride grafted polyether is prepared by a method comprising: heating vinyl polyether to 120-160 ℃, adding anhydride for reaction, cooling and powdering to obtain the anhydride grafted polyether. The end point of the reaction can be determined on the basis of the acid value, and the reaction is terminated when the acid value is unchanged (about 4 to 7 hours).

In a preferred embodiment, the vinyl polyether and the acid anhydride have a molar ratio of (1 to 2.5): 1, there may be mentioned, 1: 1. 1.1: 1. 1.2: 1. 1.3: 1. 1.4: 1. 1.5: 1. 1.6: 1. 1.7: 1. 1.8: 1. 1.9: 1. 2: 1. 2.1: 1. 2.2: 1. 2.3: 1. 2.4: 1. 2.5: 1, preferably 1.5 to 1.5, and more preferably 1.7 to 2.3.

Polypropylene

The applicant has surprisingly found that when homopolypropylene is used, it has higher antistatic properties and antistatic stability against water, heat, etc. than those of the copolymeric polypropylene, and can be used for a long time, probably because the regular molecular chain and helical structure of the homopolypropylene in the preparation process are more favorable for the reaction with the grafted polyether than those of the copolymeric polypropylene, and in the processing process, the antistatic agent containing the homopolypropylene reduces the hindrance in the polyolefin processing, thereby promoting the improvement of the antistatic properties of the finished product obtained by the processing. In one embodiment, the polypropylene of the present invention is a homo-or co-polypropylene, preferably a homo-polypropylene.

The homopolymerized polypropylene is polymerized by single propylene monomer, and the molecular chain does not contain ethylene monomer. Homo-polypropylene, obtained by copolymerization of propylene with a small amount of ethylene. The invention does not specifically limit the homo-polypropylene, and can be determined according to the properties of the polyolefin used in the subsequent processing.

In one embodiment, the raw materials for preparing the antistatic agent of the present invention further comprise an initiator.

Initiator

The initiator of the present invention is not particularly limited, and examples of the peroxide include dicumyl peroxide (DCP), di-t-butylperoxydicumyl peroxide (BIPB), di-t-butyl peroxide (dTBP), di-t-butyl peroxide, octanoyl peroxide, lauroyl peroxide, t-butyl peroxyacetate and t-butyl peroxylaurate. In one embodiment, the initiator of the present invention is 0.01 to 0.1% of the total weight of the anhydride grafted polyether and the polypropylene, and may be, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%.

The second aspect of the present invention provides a method for preparing the antistatic agent as described above, comprising: blending and extruding preparation raw materials of the antistatic agent to obtain the antistatic agent. In one embodiment, the blending extrusion speed is 30-50 r/min, and the temperature is 120-220 ℃. The blending extrusion is carried out through a screw extruder which is divided into a plurality of sections, the temperature of screws in different sections is changed between 120 ℃ and 220 ℃, and the temperature is not particularly limited, for example, the temperature of different sections of the screw extruder is 120 ℃, 160 ℃, 200 ℃, 220 ℃, 200 ℃, 175 ℃ and 165 ℃.

In a third aspect the present invention provides the use of an antistatic agent as described above for polyolefin processing. The polyolefin may be exemplified by polypropylene, polyethylene, etc.

Examples

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

Example 1

The embodiment provides an antistatic agent, which is prepared from the following raw materials in parts by weight of 1: 2; the anhydride grafted polyether is prepared from vinyl polyether and anhydride, and the molar ratio is 1.7: 1, the anhydride is hydrogenated pyromellitic anhydride; the preparation method of the anhydride grafted polyether comprises the following steps: heating vinyl polyether to 130 ℃, adding anhydride for reaction, cooling and powdering to obtain the anhydride grafted polyether; the polypropylene is homopolymerized polypropylene; the antistatic agent is characterized by also comprising an initiator, wherein the initiator is dicumyl peroxide, and the initiator accounts for 0.07 thousandth of the total weight of the anhydride grafted polyether and the polypropylene.

The vinyl polyether is available from APEG-2000.

The homopolypropylene is available from the compliant petrochemical V30G/S.

This example provides a method for preparing an antistatic agent as described above, comprising: adding the preparation raw materials of the antistatic agent into a screw extruder, and performing blending extrusion and grain cutting at the temperature of 120-220 ℃ at 40r/min to obtain the antistatic agent.

Example 2

The embodiment provides an antistatic agent, which is prepared from the following raw materials in parts by weight of 2: 3; the anhydride grafted polyether is prepared from vinyl polyether and anhydride, and the molar ratio is 2.3: 1, the anhydride is pyromellitic anhydride; the preparation method of the anhydride grafted polyether comprises the following steps: heating vinyl polyether to 150 ℃, adding anhydride for reaction, cooling and powdering to obtain the anhydride grafted polyether; the polypropylene is homopolymerized polypropylene; the antistatic agent is prepared from raw materials which also comprise an initiator, wherein the initiator is di-tert-butylperoxydiisopropylbenzene, and the initiator accounts for 0.07 thousandth of the total weight of the anhydride grafted polyether and the polypropylene.

The vinyl polyether is available from HPEG-2400.

The homopolypropylene is available from the compliant petrochemical C30G/S.

Example 3

The embodiment provides an antistatic agent, which is prepared from the following raw materials in parts by weight of 2: 2; the anhydride grafted polyether is prepared from vinyl polyether and anhydride, and the molar ratio is 2: 1, the anhydride is pyromellitic anhydride; the preparation method of the anhydride grafted polyether comprises the following steps: heating vinyl polyether to 140 ℃, adding anhydride for reaction, cooling and powdering to obtain the anhydride grafted polyether; the polypropylene is homopolymerized polypropylene; the antistatic agent is characterized by also comprising an initiator, wherein the initiator is di-tert-butyl peroxide, and the initiator accounts for 0.07 thousandth of the total weight of the anhydride grafted polyether and the polypropylene.

The vinyl polyether was purchased from APEG-2500.