CN112812313B - Antistatic agent and preparation method and application thereof - Google Patents
Antistatic agent and preparation method and application thereof Download PDFInfo
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- CN112812313B CN112812313B CN202110179724.7A CN202110179724A CN112812313B CN 112812313 B CN112812313 B CN 112812313B CN 202110179724 A CN202110179724 A CN 202110179724A CN 112812313 B CN112812313 B CN 112812313B
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- antistatic agent
- anhydride
- polyether
- polypropylene
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- 239000002216 antistatic agent Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 97
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 96
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 75
- 239000004743 Polypropylene Substances 0.000 claims abstract description 59
- 229920001155 polypropylene Polymers 0.000 claims abstract description 56
- -1 polypropylene Polymers 0.000 claims abstract description 52
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 42
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 229920000098 polyolefin Polymers 0.000 claims abstract description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 15
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 15
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 claims description 4
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000001125 extrusion Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 230000006872 improvement Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000002464 physical blending Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 description 28
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 102220293804 rs771610641 Human genes 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JHEPBQHNVNUAFL-AATRIKPKSA-N (e)-hex-1-en-1-ol Chemical compound CCCC\C=C\O JHEPBQHNVNUAFL-AATRIKPKSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- 102220470698 BUD13 homolog_V30P_mutation Human genes 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical compound CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 102220005338 rs111033604 Human genes 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
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 duration of 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.
Description
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 various 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 first aspect of the invention provides an antistatic agent, which 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) The polyether with proper chain length and the polypropylene 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". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, 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 non-specified element, step, or component. 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 claim body and not 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 specified, 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 molar ratio of the vinyl polyether to the anhydride is (1-2.5): 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 homo-polypropylene is used, it has higher antistatic properties and antistatic stability against water, heat, etc. than co-polypropylene, and can be used for a long time, probably because the regular molecular chain and helical structure of homo-polypropylene in the preparation process are more conducive to the reaction with grafted polyether than co-polypropylene, and the antistatic agent containing homo-polypropylene reduces the hindrance of polyolefin processing during processing, thereby promoting the improvement of antistatic properties of the finished product obtained by 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 by 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 is not particularly limited, for example, the temperatures of different sections of the screw extruder are respectively 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. Examples of the polyolefin include polypropylene and polyethylene.
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 of 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.
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 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.
The homopolypropylene is available from compliant petrochemical F30S.
This example provides a method of 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 4
The embodiment provides an antistatic agent, and the preparation raw materials of the antistatic agent comprise vinyl polyether and polypropylene in a weight ratio of 2: 2; 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.
The homopolypropylene is available from compliant petrochemical F30S.
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 5
The embodiment provides an antistatic agent, which is prepared from the following raw materials in a weight ratio of 2: 2; the anhydride grafted polyether is prepared from vinyl polyether and anhydride, and the molar ratio is 1: 1, the anhydride is phthalic 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.
The homopolypropylene is available from compliant petrochemical F30S.
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 6
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 is purchased from APEG-700.
The homopolypropylene is available from compliant petrochemical F30S.
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 7
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 is purchased from APEG-4000.
The homopolypropylene is available from compliant petrochemical F30S.
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 8
The embodiment provides an antistatic agent, and the preparation raw material of the antistatic agent comprises anhydride grafted polyether, the weight ratio of which is 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 copolymerized 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.
The co-polypropylene is available from EP2X32GA, which is fossilized.
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.
Evaluation of Performance
The antistatic agent provided in the examples was added to polyolefin and blended and injection molded into a sheet, and the following experiment was performed as a sample, with the weight ratio of antistatic agent to polyolefin being 1: 1, the polyolefins of examples 1, 3 to 8 were fossilized F30G/S, and the polyolefin of example 2 was fossilized Z30S.
1. Surface resistivity: the surface resistivity of the samples provided in the examples is tested according to the GB/1410 direct method, and the surface resistivity of the samples in the examples 1-3 is found to be 109Omega cm or less.
2. Water-resistant antistatic stability: the samples provided in the examples were left to stand in water at 60 ± 2 ℃ for 3 weeks, then dried, and the surface resistivity before and after the standing was measured, and the decrease rate of the surface resistivity (surface resistivity after the standing-surface resistivity before the standing)/surface resistivity before the standing was calculated as 100%, and evaluation was performed, in which the decrease rate was less than 6% in the 1-stage, less than 12% in the 2-stage, 6% or more in the 3-stage, less than 20% in the 3-stage, 12% or more in the 3-stage, and 20% or more in the 4-stage, and the results are shown in table 2.
3. Heat-resistant antistatic stability: after the sample provided in example was left to stand at 90 ± 2 ℃ for 3 weeks in an environment with a relative humidity of 95%, the surface resistivity before and after the standing was measured, and the surface resistivity decrease rate (surface resistivity after the standing-surface resistivity before the standing)/surface resistivity before the standing was calculated as 100%, and evaluation was performed, in which the decrease rate was less than 10% in the 1-stage, less than 15% in the 2-stage, 10% or more in the 3-stage, less than 25% in the 3-stage, 15% or more in the 3-stage, and 25% or more in the 4-stage, and the results are shown in table 2.
Table 2 characterization test of properties
| Examples | Water-resistant antistatic stability | Heat-resistant antistatic stability |
| 1 | Level 1 | Level 1 |
| 2 | Level 1 | Level 1 |
| 3 | Level 1 | Level 1 |
| 4 | Grade 4 | Grade 4 |
| 5 | Grade 3 | Grade 3 |
| 6 | Stage 2 | Stage 2 |
| 7 | Stage 2 | Grade 3 |
| 8 | Grade 3 | Grade 3 |
According to the test results, the antistatic agent provided by the invention has good compatibility and dispersibility with the polyolefin base material, the antistatic agent is prevented from falling off in the application process, and the obtained finished product has a high antistatic effect.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where the claims recite a range of values, such ranges are intended to include all sub-ranges subsumed therein, and variations within the ranges are intended to be encompassed by the claims as appended hereto where possible.
Claims (7)
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);
the anhydride grafted polyether is prepared from vinyl polyether and anhydride;
the number average molecular weight of the vinyl polyether is 1000-4000;
the acid anhydride is mono-anhydride and/or dianhydride.
2. The antistatic agent according to claim 1, wherein the molar ratio of the vinyl polyether to the acid anhydride is (1-2.5): 1.
3. the antistatic agent of claim 1 wherein the mono anhydride is selected from one or more of acetic anhydride, phthalic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.
4. Antistatic agent according to claim 1, characterized in that the dianhydride is selected from one or more of pyromellitic anhydride, 1,2,3, 4-butanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride.
5. The antistatic agent according to any one of claims 1 to 4, wherein the polypropylene is homo-polypropylene or co-polypropylene.
6. A method for preparing an antistatic agent according to any one of claims 1 to 5, characterized by comprising: blending and extruding preparation raw materials of the antistatic agent to obtain the antistatic agent.
7. Use of an antistatic agent according to any one of claims 1 to 5 for polyolefin processing.
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| JP2008266509A (en) * | 2007-04-24 | 2008-11-06 | Mitsubishi Rayon Co Ltd | Curable resin composition, repairing method and reinforcing method using the same |
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