CN110950900B - Boric acid ester antistatic agent and preparation method and application thereof - Google Patents
Boric acid ester antistatic agent and preparation method and application thereof Download PDFInfo
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- 239000002216 antistatic agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 Boric acid ester Chemical class 0.000 title claims description 23
- 239000004327 boric acid Substances 0.000 title claims description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001308 synthesis method Methods 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 3
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 150000003973 alkyl amines Chemical class 0.000 abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 5
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000289 Polyquaternium Polymers 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 210000000078 claw Anatomy 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a borate antistatic agent, and a preparation method and application thereof, belongs to the technical field of fine chemicals, and can solve the problems that the existing antistatic agent is poor in antistatic effect, complicated and harsh in preparation method conditions and the like. The borate antistatic agent has the following structural general formula (A):
wherein R is1Is ethyl or hydroxymethyl; r2Primary alkyl amines which are linear or branched, saturated or unsaturated hydrocarbon radicals having from 10 to 18 carbons. The borate antistatic agent provided by the invention can be effectively applied to plastic products made of PE or PP.
Description
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a borate antistatic agent as well as a preparation method and an application thereof.
Background
The plastic material is defined as a material or a plastic product which is made of synthetic or natural high molecular polymer and can be arbitrarily kneaded into various shapes and finally can keep the shapes unchanged. The resistivity of the plastic is very high, static electricity is easily generated, further harm such as dust collection, fire, explosion and the like is easily caused, and the application scene of the plastic is seriously influenced.
Surface resistivity and volume resistivity are important parameters reflecting the degree of static charge accumulation of plastic articles. Generally, the larger the surface resistivity or the volume resistivity, the lower the conductivity, the more likely the plastic product is to accumulate static electricity, and the more significant the electrostatic hazard. The surface resistivity of PE and PP can reach 1016-1020Omega, and the antistatic plastic generally has a surface resistivity of 108-1010Omega, the damage caused by static electricity can be greatly reduced.
The antistatic agent is a chemical aid added to the inside of a plastic or directly applied to the surface of a product thereof, and has the effects of reducing the surface resistivity or volume resistivity of the plastic, increasing the conductivity appropriately, preventing the accumulation of static electricity, and the like. At present, most of antistatic agents on the market are polyoxyethylene alkyl ether, polyoxyethylene alkylamine, alkyl polyol, polyquaternium and the like, and the technical problems of insignificant antistatic effect, short antistatic lasting period and the like generally exist.
The process disclosed in patent CN101029151B cannot ensure that the reaction of glycerol and boric acid produces monoester, and the structural formula of the obtained product has no hydrophilic group, and the antistatic agent uses the hydrophilic group to absorb water in air to achieve the purpose of transferring charges, so the obtained product cannot achieve any antistatic effect; the boric acid monoester disclosed in patent CN103772422A is a linear structure, and although it has an antistatic effect, the process involves operations such as supercritical conditions and molecular distillation, and the process conditions and the operation methods are complicated and harsh. Therefore, the development of a durable antistatic agent with relatively simple process and remarkable antistatic effect of the obtained product is a problem to be solved urgently.
Disclosure of Invention
The invention provides a borate antistatic agent, a preparation method and application thereof, wherein the obtained antistatic agent is a multifunctional group borate synthesized by taking a boron atom as a central atom, the antistatic agent is a novel polyalcohol ethoxylation borate antistatic agent, and the surface resistivity range of the antistatic agent is 107-109Omega, compared with the commercial product, the product reduces 1-2 orders of magnitude, and has good long-term effect.
In order to achieve the above object, the present invention provides a borate antistatic agent having the following structural formula (a):
wherein R is1Is one of ethyl, hydroxymethyl or propylene glycol group; r2Primary alkyl amines which are linear or branched, saturated or unsaturated hydrocarbon radicals having from 10 to 18 carbons.
Preferably, R1When ethyl, it is of the formula:
R1when hydroxymethyl, it is represented by the following structural formula:
R1when the propylene glycol group is the propylene glycol group, the structure formula is as follows:
the invention also provides a synthesis method of the borate antistatic agent according to the technical scheme, which comprises the following steps:
proportionally adding polyalcohol and boric acid into a reaction kettle, carrying out esterification reaction for 1-10 hours at the temperature of 100-400 ℃ at the stirring speed of 600r/min to obtain an intermediate, then proportionally adding maleic anhydride into the intermediate, and carrying out esterification reaction for 1-10 hours at the temperature of 100-400 ℃ at the stirring speed of 50-500r/min to obtain modified borate molecules;
adding deionized water into the modified borate ester molecules according to 2-30% of the solid content of the modified borate ester molecules, and emulsifying at the stirring speed of 500-8000rpm and the temperature of 30-100 ℃ for 15-100min to obtain emulsion;
adding deionized water into fatty amine according to 2-30% of the solid content of the fatty amine, and mixing to obtain a mixed solution;
and reacting the obtained emulsion and the mixed solution at the stirring speed of 50-600r/min at the temperature of 50-500 ℃ for 1-4 hours, then fully standing to enable the materials to be in a water phase, and performing filter pressing and drying to obtain the borate antistatic agent.
Preferably, the molar ratio of polyol to boric acid added is (1-2):1, and the molar ratio of intermediate to maleic anhydride is (1-2): 1.
Preferably, the polyhydric alcohol is at least one selected from the group consisting of glycerol, pentaerythritol, trimethylolethane, xylitol, and sorbitol.
Preferably, the molar ratio of pure substances in the obtained emulsion and mixed solution is 1: 1.
Preferably, the fatty amine is a primary alkyl amine having a linear or branched, saturated or unsaturated hydrocarbon group of 10 to 18 carbons.
The invention provides a plastic product prepared from PE or PP and prepared by using the borate antistatic agent in the technical scheme.
Preferably, the surface resistivity thereof under the conditions of temperature (23. + -. 2 ℃ C.) and humidity (50. + -. 5)% is in the range of 107-109Ω。
The invention provides an application of the borate antistatic agent in preparation of plastic products made of PE or PP according to the technical scheme.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the antistatic agent provided by the invention is a multifunctional boric acid ester synthesized by using a boron atom as a central atom, wherein the boric acid ester molecule has hydrophilic functional groups such as carboxyl, hydroxyl and the like, and the antistatic agent is a novel polyalcohol ethoxylated boric acid ester antistatic agent. The antistatic agent has a three-dimensional structure, belongs to a surfactant with medium molecules, remote claws and multiple functional groups, and has the molecular weight of 600-800-.
2. The molecular structure of the antistatic agent provided by the invention is a three-dimensional structure, and the antistatic agent forms orientation arrangement on an interface of resin and air, wherein the lipophilic group extends to the inside of the resin, and the hydrophilic group extends to the outside of the resin and is arranged towards the air side, so that a monomolecular conducting layer is formed, and the antistatic effect is achieved. Specifically, in the molecular structure, except for water absorption of unsaturated groups such as hydroxyl groups and the like, organic boron atoms are semipolar bonds, and electron orbitals are sp2Hybridization is carried out, the empty orbit can absorb electrons to form a conductive path, so that the remarkable antistatic effect is achieved, and compared with the conventional antistatic agent, the antistatic long-acting property is better.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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 embodiment of the invention also provides a synthesis method of the borate antistatic agent according to the embodiment, which comprises the following steps:
s1: proportionally adding polyalcohol and boric acid into a reaction kettle, carrying out esterification reaction for 1-10 hours at the temperature of 100-400 ℃ at the stirring speed of 600r/min to obtain an intermediate, then proportionally adding maleic anhydride into the intermediate, and carrying out esterification reaction for 1-10 hours at the temperature of 100-400 ℃ at the stirring speed of 50-500r/min to obtain the modified borate molecule.
In the above step, in the intermediate preparation step, the stirring speed, esterification reaction temperature and reaction time may be adjusted according to the actual reaction conditions, for example, the stirring speed may be 100, 150, 200, 250, 300, 350, 400, 450, 500, 550r/min or any value within the above range, the reaction temperature may be 150, 200, 250, 300, 350 ℃ or any value within the above range, and the reaction time may be 2, 3, 4, 5, 6, 7, 8, 9 hours or any value within the above range; in the step of preparing the modified borate molecule, the stirring speed, the esterification reaction temperature, and the reaction time may be adjusted according to the actual reaction, for example, the stirring speed may be 100, 150, 200, 250, 300, 350, 400, 450r/min or any value within the above range, the reaction temperature may be 150, 200, 250, 300, 350 ℃ or any value within the above range, and the reaction time may be 2, 3, 4, 5, 6, 7, 8, 9 hours or any value within the above range.
S2: adding deionized water into the modified borate ester molecule according to 2-30% of the solid content of the modified borate ester molecule, and emulsifying at the stirring speed of 500-8000rpm and the temperature of 30-100 ℃ for 15-100min to obtain the emulsion.
In the step of emulsifying the modified borate molecules, the amount of the deionized water added is determined by the solid content of the modified borate molecules, and can be selected according to the actual reaction conditions, for example, 5, 6, 8, 10, 12, 15, 18, 20, 25% is added, the stirring speed, the emulsification reaction temperature, and the reaction time can be adjusted according to the actual reaction conditions, for example, the stirring speed can be 1000, 2000, 3000, 4000, 5000, 6000, 7000r/min or any value in the above range, the reaction temperature can be 40, 50, 60, 70, 80, 90 ℃ or any value in the above range, and the reaction time can be 20, 30, 40, 50, 60, 70, 80, 90min or any value in the above range.
S3: adding deionized water into the fatty amine according to 2-30% of the solid content of the fatty amine, and mixing to obtain a mixed solution.
The amount of deionized water added in the step of obtaining the mixed solution is determined by the solid content of the aliphatic amine, and can be selected within the above range according to the actual reaction conditions, for example, 5, 6, 8, 10, 12, 15, 18, 20, and 25% of deionized water is added.
S4: and reacting the obtained emulsion and the mixed solution at the stirring speed of 50-600r/min at the temperature of 50-500 ℃ for 1-4 hours, then fully standing to enable the materials to be in a water phase, and performing filter pressing and drying to obtain the borate antistatic agent.
In the above step, the stirring speed, the reaction temperature and the reaction time may be adjusted according to the actual reaction, for example, the stirring speed may be 100, 150, 200, 250, 300, 350, 400, 450, 500, 550r/min or any value within the above range, the reaction temperature may be 100, 150, 200, 250, 300, 350, 400, 450 ℃ or any value within the above range, and the reaction time may be 1.5, 2, 2.5, 3, 3.5 hours or any value within the above range. The sufficient standing time can be determined according to the specific phase separation time and can be 1-3 hours.
In the synthesis method, the polyol and the boric acid are subjected to esterification condensation reaction, and according to a condensation reaction mechanism, a reaction product between multiple functionality components can obtain a three-dimensional structure, for example, the alcohol component can be trifunctional (glycerol) and tetrafunctional (pentaerythritol), and the boric acid is trifunctional, so that the borate ester central atom type surfactant obtained by the condensation reaction has a structure of a remote claw type or anchor type structure. The method is relatively simple to operate, reaction conditions are easy to control, and industrial production is facilitated.
In a preferred embodiment, the polyol to boric acid is added in a molar ratio of (1-2):1, and the intermediate to maleic anhydride is added in a molar ratio of (1-2): 1. In a preferred embodiment, the ratio of pure substances in the resulting emulsion and the mixed liquor is 1: 1. The molar ratio of the polyol to the boric acid, the intermediate to the maleic anhydride, the emulsion and the pure substances in the mixed solution in the embodiment can be selected within the above range according to the actual reaction requirement, for example, the molar ratio of the polyol to the boric acid, the intermediate to the maleic anhydride can be respectively 1:1, 1.5:1, 2:1, and the like.
In a preferred embodiment, the polyol is selected from at least one of glycerol, pentaerythritol, trimethylolethane, xylitol, and sorbitol. In a preferred embodiment, the fatty amine is a primary alkyl amine having a linear or branched, saturated or unsaturated hydrocarbon group of 10-18 carbons. It is understood that in the above examples, the molecular structure of the amine as the reaction component is required to be aliphatic amine, and primary amine is also required, and aromatic amine or secondary amine or tertiary amine is not used due to steric hindrance effect.
Based on the synthesis method provided by the above embodiment, a novel borate antistatic agent is obtained, which has the following structural general formula (A):
wherein R is1Is one of ethyl, hydroxymethyl or propylene glycol group; r2Primary alkyl amines which are linear or branched, saturated or unsaturated hydrocarbon radicals having from 10 to 18 carbons.
The antistatic agent provided in the above embodiment is a multifunctional borate synthesized by using a "boron" atom as a central atom, and the borate molecule has hydrophilic functional groups such as carboxyl, hydroxyl and the like, so that the antistatic agent is a novel polyol ethoxylated borate antistatic agent and a novel polyol ethoxylated borate antistatic agent. The antistatic agent has a three-dimensional structure, belongs to a surfactant with medium molecules, remote claws and multiple functional groups, and has the molecular weight of 600-800-. The surfactant is a remote claw type functional group, so that the antistatic function can be effectively improved; because the antistatic agent is not in a small molecular type, the slow release effect is large, and the antistatic function has longer durability.
In a preferred embodiment, R1When ethyl, the following specific structural formula is included:
R1when hydroxymethyl, the following specific structural formula is included:
R1when the propylene glycol group is the propylene glycol group, the structure formula comprises the following specific structures:
the invention provides a plastic product prepared from PE or PP and prepared by using the borate antistatic agent in the technical scheme. For example, the plastic product can be PE film, PP foaming board, PP non-woven fabric and EVA foaming shoe material. When applied to the above-mentioned products, the surface resistivity thereof is only 10 in the range of 23. + -. 2 ℃ and 50. + -. 5% of humidity7-109Ω, preferably 107-108Ω。
In order to more clearly and specifically describe the borate-based antistatic agent provided in the embodiments of the present invention, the preparation method and the application thereof, the following description will be given with reference to specific embodiments.
Example 1
Mixing a mixture of 1:1, 2-butanediol and boric acid are put into a reaction kettle, esterification reaction is carried out for 6 hours at the reaction temperature of 300 ℃, the stirring speed is 400r/min, and modified boric acid ester molecules are prepared through reaction; then adding maleic anhydride into the intermediate in proportion, and carrying out esterification reaction for 3 hours at 100 ℃ at a stirring speed of 200r/min to obtain modified borate molecules;
adding deionized water into modified borate molecules according to the solid content of 10%, and emulsifying at the reaction temperature of 100 ℃ and the stirring speed of 1500rpm for 20min to obtain an emulsion;
mixing fatty amine with deionized water according to the solid content of 10 percent to obtain a mixed solution;
reacting the emulsion and the mixed solution in a reaction kettle at a stirring speed of 300r/min at a reaction temperature of 100 ℃ for 2 hours to obtain a reaction product, standing for 2 hours to enable the material to be in a water phase, performing pressure filtration on the material, drying and dehydrating to obtain a compound A1。
Example 2
Mixing the components in a molar ratio of 1.5:1, putting glycerol and boric acid into a reaction kettle, carrying out esterification reaction for 10 hours at the reaction temperature of 400 ℃, and preparing modified boric acid ester molecules through reaction at the stirring speed of 600 r/min; then adding maleic anhydride into the intermediate in proportion, and carrying out esterification reaction for 9 hours at 400 ℃ at a stirring speed of 500r/min to obtain modified borate molecules;
adding deionized water into modified borate molecules according to the solid content of 25%, and emulsifying for 30min at the reaction temperature of 100 ℃ and the stirring speed of 4000rpm to obtain emulsion;
mixing fatty amine with deionized water according to the solid content of 25 percent to obtain a mixed solution;
reacting the emulsion and the mixed solution in a reaction kettle at a stirring speed of 600r/min at a reaction temperature of 500 ℃ for 1.5 hours to obtain a reaction product, standing for 2 hours to enable the material to be in a water phase, and performing pressure filtration, drying and dehydration on the material to obtain a compound B1。
Example 3
Mixing the components in a molar ratio of 2: putting pentaerythritol and boric acid of 1 into a reaction kettle, carrying out esterification reaction for 8 hours at the reaction temperature of 300 ℃, and carrying out reaction at the stirring speed of 400r/min to prepare modified boric acid ester molecules; then adding maleic anhydride into the intermediate in proportion, and carrying out esterification reaction for 7 hours at the temperature of 300 ℃ at the stirring speed of 450r/min to obtain modified borate molecules;
adding deionized water into the modified borate molecules according to the solid content of 20%, and emulsifying at the reaction temperature of 60 ℃ and the stirring speed of 5000rpm for 60min to obtain emulsion;
mixing the fatty amine with deionized water according to the solid content of 20 percent to obtain a mixed solution;
reacting the emulsion and the mixed solution in a reaction kettle at a stirring speed of 400r/min at a reaction temperature of 200 ℃ for 3 hours to obtain a reaction product, standing for 2 hours to enable the material to be in a water phase, performing pressure filtration on the material, drying and dehydrating to obtain a compound C1。
Evaluation of antistatic agent Performance test
Evaluation test conditions:
all the data of the following examples were measured at a temperature of (23. + -. 2 ℃ C.) and a humidity of (50. + -. 5%).
Experiment one
When the product is a PE film (6 silk) and the adding amount is 4 per mill, the surface resistivity changes of several groups of antistatic agent formulas are tracked at regular time, and the data are as follows:
TABLE 1 variation of surface resistivity (ohm) with time for different antistatic agents
Note: 1-3# antistatic PE films prepared according to Synthesis examples 1-3, respectively; and No. 4-6 is an antistatic agent compounded by polyoxyethylene alkyl ether, polyquaternium, alkyl polyhydric alcohol and the like on the market.
As can be seen from the above table, the surface resistivity of the borate antistatic agents in the first three groups is lower than that of the borate antistatic agents in the second three groups as a whole, and the surface resistivity of No. 3 in the first three groups is the lowest as time goes on, so that the antistatic effect is the best.
Experiment two
When the product is a PP foam board, with an addition of 3%, the test data for the formulations of the different antistatic agents are as follows: (this data was determined by SGS third party)
TABLE 2 TABLE of the surface resistivity (ohm) of the different antistatic agents
Note: sample I # is the antistatic agent foam prepared according to Synthesis example 1 of the present invention, sample A, B; II # is an antistatic agent compounded by polyoxyethylene alkyl ether, polyquaternium, alkyl polyhydric alcohol and the like on the market, and a sample is taken from C, D.
As shown in the table, the surface resistivity values of the two samples I # are lower than II # and the antistatic effect is better than II # from the surface resistivity.
Experiment three
When the product is PP non-woven fabric and the adding amount is 1%, the surface resistivity changes of several groups of antistatic agent formulas are tracked regularly, and the data are as follows:
TABLE 3 change of surface resistivity (ohm) with time for different antistatic agents
Note: 1-3# are antistatic agent PP nonwoven materials prepared according to Synthesis examples 1-3 of the present invention; no. 4 is a British cereal large antistatic agent, and No. 5 is an antistatic agent which is compounded by polyoxyethylene alkyl ether, polyquaternium, alkyl polyhydric alcohol and the like on the market.
As can be seen from the above table, the surface resistivity of each group of the components basically shows the trend of firstly decreasing and then increasing along with the time extension, the surface resistivity of the No. 3 is the lowest overall, the antistatic effect is the best, and the durability is better than that of the other groups, and then 1#, 2#, 4#, and 5 #.
Experiment four
When the product is EVA foaming shoe material and the adding amount is 1.5%, the surface resistivity changes of several groups of antistatic agent formulas are tracked at regular time, and the data is as follows:
TABLE 4 change of surface resistivity (ohm) of different antistatic agents with time
Note: no. 1-3 are EVA foam materials of antistatic agents prepared according to Synthesis examples 1-3 of the present invention; and No. 4-5 is an antistatic agent compounded by polyoxyethylene alkyl ether, polyquaternium, alkyl polyhydric alcohol and the like on the market.
As can be seen from the table above, the surface resistivity of each formula is reduced in two months, the overall results of the No. 1-3 are superior to those of the No. 4 and the No. 5, wherein the surface resistivity of the No. 3 is the lowest, and the antistatic effect is the best.
Claims (6)
1. The synthesis method of the borate antistatic agent is characterized by comprising the following steps:
proportionally adding polyalcohol and boric acid into a reaction kettle, carrying out esterification reaction for 1-10 hours at the temperature of 100-400 ℃ at the stirring speed of 600r/min to obtain an intermediate, then proportionally adding maleic anhydride into the intermediate, and carrying out esterification reaction for 1-10 hours at the temperature of 100-400 ℃ at the stirring speed of 50-500r/min to obtain modified borate molecules, wherein the polyalcohol is selected from 1, 2-butanediol or glycerol;
adding deionized water into the modified borate ester molecules according to 2-30% of the solid content of the modified borate ester molecules, and emulsifying at the stirring speed of 500-8000rpm and the temperature of 30-100 ℃ for 15-100min to obtain emulsion;
adding deionized water into fatty amine according to 2-30% of the solid content of the fatty amine, and mixing to obtain a mixed solution;
reacting the obtained emulsion and the mixed solution at the stirring speed of 50-600r/min at the temperature of 50-500 ℃ for 1-4 hours, then fully standing to enable the materials to be in a water phase, and performing filter pressing and drying to obtain the borate antistatic agent with the structural formula shown as A1 or B1;
（A1）
（B1）。
2. the synthesis method according to claim 1, wherein the molar ratio of the added polyol to the boric acid is (1-2):1, and the molar ratio of the intermediate to the maleic anhydride is (1-2): 1.
3. The synthesis method according to claim 1, wherein the molar ratio of pure substances in the obtained emulsion and mixed solution is 1: 1.
4. a plastic article made of PE or PP prepared using the borate antistatic agent prepared by the synthesis method of any of claims 1-3.
5. Plastic article according to claim 4, characterized in that it has a surface resistivity in the range of 10 at a temperature (23 ± 2 ℃) and a humidity (50 ± 5)% of the temperature7-109Ω。
6. Use of the borate antistatic agent prepared according to the synthesis method of any one of claims 1 to 3 for the preparation of plastic articles made of PE or PP.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852314A (en) * | 1970-12-03 | 1974-12-03 | Toho Chem Ind Co Ltd | Surface-active organoboron compounds |
| CN102000527A (en) * | 2010-09-30 | 2011-04-06 | 青岛四维化工有限公司 | Modified boric acid ester interface activating agent and preparation method thereof |
| CN103772422A (en) * | 2014-02-21 | 2014-05-07 | 博兴县沙索新材料有限公司 | Boric acid monoester used as static-resistant agent and preparation method thereof |
| CN111068577B (en) * | 2019-12-18 | 2021-07-30 | 烟台融晟新材料有限公司 | Boric acid ester drip agent, preparation method thereof and greenhouse film prepared by same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852314A (en) * | 1970-12-03 | 1974-12-03 | Toho Chem Ind Co Ltd | Surface-active organoboron compounds |
| CN102000527A (en) * | 2010-09-30 | 2011-04-06 | 青岛四维化工有限公司 | Modified boric acid ester interface activating agent and preparation method thereof |
| CN103772422A (en) * | 2014-02-21 | 2014-05-07 | 博兴县沙索新材料有限公司 | Boric acid monoester used as static-resistant agent and preparation method thereof |
| CN111068577B (en) * | 2019-12-18 | 2021-07-30 | 烟台融晟新材料有限公司 | Boric acid ester drip agent, preparation method thereof and greenhouse film prepared by same |
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Denomination of invention: Boric acid ester antistatic agents and their preparation methods and applications Granted publication date: 20220513 Pledgee: Postal Savings Bank of China Limited Laiyang sub branch Pledgor: Yantai Rongsheng New Material Co.,Ltd. Registration number: Y2024980039978 |