CN1670118A - Polymer base antistatic agent and method for preparing same - Google Patents
Polymer base antistatic agent and method for preparing same Download PDFInfo
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- CN1670118A CN1670118A CN 200510033477 CN200510033477A CN1670118A CN 1670118 A CN1670118 A CN 1670118A CN 200510033477 CN200510033477 CN 200510033477 CN 200510033477 A CN200510033477 A CN 200510033477A CN 1670118 A CN1670118 A CN 1670118A
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Abstract
The invention relates to polymeric matrix antistatic agent and the method for preparation. The antistatic agent comprises 50~90% weight polymer provided with polar groups and 10~50% weight metal-sol. The process comprises the steps of: dissolving the polymer provided with polar groups and metal-sol into the dissolvent; under the condition of agitating, refluxing 24~48 hours, make the chelate reaction occurred between the polymer provided with polar groups and the metal-sol; under vacuum conditions, removing the dissolvant, cleaning, drying the product and acquire the said polymeric matrix antistatic agent. The good characteristics of antistatic can be acquired by adding no more than 10% weight antistatic agents in the insulating resin.
Description
Technical field
The present invention relates to static inhibitor and preparation thereof, particularly be fit to can be applicable to polymer base antistatic agent in plastics, the rubber item and preparation method thereof.
Background technology
U.S. Pat 6225386 discloses a kind of static inhibitor based on phosphine sulfuric ester and polyol compound or polymkeric substance, its preparation process is that phosphine sulfuric ester and polyol compound or polymkeric substance are mixed in solvent, afterwards solvent is removed, drying promptly makes static inhibitor.The prepared static inhibitor of this method can be used in the plastics such as polyethylene terephthalate, polycarbonate; But, in the static inhibitor of this method preparation, there is not organic combination between phosphine sulfuric ester and the polyhydric alcohol polymer, belong to simple doping type; When this static inhibitor used in plastics, one of its active ingredient phosphine sulfuric ester was easy to separate out in the plastic substrate, thereby may cause disadvantageous effect to the performance and the use of plastics, has so just limited its range of application.
The patent No. of Sumitomo Rubber Industrie. Ltd and Sanko Chemical Industry Co., Ltd application is the making method that 200410002716.1 Chinese invention patent " polymer type antistatic agent, antistatic behaviour polymer and manufacture method thereof " discloses a kind of polymer type antistatic agent; this invention is directly to sneak in thermoplastic resin or the elastomerics containing fluorine-based and anionic compound alkylsulfonyl, thereby makes static inhibitor.Equally there is not combination between its active ingredient of the polymer type antistatic agent that this method makes and thermoplastic resin or the elastomerics yet, belongs to mixed type.In addition, this static inhibitor must be considered the consistency of the resin that adopts in the static inhibitor or elastomerics and concrete plastics or rubber item material when being used to prepare plastics or rubber item; Therefore, this static inhibitor should customize at the plastics or the elastomeric material of concrete goods in use.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of excellent performance, stable polymer base antistatic agent and easy and practical preparation method thereof are provided.
Purpose of the present invention can realize by following measure:
The composition of polymer base antistatic agent:, comprise 50～90 parts polymkeric substance of band polar group and 10～50 parts metal-sol in parts by weight.
The polymkeric substance of band polar group is selected from one or more the polymkeric substance of functional group that contains in hydroxyl, carboxyl and the ether, and its molecular weight is between 10000 to 100000;
Metal-sol is tindioxide colloidal sol, tin indium oxide colloidal sol, silver sol or gold sol.
The preparation method of polymer base antistatic agent may further comprise the steps:
Step 1 is counted by weight, is equipped with polymkeric substance and 10～50 parts of metal-sols of 50～90 parts of band polar groups;
In the polymkeric substance of the band polar group that step 2 is prepared step 1 and one or more blended solvents that metal-sol is dissolved in alcohols, ketone or ester class, under the agitation condition, refluxed 24～48 hours;
Step 3 is removed the solvent in the step 2 gains (solution) under vacuum condition, and products therefrom is clean with massive laundering, and drying makes polymer base antistatic agent.
Compared with prior art, the present invention has following advantage:
1, utilize the polymkeric substance of band polar group, this polymkeric substance is because the wetting ability of itself, and himself also can play certain antistatic property, thereby this polymkeric substance also can be used as antistatic active ingredient, and has been not only the effect of base material.In addition, adopt the polymkeric substance that has polar group can guarantee that complex reaction takes place with it conducting metal colloidal sol, organically combine, be uniformly dispersed; This static inhibitor is used for plastics or the rubber item consumption is few, adds deal few (in 10 parts) and can obtain the excellent antistatic energy in insulating resin, and phenomenon can not occur separating out; Simultaneously, because this polymer base antistatic agent has certain polarity, guaranteed that itself and the plastics or the elastomeric material that contain polar group have consistency preferably; Its consumption is few, does not therefore influence the mechanical property of plastics or rubber item.
2, the antistatic property excellence of the polymer base antistatic agent of manufacturing of the present invention and have long-lasting.Because adopted molecular weight to prepare static inhibitor at 10000～100000 polymkeric substance, and organically combined between the each component in the static inhibitor, therefore, this static inhibitor can water-fastly be washed, have long-lasting.
3, the polymer base antistatic agent of the present invention's manufacturing is applied to form in the polyamide resin antistatic nylon material, its antistatic property and good mechanical performance.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
Meter takes by weighing 50 parts of poly-(VINYL ISOBUTYL ETHER-Hydroxyethyl acrylate) and 50 parts of tindioxide colloidal sols by weight, is dissolved in 100 parts of ethanol; Under the agitation condition, refluxed 24 hours, make the polymkeric substance generation complex reaction of metal-sol and band polar group; Under vacuum condition, solvent is removed then, products therefrom washes, and drying promptly makes polymer base antistatic agent.
Meter adds 3 parts of resulting polymers base antistatic agents in 97 parts of Nylon 6s to by weight, mixes, form the antistatic nylon material, then with gained material extruding pelletization in forcing machine, and injection moulding makes sample, carries out the test of antistatic property and mechanical property.Its antistatic property is tested according to GB1410-1989 " solid insulating material volume specific resistance and surface resistivity test method ", and volume specific resistance is 10
-9Ω .m.Compare with the blank sample that does not add described polymer base antistatic agent, press the test of GB/T1040-1992 " plastic tensile test method " method, tensile strength changes in 5%; Press the method test of GB/T1843-1996 " plastics izodtest method ", the shock strength variation range is in 3%; Press the method test of GB9341-1988 " plastics bend test method ", the flexural strength variation range is in 2%.
Embodiment 2
Meter takes by weighing 60 parts of poly-(VINYL ISOBUTYL ETHER-vinylformic acid) and 40 parts of tin indium oxide colloidal sol parts by weight, and the volume ratio that is dissolved in 100 parts is in 2: 1 the ethanol and ethyl acetate mixed solvent; Under agitation condition, refluxed 36 hours, make the polymkeric substance generation complex reaction of metal-sol and band polar group; Under vacuum condition, solvent to be removed, products therefrom washes, and drying promptly makes polymer base antistatic agent.
Meter is applied to 5 parts of resulting polymers base antistatic agents to mix in 95 parts of Nylon 6s by weight, form the antistatic nylon material, then with gained material extruding pelletization in forcing machine, and injection moulding makes sample, carries out the test of antistatic property and mechanical property.Its antistatic property is according to the test of GB1410-1989 " solid insulating material volume specific resistance and surface resistivity test method " method, and volume specific resistance is 10
-9Ω .m.Compare with the blank sample that does not add described polymer base antistatic agent, press the test of GB/T1040-1992 " plastic tensile test method " method, tensile strength changes in 5%; Press the method test of GB/T1843-1996 " plastics izodtest method ", the shock strength variation range is in 3%; Press the method test of GB9341-1988 " plastics bend test method ", the flexural strength variation range is in 2%.
Embodiment 3
Meter is got 70 parts of poly-(VINYL ISOBUTYL ETHER-propane oxide) and 30 parts of silver sols by weight, and the volume ratio that is dissolved in 100 parts is in the mixed solvent of 3: 2 butanols and acetone; Under agitation condition, refluxed 48 hours, make the polymkeric substance generation complex reaction of metal-sol and band polar group; Under vacuum condition, solvent to be removed, products therefrom washes, and drying promptly makes polymer base antistatic agent.
Meter is applied to 7 parts of resulting polymers base antistatic agents to mix in 93 parts of Nylon 6s by weight, form the antistatic nylon material, then with gained material extruding pelletization in forcing machine, and injection moulding makes sample, carries out the test of antistatic property and mechanical property.Its antistatic property is according to the test of GB1410-1989 " solid insulating material volume specific resistance and surface resistivity test method " method, and volume specific resistance is 10
-8Ω .m.Compare with the blank sample that does not add described polymer base antistatic agent, press the test of GB/T1040-1992 " plastic tensile test method " method, tensile strength changes in 5%; Press the method test of GB/T1843-1996 " plastics izodtest method ", the shock strength variation range is in 3%; Press the method test of GB9341-1988 " plastics bend test method ", the flexural strength variation range is in 2%.
Embodiment 4
Meter takes by weighing 90 parts of poly-(ethyl vinyl ether-Propylene glycol monoacrylate) and 10 parts of gold sols by weight, and the volume ratio that is dissolved in 100 parts is in the mixed solvent of 4: 1 ethanol and butanone; Under the agitation condition, refluxed 30 hours, make the polymkeric substance generation complex reaction of metal-sol and band polar group; Under vacuum condition, solvent is removed then, products therefrom washes, and drying promptly makes polymer base antistatic agent.
Meter is applied to 8 parts of resulting polymers base antistatic agents to mix in 92 parts of Nylon 6s by weight, form the antistatic nylon material, then with gained material extruding pelletization in forcing machine, and injection moulding makes sample, carries out the test of antistatic property and mechanical property.Its antistatic property is according to the test of GB1410-1989 " solid insulating material volume specific resistance and surface resistivity test method " method, and volume specific resistance is 10
-9Ω .m.Compare with the blank sample that does not add described polymer base antistatic agent, press the test of GB/T1040-1992 " plastic tensile test method " method, tensile strength changes in 5%; Press the method test of GB/T1843-1996 " plastics izodtest method ", the shock strength variation range is in 3%; Press the method test of GB9341-1988 " plastics bend test method ", the flexural strength variation range is in 2%.
Embodiment 1 to embodiment 4 gained sample antistatic property and mechanical property such as table 1
Table 1 embodiment 1 to embodiment 4 gained sample antistatic property and mechanical property table
| Antistatic property (Ω m) | Compare mechanical property changing conditions (%) with blank sample | |||
| Tensile strength | Shock strength | Flexural strength | ||
| Embodiment 1 | ????10 -9, good | Less than 5% | Less than 3% | Less than 2% |
| Embodiment 2 | ????10 -9, good | Less than 5% | Less than 3% | Less than 2% |
| Embodiment 3 | ????10 -8, good | Less than 5% | Less than 3% | Less than 2% |
| Embodiment 4 | ????10 -9, good | Less than 5% | Less than 3% | Less than 2% |
Claims (6)
1, a kind of polymer base antistatic agent is characterized in that: in parts by weight, comprise following material:
50～90 parts in the polymkeric substance of band polar group
10～50 parts of metal-sols
The polymkeric substance of described band polar group is the polymkeric substance that contains one or more functional groups in hydroxyl, carboxyl or the ether;
Described metal-sol is tindioxide colloidal sol, tin indium oxide colloidal sol, silver sol or gold sol.
2, a kind of polymer base antistatic agent according to claim 1 is characterized in that: the described polymkeric substance that contains one or more functional groups in hydroxyl, carboxyl or the ether comprises poly-(VINYL ISOBUTYL ETHER-Hydroxyethyl acrylate), poly-(VINYL ISOBUTYL ETHER-vinylformic acid), poly-(VINYL ISOBUTYL ETHER-propane oxide) or poly-(ethyl vinyl ether-Propylene glycol monoacrylate).
3, a kind of polymer base antistatic agent according to claim 1 is characterized in that: the molecular weight of the polymkeric substance of described band polar group is 10000～100000.
4, the method for preparing the described polymer base antistatic agent of claim 1, its feature may further comprise the steps:
Step 1 is counted by weight, is equipped with polymkeric substance and 10～50 parts of metal-sols of 50～90 parts of band polar groups;
Step 2 is dissolved in the polymkeric substance and the metal-sol of the band polar group that step 1 is prepared in the solvent, under the agitation condition, refluxes 24～48 hours;
Step 3 is removed the solvent in the step 2 gains under vacuum condition, and products therefrom washes, and drying makes polymer base antistatic agent.
5, polymer base antistatic agent preparation method according to claim 4 is characterized in that: the solvent in the described step 2 is one or more mixtures in alcohols, ketone or the ester class.
6, polymer base antistatic agent preparation method according to claim 5 is characterized in that: described solvent comprises the mixture of mixture, butanols and acetone of ethanol, ethanol and ethyl acetate or the mixture of ethanol and butanone.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100334770A CN100340627C (en) | 2005-03-11 | 2005-03-11 | Polymer base antistatic agent and method for preparing same |
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| CNB2005100334770A CN100340627C (en) | 2005-03-11 | 2005-03-11 | Polymer base antistatic agent and method for preparing same |
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| CN1670118A true CN1670118A (en) | 2005-09-21 |
| CN100340627C CN100340627C (en) | 2007-10-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230186B (en) * | 2008-01-07 | 2010-12-01 | 广州市合诚化学有限公司 | Anti-static poly(ethylene terephthalate) material and preparation method thereof |
| CN102775697A (en) * | 2012-07-27 | 2012-11-14 | 华南理工大学 | Halogen-free environmentally-friendly cationic antistatic agent and preparation method thereof |
| CN104788865A (en) * | 2015-03-20 | 2015-07-22 | 复旦大学 | Composite antistatic agent of nano-metal oxide/polymer antistatic agent, as well as preparation method and application of composite antistatic agent |
| CN104945730A (en) * | 2015-05-28 | 2015-09-30 | 复旦大学 | Nucleating agent and polymer composite antistatic agent, preparation method and applications thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594367A (en) * | 1985-04-01 | 1986-06-10 | Bata Limited | Antistatic composition and articles made therefrom |
| JPS6363726A (en) * | 1986-09-05 | 1988-03-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Composition for surface treatment |
| JPH11199773A (en) * | 1997-12-24 | 1999-07-27 | E I Du Pont De Nemours & Co | Antistatic polymer composition and molded article thereof |
-
2005
- 2005-03-11 CN CNB2005100334770A patent/CN100340627C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230186B (en) * | 2008-01-07 | 2010-12-01 | 广州市合诚化学有限公司 | Anti-static poly(ethylene terephthalate) material and preparation method thereof |
| CN102775697A (en) * | 2012-07-27 | 2012-11-14 | 华南理工大学 | Halogen-free environmentally-friendly cationic antistatic agent and preparation method thereof |
| CN102775697B (en) * | 2012-07-27 | 2014-04-02 | 华南理工大学 | Halogen-free environmentally-friendly cationic antistatic agent and preparation method thereof |
| CN104788865A (en) * | 2015-03-20 | 2015-07-22 | 复旦大学 | Composite antistatic agent of nano-metal oxide/polymer antistatic agent, as well as preparation method and application of composite antistatic agent |
| CN104788865B (en) * | 2015-03-20 | 2017-11-17 | 复旦大学 | Composite antistatic agent of nano-metal-oxide/Polymer-metallic Catalyst and its preparation method and application |
| CN104945730A (en) * | 2015-05-28 | 2015-09-30 | 复旦大学 | Nucleating agent and polymer composite antistatic agent, preparation method and applications thereof |
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| CN100340627C (en) | 2007-10-03 |
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Granted publication date: 20071003 Termination date: 20120311 |