CN104311969B - Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch and its preparation method and application - Google Patents

Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch and its preparation method and application Download PDF

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CN104311969B
CN104311969B CN201410627441.4A CN201410627441A CN104311969B CN 104311969 B CN104311969 B CN 104311969B CN 201410627441 A CN201410627441 A CN 201410627441A CN 104311969 B CN104311969 B CN 104311969B
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glutamic acid
master batch
triethanolamine salt
cocoyl glutamic
rust master
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CN104311969A (en
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詹天荣
刘晓林
张跃
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Yangzhou Suda Technology Development Co. Ltd.
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Qingdao University of Science and Technology
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  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

A kind of cocoyl glutamic acid triethanolamine salt anti-rust master batch and its preparation method and application. The percent mass accounting of each component of anti-rust master batch is 30��50% composite antirust agent, 40��60% carrier plastics and 10��20% auxiliary agents; Composite antirust agent is mixed by the ratio of sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA 1��1.5:1.2 in mass ratio��1.6:2.2��3.5:0.8��1.2:1��1.4; Auxiliary agent by the double; two stearic acid amide of ethylene, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1,706 0.9��1.3:4.8 in mass ratio��6.5:2.5��3.3:0.9��1.3 ratio mixing. Cocoyl glutamic acid triethanolamine salt and triethanolamine borate is adopted to do additive; not only have peptizaiton but also can be antirust, carrier plastics can be penetrated and evaporate into metal surface formation protecting film, intercept corrosive deposit and corrode; crystallization, not only environmental protection but also safety also will not be there is on carrier plastics surface.

Description

Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch and its preparation method and application
Technical field:
The present invention relates to the adaptation nontoxic volatile rust prevention field of plastic products of various metals goods, in particular to a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch and preparation method thereof and concrete application.
Background technology:
Corrosion of metal relates to the common problem of national economy every field, it is to generate the electrochemical process of oxide and hydroxide mixture owing to oxygen and water act on metal surface, performance and value to metal and goods thereof have high risks, and can cause a serious accident time serious causes equipment scrapping. Metal and goods thereof are producing, are transporting and in storage process, particularly in the overland transport process that marine transportation and high upsurge are wet, inevitably meet with corrosion and corrosion occurs. According to statistics, within 2005, the annual economic loss caused because of corrosion of China is more than 36,000,000,000 yuan, and its harm is very serious. It is at present conventional that to smear anti-corrosive grease owned by France antirust in contact; not only technique bothersome, poor effect loaded down with trivial details, consuming time; but also need before unpacking, carry out cleaning by degreasing operation; very easily cause the secondary pollution of environment; and the turning of antirust oil, position, gap are not reached for those; then can not forming effective corrosion protection, this method increasingly can not be accepted by people. Adopt vacuum-packing method then relatively costly, and for extremely difficult reality large-scale workpiece. Although desiccant is antirust less costly, easy to use, but affected by environment relatively big, effect it is difficult to ensure that.
Vapor phase inhibitor technology (i.e. VCI technology, VCI is the abbreviation of English VolatileCorrosionInhibitor) is one of current untouchable antirust important method.It utilizes vapour phase inhibitor automatically to volatilize gas at normal temperatures and forms layer protecting film in metal surface; inhibit the generation of electrochemical reaction; also block some simultaneously and accelerate the metal eroding substance erosion to metal surface, thus slowing down or stoping metal surface corrosion. Vapor phase inhibitor technology have environmental friendliness, easy to use, clean the features such as clean, be widely used in the anti-corrosion of the links such as metal and production of articles, transport and storage in recent years. Domestic based on vapor phase inhibitor technology exploitation volatile rust prevention product be also commonly reported that, the gas-phase antirusting film particularly produced with plastics for the carrier of vapor phase inhibitor, have transparent, pliable and tough, can machine-shaping, barrier high. But gas-phase antirusting film conventional at present has blown film type and application type, but they equal existing defects, in the former gas-phase antirusting film as disclosed in CN01128198.7, CN01127534.0, vapour phase inhibitor component all contains the strong carcinogen nitrite disabled in the world, and vapour phase inhibitor is added directly in resin blown film by technique disclosed in CN01127534.0, owing to not carrying out mixing pretreatment, vapour phase inhibitor distribution of particles is uneven, and gained membrane product there will be rough surface and crystallization phenomenon; The latter is then with plastic foil for base material; coat on plastic sheeting after corrosion inhibiter and bonding agent are mixed; not only energy consumption is big for this; complex procedures; more can not clean production; being also easy to affect rust-proof effect because mixing uneven, ferrous metal is only had rust inhibition by the antirust film of this kind of technique gained, and lacks coloured or many metallic combinations part even without defencive function.
This shows, multiple many metals are all had excellent rust-proof effect by development and production one, and with environmental friendliness, gas-phase antirusting film easy and simple to handle, rakish, the corrosion of metal problem solving to relate to national economy is seemed particularly urgent, and developing high-quality and efficient gas-phase anti-rust master batch is then realize the most basic approach of these needs and key point.
It is generally acknowledged in organic carboxyl acid and derivant the groups such as-COOH and-CONH-containing polarized, certain affinity is had with metal, easily produce absorption in metal surface, thus playing certain rust-proof effect, wherein organic carboxyl acid alcohol amine salt structure just can meet this requirement. Because after carboxylic acid mixes with hydramine, system has highly polar-COOH and-CONH-group, the N on these polar groups and the lone pair electrons on O atom simultaneously and forms coordinate bond with the empty d track on Fe atom, align in metal surface. Longer non-polar group then aligns the outer surface in metal, hinder the ionizing of ferrum on the one hand, the electronics in the hydrone of metal surface is made to reduce, hinder hydrion on the other hand and inhibit the reduction reaction of negative electrode to metal surface diffusion, therefore hinder the corrosion of anode metal, be the corrosion inhibiter of function admirable.
Boric acid is combined with oxygen atom with SP2 hydridization due to each boron atom, and boron is still electron deficiency, is easy to react generation perborate tetrahydrate monoesters, dibasic acid esters, three esters and four replacement spirane structures with organic alcohols compound. borate has the performances such as good lubrication, antirust, sterilization, and to human non-toxic's evil effect. but just at present, as the desirable environmental type additive of one, borate is mainly used in water-base cutting fluid field (Li Wei, Ma Tao, Wang Sen, Tan Hailin. borate application in water-base cutting fluid. tool technique, 2010, 44 (5): 93-95.), each serve as extreme-pressure lubricant, surfactant, antirust agent, the effect of anticorrosion and bactericidal agent, and they yet there are no in vapor phase inhibitor technology as additive and relate to, especially yet there are no about with nontoxic inorganic salt, carboxylic acid alcohol amine salt, organic amine borate is the report of the gas-phase anti-rust master batch of compound corrosion inhibitor and its preparation method and application aspect.
Summary of the invention:
It is an object of the invention to solve deficiency of the prior art, it is provided that a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch and its preparation method and application.
For achieving the above object, a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch provided by the invention, it is characterised in that in described gas-phase anti-rust master batch, the percent mass accounting of each component is: 35��50% composite antirust agent, 40��80% carrier plastics and 10��20% auxiliary agents; Described composite antirust agent is mixed by the ratio that sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA are 1��1.5:1.2��1.6:2.2��3.5:0.8��1.2:1��1.4 in mass ratio; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 0.9��1.3:4.8��6.5:2.5��3.3:0.9��1.3 in mass ratio.
Further, described composite antirust agent is mixed for the ratio of 1.2:1.3:3:1:1.2 in mass ratio by sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 1:5.5:3:1 in mass ratio.
Further, described carrier plastics is density is 0.90��0.96g/cm3Polyethylene.
Further, described carrier plastics is one or both the mixture in Low Density Polyethylene, linear low density polyethylene.
Further, the particle diameter of described composite antirust agent is 800��2800 orders.
Further, the particle diameter of described composite antirust agent is 900��1100 orders.
A kind of method preparing above-mentioned cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch, comprises the following steps: (a) by described quality proportioning by composite antirust agent, carrier plastics and 4��5 minutes prepared compounds of auxiliary agent mixed at high speed; B gained compound is mediated by (), melt process, and mixing under 150��180 DEG C of temperature conditions, plasticizing extrusion, prepares described cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch afterwards.
A kind of application of above-mentioned cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch, comprise the following steps: described gas-phase anti-rust master batch is added in the raw material of thermoplastic by (a) according to the ratio that mass ratio is 1:25��50, is sufficiently stirred for and makes hybrid particles; (b) again by described hybrid particles through blown film or film, be processed into gas-phase antirusting film packaging material.
The beneficial effects are mainly as follows: a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch is provided; first cocoyl glutamic acid triethanolamine salt and triethanolamine borate are simultaneously used for preparing the composite antirust agent of gas-phase anti-rust master batch; it not only has peptizaiton but also play rust-proof effect; and produce synergistic effects between other three kinds of corrosion inhibiter components, strengthen rustless property. The compound corrosion inhibitor adopted is size-reduced particle diameter is the sodium tetraborate about 1000 orders, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA mixture. This mixed inhibitor had both had certain polarity; carrier plastics can be penetrated and evaporate into packaged metallic surface formation protecting film; intercept the erosion of extraneous corrosive deposit; also will not cross strong and incompatible with carrier plastics and crystallization phenomenon occurs because its polarity; and do not contain nitrite harmful constituent; enable gained corresponding organic carboxyl acid alcohol amine salt gas-phase anti-rust master batch to be applicable to more metal types, use more environment-friendly and safer.
Detailed description of the invention:
For being further appreciated by the present invention, below in conjunction with embodiment, the invention will be further described, but and does not limit the present invention in any way.
The preparation method that cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch in following embodiment adopts, including step in detail below: composite antirust agent, carrier plastics and auxiliary agent are poured in plastic high-speed mixer by described quality proportioning by (a), 4��5 minutes prepared compounds of mixed at high speed; B gained compound is mediated by () by Double-rotor continuous mixing comminutor, melt process, and mixing under 150��180 DEG C of temperature conditions, plasticizing extrusion, prepares described cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch afterwards.
Embodiment 1:
Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch a, wherein the percent mass accounting of each component is: 38% composite antirust agent, 49% carrier plastics and 13% auxiliary agent; The ratio that described composite antirust agent is 1.2:1.3:3:1:1.2 in mass ratio by sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA mixes, and the particle diameter of composite antirust agent is 900��1100 orders; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 1:5.5:3:1 in mass ratio.
Embodiment 2:
Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch b, wherein the percent mass accounting of each component is 38% composite antirust agent, 49% carrier plastics and 13% auxiliary agent; The ratio that described composite antirust agent is 1.2:1.3:3:1:1.2 in mass ratio by sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA mixes, and the particle diameter of composite antirust agent is 900��1100 orders; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 1:5.5:3:1 in mass ratio.
Embodiment 3:
Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch c, wherein the percent mass accounting of each component is: 40% composite antirust agent, 44% carrier plastics and 16% auxiliary agent; The ratio that described composite antirust agent is 1.2:1.3:3:1:1.2 in mass ratio by sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA mixes, and the particle diameter of composite antirust agent is 900��1100 orders; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 1:5.5:3:1 in mass ratio. .
Embodiment 4:
Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch d, wherein the percent mass accounting of each component is: 38% composite antirust agent, 43% carrier plastics and 19% auxiliary agent; The ratio that described composite antirust agent is 1.2:1.3:3:1:1.2 in mass ratio by sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA mixes, and the particle diameter of composite antirust agent is 900��1100 orders; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 1:5.5:3:1 in mass ratio.
Embodiment 5 applies effect test example
The gas-phase anti-rust master batch of embodiment 1,2,3,4 gained is added to according to the ratio that mass ratio is 1:25��50 in the raw material of thermoplastic, be sufficiently stirred for and make hybrid particles; Again by the hybrid particles antirust plastic hybrid particles of gained through blown film or film, it is processed into gas-phase antirusting film packaging material.
In the above embodiments 5, color masterbatch or the fire retardant of appropriate different colours can also be added when coextrusion film blowing, making gas-phase antirusting film present required color or have certain fire resistance, the rustless property of gas-phase antirusting film is not produced any harmful effect by these additional characteristics.
By embodiment 1,2,3, many metals are carried out volatile rust prevention process by the gas-phase antirusting film packaging material corresponding to 4 together with multiple like products without organic amine Borated Ester Additives, and their rustless property is compared, test standard is with reference to GB/T19532-2004, and result of the test is in Table 1:
In table 1, same kind of products at abroad selects the clean happy special market products of Germany's Blanc promise and the U.S., and its market price is higher than antirust film of the present invention two to three times; Domestic like product selects China's grace east market products, and price is suitable with antirust film of the present invention. Comparative test result shows, the rust-proof effect of various metals is better than the selected external and domestic similar-type products without organic amine Borated Ester Additives by gas-phase antirusting film of the present invention, the wherein best results of embodiment 3, for the preferably embodiment of the present invention. Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch of the present invention and thin film price only have 1/2nd or 1/3rd of same kind of products at abroad; and have no side effect, free from environmental pollution; meet national environmental standard requirement, completely can substituting import one product. Think that their vapor phase corrosion inhibitor mechanism is likely: evaporate into cocoyl glutamic acid triethanolamine salt and the triethanolamine borate of metal surface, in its molecule N and O atom all contain lone pair electrons, coordinate bond can be formed with the d electronics unoccupied orbital of Fe, there occurs chemisorbed; Add the corrosion inhibition of inorganic salt in compound corrosion inhibitor, make compound corrosion inhibitor form firmly adsorbed film in metal surface, to suppress the contact to metal surface of oxygen and water, from having played good rust-proof effect.

Claims (8)

1. a cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch, it is characterised in that in described anti-rust master batch, the percent mass accounting of each component is: 30��50% composite antirust agent, 40��60% carrier plastics and 10��20% auxiliary agents; Described composite antirust agent is mixed by the ratio that sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA are 1��1.5:1.2��1.6:2.2��3.5:0.8��1.2:1��1.4 in mass ratio; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 0.9��1.3:4.8��6.5:2.5��3.3:0.9��1.3 in mass ratio.
2. a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch according to claim 1, it is characterised in that the ratio that described composite antirust agent is 1.2:1.3:3:1:1.2 in mass ratio by sodium tetraborate, decanedioic acid sodium, cocoyl glutamic acid triethanolamine salt, triethanolamine borate, BTA mixes; Described auxiliary agent is mixed by the ratio that ethylene double; two stearic acid amide, ground calcium carbonate, sucrose fatty acid ester, antioxidant 1706 are 1:5.5:3:1 in mass ratio.
3. a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch according to claim 1, it is characterised in that described carrier plastics is density is 0.90��0.96g/cm3Polyethylene.
4. a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch according to claim 3, it is characterised in that described carrier plastics is one or both the mixture in Low Density Polyethylene, linear low density polyethylene.
5. a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch according to claim 1 and 2, it is characterised in that the particle diameter of described composite antirust agent is 800��2800 orders.
6. a kind of cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch according to claim 5, it is characterised in that the particle diameter of described composite antirust agent is 900��1100 orders.
7. the preparation method of the cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch described in a claim 1, it is characterised in that comprise the following steps: (a) by described quality proportioning by composite antirust agent, carrier plastics and 4��5 minutes prepared compounds of auxiliary agent mixed at high speed; B gained compound is mediated by (), melt process, and mixing under 150��180 DEG C of temperature conditions, plasticizing extrusion, prepares described cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch afterwards.
8. the application of the cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch described in claim 1, it is characterized in that this application comprises the following steps: described anti-rust master batch is added in the raw material of thermoplastic by (a) according to the ratio that mass ratio is 1:25��50, is sufficiently stirred for and makes hybrid particles; (b) again by described hybrid particles through blown film or film, be processed into gas-phase antirusting film packaging material.
CN201410627441.4A 2014-11-10 2014-11-10 Cocoyl glutamic acid triethanolamine salt gas-phase anti-rust master batch and its preparation method and application Expired - Fee Related CN104311969B (en)

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CN107849817A (en) * 2015-07-31 2018-03-27 纳尔逊·郑吉耀 Anti-corrosion mineral paper Chemical composition that
CN105199190B (en) * 2015-09-10 2018-01-30 苏州贝达新材料科技有限公司 A kind of Mobyneb environment protection gas-phase rust-proofing master batch and its preparation method and application
CN113512234A (en) * 2021-04-28 2021-10-19 青岛鑫盈鑫包装材料有限公司 Sulfamide acid type gas-phase antirust master batch for cast iron product and preparation method thereof
CN114105511B (en) * 2021-11-10 2022-12-27 国网电子商务有限公司 Corrosion-resistant gas-phase rust inhibitor, preparation method thereof and gas-phase rust-resistant film box

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