CN103772422A - Boric acid monoester used as static-resistant agent and preparation method thereof - Google Patents
Boric acid monoester used as static-resistant agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to boric acid monoester used as a static-resistant agent and a preparation method thereof. The boric acid monoester is used for resisting static electricity. The name of the boric acid monoester is N, N-ethoxyl fatty-acid amine boric-acid monoester, and the structure is shown in a formula (I) described in the specification. The preparation method comprises the three steps: (a) esterification reaction of diethanol amine and fatty acid; (b) molecular distillation of mono-fatty-acid ethanolamine ester; and (c) supercritical esterification reaction of the boric acid. The boric acid monoester is stable in structure and good in static resistance and can resist high temperature and low humidity when being used as the static-resistant agent; the preparation method has the advantages that the problem that borate is difficult to esterify due to color change and coking caused by intramolecular dehydration under high temperature is avoided and due to reaction under the supercritical condition, the reaction time is greatly shortened.
Description
Technical field
The present invention relates to a kind of boric acid monoesters and preparation method thereof, be specifically related to a kind of boric acid monoesters as static inhibitor and preparation method thereof.
Background technology
Most polymers material has stronger electrical insulation capability, and they are widely used in many aspects.But the high resistivity of polymer materials in use often easily produces build-up of static charges, these static charges can stop several hours even several days at polymer surfaces, cause magnetism and repulsion, produce sometimes electroshock, electric shock, even spark discharge.At present, the industrial effective means of this type of phenomenon that forfends is to add static inhibitor.
Known according to existing theory, static inhibitor is generally the organic substance with surfactant structure feature.Boracic surfactant is take boric acid as parent, forms the compound of the borate ester of B, O key, is a kind of tensio-active agent of uniqueness.Boric acid structural unit is plane triangle, and each boron atom is with SP
2hydridization is combined with Sauerstoffatom, and now boron is still electron deficiency structure, and the hydroxyl easily and in organic compound reacts, and forms boric acid ester after dehydration.According to the ratio of boric acid and oxy-compound and the difference of type, it can form boric acid monoesters, dibasic acid esters, three esters and four replacement spirane structures.
The method great majority that at present synthetic boric acid ester adopts are direct method, ester-interchange method and solvent method, and for borate surfactant, most study be the cats product of boric acid Glycerol dimer mono fatty acid ester and boric acid diacylglycerol polyoxyethylene mono fatty acid ester.
Dong Bang chemical industrial company of Japan utilizes glycerol and acid reaction to generate glycerol boric acid ester, and then, with the carboxylated fatty acid ester that obtains of lipid acid, the product making is widely used in fiber process, as emulsifying agent, static inhibitor, flexible smooth agent etc.Dong Bang chemical industrial company is water-soluble in order to improve it, and synthetic point of three steps are carried out: glycerol first with boric acid effect, generate glycerol boric acid ester; Then introduce oxyethane, play polyreaction, generate glycerol Soxylat A 25-7; Finally, with lipid acid effect, make product.
Ciba company utilizes stearylamine with Racemic glycidol two (2,3-hydroxypropyl stearylamine) reaction, then generates Spirocyclic product with acid reaction.
Chinese scholar Zhang Xiuling etc. has reported " boron is synthesis of surfactant and performance study " literary composition in the Speciality Petrochemicals of the 5th phase in 1997, and it determines that according to esterification glycerol, lipid acid, boric acid mol ratio are 2:0.9:0.4, has synthesized BOR; And 4 parts of alkyl alcoholamines are added to reactor, and be warmed up to 60 ℃ and add 5 parts of lipid acid, keep 60-70 ℃, reaction l h generates alkylol amide, then adds acid reaction to obtain BONR.Test shows: they have good diffusion permeability, emulsifying property, spumescence.
In the patent CN101029151B of China's bulletin on December 8th, 2012, disclose and adopted the composition of the static inhibitor of boric acid ester, and disclosed its synthesis technique, be: first, by glycerine and the reaction of boric acid decompression esterification, then added lipid acid to synthesize.
Above borate ester mainly with glycerol (glycerine) as polyol, although the wide material sources of glycerine, aspect processing organic synthesis, easily there is intramolecular dehydration polymerization in glycerine, form diester, three ester cpds, greatly reduce the antistatic property of synthetic.Specifically, with regard to Chinese patent CN101029151B, author of the present invention takes the Technology identical with this patent, and the product obtaining cannot reach any antistatic effect; The technique that this patent discloses cannot guarantee the reaction production monoesters of glycerine and boric acid, more cannot guarantee whether follow-up excessive lipid acid reacts with lipid acid, in its structure of title compound formula, there is no hydrophilic radical, and static inhibitor is to utilize hydrophilic radical to absorb airborne water to reach the object of moving electric charge.
Chinese scholar poplar is washed etc. in " the synthetic and character of boric acid alkylol amide ester " (fine chemistry industry, 3(13), 1～27,1996) in, reported and utilized 6501 (being 2:1 type) lauric acid amide of ethanol and boric acid under different ratios, to synthesize boric acid alkylamide ester, belong to boron oxa-ring surface promoting agent through characterizing this product, not only belong to nonionogenic tenside but also there is some characteristic of anion surfactant, there is the capillary performance of reduction and stronger emulsifying power.
Chinese scholar Wang Hui is quick in " ricinoleic alkyl alcohol amide borate synthetic and applied research " (fine chemistry industry, 6(16), 24～27,1999) in utilize Viscotrol C, diethanolamine and boric acid are that raw material has synthesized ricinoleic alkyl alcohol amide borate.This synthesis technique, under residual diethanolamine (not molecular distillation) high temperature, meeting intramolecular dehydration, causes monoester content low; Synthetic product makes an addition in polyethylene take poly mass ratio as 2%, only makes its surface resistivity drop to 10
9Ω, the antistatic property of visible product is very low.
Summary of the invention
The object of the present invention is to provide a kind of boric acid monoesters as static inhibitor, this boric acid monoesters static inhibitor Stability Analysis of Structures, antistatic property are good, and high temperature resistant, resistance to low humidity.
Correspondingly, another object of the present invention is to provide a kind of method of preparing the above-mentioned boric acid monoesters as static inhibitor.
Boric acid monoesters as static inhibitor provided by the invention, its name is called N, N-hydroxyethyl fatty acid amine boric acid monoesters, its structure is shown in logical formula I:
Wherein R is C
12～C
22straight chain or branched saturated or unsaturated alkyl.
The above-mentioned boric acid monoesters as static inhibitor, the preferred C of R in logical formula I
15～C
17straight chain or branched saturated or unsaturated alkyl, most preferred R is C
15or C
17straight chain saturation alkane base.
The method of preparing the above-mentioned boric acid monoesters as static inhibitor, comprises following three steps ("-" before following force value only represents vacuum, and for example " 0.06～-0.1Mpa " expression vacuum tightness is 0.06～0.1Mpa):
The esterification of step a. diethanolamine and lipid acid: the diethanolamine that is 2.2～2.8:1 by mol ratio (seeing structural formula I) drops in reactor with lipid acid, be to carry out esterification under the pressure of-0.06～-0.1Mpa at vacuum condition, the temperature of esterification is 100 ℃～180 ℃, esterification time is 2～8 hours, and simultaneous reactions still stirs with the speed of 400～1000r/min (r/min represent rev/min).Carbonyl displacement has occurred in the esterification reaction process of diethanolamine and lipid acid, and the principle of the silver mirror reaction of carbonyl is followed in reaction, and this esterification obtains mono fatty acid thanomin ester (seeing general formula II) and bis-fatty acid thanomin ester (seeing general formula III) mixture.
The molecular distillation of step b. mono fatty acid thanomin ester: by after the mixture cooling of step a gained, (temperature after cooling is without specific requirement, can be made as 60～120 ℃), be driven in molecular distillation system and carry out three grades of molecular distillations, obtain mono fatty acid thanomin ester; The temperature of first step molecular distillation is 120 ℃～140 ℃, and vacuum pressure is :-0.08～-0.1Mpa; The temperature of second stage molecular distillation is 140 ℃～160 ℃, and vacuum pressure is :-1000～-10pa; The temperature of third stage molecular distillation is 160 ℃～180 ℃, and vacuum pressure is :-50～-0.1pa; In three grades of molecule still-process, blade applicator rotating speed is 50r/min left and right.
The supercritical esterification reaction of step c boric acid: the mono fatty acid thanomin ester of the boric acid that is 2～10:1 by mol ratio and above-mentioned steps b gained is put in overcritical synthesis reactor, esterification 10～50 minutes at the temperature of 10 ℃～40 ℃, obtain N, N-hydroxyethyl fatty acid amine boric acid monoesters; Supercritical reaction medium is carbonic acid gas, and supercritical pressure is: 18～25Mpa.
In above-mentioned steps a, the preferred molar ratio of described diethanolamine and lipid acid is 2.4～2.6:1, and vacuum pressure preferred value is-0.08～-0.1Mpa, and esterification temperature is preferably 140 ℃～160 ℃, esterification time preferred value is 3～5 hours, and reactor stirring velocity recommendation is 600～8000r/min.
Lipid acid described in step a, its alkyl is C
12～C
22straight chain or branched saturated or unsaturated alkyl, preferably C
15～C
17, for example, lipid acid can be stearic acid, palmitinic acid.Above-mentioned lipid acid can derive from the grease of hydrolysis, as the hydrolysate of tallow or Vegetable oil lipoprotein.
Detect through chromatogram, in the mixture that discovery above-mentioned steps a esterification makes, mono fatty acid thanomin ester and bis-fatty acid thanomin ester respectively account for 50%.Meanwhile, detected also and found by chromatogram, after three grades of molecular distillations of above-mentioned steps b, the content of gained mono fatty acid thanomin ester is more than 90%.
The preferred molar ratio of the boric acid described in above-mentioned steps c and mono fatty acid thanomin ester is 6～8:1, and esterification temperature preferred value is 20 ℃～30 ℃, and esterification time is preferably 20～30 minutes, and supercritical pressure is preferably 20～22Mpa.
Upper step c is the esterification of carrying out under super critical condition, and supercutical fluid has nontoxicity and uninflammability, and it is as reaction medium, and not only dissolving power is high, spread coefficient is large, and can effectively control reactive behavior and selectivity.Under super critical condition, accelerated by the homogeneous reaction speed of rate of diffusion control, pressure strengthens the impact of reaction rate constant simultaneously.In addition, the chemical reaction carrying out under super critical condition can also realization response and the coupling separating: in supercutical fluid, the solubleness of solute has obvious variation with the change of its relative molecular mass, temperature and pressure, can utilize this character in time reaction product to be removed from reaction system, to obtain larger transformation efficiency.
The invention has the advantages that: reactant diethanolamine of the present invention is more stable compared with glycerol, be not easy to occur molecule inner injection and close; The present invention makes with diethanolamine the boric acid monoesters that reactant generates, because it is the boric acid structure that contains nitrogen element, therefore be the most stable borate ester; Because this boric acid monoesters contains boric acid hydroxyl and long chain hydrocarbon groups, good as static inhibitor antistatic property again, and can high temperature resistant, resistance to low humidity.In addition, the present invention adopts the technological design of novelty, uses supercritical extraction reactor, reactant is reacted in supercritical co under normal temperature, avoided boric acid ester at high temperature intramolecular dehydration cause variable color, coking and the problem that is difficult to esterification; And under super critical condition, react, the reaction times shortens greatly.
Embodiment
Further illustrate the present invention below by embodiment and application examples.In embodiment, in three grades of molecule still-process, blade applicator rotating speed is 50r/min, and the medium of supercritical esterification reaction is carbonic acid gas.The reaction parameter of each embodiment is in table 1.
Embodiment 1
Boric acid monoesters as static inhibitor is: N, and N-hydroxyethyl Stearyl Amine boric acid monoesters, its structural formula is by N, the R in the logical formula I of N-hydroxyethyl fatty acid amine boric acid monoesters is changed to n-heptadecane base, specifically sees structure formula II.
N, the preparation method of N-hydroxyethyl Stearyl Amine boric acid monoesters is:
Step a: take 50 kilograms of diethanolamine, 56 kilograms of stearic acid (diethanolamine and stearic mol ratio are 2.4::1), put in the reactor of 200 kilograms, at vacuum condition be-carry out esterification under the pressure of 0.1Mpa, esterification temperature is 140 ℃, esterification time is 4 hours, reactor mixing speed is 700r/min, obtains Stearinsaeure thanomin ester and two stearic acid thanomin ester mixture through reaction.
Step b: cool to 100 ℃ after esterification is complete, step a reaction gained mixture is driven in molecular distillation system and carries out three grades of molecular distillations, keeping first step molecular distillation temperature is 130 ℃, and vacuum tightness is-0.1Mpa that blade applicator rotating speed is 50r/min; Second stage molecular distillation temperature is 150 ℃, and vacuum tightness is-100pa that blade applicator rotating speed is 50r/min; Third stage molecular distillation temperature is 170 ℃, and vacuum pressure is-5pa, blade applicator rotating speed 50r/min.After three grades of molecular distillations, obtain the Stearinsaeure thanomin ester that 55.4 kilograms of content are 95%.
Step c: 55.4 kilograms of Stearinsaeure thanomin esters of above-mentioned steps b gained and 54 kilograms of boric acid (mol ratio of boric acid and Stearinsaeure thanomin ester is 5.9:1) are put in 100 liters of overcritical synthesis reactors and carried out esterification.The temperature of synthesis reactor is 25 ℃, and esterification time is 25 minutes; Supercritical reaction medium is carbonic acid gas, and supercritical pressure is 21Mpa, obtains the finished product N after reaction, 98.6 kilograms of N-hydroxyethyl Stearyl Amine boric acid monoesters.
Embodiment 2
Boric acid monoesters as static inhibitor is: N, and N-hydroxyethyl palm acid amide boric acid monoesters, its structural formula is by N, the R in the logical formula I of N-hydroxyethyl fatty acid amine boric acid monoesters is changed to Pentadecane base, specifically sees structure formula III:
N, the preparation method of N-hydroxyethyl palm acid amide boric acid monoesters is:
Step a: take 50 kilograms of diethanolamine and 52 kilograms of palmitinic acids (mol ratio of diethanolamine and palmitinic acid is 2.3:1), put in the reactor of 200 kilograms, carry out esterification under vacuum condition.Vacuum pressure, esterification temperature, esterification time, reactor stirring velocity, in table 1, obtain single palmitinic acid thanomin ester and two palmitinic acid thanomin ester mixture through reaction.
Step b: cool to 100 ℃ after esterification is complete, step a reaction gained mixture is driven into and carries out three grades of molecular distillations in molecular distillation system.In three grades of molecule still-process, blade applicator rotating speed is 50r/min, and after each grade of molecule distillation temperature, vacuum pressure, three grades of molecular distillations, the quality of gained list palmitinic acid thanomin ester and content are in table 1.
Step c: boric acid and step b gained list palmitinic acid thanomin ester are put in 100 liters of overcritical synthesis reactors and carried out esterification.The mol ratio of boric acid quality, boric acid and single palmitinic acid thanomin ester, esterification temperature, esterification time, supercritical pressure are in table 1.Above-mentioned reactant carries out, after supercritical esterification reaction, obtaining the finished product N in carbonic acid gas, 103.8 kilograms of N-hydroxyethyl palm acid amide boric acid monoesters.
Embodiment 3
Boric acid monoesters as static inhibitor is: N, and N-hydroxyethyl 11-methyl dodecane acid amide boric acid monoesters, its structure formula IV is:
N, the preparation method of N-hydroxyethyl 11-methyl dodecane acid amide boric acid monoesters is:
Repeat embodiment 2 according to Parameter Conditions in table 1, but with 11-methyl dodecylic acid replacement palmitinic acid, the quality of diethanolamine and 11-methyl dodecylic acid is respectively 50 kilograms, 46.2 kilograms, the mol ratio of the two is 2.2:1; After step a, b, c, finally obtain N, 68 kilograms of N-hydroxyethyl 11-methyl dodecane acid amide boric acid monoesters.
Embodiment 4
Boric acid monoesters as static inhibitor is: N, and N-hydroxyethyl docosahexenoic acid amine boric acid monoesters, its structural formula (V) is:
N, the preparation method of N-hydroxyethyl docosahexenoic acid amine boric acid monoesters is:
Repeat embodiment 2 according to Parameter Conditions in table 1, but with docosahexenoic acid (DHA) replacement palmitinic acid, the quality of diethanolamine and docosahexenoic acid is respectively 50 kilograms, 55.8 kilograms, the mol ratio of the two is 2.8:1; After step a, b, c, finally obtain N, 110 kilograms of N-hydroxyethyl docosahexenoic acid amine boric acid monoesters.
Table 1
Application examples
Make 15% master batch with preparing gained boric acid monoesters in embodiment 1,15 parts of boronic acid containing monoesters in master batch, 85 parts, PVC material, it is normally extruded with twin screw.Master batch is added in PVC to preparation experiment sample.The sample making is the thick white injection moulding PVC sheet material of 3mm (it adopts the sharp injection moulding machine TR-D03 in Hai Tian molding machine company sky to make), and its size is 10 × 10cm; In laboratory sample, contain static inhibitor 1%, nano-calcium carbonate 5%, proportioning 94% HHP3-PP of China Petrochemical Industry.
Replace the boric acid monoesters of preparing gained in embodiment 1 with Armostat600 (production of Aksu-Nobel company), prepare control sample with above-mentioned same procedure.
Using laboratory sample and control sample as test sample, test its surface resistivity.Testing standard is: " GB1410 solid insulating material volume specific resistance and surface resistivity test method ", " SJ/T10694 electronic product is manufactured anti-static system testing method "; Testing tool is: this measuring technology company limited of HY-779(Tianjin Nico).
Sample test Pretreatment is: represent relative humidity at 50%RH(RH), place 12 hours at 20 ℃.The test result of laboratory sample and control sample surface resistivity (unit is Ω, and Ω represents ohm) is as follows: one, water-fastness test
When water-fastness test, will in 20 ℃ of distilled water, soak 1h through the sample of above-mentioned pre-treatment, test it and soaks the surface resistivity of (washing) front and back in water, test result is in table 2.
Table 2
| ? | Laboratory sample surface resistivity/Ω | Control sample surface resistivity/Ω |
| Before washing | 10 8 | 10 10-10 11 |
| After washing | 10 8-10 9 | 10 10-10 11 |
Two, weather-proof test
While carrying out weather-proof test, first will under 80 ℃, 20%RH condition, place the surface resistivity of testing it for 3 days and placing different time before 3 days and after placing 3 days through the sample of pre-treatment, test result is in table 3.
Table 3
#
| ? | Laboratory sample surface resistivity/Ω | Control sample surface resistivity/Ω |
| Before processing | 10 8 | 10 10-10 11 |
| Process latter 1 day | 10 8-10 9 | 10 10-10 11 |
| Process latter 7 days | 10 8-10 9 | 10 11-10 12 |
| Process latter 14 days | 10 8-10 9 | 10 11 |
| Process latter 30 days | 10 8-10 9 | Nothing |
| Process latter 60 days | 10 9-10 10 | Nothing |
#: the processing in table refers to place 3 days under 80 ℃, 20%RH condition.
Three, normal temperature humidity measurement
Test respectively through the sample of pre-treatment and under 20%RH, 60%RH, 80%RH, 100%RH condition, place the surface resistivity after 24h at 20 ℃, test result is in table 4.
Table 4
| Placement condition | Laboratory sample surface resistivity/Ω | Control sample surface resistivity/Ω |
| Before placement | 10 8 | 10 10-10 11 |
| 20%RH | 10 9-10 10 | 10 11 |
| 60%RH | 10 9 | 10 11 |
| 80%RH | 10 9 | 10 11 |
| 100%RH | 10 9 | 10 10 |
Can find out from the data of table 2～table 4, product of the present invention has outstanding antistatic property, particularly under the condition of low humidity.
Claims (10)
1. as a boric acid monoesters for static inhibitor, its name is called N, N-hydroxyethyl fatty acid amine boric acid monoesters, and its structure is logical formula I:
Wherein R is C
12～C
22straight chain or branched saturated or unsaturated alkyl.
2. a kind of boric acid monoesters as static inhibitor according to claim 1, is characterized in that: in logical formula I, R is C
15～C
17straight chain or branched saturated or unsaturated alkyl.
3. a kind of boric acid monoesters as static inhibitor according to claim 1, is characterized in that: in logical formula I, R is C
15or C
17straight chain saturation alkane base.
4. prepare described in claim 1 method as the boric acid monoesters of static inhibitor, it is characterized in that: the method for preparing this boric acid monoesters comprises the following steps:
A) esterification of diethanolamine and lipid acid: the diethanolamine that is 2.2～2.8:1 by mol ratio and lipid acid drop in reactor, be to carry out esterification under the pressure of-0.06～-0.1Mpa at vacuum condition, the temperature of esterification is 100 ℃～180 ℃, esterification time is 2～8 hours, simultaneous reactions still stirs with the speed of 400～1000 revs/min, and esterification obtains mono fatty acid thanomin ester and bis-fatty acid thanomin ester mixture;
B) molecular distillation of mono fatty acid thanomin ester: by after the mixture cooling of step a gained, be driven in molecular distillation system and carry out three grades of molecular distillations, obtain mono fatty acid thanomin ester; The temperature of first step molecular distillation is 120 ℃～140 ℃, and vacuum pressure is :-0.08～-0.1Mpa; The temperature of second stage molecular distillation is 140 ℃～160 ℃, and vacuum pressure is :-1000～-10pa; The temperature of third stage molecular distillation is 160 ℃～180 ℃, and vacuum pressure is :-50～-0.1pa; In three grades of molecule still-process, blade applicator rotating speed is 50 revs/min;
C) supercritical esterification of boric acid reaction: the mono fatty acid thanomin ester of the boric acid that is 2～10:1 by mol ratio and above-mentioned steps b gained is put in overcritical synthesis reactor, esterification 10～50 minutes at the temperature of 10 ℃～40 ℃, obtain N, N-hydroxyethyl fatty acid amine boric acid monoesters; Supercritical reaction medium is carbonic acid gas, and supercritical pressure is: 18～25Mpa.
5. preparation according to claim 4 is as the method for the boric acid monoesters of static inhibitor, it is characterized in that: the mol ratio of diethanolamine described in step a and lipid acid is 2.4～2.6:1, vacuum pressure is-0.08～-0.1Mpa, and reactor stirring velocity is 600～8000 revs/min.
6. preparation according to claim 4, as the method for the boric acid monoesters of static inhibitor, is characterized in that: the esterification temperature described in step a is 140 ℃～160 ℃, and esterification time is 3～5 hours.
7. preparation according to claim 4, as the method for the boric acid monoesters of static inhibitor, is characterized in that: the mol ratio of the boric acid described in step c and mono fatty acid thanomin ester is 6～8:1.
8. preparation according to claim 4, as the method for the boric acid monoesters of static inhibitor, is characterized in that: the esterification temperature described in step c is 20 ℃～30 ℃.
9. preparation according to claim 4, as the method for the boric acid monoesters of static inhibitor, is characterized in that: the esterification time described in step c is 20～30 minutes.
10. preparation according to claim 4, as the method for the boric acid monoesters of static inhibitor, is characterized in that: the supercritical pressure described in step c is 20～22Mpa.
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| CN105949054A (en) * | 2016-05-25 | 2016-09-21 | 张秀勇 | Method for synthesizing and purifying monostearyl glycerin lactate |
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| CN107353220A (en) * | 2017-08-09 | 2017-11-17 | 赞宇科技集团股份有限公司 | A kind of aliphatic acid is the technique and device of raw material continuous production fatty acid alkanol amides |
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| CN105949054A (en) * | 2016-05-25 | 2016-09-21 | 张秀勇 | Method for synthesizing and purifying monostearyl glycerin lactate |
| CN105949055A (en) * | 2016-05-25 | 2016-09-21 | 张秀勇 | Method for synthesizing and purifying glycerin lactate |
| CN107353220A (en) * | 2017-08-09 | 2017-11-17 | 赞宇科技集团股份有限公司 | A kind of aliphatic acid is the technique and device of raw material continuous production fatty acid alkanol amides |
| CN107353220B (en) * | 2017-08-09 | 2023-05-16 | 赞宇科技集团股份有限公司 | Process and device for continuously producing fatty acid alkanolamide by taking fatty acid as raw material |
| CN110950900A (en) * | 2019-12-18 | 2020-04-03 | 烟台融晟新材料有限公司 | Borate antistatic agent and preparation method and application thereof |
| CN110950900B (en) * | 2019-12-18 | 2022-05-13 | 烟台融晟新材料有限公司 | Boric acid ester antistatic agent and preparation method and application thereof |
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