CN102000527A - Modified boric acid ester interface activating agent and preparation method thereof - Google Patents
Modified boric acid ester interface activating agent and preparation method thereof Download PDFInfo
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- CN102000527A CN102000527A CN2010102976566A CN201010297656A CN102000527A CN 102000527 A CN102000527 A CN 102000527A CN 2010102976566 A CN2010102976566 A CN 2010102976566A CN 201010297656 A CN201010297656 A CN 201010297656A CN 102000527 A CN102000527 A CN 102000527A
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Abstract
The invention discloses a modified boric acid ester interface activating agent. An inorganic boron atom in a modified boric acid ester molecule contains two polar functional groups which can participate grafting reaction with inorganic materials in the water with the temperature of 50-70 DEG C to form a chain structure, meanwhile, the molecule also contains two functional groups with long molecule chains which can be crosslinked with the molecule of a high molecular material. The invention also discloses a preparation method of the modified boric acid ester interface activating agent, which can increase compatibility of various kinds of polar and non-polar materials in the system, can increase the dispersion degree of various kinds of materials and enhance the uniform degree of the crosslinking.
Description
Technical field
The present invention relates to a kind of interfacial agent, especially a kind of modification borate that is used for macromolecular material as interfacial agent and preparation method thereof.
Background technology
In many macromolecular materials such as rubber, the processing of plastic process, relate to the different very big material system of a plurality of surface energy differentials, like this in mixing process, the compatibility of various types of materials is bad, have influence on dispersive property, and then the mechanical property of material and the quality of product impacted, by using interfacial agent, can make the compatibility of carbon black, white carbon or increase of other inorganic material and macromolecular material, make mixing process simple, even, increase the crosslinked uniformity, and then improve the quality of products.The borate surfactant is a class special surfactant, and the surface-active excellence has the irreplaceable characteristic of numerous conventional hc-surfactants, as antistatic, anti-wear lubricating, fire-retardant etc.People have carried out considerable research to the synthetic and performance of borate.Hu Xiaolan and Liang Guozheng (Hu Xiaolan, Liang Guozheng; Synthetic and the sign [J] of boric acid ester coupler; The functional polymer journal; 2003 02 phases) by the molecular structure design, synthesized the boric acid ester coupler of coordination structure in a kind of nitrogen-boron, solved the problem of borate hydrolytic stability difference, contain amino, butoxy isoreactivity group in the molecular structure simultaneously.With FFIR borate has been carried out structural characterization, the influence to borate yield and reaction rate such as raw material proportioning, synthesis technique has been discussed, and has been determined by experiment prescription and technology.Surface treatment effect to the physical property of borate, dissolubility, the timely aluminium borate whisker of hydrolytic stability characterizes.Lin Weina (Lin Weina; A kind of synthetic and performance study [D] of copolymerized macromolecule borate surfactant; Institutes Of Technology Of Nanjing; 2007) synthesized a kind of polymerizable borate surfactant B ES, and synthesized the copolymer p (BES-AM) of BES and acrylamide by free radical copolymerization.(Zhai Yujia such as Zhai Yujia; Wang Haiying; Lin Weina; Li Bindong; Lv Chunxu; Synthetic and the performance [J] of different chain length polymerizable borate surfactant; Fine chemistry industry; 2007 06 phases) be primary raw material with boric acid, N hydroxymethyl acrylamide, alkyl diethanol amine etc., having synthesized chain length is eight alkyl (octylborate ester, abbreviation OBE), dodecyl (lauryl borate ester, abbreviate LBE as) and cetyl (hexadecyl borate ester, abbreviate HBE as) polymerizable borate surfactant, studied of the influence of factors such as reaction dissolvent, polymerization inhibitor, reaction temperature, product has been carried out structural characterization by IR and 1HNMR to yield.The optimum condition that obtains is 60 ℃ of solvent benzol 50mL, polymerization inhibitor phenthazine mass fraction 0.8%, reaction temperature, and the LBE yield can reach 93.3%, and OBE and HBE yield can reach 95.7% and 89.6% respectively; And investigated the surface tension and the emulsifiability of 3 kinds of borates, and in the time of 25 ℃, the CMC of OBE is 5.2mmol/L, γ CMC is 31.8mN/m; The CMC0.069mmol/L of LBE, γ CMC are 29.5mN/m; The CMC of HBE is 0.087mmol/L, and γ CMC is 28.6mN/m.CN200810162126.3 discloses a kind of synthetic method of borate, it with acidic ion liquid as solvent and catalyst, inorganic boric acid of catalysis and pure esterification, obtain borate, wherein, the optional monobasic of alcohol, dibasic aliphatic alcohol or monobasic cycloalkyl alcohol, prepared borate can be equal trialkylboron acid esters or mixed alkyl and cycloalkyl borate, and used acidic ion liquid adopts glyoxaline ion liquid, pyridines ionic liquid or ion liquid of quaternaries.
Summary of the invention
At the deficiencies in the prior art, technical problem to be solved by this invention is, a kind of modification borate interfacial agent and preparation method thereof is provided, make the modification borate that makes can be used as interfacial agent and be used for macromolecular material, significantly improve the decentralization of inorganic material in macromolecular material and the crosslinked uniformity.
For solving the problems of the technologies described above, the technical solution used in the present invention is, a kind of modification borate interfacial agent, and its molecular structural formula is:
In the formula: R
1A kind of in ethyl, methylol or the ethoxy;
R
2Be C
12-18Fat alcohol radical, C
12-18Fatty acid-based, PEG-400 is basic, PEG-1000 is basic or a kind of in basic of PEG-2000; Preferred C
16-18Fat alcohol radical, C
16-18A kind of during fatty acid-based or PEG-1000 is basic;
R
3Be C
12-18A kind of in kiber alkyl amine, monoethanolamine, diethanol amine or the triethanolamine.
Contain two polar functional groups on the inorganic boron atom in this modification borate molecule, can be in 50-70 ℃ of water and inorganic material (CaCO
3, Al (OH)
3, potter's clay or white carbon etc.) carry out graft reaction and form chain structure, the function functional group of also containing two long strands simultaneously in its molecule, can be with macromolecular material (plastics, rubber, polymer etc.) molecule crosslinked, the compatibility of all kinds of polarity and non-polar material in the increase system, can increase the decentralization of all kinds of polar materials in non-polar material, and strengthen the crosslinked uniformity.
The preparation method of above-mentioned modification borate interfacial agent, it comprises following content:
A. will set the polyalcohol (such as glycerine) of molal quantity puts in the stainless steel cauldron, be warming up to 60～100 ℃, drop into and the equimolar boric acid of polyalcohol, sealed reactor then, being warming up to 120～160 ℃ under the stirring condition reacts, by oil water separator little molecule by product is removed, reacted and finish reaction after 3-5 hour temperature in the kettle rises to 180 ℃;
B. add and the equimolar C of polyalcohol then
12-18Fatty alcohol or aliphatic acid or selected PEG, 100～150 rev/mins of stirrings, reaction is 3-5 hour under 300～500 millimetres of mercury condition of negative pressure, and by product extract out is separated, and is warming up to 220 ℃ in the still and finishes reaction;
C. drop into C then with the polyalcohol equimolar amounts
12-18Kiber alkyl amine or hydramine were kept 160～180 ℃ of temperature in the kettle two hours, and reaction finishes; Above-mentioned all processes are all carried out under sealing, stirring condition, and solids removed by filtration impurity obtains modification borate interfacial agent.
Modification borate interfacial agent of the present invention can increase the decentralization of all kinds of polar materials in non-polar material, and strengthens the crosslinked uniformity.Preparation method's technology of modification borate interfacial agent provided by the invention is simple, can reach higher yield, reduces environmental pollution, and the reaction condition gentleness, and easy and simple to handle, product is easily separated, and ionic liquid is reusable, has the scale application prospect.
The specific embodiment
The present invention is described in more detail below in conjunction with embodiment.
Agents useful for same is industrial pure material among following each embodiment, buys from market; Described R
1A kind of in ethyl, methylol or the ethoxy; R
2Be C
12-18Fat alcohol radical, C
12-18Fatty acid-based, PEG-400 is basic, PEG-1000 is basic or a kind of in basic of PEG-2000; R
3Be C
12-18A kind of in kiber alkyl amine, monoethanolamine, diethanol amine or the triethanolamine.
Embodiment 1
A kind of modification borate interfacial agent, it is made by the following step:
At first will set the glycerine of molal quantity puts in the stainless steel cauldron, be warming up to 100 ℃, drop into and the equimolar boric acid of glycerine, sealed reactor then, being warming up to 160 ℃ under the stirring condition reacts, by oil water separator little molecule by product is removed, reacted and finish reaction after 3-5 hour temperature in the kettle rises to 180 ℃.
Add and the equimolar PEG-1000 of glycerine then, 150 rev/mins of stirrings, reaction is 3 hours under 300～500 millimetres of mercury condition of negative pressure, by product is extracted out separated, and is warming up to 220 ℃ in the still and finishes reaction.And then the diethanol amine of input and glycerine equimolar amounts, kept 180 ℃ of temperature in the kettle two hours, reaction finishes; Above-mentioned all processes are all carried out under sealing, stirring condition, and solids removed by filtration impurity obtains modification borate interfacial agent, and its molecular structural formula is:
Wherein: R
1Be methylol, R
2Be PEG-1000 base, R
3Be diethanol amine.
Embodiment 2
A kind of modification borate interfacial agent, it is made by the following step:
At first will set the glycerine of molal quantity puts in the stainless steel cauldron, be warming up to 60 ℃, drop into and the equimolar boric acid of glycerine, sealed reactor then, being warming up to 120 ℃ under the stirring condition reacts, by oil water separator little molecule by product is removed, reacted and finish reaction after 3-5 hour temperature in the kettle rises to 180 ℃.
Add and the equimolar C of glycerine then
18Fatty alcohol, 100 rev/mins of stirrings, reaction is 5 hours under 300～500 millimetres of mercury condition of negative pressure, by product is extracted out separated, and is warming up to 220 ℃ in the still and finishes reaction.And then the monoethanolamine of input and glycerine equimolar amounts, kept 160 ℃ of temperature in the kettle two hours, reaction finishes; Above-mentioned all processes are all carried out under sealing, stirring condition, and solids removed by filtration impurity obtains modification borate interfacial agent, and its molecular structural formula is:
Wherein: R
1Be methylol, R
2Be C
18The fat alcohol radical, R
3Be monoethanolamine.
Embodiment 3
A kind of modification borate interfacial agent, it is made by the following step:
At first will set the glycerine of molal quantity puts in the stainless steel cauldron, be warming up to 80 ℃, drop into and the equimolar boric acid of glycerine, sealed reactor then, being warming up to 140 ℃ under the stirring condition reacts, by oil water separator little molecule by product is removed, reacted and finish reaction after 3-5 hour temperature in the kettle rises to 180 ℃.
Add and the equimolar C of glycerine then
18Aliphatic acid, 120 rev/mins of stirrings, reaction is 4 hours under 300～500 millimetres of mercury condition of negative pressure, by product is extracted out separated, and is warming up to 220 ℃ in the still and finishes reaction.And then the C of input and glycerine equimolar amounts
18Kiber alkyl amine was kept 170 ℃ of temperature in the kettle two hours, and reaction finishes; Above-mentioned all processes are all carried out under sealing, stirring condition, and solids removed by filtration impurity obtains modification borate interfacial agent, and its molecular structural formula is:
Wherein: R
1Be methylol, R
2Be C
18Fatty acid-based, R
3Be C
18Kiber alkyl amine.
Claims (3)
1. modification borate interfacial agent, its molecular structural formula is:
In the formula: R
1A kind of in ethyl, methylol or the ethoxy;
R
2Be C
12-18Fat alcohol radical, C
12-18Fatty acid-based, PEG-400 is basic, PEG-1000 is basic or a kind of in basic of PEG-2000;
R
3Be C
12-18A kind of in kiber alkyl amine, monoethanolamine, diethanol amine or the triethanolamine.
2. modification borate interfacial agent according to claim 1 is characterized in that: described R
2Group is C
16-18Fat alcohol radical, C
16-18A kind of during fatty acid-based or PEG-1000 is basic.
3. the preparation method of the described modification borate of claim 1 interfacial agent, it comprises following content:
A. will set the polyalcohol of molal quantity puts in the stainless steel cauldron, be warming up to 60～100 ℃, drop into and the equimolar boric acid of polyalcohol, sealed reactor then, being warming up to 120～160 ℃ under the stirring condition reacts, by oil water separator little molecule by product is removed, reacted and finish reaction after 3-5 hour temperature in the kettle rises to 180 ℃;
B. add and the equimolar C of polyalcohol then
12-18Fatty alcohol or aliphatic acid or selected PEG, 100～150 rev/mins of stirrings, reaction is 3-5 hour under 300～500 millimetres of mercury condition of negative pressure, and by product extract out is separated, and is warming up to 220 ℃ in the still and finishes reaction;
C. drop into C then with the polyalcohol equimolar amounts
12-18Kiber alkyl amine or hydramine were kept 160～180 ℃ of temperature in the kettle two hours, and reaction finishes; Above-mentioned all processes are all carried out under sealing, stirring condition, and solids removed by filtration impurity obtains modification borate interfacial agent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084087A (en) * | 2014-06-27 | 2014-10-08 | 江南大学 | Boron-nitrogen-containing polyethylene glycol fatty acid ester surfactant |
| CN104448390A (en) * | 2014-12-24 | 2015-03-25 | 青岛四维化工有限公司 | Green tire functional master batch and preparation method thereof |
| 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 |
| CN111068577A (en) * | 2019-12-18 | 2020-04-28 | 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 |
| CN111269252A (en) * | 2020-03-26 | 2020-06-12 | 辽宁精华新材料股份有限公司 | Novel boric acid ester and preparation method thereof |
| CN111410711A (en) * | 2015-08-20 | 2020-07-14 | 巴黎市工业物理化学学校 | Polymer composition comprising a crosslinked polymer having borate functional groups capable of undergoing an exchange reaction, preparation method and use |
| CN111974305A (en) * | 2020-08-31 | 2020-11-24 | 郑祥康 | Surfactant, preparation method and application thereof |
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| US4073766A (en) * | 1976-12-15 | 1978-02-14 | Dart Industries, Inc. | Organic borate coupling agents |
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| CN1174841A (en) * | 1996-08-28 | 1998-03-04 | 王树熹 | Organic boric acid ester coupling agent |
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| US4073766A (en) * | 1976-12-15 | 1978-02-14 | Dart Industries, Inc. | Organic borate coupling agents |
| CN85103025A (en) * | 1985-04-19 | 1986-10-15 | 南京大学 | Process for making polyvinyl chloride composition with powdered cinder from coal as filler |
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| 陈登龙等: "螯合配位型硼酸酯偶联剂的制备及应用研究", 《塑料助剂》, no. 6, 31 December 2004 (2004-12-31), pages 19 - 22 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084087A (en) * | 2014-06-27 | 2014-10-08 | 江南大学 | Boron-nitrogen-containing polyethylene glycol fatty acid ester surfactant |
| CN104084087B (en) * | 2014-06-27 | 2017-01-25 | 江南大学 | Boron-nitrogen-containing polyethylene glycol fatty acid ester surfactant |
| CN104448390A (en) * | 2014-12-24 | 2015-03-25 | 青岛四维化工有限公司 | Green tire functional master batch and preparation method thereof |
| CN111410711A (en) * | 2015-08-20 | 2020-07-14 | 巴黎市工业物理化学学校 | Polymer composition comprising a crosslinked polymer having borate functional groups capable of undergoing an exchange reaction, preparation method and use |
| CN111410711B (en) * | 2015-08-20 | 2022-07-22 | 巴黎市工业物理化学学校 | Polymer composition comprising a crosslinked polymer having borate functional groups capable of undergoing an exchange reaction, preparation method and use |
| 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 |
| CN111068577A (en) * | 2019-12-18 | 2020-04-28 | 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 |
| 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 |
| 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 |
| CN111269252A (en) * | 2020-03-26 | 2020-06-12 | 辽宁精华新材料股份有限公司 | Novel boric acid ester and preparation method thereof |
| CN111974305A (en) * | 2020-08-31 | 2020-11-24 | 郑祥康 | Surfactant, preparation method and application thereof |
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Application publication date: 20110406 |