CN105028398A - Application and preparation method for polyhydroxyalkanoate grafted organic polyamine dispersant - Google Patents
Application and preparation method for polyhydroxyalkanoate grafted organic polyamine dispersant Download PDFInfo
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Abstract
The invention relates to a preparation method for a polyhydroxyalkanoate grafted organic polyamine dispersant and application thereof. The dispersant is applied in a pesticide oil suspension. The dispersant has a chemical formula as described in the specification. In the chemical formula, P is an organic polyamine main chain; T is a residue O-R-CO or lactone of hydroxyl fatty acid; X is a modifier or an end capping agent which is a straight-chain or branched-chain and saturated or unsaturated residue with a fatty acid of C1 to C22; T and P are connected by an amido bond; X and T are connected by an ester group; m is an integer of 1 to 100; and n may be 0 or an integer of 1 to 100. The objective of the invention is to provide the preparation method for agricultural polyhydroxyalkanoate grafted organic amine dispersants; the dispersants have amino anchoring groups and solvated polyester chains; and with a special chemical structure, the dispersants have good dispersing and stabilizing effects in an environment-friendly oil suspension.
Description
Technical field
The invention discloses a kind of preparation and application thereof of polyhydroxyalkanoate grafting organic polyamine class agricultural dispersants, be applied to in vegetable oil, vegetable oil methyl ester or the mineral oil environmental protection type agricultural chemical suspending agent that is continuous phase, grinding efficiency can be improved, reduce preparation granules particle diameter, improve preparation stability, particularly in preparation high concentration oil-suspending agent, there is well dispersion viscosity reduction effect.
Background technology
Environmental protection type agricultural chemical formulation suspending agent, aqueous emulsion, microemulsion etc. receive increasing concern.For the agricultural chemicals of some facile hydrolysis in water, make oil-suspending agent, its formulation stabilizer agent can be improved.For the weed killer herbicide that some lipophilicity is still insoluble to by force oil phase, making oil-suspending agent can improve drug effect.For the agricultural chemicals that some permeability is poor, make oil-suspending agent and can improve preparation infiltration wetability, thus improve drug effect.For now, oil-suspending agent without ripe dispersant, formulation content is low, preparation stable storage is poor, the easy problem such as flocculation and delamination.Therefore very there is strategic importance according to the mechanical development new oil suspension agent and disperser of agricultural chemicals.
EP0127325B1 discloses the preparation that polyethylene imine based fatty acid end-blocking gathers ricinoleate ester, solves the scattering problem of thermohardening lacquer in non-polar oil.EP0690745B1 discloses the polyethylene imine based coating dispersant of a class graft type, skeletal chain is hydrophilic polymine, the polyester chain residue of grafted chain to be chain terminal be carboxylic acid, such as lauric acid causes caprolactone ring-opening polymerisation, end carboxyl and polyhydroxyalkanoate esterification, amidation process afterwards between polyester chain and polymine, such dispersant is suitable for the dispersion of high content of solid in non-polar organic solvent.US6787600B1 openly reports the preparation method of a kind of coating, printing-ink dispersant, hydrophilic back bone chain is polymine or PPI structure, graft side chain is the polyester chain of two kinds of different structures, polyester chain is a ring-opening polymerisation for the cyclic lactone (as caprolactone) that long-chain fatty acid causes, and another kind of polyester chain is obtained from polycondensation by hydroxy fatty acid (12-hydroxy stearic acid, castor oil acid).EP1999185B1 discloses the new synthetic method of a kind of polyethylene imine based pigment dispersants.The ring-opening polymerisation that polymine causes cyclic lactone as macromole evocating agent (primary amine, secondary amine) obtains graft copolymer, further with end-capping reagent condensation (the saturated or unsaturated fatty acid of long-chain, hydroxy fatty acid, poly-hydroxy stearic acid ester etc.).The people such as Sun Shuzhen report a kind of preparation method of organic solvent system pigment hyper-dispersant.Main chain is polymine, side chain be poly-(10-hydroxydecanoic acid) polyester chain (Chinese coating. the preparation of Polyaziridine Super Dispersant with Hydroxyl-carboxylic Ester Graft).The people such as Wang Yong base with 12-hydroxy stearic acid and polyethylene polyamine for polyester polyamine type hyper-dispersant prepared by raw material, but do not provide its embody rule (printing and dyeing assistant, 2011,28 (1), 18-20).
Summary of the invention
The present invention is directed to above-mentioned defect, object is the preparation method providing a kind of polyhydroxyalkanoate grafting organic amine agricultural dispersants.Such dispersant has amido grappling base and solvation polyester chain, and its special chemical constitution makes to have well dispersion and stabilization in environment-friendly type oil-suspending agent.
The technical solution used in the present invention is for this reason: application of dispersant of the present invention floats among agent in pesticide oil suspension;
Described dispersant chemical formula is:
；
Wherein P is organic polyamine class main chain, and T is residue O-R-CO or the lactone of hydroxy fatty acid, and R is the alkyl of the C2-C18 of optional side chain or straight chain;
X is modifier or end-capping reagent, for straight chain or side chain, the saturated or undersaturated residue with fatty acid from C1-C22;
Connect with amido link between T and P, connect with ester group between X and T, m is the integer of 1-100, and n can be the integer of 0 or 1-100.
Described dispersant is used for in vegetable oil, vegetable oil methyl ester, the mineral wet goods environmental protection type agricultural chemical oil-suspending agent that is continuous phase.
Described P is dimethylaminopropylamine, diethylenetriamine, TEPA or polymine.
Described T derives from caprolactone or castor oil acid, hydroxylauric acid or 12-hydroxy stearic acid.
Described dispersant has following different version:
。
A preparation method for polyhydroxyalkanoate grafting organic polyamine dispersant, is characterized in that, carry out according to the following steps:
1) hydroxy fatty acid is under the effect of catalyzer, and intermolecular polycondensation reaction occurs, and obtains the poly-hydroxy stearic acid ester of fatty acid end-blocking with the further esterification of end-capping reagent;
2) polyhydroxyalkanoate and organic amine generation amidation process obtain graft copolymer.
In step 1) under nitrogen protection, reaction temperature is 120-200 DEG C; Step 2) middle nitrogen protection, reaction temperature is 120-190 DEG C.
Described catalyzer is acidic catalyst, the one in preferred zinc acetate, pyrovinic acid, p-methyl benzenesulfonic acid, zirconium naphthenate, dibutyl tin dilaurate, stannous chloride, tin caprylate, metatitanic acid orthocarbonate and butyl titanate.
Described polyhydroxyalkanoate and organic amine weight ratio are between 1:10-10:1.
Amido link of the present invention can be a) have uncle's nitrogen-atoms, b) has secondary nitrogen-atoms or c) ionic bond
。
The residue of end-capping reagent X comes from carboxylic acid or carboxylic ester derivative, itself and the condensation dehydration of polyhydroxyalkanoate terminal hydroxyl or ester exchange dealcoholization.End-capping reagent is straight or branched, the saturated or undersaturated alkanoic acid had from C1-C22, as acetic acid, sad, capric acid, undecanoic acid, lauric acid and stearic acid etc.Also can be that undersaturated fatty acid is as tall oil acid, castor oil acid, linolenic acid etc.Fatty acid ester can be methyl oleate, methyl stearate, also can be above-mentioned saturated or undersaturated C1-C10 fatty acid ester.
T is residue or the lactone open loop structure of hydroxy fatty acid, derives from caprolactone, valerolactone or castor oil acid, hydroxylauric acid and 12-hydroxy stearic acid etc., preferred 12-hydroxy stearic acid.Industrial 12-hydroxy stearic acid is obtained by castor oil acid Hydrogenation, containing 15wt% stearic acid impurity.Therefore can be end-capping reagent or modifier without the need to adding the fatty acid of stearic acid or other type.
The present invention 1) acid number that has of condensation reaction products between 10-70mgKOH/g, between molecular weight 1000-4000.Step 2) middle nitrogen protection, reaction temperature is 140-180 DEG C.Poly-hydroxy stearic acid ester and organic polyamine mass ratio are between 1:10-10:1.
The preferred acid number of described graft copolymer is between 0-30mgKOH/g.
Advantage of the present invention is: the reaction that the invention discloses end carboxyl polyhydroxyalkanoate and organic polyamine, and being formed similar is abutment with amide groups, take amido as anchorage, and end carboxyl gathers the hyper-dispersant that hydroxy stearic acid ester is solvent chain.Anchoring group is by the interaction of ionic bond, covalent bond, hydrogen bond and Van der Waals force etc., solid particles surface is adsorbed in the form of single-point absorption or multi-point-anchoring, end carboxyl gathers hydroxy stearic acid ester solvent chain and is stretched in dispersion medium, by space steric effect, stably dispersing effect is played to particle, have unique dispersion effect to non-aqueous dispersion system.Following have potential using value in the oil-suspending agent taking vegetable oil as dispersion medium.
The present invention be directed to the mechanism of action that pesticide oil suspension floats agent dispersant, prepare poly-12-hydroxy stearic acid ester grafting organic polyamine class dispersant.Polyhydroxyalkanoate and organic amine (TEPA, polymine etc.) can obtain " comb-type structure " or AB type high molecular surfactant by amido link or ion sat linkage.Organic amine is anchoring group, in the mode of single-point or multiple spot grappling, is adsorbed on the surface of agricultural chemicals tightly, prevents dispersant at the desorption of the surface of solids.Poly-hydroxyl hard ester ester is similar to the structure such as vegetable oil or vegetable oil methyl ester, can dissolve each other, play sterically hindered effect, prevent the gathering between solid particle, thus ensure the stable dispersion of solid particle in dispersion medium, such products application floats in agent in pesticide oil suspension, effectively can improve grinding efficiency, reduce grain diameter, improve oil-suspending agent concentration.
Embodiment
Embodiment 1
12-hydroxy stearic acid, dimethylbenzene, catalyzer butyl titanate, polymine, step is as follows:
(1) 210g12-hydroxy stearic acid is added in 250ml there-necked flask, heats 100 DEG C and melts material, pass into nitrogen, add 21g dimethylbenzene and 0.3g catalyzer butyl titanate, is heated to 160-180 DEG C of reaction 16h, water removing reaction generated with water knockout drum.Nitrogen decompression is except removal xylene, and cooling, measures acid number and be about 35mgKOH/g.Molecular weight is about 1600-1800.
(2) 50g polymine (EPOMINSP-012, molecular weight 1200), 20g dimethylbenzene, under nitrogen protection, is heated to boiling, removes moisture with water knockout drum.Add the poly-hydroxy stearic acid ester 66.6g that step 1 is synthesized, 150 DEG C of reaction 3h, the water generated except dereaction with water knockout drum, obtain brown viscous material, be dissolved in hydrocarbon organic solvent, acid number is about 5.0mgKOH/g.Product labelling is A.
Embodiment 2
12-hydroxy stearic acid, dimethylbenzene, catalyzer stannous chloride, polymine, step is as follows:
(1) 100g12-hydroxy stearic acid is added in 100ml there-necked flask, heats 100 DEG C and melts material, pass into nitrogen, add 30g dimethylbenzene and 3.5g catalyzer stannous chloride, be heated to 180 DEG C of reactions, treat that acid number is about 35mgKOH/g, stop reaction.Nitrogen purges except removal xylene.
(2) 11g polymine (ippon SP200, molecular weight 10000) and above-mentioned 55g polyester add in reactor, add 10g dimethylbenzene, pass into nitrogen, and 130 DEG C-160 DEG C reaction 3-6 hour, obtain brown viscous liquid, acid number is about 10-15mgKOH/g.Product labelling is B.
Embodiment 3
12-hydroxy stearic acid, toluene, catalyzer pyrovinic acid, dimethyl propylamine, step is as follows:
(1) 958.3g12-hydroxy stearic acid (containing 15wt% stearic acid), 170.4g toluene and 1.9g pyrovinic acid add in 1L reactor, pass into nitrogen protection; 160-180 DEG C of reaction, when acid number is reduced to 35mgKOH/g, stops reaction; nitrogen purges removing toluene, obtains yellow viscous liquid.
(2) above-mentioned polyester 160g, 20.4g3-DIMAPA adds in reactor, adds 30ml toluene, passes into nitrogen protection, and 130-160 DEG C of reaction, treats that acid number is reduced to 5mgKOH/g, stops reaction, and decompression nitrogen purges removing toluene.Product labelling is C.
Embodiment 4
12-hydroxy stearic acid, dimethylbenzene, catalyzer p-methyl benzenesulfonic acid, step is as follows:
(1) 400g12-hydroxy stearic acid (containing 15wt% stearic acid); 85g dimethylbenzene and 1.9g p-methyl benzenesulfonic acid add in reactor; pass into nitrogen protection; 160-180 DEG C of reaction; when acid number is reduced to about 35mgKOH/g; stop reaction, nitrogen purges except removal xylene, obtains yellow viscous liquid.
(2) above-mentioned 100g polyester and 16g TEPA add in reactor, add 30ml dimethylbenzene, pass into nitrogen protection, and 130-160 DEG C of reaction, treats that acid number is reduced to 5mgKOH/g, stop reaction, and decompression nitrogen purges except removal xylene, obtains brown viscous liquid.Product labelling is D.
Application example 54% emamectin benzoate 16% indoxacarb oil-suspending agent
Project conventional emulsification dispersion composite 1 composite 2 composite 3
The former medicine of emamectin benzoate (76%) %5.265.265.265.26
The former medicine of indoxacarb (95%) %16.816.816.816.8
Emulsifier O F3468%18131313
Dispersant A %2
Dispersant B %2
Import dispersant %2
Organobentonite %0.40.40.40.4
Methyl oleate % supplies 100 and supplies 100 and supply 100 and supply 100
Emulsifying dispersivity is good excellent good
Stable storage storage hot in nature is defective qualified qualified
Normal storage emamectin benzoate suspensibility % >=90989796
Heat storage emamectin benzoate suspensibility % >=969590
Normal storage indoxacarb suspensibility % >=85979895
Heat storage indoxacarb suspensibility % >=969693
When being used alone use emulsifier, 4% emamectin benzoate 16% indoxacarb OD heat storage stability is poor, and easy livering, cannot measure suspensibility; Use pluronic polymer collocation emulsifier, auxiliary dosage reduces, and emulsifying dispersivity is good, excellent storage stability; Performance is suitable with external import dispersing agent performance, and has part index number to exceed.
Application example 610% nicosulfuron 10% atrazine 10% makes its grand oil-suspending agent
Project conventional emulsification dispersion composite 1 composite 2 composite 3
The former medicine of nicosulfuron (95%) %10.510.510.510.05
The former medicine of atrazine (97%) %10.310.310.310.3
Make its grand former medicine (95%) 10.510.510.510.5
Emulsifier O F3468MP%16121212
Dispersant A %2
Dispersing agent C %2
Import dispersant %2
Organobentonite %0.30.30.30.3
Methyl oleate % supplies 100 and supplies 100 and supply 100 and supply 100
Emulsifying dispersivity is good excellent good
Bin stability is defective qualified qualified
Normal storage nicosulfuron suspensibility % >=90989692
Heat storage nicosulfuron suspensibility % >=969385
Normal storage atrazine suspensibility % >=85979890
Heat storage atrazine suspensibility % >=959585
Normal storage makes its grand suspensibility % >=90969394
Heat storage makes its grand suspensibility % >=939090
When being used alone use emulsifier, 10% nicosulfuron 10% atrazine 10% makes its grand oil-suspending agent heat storage stability poor, defective; Use pluronic polymer collocation emulsifier, auxiliary dosage reduces, and emulsifying dispersivity is good, excellent storage stability; External import dispersant is compared, and normal temperature storage and heat storage suspensibility are higher than the latter.
Application example 74% nicosulfuron 28% atrazine OD
Project conventional emulsification dispersion composite 1 composite 2 composite 3
The former medicine of nicosulfuron (95%) %4.24.24.24.2
The former medicine of atrazine (97%) %28.928.928.928.9
Emulsifier O F3468%20141414
Dispersant A %2
Dispersant D%2
Import dispersant %2
Organobentonite %0.50.50.50.5
Methyl oleate % supplies 100 and supplies 100 and supply 100 and supply 100
Emulsifying dispersivity is good excellent
The stable storage storage hot in nature knot end, is defective qualified qualified
Normal storage nicosulfuron suspensibility % >=90979695
Heat storage nicosulfuron suspensibility % >=959590
Normal storage atrazine suspensibility % >=90989795
Heat storage atrazine suspensibility % >=969590
When being used alone use emulsifier, 4% nicosulfuron 28% atrazine OD heat storage stability is poor, the heat storage knot end; Use pluronic polymer collocation emulsifier, auxiliary dosage reduces, and emulsifying dispersivity is good, and it is qualified to store; The heat of dispersant disclosed in this patent storage suspensibility is higher than external import dispersant.
Claims (9)
1. an application for polyhydroxyalkanoate grafting organic polyamine dispersant, is characterized in that, described application of dispersant floats among agent in pesticide oil suspension;
Described dispersant chemical formula is:
；
Wherein P is organic polyamine class main chain, and T is residue O-R-CO or the lactone of hydroxy fatty acid;
X is modifier or end-capping reagent, for straight chain or side chain, the saturated or undersaturated residue with fatty acid from C1-C22;
Connect with amido link between T and P, connect with ester group between X and T, m is the integer of 1-100, and n can be the integer of 0 or 1-100.
2. the application of a kind of polyhydroxyalkanoate grafting organic polyamine dispersant according to claim 1, is characterized in that, described dispersant is used for in vegetable oil, vegetable oil methyl ester, the mineral wet goods environmental protection type agricultural chemical oil-suspending agent that is continuous phase.
3. an a kind of polyhydroxyalkanoate grafting organic polyamine dispersant as claimed in claim 1 or 2, it is characterized in that, described P is dimethylaminopropylamine, diethylenetriamine, TEPA or polymine.
4. an a kind of polyhydroxyalkanoate grafting organic polyamine dispersant as claimed in claim 1 or 2, it is characterized in that, described T derives from caprolactone or castor oil acid, hydroxylauric acid or 12-hydroxy stearic acid.
5. an a kind of polyhydroxyalkanoate grafting organic polyamine dispersant as claimed in claim 1 or 2, it is characterized in that, described dispersant has following different version:
。
6. a preparation method for polyhydroxyalkanoate grafting organic polyamine dispersant, is characterized in that, carries out according to the following steps:
1) hydroxy fatty acid is under the effect of catalyzer, and intermolecular polycondensation reaction occurs, and obtains the poly-hydroxy stearic acid ester of fatty acid end-blocking with the further esterification of end-capping reagent;
2) polyhydroxyalkanoate and organic amine generation amidation process obtain graft copolymer.
7. the preparation method of a kind of polyhydroxyalkanoate grafting organic polyamine dispersant according to claim 6, it is characterized in that, in step 1) under nitrogen protection, reaction temperature is 120-200 DEG C; Step 2) middle nitrogen protection, reaction temperature is 120-190 DEG C.
8. the preparation method of a kind of polyhydroxyalkanoate grafting organic polyamine dispersant according to claim 6, it is characterized in that, described catalyzer is acidic catalyst, the one in preferred zinc acetate, pyrovinic acid, p-methyl benzenesulfonic acid, zirconium naphthenate, dibutyl tin dilaurate, stannous chloride, tin caprylate, metatitanic acid orthocarbonate and butyl titanate.
9. the preparation method of a kind of polyhydroxyalkanoate grafting organic polyamine dispersant involved by claim 6, it is characterized in that, described polyhydroxyalkanoate and organic amine weight ratio are between 1:10-10:1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496539A (en) * | 2016-10-19 | 2017-03-15 | 华东师范大学 | A kind of hyperbranched nonionic surfactant and its preparation method and application |
| CN110903473A (en) * | 2019-12-09 | 2020-03-24 | 苏州禾川化学技术服务有限公司 | Preparation method of degradable hyperbranched dispersant |
| CN113336975A (en) * | 2021-06-24 | 2021-09-03 | 东莞理工学院 | Method for dissolving polyhydroxyalkanoate |
| CN114456447A (en) * | 2021-11-17 | 2022-05-10 | 宁波美乐童年玩具有限公司 | Preparation method and application of never-drying children color mud |
| CN114573807A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院理化技术研究所 | Branched polyethyleneimine fatty acid amide, preparation thereof, emulsifier containing same and application thereof |
| CN115044253A (en) * | 2022-07-19 | 2022-09-13 | 上海杰立化妆品科技有限公司 | Oily organic pigment color paste, preparation method and application thereof, lipstick and lip glaze containing color paste |
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| WO2001021298A1 (en) * | 1999-09-18 | 2001-03-29 | Avecia Limited | Polyester dispersants |
| CN101410436A (en) * | 2006-03-29 | 2009-04-15 | 西巴控股有限公司 | Polyethylene imine based pigment dispersants |
| CN103159957A (en) * | 2011-12-09 | 2013-06-19 | 叶磊 | Dispersing agent and preparation method thereof |
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| WO2001021298A1 (en) * | 1999-09-18 | 2001-03-29 | Avecia Limited | Polyester dispersants |
| CN101410436A (en) * | 2006-03-29 | 2009-04-15 | 西巴控股有限公司 | Polyethylene imine based pigment dispersants |
| CN103159957A (en) * | 2011-12-09 | 2013-06-19 | 叶磊 | Dispersing agent and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496539A (en) * | 2016-10-19 | 2017-03-15 | 华东师范大学 | A kind of hyperbranched nonionic surfactant and its preparation method and application |
| CN106496539B (en) * | 2016-10-19 | 2019-01-18 | 华东师范大学 | A kind of hyperbranched nonionic surfactant and its preparation method and application |
| CN110903473A (en) * | 2019-12-09 | 2020-03-24 | 苏州禾川化学技术服务有限公司 | Preparation method of degradable hyperbranched dispersant |
| CN114573807A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院理化技术研究所 | Branched polyethyleneimine fatty acid amide, preparation thereof, emulsifier containing same and application thereof |
| CN114573807B (en) * | 2020-12-01 | 2024-05-07 | 中国科学院理化技术研究所 | Branched polyethyleneimine fatty acid amides, preparation thereof, emulsifiers comprising same and use thereof |
| CN113336975A (en) * | 2021-06-24 | 2021-09-03 | 东莞理工学院 | Method for dissolving polyhydroxyalkanoate |
| CN114456447A (en) * | 2021-11-17 | 2022-05-10 | 宁波美乐童年玩具有限公司 | Preparation method and application of never-drying children color mud |
| CN115044253A (en) * | 2022-07-19 | 2022-09-13 | 上海杰立化妆品科技有限公司 | Oily organic pigment color paste, preparation method and application thereof, lipstick and lip glaze containing color paste |
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