CN107057001A - A kind of abietyl Comblike polymers surfactant and its production and use - Google Patents
A kind of abietyl Comblike polymers surfactant and its production and use Download PDFInfo
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- CN107057001A CN107057001A CN201710173391.0A CN201710173391A CN107057001A CN 107057001 A CN107057001 A CN 107057001A CN 201710173391 A CN201710173391 A CN 201710173391A CN 107057001 A CN107057001 A CN 107057001A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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Abstract
The present invention discloses a kind of abietyl Comblike polymers surfactant, and rosin GMA methacrylic acid polyglycol ester interpolymer, the general structure of primary product is as follows：
Description
Technical field
The present invention relates to a kind of green Comblike polymers surfactant, more particularly to a kind of rosin Glycidyl methacrylate
Glyceride-methacrylic acid polyglycol ester interpolymer and preparation method thereof and the application in aqueous-phase suspending agricultural chemicals.With natural
Resource rosin is the luxuriant and rich with fragrance skeleton knot of the ternary containing rosin in the regular Comblike polymers surfactant of raw material preparation structure, structure
Structure, has preferable abrasiveness and dispersion stabilization as application of dispersant in aqueous-phase suspending agricultural chemicals.
Background technology
Amphipathic Comblike polymers by side chain of poly glycol monomethyl ether are mainly used as dispersant in the industry.Due to
Poly glycol monomethyl ether side chain it is nontoxic, easily regulation etc. advantage get the attention.This kind of surfactant master is prepared at present
There are two methods.One kind is main link branch method, and poly glycol monomethyl ether is passed through into the work in esterification and main polymer chain
Property group react to form graft polymers, but this technique grafting rate is relatively low, and grafting site position distribution is difficult to control.It is another
Kind of method is macromonomer method, this method to introduce double bond on poly glycol monomethyl ether polymeric monomer, then with other small molecules
Monomer copolymerization prepares amphipathic graft copolymer, and this method can be regular with preparation structure, and the higher amphipathic stem-grafting of grafting density gathers
Compound.
With the continuous enhancing of environmental consciousness, in the urgent need to exploitation environmental type pesticidal preparations.Aqueous suspension agricultural chemicals is main
Auxiliary agent is dispersant, and APES is often used as emulsifying agent in agricultural chemicals, but there are some researches show alkyl phenol is poly-
Oxygen vinethene can change the film infiltration function of organism, influence enzyme and lysosome activity, destruction institutional framework etc..So with natural
The dispersant that resource replaces fossil resource to prepare good biocompatibility is following inexorable trend, and natural resources rosin has and alkane
The similar cyclic structure of base phenol polyethenoxy ether, with stronger emulsion dispersion stability.
Rosin is a kind of abundance, cheap renewable natural resources.Its main component is resin acid, is utilized
The active group that resin acid has can synthesize a series of with aliphatic acid, fatty alcohol, fatty amines surfactant structure phase
Like and product that performance shows unique characteristics.Meanwhile, rosin is natural products, is had by a series of its surfactant synthesized preferable
Ecological performance.Nowadays the demand of Surfactant raw material is huge, and price rises steadily, and to the requirement of environmental protection
Under conditions of increasingly improving, Rosin Surfactants are developed, on the one hand can be with rich undoubtedly with huge resources advantage
Rich surfactant product species, on the other hand also provides an effective way to improve the added value of rosin.
The content of the invention
It is an object of the invention to provide a kind of abietyl Comblike polymers surfactant, rosin Glycidyl methacrylate
Glyceride-methacrylic acid polyglycol ester interpolymer and its preparation method and application.The surfactant is with biomass resource
Rosin is raw material, with good surface-active, and the luxuriant and rich with fragrance skeleton structure of the ternary containing rosin, and aqueous phase is used in as dispersant
There is preferable abrasiveness and dispersion stabilization in suspended pesticide.
The present invention is adopted the following technical scheme that：A kind of abietyl Comblike polymers surfactant, rosin methacrylic acid
Ethylene oxidic ester-methacrylic acid polyglycol ester interpolymer, its primary product general structure is as follows：
Use macromonomer radical polymerization：The first step, rosin is esterified with GMA
Reaction, generates rosin GMA, second step, rosin GMA and methacrylic acid
Polyethylene glycol（200~1000）With the amount of different material, than occurring free radicals copolymerization reaction, to obtain rosin Glycidyl methacrylate sweet
Grease-methacrylic acid polyglycol ester interpolymer.
Wherein the ratio between amount of material of rosin and GMA is 1:（1~1.5）, such as ratio selection
1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, toluene makees solvent, and the amount of catalyst of triethylamine is total for reactant
0.2 ~ 0.5wt% of quality, optional 0.2%, 0.3%, 0.4%, 0.5%, the amount of hydroquinone of polymerization retarder is reactant gross mass
0.2 ~ 0.5wt%, optional 0.2%, 0.3%, 0.4%, 0.5%, reaction temperature is 80 ~ 120 DEG C, such as 80 DEG C, 90 DEG C, 100 DEG C, 110
DEG C, 120 DEG C, 6 ~ 8h of reaction time, such as 6h, 7h, 8h obtain intermediate rosin GMA.
Rosin GMA and metering system acid polyethylene glycol（200~1000）Generation is free-radical polymerized
The ratio between amount of material of reaction is（0~2）:1, such as ratio chooses 0:1, 0.5:1, 1:1, 2:1, initiator is that azo two is different
Fourth cyanogen or benzoyl peroxide, consumption are the 1 ~ 3%, for example, 1%, 2%, 3% of reaction-ure mixture, and reaction temperature is 60 ~ 80 DEG C,
Such as 60 DEG C, 70 DEG C, 80 DEG C, 8 ~ 16h of reaction time, such as 8h, 12h, 16h obtain abietyl Comblike polymers surface-active
Agent, rosin GMA-methacrylic acid polyglycol ester interpolymer.
Such Comblike polymers surfactant molecule amount scope be 6339 ~ 7969, molecular weight distribution index be 1.12 ~
1.37；The critical micelle concentration of surfactant of preparation is 0.21 ~ 0.36g/L, and the scope of surface tension is in 38.3 ~ 44.6mN/
m；Being used in as dispersant in pymetrozine aqueous-phase suspending agricultural chemicals has preferable abrasiveness, and suspensibility scope is 95.7 ~ 99.9%,
And there is preferable stability in storage.
The family macromolecule surfactant is pectinate texture, and its regular structure has controllability and controllability, raw material
For natural resources rosin, meet the theory of Green Sustainable, introduce the luxuriant and rich with fragrance skeleton structure of ternary of rosin, transported as dispersant
There is preferable abrasiveness and dispersion stabilization in aqueous-phase suspending agricultural chemicals.
The present invention obtains following technique effect：
1. the present invention combines the design feature of rosin, through over-churning, the method such as free-radical polymerized has synthesized a series of abietyl combs
Shape high molecular surfactant rosin GMA-methacrylic acid polyglycol ester interpolymer, this knot
Structure has controllability and controllability.Product has compared with high added value.
2. such Comblike polymers surfactant molecule amount scope is 6339 ~ 7969, molecular weight distribution index is 1.12
~1.37；The critical micelle concentration of surfactant of preparation is 0.21 ~ 0.36g/L, and the scope of surface tension is in 38.3 ~ 44.6mN/
m；Such surfactant its viscosity when mass concentration is 50g/L rises with the increase of shear rate, is dilatant fluid；
Being used in as dispersant in pymetrozine aqueous-phase suspending agricultural chemicals has preferable abrasiveness, and suspensibility scope is 95.7 ~ 99.9%, and
There is preferable stability in storage.
3. present invention process uses biomass resource rosin for raw material, principle is spliced using active group, by abietyl three
Ring diterpene structure is introduced into surfactant structure, with preferable biocompatibility and degradability.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of reaction raw materials of the present invention, intermediate and product.
Embodiment
Embodiment 1
A kind of abietyl Comblike polymers surfactant rosin GMA-metering system acid polyethylene glycol
The general structure of ester copolymer primary product is：
Wherein, the molecular weight ranges of methacrylic acid macrogol ester are 200 ~ 1000.
Embodiment 2
A kind of abietyl Comblike polymers surfactant rosin GMA-metering system acid polyethylene glycol
The synthesis of ester copolymer comprises the following steps：
37.6g rosin and 17.8g GMAs are taken in temperature sleeves, agitating device, reflux
In four-hole boiling flask, appropriate hydroquinones is added thereto as polymerization inhibitor（The amount of hydroquinones accounts for reactant gross mass
0.2-0.5%）, triethylamine is used as catalyst（The amount of triethylamine accounts for the 0.2-0.5% of reactant gross mass）, in toluene solvant
In, solvent rotary evaporation is obtained rosin GMA by back flow reaction 7h after completion of the reaction.
By above-mentioned reaction product and methacrylic acid macrogol ester 950 with 1:The amount of 1 material is dried than input 250mL
Three-necked flask in, ethanol as solvent, at 60 DEG C stir 1h after, by initiator dissolving in a solvent, reactor is added dropwise
In, be warming up to after completion of dropping 80 DEG C reaction 12h after solvent is steamed, obtain product rosin GMA-
Methacrylic acid polyglycol ester interpolymer high molecular surfactant.
Embodiment 3
Synthesis technique is similar to Example 2, changes rosin GMA and methacrylic acid macrogol ester
The amount ratio of 950 material, chooses 1 respectively:2, 2:1.
Embodiment 4
Raw material, intermediate and product carry out IR Spectral Identifications：1694.96cm in the infrared general figure of rosin-1For-CO- in carboxyl
Absorb carboxyl characteristic peak in vibration peak, intermediate rosin GMA to disappear, in 1723.82cm-1Place occurs
Ester-CO- characteristic absorption peak, in 1637.69 cm-1Locate appearance-C=C- and absorb vibration peak, it was demonstrated that esterification is complete, and is successfully introduced into
Double bond, after polymerization, GMA disappears with double bond peak in methacrylic acid polyglycol ester interpolymer, it was demonstrated that
Polymerization is complete, and product structure is correct.
Embodiment 5
The some surface active property of rosin-based surfactant is determined, and surface tension is the important parameter of surfactant properties, this
Research determines the surface tension and CMC of surfactant using film pull-up method, and it is 25 DEG C to determine temperature, by determining series production
The surface tension of the aqueous solution during various concentrations of product.
Foaming properties：Prepare the product aqueous solution that mass fraction is 0.5%.The 20 mL product aqueous solution are taken to pour into 100 mL
Tool plug graduated cylinder in, add the mL of warm water 10, up and down acutely after vibration 25 times, record foam height now stands 5 min
Afterwards, foam height is recorded again.Retest 3 times, takes its average value.
Hydrophilic lipophilic balance（HLB value）：0.2 g surfactant products to be measured are weighed, 20 ml dioxanes-benzene is added
（90：4 volume ratios）Solution dissolves it, then is titrated to appearance substantially muddiness with distilled water, records the milliliter of distilled water used
Number V, is then calculated as follows HLB value：HLB=23.64lgV-10.16
Three kinds of GMAs and methacrylic acid polyglycol ester interpolymer（1:2, 1:1, 2:1）Live on surface
Property performance is respectively：Critical micelle concentration is respectively 1.59g/L, 1.27g/L, 0.77g/L；Corresponding surface tension is
36.2mN/m, 40.8mN/m, 42.6mN/m；Foam height is respectively 100mm, 103mm, 125mm, and foam stabilizing highly divides after 5min
Wei not 61mm, 71mm, 88mm；HLB value is respectively 18.6,18.2,17.6；And polymethylacrylic acid macrogol ester faces
Boundary micellar concentration 14.59g/L, corresponding surface tension is 35.1mN/m, and foam height is that foam stabilizing is highly after 63mm, 5min
0mm, HLB value is 19.3.With the increase of rosin introduction volume, critical micelle concentration reduces, and surface tension increase, foaming properties increase
By force, lipophile strengthens.
Embodiment 6
The flow measurement Stress Control rheometers of HAAKE MARS II, plate diameter is 60mm, and gap is 0.105mm, and stable state is swept
Speed control is retouched in 0.1 ~ 600s-1.Rheological property research is carried out to concentration for 50g/L this kind of surfactant solution to show,
With the increase of shear rate, solution viscosity enhancing, is dilatant fluid, and with the increase of rosin introduction volume, the aqueous solution
Viscosity enhancing.Occur a turning point in viscosity-shear rate curve, and with the increase of rosin introduction volume, the turnover
Point is moved to low shearing rate direction.
Embodiment 7
It is used in this kind of surfactant as dispersant in pymetrozine aqueous-phase suspending agricultural chemicals, the formula of suspended pesticide is：10%
Pymetrozine, 6% dispersant, 6% wetting agent, 5% antifreezing agent, 73% water grinds 4h, ball milling after loading ball grinder under 200rpm rotating speeds
The suspensibility for having the dispersant of rosin introducing after machine grinding is all higher than 95%, and after refrigerating 15 days, suspensibility is still all higher than 80%, especially
It is rosin GMA-methacrylic acid polyglycol ester interpolymer（1:2）After refrigeration suspensibility still greater than
95%。
Claims (4)
1. a kind of abietyl Comblike polymers surfactant, the rosin GMA-poly- second of methacrylic acid
Ethylene terephthalate copolymers, its primary product general structure is as follows：
Wherein, the molecular weight ranges of methacrylic acid polyethylene glycol ester monomer are（200~1000）.
2. the preparation method of abietyl Comblike polymers surfactant according to claim 1, it is characterised in that use
Be macromonomer radical polymerization：The ratio between amount of material of the first step, rosin and GMA is
1:（1~1.5）, the amount of catalyst of triethylamine is 0.2 ~ 0.5wt% of reactant gross mass, and the amount of hydroquinone of polymerization retarder is anti-
0.2 ~ 0.5wt% of thing gross mass is answered, toluene makees solvent, and reaction temperature is 80 ~ 120 DEG C, reacts 6 ~ 8h, obtains intermediate rosin
GMA；Second step, under nitrogen protection, rosin Glycidyl methacrylate is sweet in anhydrous ethanol solvent
The ratio between amount of material of free radicals copolymerization reaction occurs with methacrylic acid macrogol ester for grease（0~2）:1, initiator is
Azo-bis-isobutyl cyanide or benzoyl peroxide, consumption are the 1 ~ 3% of reactant gross mass, and reaction temperature is 60 ~ 80 DEG C, during reaction
Between 8 ~ 16h, obtain abietyl Comblike polymers surfactant, rosin GMA-methacrylic acid gathers
Glycol ester copolymer.
3. abietyl Comblike polymers surfactant according to claim 1, molecular weight ranges are 6339 ~ 7969；System
Standby critical micelle concentration of surfactant is 0.21 ~ 0.36g/L, and the scope of surface tension is in 38.3 ~ 44.6mN/m.
4. abietyl Comblike polymers surfactant according to claim 1 is as application of dispersant in aqueous-phase suspending agriculture
In medicine, with preferable abrasiveness and dispersion stabilization, when the formula of suspended pesticide is：10% pymetrozine, 6% dispersant, 6% profit
Humectant, when 5% antifreezing agent and 73% water, 4h is ground after loading ball grinder under 200rpm rotating speeds, and suspensibility scope is 95.7 ~
99.9%, and with preferable stability in storage.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710173391.0A CN107057001B (en) | 2017-03-22 | 2017-03-22 | Rosin-based comb-shaped high-molecular surfactant and preparation method and application thereof |
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| CN201710173391.0A CN107057001B (en) | 2017-03-22 | 2017-03-22 | Rosin-based comb-shaped high-molecular surfactant and preparation method and application thereof |
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| CN107057001A true CN107057001A (en) | 2017-08-18 |
| CN107057001B CN107057001B (en) | 2020-04-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459608A (en) * | 2017-09-14 | 2017-12-12 | 中国林业科学研究院林产化学工业研究所 | A kind of acrylic acid rosin based high molecular surfactant and its production and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091564A (en) * | 2010-12-07 | 2011-06-15 | 余林华 | Acrylic ester polymer surfactant and preparation method thereof |
| KR20110070246A (en) * | 2009-12-18 | 2011-06-24 | 동우 화인켐 주식회사 | Composition of pigment dispersed liquid, colored resin composition, color filter and display device having the same |
| CN105985499A (en) * | 2015-02-28 | 2016-10-05 | 上海东升新材料有限公司 | Polymeric emulsifier for preparing cationic rosin size and preparation method of polymeric emulsifier |
-
2017
- 2017-03-22 CN CN201710173391.0A patent/CN107057001B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110070246A (en) * | 2009-12-18 | 2011-06-24 | 동우 화인켐 주식회사 | Composition of pigment dispersed liquid, colored resin composition, color filter and display device having the same |
| CN102091564A (en) * | 2010-12-07 | 2011-06-15 | 余林华 | Acrylic ester polymer surfactant and preparation method thereof |
| CN105985499A (en) * | 2015-02-28 | 2016-10-05 | 上海东升新材料有限公司 | Polymeric emulsifier for preparing cationic rosin size and preparation method of polymeric emulsifier |
Non-Patent Citations (1)
| Title |
|---|
| 任鹏等: "松香和甲基丙烯酸缩水甘油酯酯化反应研究", 《化学研究与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459608A (en) * | 2017-09-14 | 2017-12-12 | 中国林业科学研究院林产化学工业研究所 | A kind of acrylic acid rosin based high molecular surfactant and its production and use |
| CN107459608B (en) * | 2017-09-14 | 2020-03-24 | 中国林业科学研究院林产化学工业研究所 | Acrylic acid rosin-based high-molecular surfactant and preparation method and application thereof |
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Effective date of registration: 20221111 Address after: 457162 East of Plant 2, Zhongyuan Jiusheng Petrochemical Park, Puyang Industrial Park, Henan Province Patentee after: Henan heruida Petroleum Engineering Technology Co.,Ltd. Address before: No. 16, No. five village, Xuanwu District, Nanjing, Jiangsu Province Patentee before: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF |