CN105837733B - [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application - Google Patents
[(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application Download PDFInfo
- Publication number
- CN105837733B CN105837733B CN201610247479.8A CN201610247479A CN105837733B CN 105837733 B CN105837733 B CN 105837733B CN 201610247479 A CN201610247479 A CN 201610247479A CN 105837733 B CN105837733 B CN 105837733B
- Authority
- CN
- China
- Prior art keywords
- oxygen
- acryloyls
- capsiate
- acid
- dehydroabietic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a kind of [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer, its molecular structural formula such as formula (I) are shown.The present invention will directly have fungi-proofing, the natural organic-compound (capsaicine and dehydroabietic acid) of sterilization and marine organisms avoidance effect carries out chemical synthesis with anti-fouling paint base-material and [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer is made, poison without cuprous oxide and other world disablings, reach the novel sea antifouling paint of national requirements for environmental protection, effectively marine growth can be prevented to be stained hull bottom in two years, the speed of a ship or plane of ship can be kept unaffected, save fuel, grown with timeliness, it is nontoxic, the characteristics of green, the synergy of dehydroabietic acid and capsaicine is utilized simultaneously, obtain more preferable anti-fouling effect.
Description
Technical field
The invention belongs to marine biofouling Prevention Technique field, and in particular to [(12- acryloyls-oxygen)-dehydrogenated rosin
Acid-capsiate]-acrylic copolymer and preparation method thereof, and it is in the application of the antifouling aspect of marine organisms.
Background technology
In marine environment, ship can by seawater corrosion, while also by marine microorganism adhere to and caused by biology
Pollution.According to statistics, there is more than 2000 kinds of aufwuch in the marine site all over the world, the larva of these microorganisms and spore are in ocean
It is middle floating, travelling, when its development can alow be adhered to, settles down and further bred to a certain extent, when ship attachment marine growth
Afterwards, skin friction resistance can be caused to increase, reduces ship's speed, increase fuel consumption, increase the maintenance frequency that lies up.It is estimated that do not having
In the case of having anti-pollution measure, by the navigation of 6 months or berth, it will the alow raw pollutant 150kg/ in place's attachment sea
m2, the Fuel Consumption that directly contributes rises 50%.Meanwhile these biologies can also secret out of the metabolins such as organic acid, make hull bottom
The aggravation of the corrosion failure of steel plate and underwater facility, service life significantly shorten.To solve this problem, various anti-fouling ship paints are just
Arise at the historic moment.
Antifouling paint coat of the action principle of anti-fouling paint for coating alow discharges toxin, in the underwater shape close to hull bottom
The pool poisonous into thin layer, so as to drive larva and spore, its attachment and " colonization " is not allowed to be grown in hull surface.It is antifouling
Paint toxin used, referred to as antifouling pigment, mainly there is cuprous oxide and organotin resin.
Cuprous oxide is most widely used toxin in anti-fouling paint, and it has antifouling effect to animal class and plant marine growth
Fruit, can be used as the antifouling pigment in antifouling paint formula, and it has been continued to use decades as antifouling pigment, and antifouling at present
Paint the main poison kind being used.But experience have shown that cuprous oxide is poor to the antifouling capacity of seaweeds when ship berths.
Tributyl tin, TBT is commonly called as, is a kind of organic toxicity additive for being once widely used in anti-fouling paint, it can be non-
Often effectively suppress the growth of barnacle and marine alga simultaneously, and there is length using anti-fouling paint toxic effect duration length 3 made of TBT
The advantages of antifouling is imitated, can effectively extend ship must lie up the maintenance cycle of application because hull bottom pollutes, economization operation maintenance
Cost.It effectively reduces combustion delaying to show in terms of the slack-off process of the speed of a ship or plane because of the increase of hull surface roughness very prominent
Expect cost.But to later stage the 1970s, people gradually have found and confirm that sea can be caused using TBT toxin in anti-fouling paint
The heavy damage of foreign ecological environment.From nineteen eighty-two, the manufacturer of the state such as Great Britain and France stops producing the TBT of anti-fouling paint in succession.With
The disabling of organic tin anti-fouling paint, it is extremely urgent to find new bioantifouling paint.
The content of the invention
It is an object of the invention to provide a kind of [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic acid copolymer
Thing, it can be combined closely containing two kinds of functional groups with antifouling coating in copolymer, it is slowly discharged, protection is ageing
Long, biology walks quickly and keeps away what is be combined with biological control, marine organisms is had no adverse effects, to make up the deficiencies in the prior art.
[(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer, molecular structural formula such as formula (I)
It is shown：
Wherein m is 1000-5000 natural number.
[(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin mixes with anti-fouling paint base-material
After on naval vessel hull, in the environment of seawater, capsaicine and rosin acid in resin can slowly discharge, the capsicum discharged
Element and rosin acid reach the purpose of dual preventing and treating marine organisms attachment.
[(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin is that hydrolysis-type is anti-from polishing
Dirty coating, its in the seawater by chemically react (ion-exchange type and pure hydrolysis-type) reach coating polish purpose, had oneself
The effect of smooth finish surface.Can effectively it reduce because of initial roughness caused by application techniques so that hull surface is in shipping
During, what can be become is more smooth, can reduce the frictional force of navigation, and then reduces Fuel Dosage, reaches the purpose of energy-saving and emission-reduction.
Second object of the present invention there is provided a kind of method for preparing copolymer shown in formula (I), comprise the following steps：
(1) 12- hydroxyl dehydroabietic acids are dissolved in absolute ether, add alkalescent catalyst and stir, then to
Acryloyl chloride is added in reaction solution, after back flow reaction 5-6 hours, is evaporated under reduced pressure and removes the complete acryloyl chloride of unreacted, ether
After catalyst, (12- acryloyls-oxygen)-dehydroabietic acid is made；
(2) by (12- acryloyls-oxygen) obtained by step (1) ,-dehydroabietic acid is dissolved in chloroform, and is added dropwise into reaction solution
Thionyl chloride, after being added dropwise, temperature rising reflux reaction 24h, it is evaporated under reduced pressure removing chloroform and unnecessary thionyl chloride obtains (12-
Acryloyl-oxygen)-dehydrogenated rosin acyl chlorides；
(3) capsaicine is dissolved in absolute ether, adds alkalescent catalyst and stir, then added into reaction solution
(12- acryloyls-oxygen)-dehydrogenated rosin acyl chlorides obtained by step (2), after back flow reaction 7-8 hours, it is evaporated under reduced pressure and removes ether, urges
Agent and (12- acryloyls-oxygen)-dehydrogenated rosin acyl chlorides, obtain (12- acryloyls-oxygen)-dehydroabietic acid-capsiate；
(4) (12- acryloyls-oxygen)-dehydroabietic acid-capsiate obtained by acrylic acid and step (3) is well mixed, treated
With；
(5) (4) resulting polymers monomer mixture the step of 25-30% is added in lauryl sodium sulfate and emulsifies 30
Minute, 60-70 DEG C is heated to, 0.5mol/L persulfate aqueous solution is added dropwise, after reacting 30 minutes, continues that potassium peroxydisulfate is added dropwise
The aqueous solution, then residual monomer mixture is added dropwise, it is added dropwise in 2 hours, keeps 60-70 DEG C to react after being added dropwise 30 minutes
Afterwards, filter, wash, dry, grind [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer.
Preferably, alkalescent catalyst described in step (1) is diethylamine or sodium acid carbonate.
Preferably, concentration of the 12- hydroxyl dehydroabietic acids in absolute ether described in step (1) are 2mol/L, institute
It is 2.5mol/L to state addition concentration of the acryloyl chloride in reaction solution.
Preferably, the amount of thionyl chloride material described in step (2) is (12- acryloyls-oxygen)-dehydrogenated rosin acid substance
3-5 times of amount.
Preferably, alkalescent catalyst described in step (3) is diethylamine or sodium acid carbonate.
Preferably, (12- acryloyls-oxygen)-concentration of the dehydrogenated rosin acyl chlorides in absolute ether is described in step (3)
3mol/L, addition concentration of the capsaicine in reaction solution are 4mol/L.
Preferably, the amount of (12- acryloyls-oxygen)-dehydroabietic acid-capsiate material described in step (4) is third
3-5 times of the amount of olefin(e) acid material.
Preferably, the mass concentration of lauryl sodium sulfate described in step (5) is 9%, lauryl sodium sulfate
The amount of material is 0.01 times of (12- acryloyls-oxygen)-dehydroabietic acid-capsiate amount of substance, total thing of the potassium peroxydisulfate
The amount of matter is 0.005-0.015 times of (12- acryloyls-oxygen)-dehydroabietic acid-capsiate amount of substance.
The synthetic route of [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer of the present invention
For：
Wherein m is 1000-5000 natural number.
Third object of the present invention is to provide a kind of [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-propylene
The application of acid copolymer, naval vessel hull is painted on, can reach the purpose for preventing that marine organisms from adhering to.
The copolymer new material that the present invention obtains has the characteristics of timeliness is long, nontoxic, green, can be widely applied
In naval vessels, ship for civil use, offshore drilling platformses, submarine cable, nuclear power station sea water desalting equipment and aquaculture net
Case etc., has broad application prospects and economic value.
Beneficial effects of the present invention are：
1st, the present invention is directly by the natural organic-compound (capsaicine with fungi-proofing, sterilization and marine organisms avoidance effect
And dehydroabietic acid) and obtained [(12- acryloyls-oxygen)-dehydroabietic acid-capsaicine of anti-fouling paint base-material progress chemical synthesis
Ester]-acrylic copolymer, there is the characteristics of timeliness is long, nontoxic, green, while utilize dehydroabietic acid and capsaicine
Synergy, obtains more preferable anti-fouling effect.
2nd, [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin hydrolyzes meeting in the seawater
The not only slippery of nonpolluting coating is reduced, reduces the frictional force of navigation, and then reduces Fuel Dosage, reaches the purpose of energy-saving and emission-reduction.
Embodiment
Below by specific embodiment, technical scheme is described in further detail.
The preparation of embodiment 1 (12- acryloyls-oxygen)-dehydroabietic acid
450.66g (1.5mol) 12- hydroxyl dehydroabietic acids are dissolved in 500ml absolute ethers as reaction solution, then added
Enter the stirring of 8.4g (0.1mol) alkalescent catalyst sodium acid carbonate, then add 162.48ml (2mol) third in reaction solution again
Olefin(e) acid acyl chlorides, return stirring 7h, ether, catalyst and propylene isoxazolecarboxylic acid are distilled off under vacuo, obtains 405.59g
(1.35mol) (12- acryloyls-oxygen)-dehydroabietic acid.
The preparation of embodiment 2 (12- acryloyls-oxygen)-dehydrogenated rosin acyl chlorides
532.41g (1.5mol) (12- acryloyls-oxygen)-dehydroabietic acid is dissolved in 500ml chloroforms as reaction solution,
326.4ml (4.5mol) thionyl chloride is added dropwise with constant pressure funnel, temperature rising reflux reaction 24h, chlorine is distilled off under vacuo
Imitative and unnecessary thionyl chloride obtains 424.76g (1.45mol) acryloyl-(12- hydroxyls) dehydrogenated rosin isoxazolecarboxylic acid.
Embodiment 3 (12- acryloyls-oxygen)-dehydroabietic acid-capsiate
457.5g (1.5mol) capsaicine is dissolved in 500ml absolute ethers as reaction solution, adds alkalescent catalysis
Agent sodium acid carbonate stirs, and then adds 292.94g (1mol) (12- acryloyls-oxygen)-dehydroabietic acid acyl in reaction solution again
Chlorine, return stirring, ether, catalyst and acryloyl-(12- hydroxyls) dehydroabietic acid are distilled off under vacuo, obtains
562.34g (1mol) (12- acryloyls-oxygen)-dehydroabietic acid-capsiate.
Embodiment 4 [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer synthesizes
By 562.34g (1mol) (12- acryloyls-oxygen)-dehydroabietic acid-capsiates and 205.89ml (3mol) third
Olefin(e) acid in molar ratio 1:3 mixing, then mix 300ml water and 30g emulsifying agents SDS (sodium dodecyl benzenylsulfonate), stirring
Under be heated to 60 DEG C after, then by polymerized monomer by volume 25% be added in 0.1g/ml sodium dodecyl sulfate solution it is newborn
Change 30 minutes, continue to be heated to 70 DEG C, 15ml 0.5M initiator potassium persulfate is added dropwise, maintenance reaction 30 minutes, adds with before
The potassium peroxydisulfate of secondary equivalent, remaining polymerized monomer is then added dropwise, reaction temperature is maintained at 70 DEG C, is added dropwise, then ties up within 2 hours
Reaction 30 minutes is held, filtering, is washed with water, is dried at 80 DEG C, ground 70 mesh sieve, the product of preparation is yellowish coloured particles, is gathered
Right is 1000-5000, and mean molecule quantity is 70-300 ten thousand.FTIR characteristic absorption peak interpretations of result are as follows：3626.6 (N-H stretches
Contracting vibration), 3400.5 (O-H stretching vibrations), 3056.7 (phenyl ring C-H stretching vibrations), 2993.7 (methyl C-H stretching vibrations),
2987.3 (methyl C-H stretching vibrations), 1738.3 (ester bond C=O stretching vibrations), 1650.9 (C=O stretching vibrations), 1610.9
(phenyl ring breathing vibration), 1508.2 (phenyl ring breathing vibrations), 1456.2 (CH flexural vibrations), 1358.4 (C-H rocking vibrations),
1233.9 (C-N stretching vibrations), 1154.5 (ehter bond C-O stretching vibrations), -986.7 (=C-H flexural vibrations), 947.6,
817.2,647.0cm-1, it was demonstrated that synthesized compound is [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-propylene
Acid copolymer resin.
The application of [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin
Embodiment 5：The attachment experiment of antibacterial and kentrogon
By [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic resin in mass ratio 1% and 2216E
High-temperature sterilization 20 minutes, is then poured into 9cm culture dish and flat board is made, without [(12- propylene after solid medium mixing
Acyl-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin 2216E culture mediums as control, will collection from Hangzhoupro
Seawater near the gulf of state is uniformly coated on flat board, and each flat board applies 1ml seawater, and 36h is cultivated in 20 DEG C of incubator, is tied
Fruit shows do not have in the culture medium containing [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin
The growth of bacterial strain, and have substantial amounts of strain growth in control group, show [(12- acryloyls-oxygen)-dehydroabietic acid-capsaicine
Ester]-acrylic copolymer resin has bacteriostasis.
The acetone of [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic resin in mass ratio 1% is molten
Liquid is evenly coated in culture dish, after acetone solvent volatilization is dry, adds 10ml non-filtering sea, without [(12- acryloyls-oxygen)-it is de-
Hydrogen rosin acid-capsiate]-acrylic resin culture dish as control, about 10 collection Hangzhou are put into each culture dish
Cypris-form larva near gulf, cultivate 30 days under room temperature (20 DEG C), as a result show, scribble [(12- acryloyls-oxygen)-dehydrogenation pine
Fragrant acid-capsiate] culture dish of-acrylic resin does not have a cypris-form larva attachment, and there is no [(12- propylene as control
Acyl-oxygen)-dehydroabietic acid-capsiate] culture dish of-acrylic resin has 6 cypris-form larvas to be attached on inwall, shows
[(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic resin can prevent the attachment of barnacle.
Embodiment 6：Marine panel experiment
[(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer resin of the present invention can be used for preventing
Control hull surface biological attachment, i.e., by [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-propylene that mass ratio is 1%
Acid copolymer resin mixes with antifouling of ship's hull paint base-material, is coated on naval vessel hull, can reach the effect for preventing that marine organisms from adhering to.
Ship plate is cut into 20 × 40 sheet material, derusted with 0.3N watery hydrochloric acid, then application L44-83
Aluminum powder pitch ship bottom paint (application at twice, about 40um is thick every time), after being completely dried, by the [(12- of mass ratio 2%~10%
Acryloyl-oxygen)-dehydroabietic acid-capsiate]-acrylic acid and 50% three isopropyl methyl-monosilane base acrylate-methyl-prop
Olefin(e) acid ester copolymer (base-material), 10% cuprous oxide, the 5% sub- zinc of oxidation, 5% aerosil, 20% diformazan
The antifouling paint of benzene mixing composition, uniform application and surface of steel plate, coating layer thickness are about 200~400um.This experiment is with reference to state
Family standard GB 5370-85《Anti-fouling paint model shallow sea soak test method》Carry out.The model prepared is fixed in wooden frame,
Leaching carries out notable mark before sea, records reset condition, after model soaks extra large depth to be completely dried, selects suitable intertidal belt submarine
Domain, steel plate is hung at underwater 1.5 meters.The model in leaching sea is vertically securely fixed on framework, and specimen surface is parallel to sea
Water is controlled the trend.Spacing >=200mm of framework.Behind model leaching sea, model is inspected periodically as needed.In order to investigate not
With the effects of accrete organisms of marine site antifouling paint, test site selects Hangzhou respectively, and Shanghai, Fujian, the marine site in Guangzhou is carried out
Experiment, is put into marine 6 months, and without any biological attachment, inanimate object adheres to experiment steel plate after 1 year, still attached without marine organisms after 2 years
.
It is excellent that embodiment 5,6 shows that [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer has
Different prevents marine organisms adhewsive action.
Embodiment described above is a kind of preferable scheme of the present invention, not the present invention is made any formal
Limitation, there are other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (9)
- [1. (12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-acrylic copolymer, molecular structural formula such as formula (I) institute Show：Wherein m is 1000-5000 natural number.
- 2. prepare the method for the copolymer described in claim 1, it is characterised in that the preparation method comprises the following steps：(1) 12- hydroxyl dehydroabietic acids are dissolved in absolute ether, add alkalescent catalyst and stir, then to reaction Acryloyl chloride is added in liquid, after back flow reaction 5-6 hours, is evaporated under reduced pressure and removes the complete acryloyl chloride of unreacted, ether and urge After agent, (12- acryloyls-oxygen)-dehydroabietic acid is made；(2) by (12- acryloyls-oxygen) obtained by step (1) ,-dehydroabietic acid is dissolved in chloroform, and dichloro is added dropwise into reaction solution Sulfoxide, after being added dropwise, temperature rising reflux reaction 24h, it is evaporated under reduced pressure removing chloroform and unnecessary thionyl chloride obtains (12- propylene Acyl-oxygen)-dehydrogenated rosin acyl chlorides；(3) capsaicine is dissolved in absolute ether, adds alkalescent catalyst and stir, then step is added into reaction solution (2) gained (12- acryloyls-oxygen)-dehydrogenated rosin acyl chlorides, after back flow reaction 7-8 hours, it is evaporated under reduced pressure and removes ether, catalyst (12- acryloyls-oxygen)-dehydrogenated rosin acyl chlorides, obtain (12- acryloyls-oxygen)-dehydroabietic acid-capsiate；(4) (12- acryloyls-oxygen)-dehydroabietic acid-capsiate obtained by acrylic acid and step (3) is well mixed, it is stand-by；(5) (4) resulting polymers monomer mixture the step of 25-30% is added in lauryl sodium sulfate aqueous solution and emulsifies 30 Minute, be heated to 60-70 DEG C, be added dropwise 0.5mol/L persulfate aqueous solution, after reaction 30 minutes, continue to be added dropwise with it is previous The persulfate aqueous solution of equivalent, then residual monomer mixture is added dropwise, it is added dropwise in 2 hours, 60- is kept after being added dropwise After 70 DEG C are reacted 30 minutes, filter, wash, dry, grind [(12- acryloyls-oxygen)-dehydroabietic acid-capsiate]-the third Olefin(e) acid copolymer.
- 3. preparation method as claimed in claim 2, it is characterised in that alkalescent catalyst described in step (1) is diethylamine Or sodium acid carbonate.
- 4. preparation method as claimed in claim 2, it is characterised in that 12- hydroxyl dehydroabietic acids are in nothing described in step (1) Concentration in water ether is 2mol/L, and addition concentration of the acryloyl chloride in reaction solution is 2.5mol/L.
- 5. preparation method as claimed in claim 2, it is characterised in that the amount of thionyl chloride material is described in step (2) 3-5 times of the amount of (12- acryloyls-oxygen)-dehydrogenated rosin acid substance.
- 6. preparation method as claimed in claim 2, it is characterised in that alkalescent catalyst described in step (3) is diethylamine Or sodium acid carbonate.
- 7. preparation method as claimed in claim 2, it is characterised in that (12- acryloyls-oxygen)-dehydrogenation described in step (3) pine Concentration of the fragrant acyl chlorides in absolute ether is 3mol/L, and addition concentration of the capsaicine in reaction solution is 4mol/L.
- 8. preparation method as claimed in claim 2, it is characterised in that (12- acryloyls-oxygen)-dehydrogenation described in step (4) pine The amount of fragrant acid-capsiate material is 3-5 times of the amount of acrylic substance.
- 9. preparation method as claimed in claim 2, it is characterised in that the quality of lauryl sodium sulfate described in step (5) Concentration is 9%, and the amount of the material of lauryl sodium sulfate is (12- acryloyls-oxygen)-dehydroabietic acid-capsiate amount of substance 0.01 times, the amount of the total material of the potassium peroxydisulfate is (12- acryloyls-oxygen)-dehydroabietic acid-capsiate amount of substance 0.005-0.015 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610247479.8A CN105837733B (en) | 2016-04-19 | 2016-04-19 | [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610247479.8A CN105837733B (en) | 2016-04-19 | 2016-04-19 | [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105837733A CN105837733A (en) | 2016-08-10 |
| CN105837733B true CN105837733B (en) | 2017-11-17 |
Family
ID=56588944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610247479.8A Active CN105837733B (en) | 2016-04-19 | 2016-04-19 | [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105837733B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519109B (en) * | 2016-11-28 | 2019-01-15 | 华南理工大学 | A kind of capsaicine modified acrylic acid emulsion and its preparation method and application |
| CN108341909A (en) * | 2018-03-25 | 2018-07-31 | 华南理工大学 | A kind of antibacterial capsaicine is acrylic resin modified and its preparation method and application |
| CN111662639B (en) * | 2020-07-03 | 2021-10-01 | 浙江工业大学 | Film forming material and preparation method thereof |
| CN112778448A (en) * | 2020-12-13 | 2021-05-11 | 赤峰福来特化工有限公司 | Dihydrocapsaicin modified acrylic resin and preparation method thereof |
| CN114805717B (en) * | 2022-03-22 | 2023-06-16 | 华南理工大学 | Capsaicin phenolic resin, and preparation and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1288234A1 (en) * | 2001-08-27 | 2003-03-05 | Sigma Coatings B.V. | Binders with low content in hydrolysable monomer suitable for selfpolishing antifouling paints |
| CN1323121C (en) * | 2005-05-25 | 2007-06-27 | 上海雷辣婆食品有限公司 | Capsaicin antifouling paint |
| CN102399486A (en) * | 2010-09-12 | 2012-04-04 | 珠海中金纳米科技有限公司 | Nano marine anti-fouling coating |
-
2016
- 2016-04-19 CN CN201610247479.8A patent/CN105837733B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105837733A (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105837733B (en) | [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application | |
| CN102300944B (en) | Marine organism anti-fouling paint and preparing method and use thereof | |
| CN102010639B (en) | Environmentally-friendly marine antifouling coating and preparation method thereof | |
| JP5607633B2 (en) | Spinosyn antifouling composition, method of use thereof, and article protected from fouling organisms | |
| CN105542607B (en) | A kind of acrylate self polishing copolymer antifouling paint of the ion modification containing betaine type amphoteric and preparation method thereof | |
| CN103122187B (en) | ionic liquid modified marine antifouling paint | |
| WO2007030389A2 (en) | Marine antifouling coating compositions | |
| CN101845262B (en) | Low surface energy liquid control release type marine anti-fouling paint | |
| CN102807797B (en) | Efficient marine antifouling coating and broad-spectrum controlled-release antifouling agent for same | |
| CN102702880A (en) | Anti-fouling paint composition | |
| CN101550304A (en) | Environment-friendly marine antifouling coating for finishing boat | |
| CN104761991A (en) | Environmental-protection type multi-element collaborative marine anti-fouling coating | |
| CN101696340A (en) | Strippable anti-fouling paint | |
| CN103044632A (en) | Hybrid hydrolysis resin, and preparation method and application thereof | |
| CN103160205A (en) | Ionic liquid marine antifouling coating | |
| Wang et al. | Performance assessment of capsaicin derivatives containing amide groups used as active substances for antifouling coatings | |
| CN106905780A (en) | A kind of capsicim environmental protection type anti-pollution paint and preparation method thereof | |
| CN106700787A (en) | Environmentally-friendly ocean antifouling paint based on self-polishing polymer/butenolide and derivatives thereof | |
| CN100341964C (en) | Antifouling paint for sea deep water net cage | |
| CN102504697A (en) | High-efficiency tin-free self-polishing antifouling paint composition and application thereof | |
| CN105331168A (en) | Application of cardiac glycoside compound in marine biofouling prevention | |
| CN109266172A (en) | A kind of marine antifouling coating and its preparation method and application | |
| CN105969097B (en) | A kind of pollution resisting coating | |
| CN1772828A (en) | Antifouling Coating for marine nesh cage cover | |
| CN107603396A (en) | A kind of aquiculture net cage etting antifouling paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |