CN105199041A - Method for preparing antifouling resin from hexadecanoic acid grafted acrylic prepolymer - Google Patents
Method for preparing antifouling resin from hexadecanoic acid grafted acrylic prepolymer Download PDFInfo
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- CN105199041A CN105199041A CN201510715712.6A CN201510715712A CN105199041A CN 105199041 A CN105199041 A CN 105199041A CN 201510715712 A CN201510715712 A CN 201510715712A CN 105199041 A CN105199041 A CN 105199041A
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Abstract
A method for preparing antifouling resin from hexadecanoic acid grafted acrylic prepolymer comprises acrylic prepolymer preparation and antifouling resin preparation, a benzene series solvent, an alcohol series solvent, acrylic acid, an acrylate soft monomer, an acrylate hard monomer, an initiator and a polymerization inhibitor are used in the acrylic prepolymer preparation process, and an acrylic prepolymer, hexadecanoic acid, a zinc-containing substance and a solvent are used in the antifouling resin preparation process. Hexadecanoic acid is grafted to the side chain of the acrylic prepolymer in a zinc bridge designing mode with hexadecanoic acid as an antifouling side chain fragment, so the antifouling resin has an antifouling function; the grafting proportion of hexadecanoic acid is controlled to adjust the hydrophilicity and control the degradation rate of the antifouling resin, so degradation of the antifouling resin and effusion of an antifouling agent form synergism, so the use amount of the antifouling agent is effectively solved, and the problem of no antifouling activity of present self-polishing resin bodies is solved. The method is of great significance in environmental protection, society and economy.
Description
Technical field
The invention belongs to chemical material technical field, refer more particularly to a kind of method being prepared antifouling resin by hexadecanoic acid graft acrylic acid prepolymer.
Background technology
The research of natural biological stain control agent is an important research direction in bionical antifouling field, current ocean, many marine lifes, meta-bolites as secreted in coral, sponge, algae etc. has certain antifouling activity, as the people such as Hattori isolate from sponge Aplysilla the growth that 1-methyladenine effectively can stop marine bacteria, and also effectively can suppress the attachment of macro sea lettuce from the isolated ceramide of sponge HaliclonaKoremella.
Herrero etc. have also discovered 15 kinds of different meta-bolitess from Dunaliella salina in addition, and mainly hexadecanoic acid, alpha-linolenic acid, oleic acid etc. have anti-microbial activity.
With the exception of this, the meta-bolites of part mushroom has antifouling activity too, the big still people such as grade that records just has found produce in thiobacillus thiooxidant and thiobacillus thioparus metabolic process sulfuric acid, change body surface pH environment, effectively can suppress the attachment of large ocean biology, but this discovery is still in the laboratory study stage, there is no bibliographical information actual application.
Summary of the invention
For solving the problem, the invention provides a kind of method being prepared antifouling resin by hexadecanoic acid graft acrylic acid prepolymer, the method is divided into the preparation of acrylic polymer and the preparation of antifouling resin, first by vinylformic acid, esters of acrylic acid soft monomer and esters of acrylic acid hard monomer are at initiator, mixture is prepared under the effect of stopper, again this mixture is slowly instilled in mixed solvent and prepare acrylic polymer, zinc-containing substance is added afterwards in acrylic polymer, solvent and Hai Sheng meta-bolites hexadecanoic acid, antifouling resin is prepared finally by control grafting temperature and grafting time.
For achieving the above object, the present invention adopts following technical scheme:
Prepared a method for antifouling resin by hexadecanoic acid graft acrylic acid prepolymer, the method comprises the preparation of acrylic polymer and the preparation of antifouling resin, it is characterized in that:
The preparation of acrylic polymer: add the benzene series kind solvent of 90 ~ 140 weight parts and the alcohol system kind solvent of 60 ~ 120 weight parts in 500ml flask with four necks,round bottom, make flask with four necks,round bottom be warming up to 95 ± 5 DEG C under nitrogen protection and prepare mixed solvent; Get the vinylformic acid of 40 ~ 60 weight parts, the esters of acrylic acid soft monomer of 80 ~ 160 weight parts and the esters of acrylic acid hard monomer of 50 ~ 80 weight parts to be respectively placed in flask and to mix, add the initiator of 3 ~ 4 weight parts and the stopper of 1 ~ 2 weight part afterwards and mix and prepare mixture; Constant pressure funnel is placed on 500ml flask with four necks,round bottom, described mixture in flask to be poured in constant pressure funnel and described mixed solvent is slowly dripped, the time for adding of described mixture controls at 1 ~ 4h, the soaking time dripping rear 500ml flask with four necks,round bottom controls at 6 ~ 10h, and insulation then can prepare the acrylic polymer that solid content is 50 ± 5% afterwards;
Above-mentioned benzene series kind solvent or toluene, or dimethylbenzene;
Above-mentioned alcohol system kind solvent or ethanol, or propyl carbinol;
Aforesaid propylene esters of gallic acid soft monomer or butyl acrylate, or ethyl propenoate, or hydroxyl ethyl acrylate;
Aforesaid propylene esters of gallic acid hard monomer or β-dimethyl-aminoethylmethacrylate, or methyl methacrylate;
Above-mentioned initiator or dibenzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN or peroxidation second propyl benzene DCP;
Above-mentioned stopper is n-dodecyl mereaptan;
The preparation of antifouling resin: the solvent adding the acrylic polymer of 140 ~ 150 weight parts, the hexadecanoic acid of 40 ~ 60 weight parts, the zinc-containing substance of 15 ~ 25 weight parts and 170 ~ 190 weight parts in four-hole boiling flask respectively, under 80 ± 5 DEG C of conditions, react 2 ~ 5h, be warming up to 110 ± 5 DEG C afterwards and be incubated 8 ~ 15h and can prepare from the stable antifouling resin of polishing speed;
Above-mentioned zinc-containing substance is zinc oxide;
Above-mentioned solvent is any one in ethanol, toluene, N-BUTYL ACETATE, dimethylbenzene, propyl carbinol, or its any two mixture, or its mixture of wantonly three kinds, or its mixture of wantonly four kinds, or its mixture of five kinds.
Owing to adopting technical scheme described above, the present invention produces following positively effect:
1. the antifouling resin that the present invention prepares not only can act synergistically with stain control agent, improve its antifouling property, and the heavy metal stain control agent content that can reduce in antifouling paint, product performance and the cost control problem of antifouling paint are taken into account, there is good economic worth, be expected to replace the used routine in market from polishing resin, there are wide market outlook.
2. the present invention adopts hexadecanoic acid as the zinc acrylate resin of antifouling side chain segments, by zinc bridge design, hexadecanoic acid is grafted to acrylic polymer side chain, give antifouling resin and there is anti-pollution function, simultaneously by controlling the graft ratio of hexadecanoic acid, regulate its wetting ability, to control antifouling resin hydrolysis rate, antifouling resin is hydrolyzed ooze out to be formed act synergistically with stain control agent, effective reduction stain control agent consumption, solve current from the problem of polishing resin body without antifouling activity, there is important environmental protection meaning and social and economic significance.
3. the antifouling resin that the present invention prepares has good fungistatic effect, method simple practical compared with commercially available zinc acrylate resin.
Accompanying drawing explanation
Fig. 1 is the absorbancy variation tendency reference drawing of the antibacterial sample of pseudoalteromonas at 0 ~ 6h of antifouling resin and commercially available zinc acrylate resin.
Fig. 2 is the absorbancy variation tendency reference drawing of the antibacterial sample of pseudoalteromonas at 18 ~ 24h of antifouling resin and commercially available zinc acrylate resin.
Fig. 3 is the absorbancy variation tendency reference drawing of the antibacterial sample of vibrio cholerae at 0 ~ 6h of antifouling resin and commercially available zinc acrylate resin.
Fig. 4 is the absorbancy variation tendency reference drawing of the antibacterial sample of vibrio cholerae at 18 ~ 24h of antifouling resin and commercially available zinc acrylate resin.
Embodiment
The present invention is a kind of method being prepared antifouling resin by hexadecanoic acid graft acrylic acid prepolymer, and method of the present invention comprises the preparation of acrylic polymer preparation and antifouling resin, and concrete preparation process, see described technical scheme, does not separately repeat.
Real in four embodiments according to described technical scheme, in four embodiments, the occurrence of each parameter is not the whole of described technical scheme, does not state part and is all as the criterion with described technical scheme.
Embodiment 1:
1) add 140g dimethylbenzene and 60g ethanol respectively to 500ml flask with four necks,round bottom, make it be warming up to 95 ± 5 DEG C under nitrogen protection and prepare mixed solvent.
2) get 40g vinylformic acid, 60g β-dimethyl-aminoethylmethacrylate and 160g butyl acrylate respectively, then get 4g dibenzoyl peroxide BPO and 2g n-dodecyl mereaptan and mix and prepare mixture.Constant pressure funnel is placed on 500ml flask with four necks,round bottom, described mixture in flask to be poured in constant pressure funnel and described mixed solvent is slowly dripped, time for adding controls at 3.5h and is incubated 9h, prepares the acrylic polymer that solid content is 55%.
3) 150g acrylic polymer, 60g hexadecanoic acid, 20g zinc oxide, 70g dimethylbenzene, 50g ethanol and 50g N-BUTYL ACETATE is added respectively to four-hole boiling flask, 2h is reacted under 80 ± 5 DEG C of conditions, react 10h under being warming up to 110 ± 5 DEG C of conditions again, can antifouling resin be prepared.
Embodiment 2:
1) add 140g toluene and 80g ethanol respectively to 500ml flask with four necks,round bottom, make it be warming up to 95 ± 5 DEG C under nitrogen protection and prepare mixed solvent.
2) get 60g vinylformic acid, 50g methyl methacrylate and 140g ethyl propenoate respectively, then get 3g Diisopropyl azodicarboxylate and 1g n-dodecyl mereaptan and mix and prepare mixture.Constant pressure funnel is placed on 500ml flask with four necks,round bottom, described mixture in flask to be poured in constant pressure funnel and described mixed solvent is slowly dripped, time for adding controls at 2.5h and is incubated 10h, prepares the acrylic polymer that solid content is 53%.
3) 150g acrylic polymer, 60g hexadecanoic acid, 15g zinc oxide, 60g toluene, 70g ethanol and 60g N-BUTYL ACETATE is added respectively to four-hole boiling flask, 5h is reacted under 80 ± 5 DEG C of conditions, react 15h under being warming up to 110 ± 5 DEG C of conditions again, can antifouling resin be prepared.
Embodiment 3:
1) add 130g dimethylbenzene and 100g propyl carbinol respectively to 500ml flask with four necks,round bottom, make it be warming up to 95 ± 5 DEG C under nitrogen protection and prepare mixed solvent.
2) get 55g vinylformic acid, 80g methyl methacrylate and 80g ethyl propenoate respectively, then get 4g dicumyl peroxide and 1.5g n-dodecyl mereaptan and mix and prepare mixture.Constant pressure funnel is placed on 500ml flask with four necks,round bottom, described mixture in flask to be poured in constant pressure funnel and described mixed solvent is slowly dripped, time for adding controls at 3.5h and is incubated 10h, prepares the acrylic polymer that solid content is 48%.
3) 140g acrylic polymer, 60g hexadecanoic acid, 25g zinc oxide, 60g dimethylbenzene, 60g propyl carbinol and 50g N-BUTYL ACETATE is added respectively to four-hole boiling flask, 3h is reacted under 80 ± 5 DEG C of conditions, react 12h under being warming up to 110 ± 5 DEG C of conditions again, can antifouling resin be prepared.
Embodiment 4:
1) add 90g toluene and 120g propyl carbinol respectively to 500ml flask with four necks,round bottom, make it be warming up to 95 ± 5 DEG C under nitrogen protection and prepare mixed solvent.
2) get 45g vinylformic acid, 60g methyl methacrylate and 110g ethyl propenoate respectively, then get 3.6g dibenzoyl BPO and 1.6g n-dodecyl mereaptan and mix and prepare mixture.Constant pressure funnel is placed on 500ml flask with four necks,round bottom, described mixture in flask to be poured in constant pressure funnel and described mixed solvent is slowly dripped, time for adding controls at 3h and is incubated 12h, prepares the acrylic polymer that solid content is 49%.
3) 150g acrylic polymer, 40g hexadecanoic acid, 15g zinc oxide, 50g toluene, 60g propyl carbinol and 60g N-BUTYL ACETATE is added respectively to four-hole boiling flask, 4h is reacted under 80 ± 5 DEG C of conditions, react 15h under being warming up to 110 ± 5 DEG C of conditions again, can antifouling resin be prepared.
The antifouling resin that above-mentioned four embodiments are prepared is made coating and carries out shallow sea and soak board experiment, 2 years test periods, its anti-fouling effect detects can reach more than 98% with reference to respective standard.
The antifouling resin that above-mentioned four embodiments and technical scheme of the present invention are prepared is a kind of antifouling resin stable from polishing speed, be verified in marine bacteria growth-inhibiting simultaneous test by antifouling resin and commercially available zinc acrylate resin: the pseudoalteromonas selecting ocean common and vibrio cholerae are as antibacterial sample, adopt absorbancy to characterize bacterial concentration, the larger then bacterial concentration of absorbancy is higher.
As can be seen from Fig. 1-2: the bacterial concentration of commercially available zinc acrylate resin increases sharply in time, absorbancy rises to 0.12 after 6 hours, after 24 hours, absorbancy is more than 0.4, and the bacterial concentration of antifouling resin is almost constant, be stabilized in about 0.04, be 1/10th of commercially available zinc acrylate resin, show that antifouling resin of the present invention has good fungistatic effect to alternately false unicellular.
As can be seen from Fig. 3-4: the bacterial concentration of commercially available zinc acrylate resin increases sharply in time, absorbancy rises to about 0.2 after 6 hours, after 24 hours, absorbancy is more than 0.7, and the bacterial concentration of antifouling resin is almost constant, be stabilized in about 0.04, be 1/17th of commercially available zinc acrylate resin, show that antifouling resin of the present invention has good fungistatic effect to arc vibrios suddenly.
Molecular structure reaction reference process of the present invention is as follows:
The hydrolysate of antifouling resin of the present invention after making coating is the hexadecanoic acid with Biostatic, as follows with reference to hydrolytic process:
。
Claims (1)
1. prepared a method for antifouling resin by hexadecanoic acid graft acrylic acid prepolymer, the method comprises the preparation of acrylic polymer and the preparation of antifouling resin, it is characterized in that:
The preparation of acrylic polymer: add the benzene series kind solvent of 90 ~ 140 weight parts and the alcohol system kind solvent of 60 ~ 120 weight parts in 500ml flask with four necks,round bottom, make flask with four necks,round bottom be warming up to 95 ± 5 DEG C under nitrogen protection and prepare mixed solvent; Get the vinylformic acid of 40 ~ 60 weight parts, the esters of acrylic acid soft monomer of 80 ~ 160 weight parts and the esters of acrylic acid hard monomer of 50 ~ 80 weight parts to be respectively placed in flask and to mix, add the initiator of 3 ~ 4 weight parts and the stopper of 1 ~ 2 weight part afterwards and mix and prepare mixture; Constant pressure funnel is placed on 500ml flask with four necks,round bottom, described mixture in flask to be poured in constant pressure funnel and described mixed solvent is slowly dripped, the time for adding of described mixture controls at 1 ~ 4h, the soaking time dripping rear 500ml flask with four necks,round bottom controls at 6 ~ 10h, and insulation then can prepare the acrylic polymer that solid content is 50 ± 5% afterwards;
Above-mentioned benzene series kind solvent or toluene, or dimethylbenzene;
Above-mentioned alcohol system kind solvent or ethanol, or propyl carbinol;
Aforesaid propylene esters of gallic acid soft monomer or butyl acrylate, or ethyl propenoate, or hydroxyl ethyl acrylate;
Aforesaid propylene esters of gallic acid hard monomer or β-dimethyl-aminoethylmethacrylate, or methyl methacrylate;
Above-mentioned initiator or dibenzoyl peroxide BPO or Diisopropyl azodicarboxylate AIBN or peroxidation second propyl benzene DCP;
Above-mentioned stopper is n-dodecyl mereaptan;
The preparation of antifouling resin: the solvent adding the acrylic polymer of 140 ~ 150 weight parts, the hexadecanoic acid of 40 ~ 60 weight parts, the zinc-containing substance of 15 ~ 25 weight parts and 170 ~ 190 weight parts in four-hole boiling flask respectively, under 80 ± 5 DEG C of conditions, react 2 ~ 5h, be warming up to 110 ± 5 DEG C afterwards and be incubated 8 ~ 15h and can prepare from the stable antifouling resin of polishing speed;
Above-mentioned zinc-containing substance is zinc oxide;
Above-mentioned solvent is any one in ethanol, toluene, N-BUTYL ACETATE, dimethylbenzene, propyl carbinol, or its any two mixture, or its mixture of wantonly three kinds, or its mixture of wantonly four kinds, or its mixture of five kinds.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106632876A (en) * | 2016-11-11 | 2017-05-10 | 浙江大学 | Resin for antifouling paint and preparation method thereof |
| CN106317346B (en) * | 2016-08-17 | 2019-02-01 | 厦门双瑞船舶涂料有限公司 | A kind of preparation method and its usage of degradable antifouling resin |
| CN109651914A (en) * | 2018-11-27 | 2019-04-19 | 中国船舶重工集团公司第七二五研究所 | A kind of antifouling paint ocean temperature response type resin combination and preparation method thereof |
| CN114716684A (en) * | 2022-03-31 | 2022-07-08 | 吴晓金 | Self-polishing antifouling resin with degradation and hydrolysis performances and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106317346B (en) * | 2016-08-17 | 2019-02-01 | 厦门双瑞船舶涂料有限公司 | A kind of preparation method and its usage of degradable antifouling resin |
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| CN109651914A (en) * | 2018-11-27 | 2019-04-19 | 中国船舶重工集团公司第七二五研究所 | A kind of antifouling paint ocean temperature response type resin combination and preparation method thereof |
| CN109651914B (en) * | 2018-11-27 | 2021-04-02 | 中国船舶重工集团公司第七二五研究所 | Seawater temperature response type resin composition for antifouling paint and preparation method thereof |
| CN114716684A (en) * | 2022-03-31 | 2022-07-08 | 吴晓金 | Self-polishing antifouling resin with degradation and hydrolysis performances and preparation method thereof |
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Application publication date: 20151230 |