CN102532396B - Lateral-chain stem grafting glyphosate derivative acrylic resin and preparation method and application thereof - Google Patents

Lateral-chain stem grafting glyphosate derivative acrylic resin and preparation method and application thereof Download PDF

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Publication number
CN102532396B
CN102532396B CN201110452365.4A CN201110452365A CN102532396B CN 102532396 B CN102532396 B CN 102532396B CN 201110452365 A CN201110452365 A CN 201110452365A CN 102532396 B CN102532396 B CN 102532396B
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acrylic resin
lateral
glyphosate
chain
glyphosate derivative
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CN102532396A (en
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江学志
黄从树
王晶晶
任润桃
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725th Research Institute of CSIC
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725th Research Institute of CSIC
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Abstract

The invention introduces lateral-chain stem grafting glyphosate derivative acrylic resin and a preparation method and application thereof. According to the constitutional formula, R1, R2 and R3 in the formula are CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2OH, CH2CH2OH, CH2CH2CH2O or CH2CH2CH2CH2OH, m ranges from 0 to 1000, n ranges from 2 to 500, p ranges from 0 to 1000, and the sum of the m, the n and the P is larger than 10. By means of the preparation method, a plurality of ester linkages are designed on a resin molecule chain, glyphosate derivative is grafted on the lateral chain, products can serve as film forming materials of ocean antifouling paint, antifouling performance and environment-friendly performance are good, and the products have good self polishing performance and eco-friendly performance.

Description

A kind of lateral-chain stem grafting glyphosate derivative acrylic resin and method for making and application
Technical field
The present invention relates to a kind of chemical material field technology, particularly a kind of lateral-chain stem grafting glyphosate derivative acrylic resin and method for making thereof and application.
Background technology
As everyone knows, once marine biofouling will produce serious harm in maritime facilities surface attachment: shell is stained will obviously increase frictional resistance of ship body, reduce ship's speed, increase fuel consumption and the frequency of maintenance that lies up; Buoy is stained rear because of often replacing of weight increase; In salt water cooling system, biodeterioration usually causes the obstruction of velocity in pipes reduction and pipeline.Solving the most frequently used, the simple method of extra large sample biodeterioration is to apply antifouling paint.
A large amount of uses both at home and abroad is that Tin-free Spc Anti-fouling Paint is the antifouling paint taking vinylformic acid copper polymer, zinc acrylate resin polymkeric substance and acrylic silane ester polymer etc. as base-material at present.This type of coating is water insoluble, and coating plays polishing effect by ion exchange release metal ions in seawater, stain control agent stripping in polishing process.But this class tin-free self-polishing coating exists certain defect, and the performance of its performance has certain requirement to ship's speed, in the time that ship running is too slow or the time in port is oversize, self-polishing coating usefulness declines; In the time that ship running is too fast, stain control agent can excessively discharge, thereby antifouling life is shortened, and does not reach the antifouling time limit of expection.Therefore, be badly in need of that exploitation is a kind of not only to be had well in polishing performance in static seawater, and can in the situation that reducing Red copper oxide content, still there are the novel environment-friendly antifouling paint product as an alternative of good antifouling property.
summary of the inventiontechnical problem to be solved by this invention is to provide a kind of lateral-chain stem grafting glyphosate derivative acrylic resin and method for making and application, this resin is as the filmogen of marine antifouling coating, not only have good in polishability, and there is the friendly performance of nontoxic ecology, to make up the deficiencies in the prior art.
In order to realize the object solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of lateral-chain stem grafting glyphosate derivative acrylic resin, its structural formula is:
R in formula 1, R 2, R 3for CH 3, CH 2cH 3, CH 2cH 2cH 3, CH 2cH 2cH 2cH 3, CH 2oH, CH 2cH 2oH, CH 2cH 2cH 2o or CH 2cH 2cH 2cH 2oH; M is 0~1000; N is 2~500; P is 0~1000; And m, n, p sum are greater than 10.
The preparation method of lateral-chain stem grafting glyphosate derivative acrylic resin is: first glyphosate and alcohols monomer are carried out to esterification, prepare glyphosate ester derivative, glyphosate ester derivative is reacted with acrylate chloride and make acryloyl glyphosate ester derivative again, last under the effect of radical initiator, acryloyl glyphosate derivative reacts the acrylic resin that obtains lateral-chain stem grafting glyphosate derivative with methacrylic ester, acrylate etc.
Described radical initiator, comprises azo radical initiator, peroxide radical initiator.
Lateral-chain stem grafting glyphosate derivative acrylic resin is being prepared the application of marine antifouling coating.
Antifouling paint prepared by this lateral-chain stem grafting glyphosate derivative acrylic resin is made up of acrylic resin soln, softening agent, stopping composition and auxiliary stain control agent four parts of lateral-chain stem grafting glyphosate derivative substantially, and its weight percent consists of acrylic resin soln 20~60%, softening agent 1~25%, stopping composition 1~30%, the auxiliary stain control agent 1~35% of the chain grafting glyphosate derivative of concentration range 30~60%.
As shown in table 1:
marine antifouling coating integral part prepared by table 1
Component Weight percentage
The acrylic resin soln of lateral-chain stem grafting glyphosate derivative 20~60
Softening agent 1~25
Stopping composition 1~30
Stain control agent 1~35
Described organic solvent is any or its arbitrary proportion mixture of dimethylbenzene, toluene, ethyl acetate, butylacetate, DMF or hexone (MIBK); Described softening agent is any or its arbitrary proportion mixture of clorafin, Vaseline, dibutyl phthalate or dioctyl phthalate (DOP); Described stopping composition is one or more the arbitrary proportion mixtures in red iron oxide, zinc oxide, talcum powder, titanium dioxide or aerosil solid particulate; Described stain control agent is N-phenylmaleimide, a-bromo cinnamaldehyde, tetramethyl-thiuram disulfide or SeaNine211 tMin one or more arbitrary proportion mixtures.
The evaluation of antifouling property:
With reference to national standard " antifouling varnish model shallow sea soak test method " (GB 5370-85), be 250mm by antifouling paint brushing in plate length, wide 150mm, thick is the soft steel experiment model of 1.5mm, this experiment model is hung over to Xiamen sea area and test floating cutting down, respectively at 1,2 and 6 months after measure the area of each model Shanghai ocean biodeterioration, obtained good experimental result, as shown in table 2.
table 2 antifouling paint model shallow sea panel experiment result
Synthetic lateral-chain stem grafting glyphosate derivative acrylic resin not only can be used as the filmogen of antifouling paint, and has good antifouling property and environment friendly.
By adopting technique scheme, the present invention has following beneficial effect:
The present invention by design multiple ester bonds at molecular resin chain and on side chain grafting glyphosate derivative, obtain a kind of well lateral-chain stem grafting glyphosate derivative acrylic resin from polishability and certain didirtresistance that has.This resin is as the filmogen of marine antifouling coating, there is good antifouling property and environment friendly, not only have good in polishability, and there is the friendly performance of nontoxic ecology, make up the deficiency of existing not stanniferous self polishing copolymer antifouling paint performance, therefore there is higher economic benefit and social benefit.
Brief description of the drawings
Fig. 1 is the acrylic resin synthetic route chart of lateral-chain stem grafting glyphosate derivative.
In figure, R1, R2, R3 are CH 3, CH 2cH 3, CH 2cH 2cH 3, CH 2cH 2cH 2cH 3, CH 2oH, CH 2cH 2oH, CH 2cH 2cH 2o or CH 2cH 2cH 2cH 2oH.M is 0~1000; N is 2~500; P is 0~1000; And m, n, p sum are greater than 10.In order to ensure that resin of the present invention has good didirtresistance, after fixing n value, regulating m to make aforesaid propylene acyl glyphosate derivative account for weight resin percentage ratio with p value (being 0 when m is different with p value) is 2-50%.
Embodiment
Embodiment 1
A. the preparation of glyphosate ester derivative
When preparation, in the there-necked flask that whipping appts is housed, add successively 10g glyphosate, 50ml ethanol and 3g trimethylchlorosilane, after room temperature reaction 5 hours, in above-mentioned reaction mixture, add propylene oxide, leave standstill and generate white precipitate, filter, and be washed with water to neutrality, obtain the present invention's glyphosate derivative used.
B. the preparation of acryloyl glyphosate ester derivative
When preparation, above-mentioned 10g glyphosate derivative, 50gNaOH solution are added in the there-necked flask that whipping appts is housed, under room temperature, drip 6g acrylate chloride, within approximately 1 hour, dropwise, then continue reaction 24h.Regulate pH value to 2.0 left and right of mixing solutions with HCl solution, distillation precipitated sodium chloride, filtrate regulates pH value to 5.0 left and right with NaOH solution, then underpressure distillation, except after desolventizing, by product vacuum-drying, obtains the present invention's acryloyl glyphosate derivative used.
C. the preparation of lateral-chain stem grafting glyphosate derivative acrylic resin
When preparation, the mixed solvent that is 4:1 by 30g toluene and propyl carbinol mass ratio adds in 500ml there-necked flask, be heated with stirring to after 95 DEG C, by 4g acryloyl glyphosate derivative, 53g methyl methacrylate, 20g ethyl propenoate, 27g Propylene glycol monoacrylate, 2g Diisopropyl azodicarboxylate (AIBN) is dissolved in the mixed solvent that 70g toluene and propyl carbinol mass ratio are 4:1, move in constant pressure funnel and to there-necked flask and drip solution, in approximately 1 hour, drip, then maintain 95 DEG C of temperature of reaction, continue stirring reaction 10 hours, obtain the acrylic resin soln of lateral-chain stem grafting glyphosate derivative, the molecular weight of resin is 10500.
D. the preparation of lateral-chain stem grafting glyphosate derivative acrylic resin antifouling paint
When preparation, the mixture of 45g lateral-chain stem grafting glyphosate derivative acrylic resin solution, 8g red iron oxide, 8g Vaseline, 20gN-phenyl maleimide, 10g talcum powder, 4g tetramethyl-thiuram disulfide, 5g clorafin is placed in the paint shaker that contains steel ball and shakes 24h, then filter with 100 object strainers, obtain lateral-chain stem grafting glyphosate derivative acrylic resin antifouling paint.
Embodiment 2
A. the preparation of glyphosate ester derivative
When preparation, in the there-necked flask that whipping appts is housed, add successively 10g glyphosate, 50ml ethanol and 3g trimethylchlorosilane, after room temperature reaction 8 hours, in above-mentioned reaction mixture, add propylene oxide, leave standstill and generate white precipitate, filter, and be washed with water to neutrality, obtain the present invention's glyphosate derivative used.
B. the preparation of acryloyl glyphosate ester derivative
When preparation, above-mentioned 10g glyphosate derivative, 50gNaOH solution are added in the there-necked flask that whipping appts is housed, under room temperature, drip 6g acrylate chloride, within approximately 1 hour, dropwise, then continue reaction 24h.Regulate pH value to 3.0 left and right of mixing solutions with HCl solution, distillation precipitated sodium chloride, filtrate regulates pH value to 4.0 left and right with NaOH solution, then underpressure distillation, except after desolventizing, by product vacuum-drying, obtains the present invention's acryloyl glyphosate derivative used.
C. the preparation of lateral-chain stem grafting glyphosate derivative acrylic resin
When preparation, the mixed solvent that is 4:1 by 30g toluene and propyl carbinol mass ratio adds in 500ml there-necked flask, be heated with stirring to after 105 DEG C, by 4g acryloyl glyphosate derivative, 53g methyl methacrylate, 20g ethyl propenoate, 27g Propylene glycol monoacrylate, 2g Diisopropyl azodicarboxylate (AIBN) is dissolved in the mixed solvent that 70g toluene and propyl carbinol mass ratio are 4:1, move in constant pressure funnel and to there-necked flask and drip solution, in approximately 3 hours, drip, then maintain 105 DEG C of temperature of reaction, continue stirring reaction 5 hours, obtain the acrylic resin soln of lateral-chain stem grafting glyphosate derivative, molecular resin amount is 12000.
Described toluene and n-butanol mixed solvent can change ethyl acetate and n-butanol mixed solvent, butylacetate and n-butanol mixed solvent, dimethylbenzene and n-butanol mixed solvent, toluene or dimethylbenzene into.
D. the preparation of lateral-chain stem grafting glyphosate derivative acrylic resin antifouling paint
When preparation, the mixture of 45g lateral-chain stem grafting glyphosate derivative acrylic resin solution, 8g red iron oxide, 8g dibutyl phthalate, 20gN-phenyl maleimide, 10g zinc oxide, 4g tetramethyl-thiuram disulfide, 5g clorafin is placed in the paint shaker that contains steel ball and shakes 24h, then filter with 100 object strainers, obtain lateral-chain stem grafting glyphosate derivative acrylic resin antifouling paint.
the antifouling paint model shallow sea panel experiment result of table 3 embodiment

Claims (1)

1. lateral-chain stem grafting glyphosate derivative acrylic resin is being prepared an application for marine antifouling coating, and the structural formula of lateral-chain stem grafting glyphosate derivative acrylic resin is:
R in formula 1, R 2, R 3for CH 3, CH 2cH 3, CH 2cH 2cH 3, CH 2cH 2cH 2cH 3, CH 2oH, CH 2cH 2oH or CH 2cH 2cH 2cH 2oH; M is 0~1000; N is 2~500; P is 0~1000; And m, n, p sum are more than or equal to 10;
It is characterized in that: marine antifouling coating is made up of acrylic resin soln, softening agent, stopping composition and auxiliary stain control agent four parts of lateral-chain stem grafting glyphosate derivative, its weight percent consists of acrylic resin soln 20~60%, softening agent 1~25%, stopping composition 1~30%, the auxiliary stain control agent 1~35% of the chain grafting glyphosate derivative of concentration range 30~60%; Solvent is any or its arbitrary proportion mixture of dimethylbenzene, toluene, ethyl acetate, butylacetate, DMF or hexone; Described softening agent is any or its arbitrary proportion mixture of clorafin, Vaseline, dibutyl phthalate or dioctyl phthalate (DOP); Described stopping composition is one or more the arbitrary proportion mixtures in red iron oxide, zinc oxide, talcum powder, titanium dioxide or aerosil solid particulate; Described stain control agent is N-phenylmaleimide, a-bromo cinnamaldehyde, tetramethyl-thiuram disulfide or SeaNine211 tMin one or more arbitrary proportion mixtures.
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CN103864985B (en) * 2014-04-04 2016-02-10 段小宁 A kind of fast light preparation method with flame retardant resistance coating, finish paint
CN109666042A (en) * 2017-10-17 2019-04-23 中石化石油工程技术服务有限公司 A kind of preparation method of methacryl glyphosate
KR102130684B1 (en) * 2019-02-19 2020-07-06 부산대학교 산학협력단 Nonmetallic self-polishing copolymers, and anti-fouling composition comprising the same
CN111234162A (en) * 2020-03-19 2020-06-05 嘉兴学院 Side chain grafted glyphosate degradable polyurethane and preparation method and application thereof

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US20080317700A1 (en) * 2006-12-21 2008-12-25 Bowling Green State University Synthesis and biological activity of photopolymerizable derivatives of glyphosate

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Title
Aneta Bogdanove et al..Synthesis and Biological Activity of Photopolymerizable Derivatives of Glyphosate.《Biomacromolecules》.2007,第8卷(第2期),第439-447页.
Synthesis and Biological Activity of Photopolymerizable Derivatives of Glyphosate;Aneta Bogdanove et al.;《Biomacromolecules》;20070106;第8卷(第2期);第439-447页 *

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