Asparagus fern polyureas performed polymer and preparation method and a kind of coatingTechnical field
The present invention relates to polyureas synthesis technical field more particularly to asparagus fern polyureas performed polymer and preparation method and a kind of paintingsMaterial.
Background technique
Polyaspartic ester SPUA material is a kind of novel aliphatic coating material that polyurea industry field occurs in recent yearsMaterial, it has, and reaction is slow, the high feature of performance, referred to as third generation polyureas.Polyaspartic ester is a kind of steric-hindranceBinary aliphatic secondary amine, it is different from traditional carbamide paint in application and aspect of performance, revolutionize the gel of traditional polyureasThe disadvantages of time is short, poor adhesive force, easy xanthochromia.Polyaspartic Ester-Based Coatings are close with bi-component aliphatic polyurethane coating.Compared with conventional urethane coating, and there is solid content high, hardness and gel time is adjustable, good corrosion resistance, wear-resisting, resistance to HuangBecome, the excellent properties such as adhesive force is strong, thick can apply, is insensitive to temperature and humidity, and is not required to special spraying application equipment.It can be preparedHigh-weatherability and protective coating resistant to chemical etching, expediting setting type finishing coat, the fast-curing paint for being directly applied to metal baseAnd industry ground slab, the anti-corrosion protection for being widely used in outdoor iron structure, the petrochemical facility coating for needing antistatic heat insulating and corrosion,The fields etc. such as are overhauled in the industrial coating of electric power machine, the protection of wind-power tower and fan blade, the protection of concrete surface decoration, tunnel.
The asparagus fern polyurea products of existing market are in order to obtain the longer construction time, it is necessary to a kind of binary primary of big steric hindranceAmine and diethyl maleate form the performed polymer of asparagus fern polyureas.This amine high production cost, and production process is complicated.Therefore,The current asparagus fern carbamide resin production cycle is long, generally at least 7 days generated times, and energy consumption is high, and the time of delivery is long, and cost occupies height notUnder.
Summary of the invention
The technical problem to be solved by the present invention is to overcome, prior art synthetic method is complicated, energy consumption is high, the production cycle is longDefect, asparagus fern polyureas performed polymer and preparation method thereof and a kind of coating are provided.
To solve the above-mentioned problems, the present invention proposes following technical scheme:
A kind of asparagus fern polyureas performed polymer, comprises the following structure formula:
Wherein, R is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 and 20 or less；
R ' is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 and 20 or less；
R1For low carbon chain alkyl or cyclic alkyl, carbon atom number is six or six or less.
The present invention also proposes the method for preparing above-mentioned asparagus fern polyureas performed polymer, comprising the following steps:
Maleic anhydride and dihydric alcohol are pressed equivalent proportion 2:1, carry out alcoholysis reaction, generate two maleic acid binary alcohol esters by S1；
The two maleic acids binary alcohol esters and excessive alkylol are carried out esterification, obtain maleate, reacted by S2Catalyst is Bronst acid, Lewis acid or solid acid catalyst；
The maleate and excessive bulky amine are carried out addition reaction, obtain the performed polymer by S3.
Further, the carbon-chain structure of the dihydric alcohol is that linear carbon chain, cyclic carbon chain or straight chain ehter bond, carbon atom number exist20 or 20 or less；The carbon-chain structure of the bulky amine is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 or 20Below.
Further, the alkylol is low carbon chain alkylol or cyclic alkyl alcohol, carbon atom number be six or six withUnder.
Further, the reaction temperature of the step S1 is -100 DEG C of room temperature.
Further, the reaction temperature of the step S2 is 65-120 DEG C.
Further, the reaction temperature of the step S3 is -80 DEG C of room temperature.
It further, further include removing excessive alkylol step before the step S3.
Further, after the step S3, further include the steps that removing excessive bulky amine.
The present invention also provides a kind of coating, including poly- asparagus fern resin, the raw material of the poly- asparagus fern resin includes the dayWinter polyureas performed polymer.
Compared with prior art, the accessible technical effect of the present invention includes:
The present invention provides a kind of asparagus fern polyureas performed polymer and preparation method thereof, which is to prepare poly- asparagus fernThe elongation and wearability of poly- asparagus fern resin can be improved in the primary raw material of resin.
The present invention also provides the method for preparing asparagus fern polyureas performed polymer, by two maleic anhydrides and a dihydric alcohol alcoholysis atMaleic acid monoester, then this monoesters is esterified completely with ethyl alcohol, obtained maleate and amine carry out addition reaction and obtain；The techniqueThe features such as method has high income, and by-product is few, at low cost, easily separated, is a kind of route of environment friendly and economical, is overcome existingHave that technical operation is complicated, the low defect of yield, development prospect is wide.
Coating provided by the invention includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includes the asparagus fern polyureasPerformed polymer；The coating is compared compared with traditional coating, has excellent elongation, adhesive force and wearability.
Specific embodiment
The technical solution in embodiment will be clearly and completely described below.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instructionDescribed feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precludedBody, step, operation, the presence or addition of element, component and/or its set.
It is also understood that in this embodiment of the present invention term used in the description merely for the sake of description particular implementationExample purpose and be not intended to limit the embodiment of the present invention.Such as the institute in specification and appended book of the embodiment of the present inventionAs use, other situations unless the context is clearly specified, otherwise " one " of singular, "one" and "the" are intended to wrapInclude plural form.
The embodiment of the present invention provides a kind of asparagus fern polyureas performed polymer, comprises the following structure formula:
Wherein, R is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 and 20 or less；
R ' is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 and 20 or less；
R1 is low carbon chain alkyl or cyclic alkyl, and carbon atom number is six or six or less.
The present invention also proposes a kind of method for preparing above-mentioned asparagus fern polyureas performed polymer, comprising the following steps:
Maleic anhydride and dihydric alcohol are pressed equivalent proportion 2:1, carry out alcoholysis reaction, generate two maleic acid binary alcohol esters by S1；
The two maleic acids binary alcohol esters and excessive alkylol are carried out esterification, obtain maleate, reacted by S2Catalyst is Bronst acid, Lewis acid or solid acid catalyst；
The maleate and excessive bulky amine are carried out addition reaction, obtain the performed polymer by S3.
It is appreciated that in step S2 that two maleic acid binary alcohol esters and excessive alkylol carry out esterification, wherein alkylThe dosage of alcohol should ensure that two maleic acid binary alcohol esters of reactant react completely and use up, and obtains maleate, is passed through excessive alkylAlcohol can promote reaction forward to carry out.In addition, alkylol have the characteristics that it is segregative, after reaction can pass through vacuum distillation purificationMode remove excessive alkylol, process is simple and easy.
It is appreciated that the maleate that step S2 is obtained contains, there are two unsaturated double-bonds, in the addition reaction of step S3,The dosage of bulky amine should be at least 2 times of maleate dosage, so that the complete addition of maleate；In order to promote reaction forward intoRow, and ensure the complete addition of maleate, therefore the bulky amine of the maleate content greater than 2 times need to be passed through.In addition, bulky amineHave the characteristics that it is segregative, after reaction can vacuum distillation purification by way of remove excessive bulky amine.
Further, in step S1, dihydric alcohol is added in maleic anhydride several times, so that reactant can sufficiently react,The reaction can be in room temperature to carrying out at 100 DEG C.It is appreciated that being repeatedly at least once, in order to accelerate described in the present embodimentReaction rate, those skilled in the art can be added reactant in proportional region of the invention according to the actual situation and carry out insteadIt answers, all falls in the scope of protection of the present invention.
Catalyst used in the step S2 is Bronst acid catalyst, Lewis acid catalyst or solid acid catalyst.
It should be noted that the solid acid catalyst include alkyl-substituted benzene sulfonic acid, it is alkyl-substituted naphthalene sulfonic acids, non-Alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorosulfonic acid type resin, heteropoly acid and miscellaneousMulti-acid salt, molecular sieve, acidic ion liquid, single complex carrier SO42-/MXOYSolid super-strong acid, S2O82-/MXOYSolid super strongAt least one of acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3In at least oneKind.
Further, the carbon-chain structure of the dihydric alcohol is that linear carbon chain, cyclic carbon chain or straight chain ehter bond, carbon atom number exist20 or 20 or less；The carbon-chain structure of the bulky amine is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 or 20Below.
In other embodiments, the bulky amine can be kiber alkyl amine or polyetheramine, carbon-chain structure be linear carbon chain,Cyclic carbon chain or straight chain ehter bond, carbon atom number is 20 or 20 or less.
Further, in step S2, the temperature of esterification is 65-120 DEG C.Reaction product includes water, by the alkylAlcohol band water, promotes reaction forward to carry out.Excessive alkylol is removed by way of vacuum distillation purification after reaction.
Further, the alkylol is low carbon chain alkylol or cyclic alkyl alcohol, carbon atom number be six or six withUnder.
Further, the Michael addition reaction in step S3 can be in room temperature to carrying out at 80 DEG C.Pass through after reactionThe mode of vacuum distillation removes excessive bulky amine.
Specifically, step S1 reaction equation is as follows:
Step S2 reaction equation is as follows:
Step S3 reaction equation is as follows:
Wherein, in reaction equation 1-3, R is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 and 20 or less；
R ' is linear carbon chain, cyclic carbon chain or straight chain ehter bond, and carbon atom number is 20 and 20 or less；
R1 is low carbon chain alkyl or cyclic alkyl, and carbon atom number is six or six or less.
Embodiment one:
The present embodiment proposes a kind of asparagus fern polyureas performed polymer A comprising following structural formula:
The present embodiment also provides the preparation method of performed polymer A:
The three neck round bottom flask containing 106 grams of diethylene glycol of 500mL is added in five times by 196 grams of maleic anhydride, reactsTemperature 50 C.Extent of reaction is monitored by gas-chromatography and TLC.Work as fully reacting, carries out second step reaction.By above-mentioned reactionTwo maleic acid monoesters and 184 grams of ethyl alcohol are under 15 grams of 15 catalyst actions of Amberlyst, 80 DEG C of reactions, with ethyl alcohol for water, TLCMonitor extent of reaction.Work as fully reacting, filter out catalyst, removes excessive ethyl alcohol with vacuum distillation.The horse that above-mentioned reaction obtainsCarry out acid esters to be slowly added dropwise in excessive ring amine, temperature is 60 DEG C, and wait be added dropwise, reaction continues 8 at this temperatureHour.Extent of reaction is monitored with TLC.When reaction is completed, vacuum distillation obtains poly-aspartic-acid except the ring amine of end removing reactionAbout 520 grams of the performed polymer A of ester resin, yield 93.5%.
The present embodiment also provides a kind of coating, which includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includesAsparagus fern polyureas performed polymer A.
Embodiment two:
The present embodiment proposes a kind of asparagus fern polyureas performed polymer B comprising following structural formula B:
The present embodiment also provides the preparation method of performed polymer B:
By 196 grams of the maleic anhydride three neck round bottom flask that the 500mL containing 104 grams of 1,5-PD is added secondary in five batches,60 DEG C of reaction temperature.Extent of reaction is monitored by gas-chromatography and TLC.Work as fully reacting, carries out second step reaction.It will be above-mentioned anti-Under 15 grams of Amberlyst35 catalyst actions, n-butanol is used in 117 DEG C of reactions for two maleic acid monoesters answered and 300 grams of n-butanolsDai Shui, TLC monitor extent of reaction.Work as fully reacting, filter out catalyst, removes excessive n-butanol with vacuum distillation.It is above-mentioned anti-The maleate that should be obtained is slowly added dropwise in excessive isobutyl amine, and temperature is 70 DEG C, and wait be added dropwise, reaction is at this temperatureContinue 8 hours.Extent of reaction is monitored with TLC.When reaction is completed, vacuum distillation obtains day except the isobutyl amine of end removing reactionAbout 500 grams of winter polyureas performed polymer B, yield 89.6%.
The present embodiment also provides a kind of coating, which includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includesAsparagus fern polyureas performed polymer B.
Embodiment three:
The present embodiment proposes a kind of asparagus fern polyureas performed polymer C comprising following structural formula:
The present embodiment also provides the preparation method of performed polymer C:
The three neck round bottom flask of 116 grams of Isosorbide-5-Nitrae-cyclohexandiol of 500mL is added in 196 grams of maleic anhydride in five batches, reactionTemperature 60 C.Extent of reaction is monitored by gas-chromatography and TLC.Work as fully reacting, carries out second step reaction.By above-mentioned reactionTwo maleic acid monoesters and 184 grams of ethyl alcohol are under 15 grams of 35 catalyst actions of Amberlyst, 80 DEG C of reactions, with ethyl alcohol for water, TLCMonitor extent of reaction.Work as fully reacting, filter out catalyst, removes excessive ethyl alcohol with vacuum distillation.The horse that above-mentioned reaction obtainsCarry out acid esters to be slowly added dropwise in excessive tert-butylamine, temperature is 80 DEG C, and wait be added dropwise, reaction continues 18 at this temperatureHour.Extent of reaction is monitored with TLC.When reaction is completed, vacuum distillation obtains asparagus fern polyureas pre-polymerization except the tert-butylamine of end removing reactionAbout 500 grams of body C, yield 97.3%.
The present embodiment also provides a kind of coating, which includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includesAsparagus fern polyureas performed polymer C.
Example IV:
The present embodiment proposes a kind of asparagus fern polyureas performed polymer D comprising following structural formula:
The present embodiment also provides the preparation method of performed polymer D:
Three mouthfuls of circles of the 500mL of 212 grams of 4,4'- dihydroxyl dicyclohexyl methane are added in 196 grams of maleic anhydride in five batchesBottom flask, 60 DEG C of reaction temperature.Extent of reaction is monitored by gas-chromatography and TLC.Work as fully reacting, carries out second step reaction.By two maleic acid monoesters of above-mentioned reaction and 184 grams of ethyl alcohol under 30 grams of Amberlyst35 catalyst actions, 80 DEG C of reactions are usedEthyl alcohol monitors extent of reaction for water, TLC.Work as fully reacting, filter out catalyst, removes excessive ethyl alcohol with vacuum distillation.It is above-mentionedIt reacts obtained maleate to be slowly added dropwise in excessive 2- methyl ring amine, temperature is 80 DEG C, and wait be added dropwise, reaction existsContinue at a temperature of this 18 hours.Extent of reaction is monitored with TLC.When reaction is completed, vacuum distillation removes the 2- first of end removing reactionBase ring amine obtains about 600 grams of asparagus fern polyureas performed polymer D, yield 87%.
The present embodiment also provides a kind of coating, which includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includesAsparagus fern polyureas performed polymer D.
Embodiment five:
The present embodiment proposes a kind of asparagus fern polyureas performed polymer E comprising following structural formula:
The present embodiment also provides the preparation method of performed polymer E:
PEG200, the three neck round bottom flask of 200 grams of 500mL, reaction temperature 70 is added in 196 grams of maleic anhydride in five batches℃.Extent of reaction is monitored by gas-chromatography and TLC.Work as fully reacting, carries out second step reaction.By two Malaysias of above-mentioned reactionAcid monoester and 184 grams of ethyl alcohol are under 30 grams of 35 catalyst actions of Amberlyst, 80 DEG C of reactions, and with ethyl alcohol for water, TLC monitoring is anti-Answer progress.Work as fully reacting, filter out catalyst, removes excessive ethyl alcohol with vacuum distillation.The maleate that above-mentioned reaction obtainsIt is slowly added dropwise in excessive 2- methyl ring amine, temperature is 80 DEG C, and wait be added dropwise, reaction continues 18 at this temperatureHour.Extent of reaction is monitored with TLC.When reaction is completed, it is poly- to obtain asparagus fern except the 2- methyl ring amine of end removing reaction for vacuum distillationAbout 620 grams of urea performed polymer E, yield 87%.
The present embodiment also provides a kind of coating, which includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includesAsparagus fern polyureas performed polymer E.
Embodiment six:
The present embodiment proposes a kind of asparagus fern polyureas performed polymer F comprising following structural formula:
The present embodiment also provides the preparation method of performed polymer F:
The three neck round bottom flask of 194 grams of tetraethylene glycol of 500mL, reaction temperature is added in 196 grams of maleic anhydride in five batches70℃.Extent of reaction is monitored by gas-chromatography and TLC.Work as fully reacting, carries out second step reaction.By two horses of above-mentioned reactionCome acid monoester and 184 grams of ethyl alcohol under 30 grams of 35 catalyst actions of Amberlyst, 80 DEG C of reactions, with ethyl alcohol for water, TLC monitoringExtent of reaction.Work as fully reacting, filter out catalyst, removes excessive ethyl alcohol with vacuum distillation.The maleic acid that above-mentioned reaction obtainsEster is slowly added dropwise into excessive 2,6- dimethyl cyclohexyl amine, and temperature is 80 DEG C, and wait be added dropwise, reaction continues at this temperatureIt carries out 18 hours.Extent of reaction is monitored with TLC.When reaction is completed, vacuum distillation removes 2, the 6- dimethyl cyclohexyl amine of end removing reaction,Obtain about 620 grams of asparagus fern polyureas performed polymer F, yield 88.6%.
The present embodiment also provides a kind of coating, which includes poly- asparagus fern resin, and the raw material of the poly- asparagus fern resin includesAsparagus fern polyureas performed polymer F.
Experimental formula
By asparagus fern polyureas performed polymer D made from example IV, embodiment five, embodiment six, asparagus fern polyureas performed polymer E, dayWinter polyureas performed polymer F is respectively used to preparation embodiment seven, embodiment eight, nine coating of embodiment；With traditional asparagus fern polyureas pre-polymerizationBody G preparation comparison coating；Component included by each coating and content are as shown in table 1:
The component and content that the different coating of table 1 include
Wherein, traditional asparagus fern carbamide resin G structure is as follows:
It should be noted that component II is the mixture of three kinds of curing agent, wherein polyether-modified TDI class curing agent canTo improve the brittleness of film, the rate of drying of film is can be improved in HDI trimer curing agent, and polyester modification HDI class curing agent canTo extend the up time of coating and improve the elasticity of film.In use, both component I and component II can be directly according to weightIt is more independent than 2:1 to be used cooperatively.The preparation method of coating can refer to existing method and be prepared, and the present invention does not limit thisIt is fixed.
Performance test
Now the coating of embodiment eight, embodiment nine and comparative formula is detected, wherein noxious material detection is completeNational standard is conformed to, other performance tests of coating are as shown in table 2 below.
The performance test results of the different coating of table 2
In conjunction with above-mentioned test data it is found that poly- asparagus fern resin made from asparagus fern polyureas performed polymer provided by the present invention, andFurther coating obtained is a kind of nontoxic, odorlessness product, and construction is simple is convenient in use process, and the construction time is up to30-45 minutes, it is ensured that construction quality；And comparative example curing rate is too fast, the construction time only has a few minutes.
Good with ceramic tile surface adhesion force by coating produced by the present invention, rate of drying is fast.There is paint film after drying stretches wellLong rate tensile strength (elongation is significantly increased compared with traditional asparagus fern carbamide resin), is also not easy in wet condition for a long timeMouldy, soil resistance is good, and wearability is good, and waterproof effect is good.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, is not described in some embodimentPart, reference can be made to the related descriptions of other embodiments.
The above is a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, any ripeIt knows those skilled in the art in the technical scope disclosed by the present invention, various equivalent modifications can be readily occurred in or replacesIt changes, these modifications or substitutions should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with rightIt is required that protection scope subject to.