CN101863792A - Amide oligomer and polyamide paste rheological aid prepared by swelling same - Google Patents
Amide oligomer and polyamide paste rheological aid prepared by swelling same Download PDFInfo
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- CN101863792A CN101863792A CN201010187690A CN201010187690A CN101863792A CN 101863792 A CN101863792 A CN 101863792A CN 201010187690 A CN201010187690 A CN 201010187690A CN 201010187690 A CN201010187690 A CN 201010187690A CN 101863792 A CN101863792 A CN 101863792A
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Abstract
The invention discloses an amide oligomer and a polyamide paste rheological aid prepared by swelling the same. A preparation method for the amide oligomer comprises the following steps of: putting aliphatic binary acid, aliphatic polyamine compound and aliphatic monobasic acid with a polar group and ester thereof into a reactor, adding a catalyst into the reactor, and reacting the mixture at the temperature of between 150 and 200 DEG C to obtain the amide oligomer. The polyamide has proper melting point and relative molecular weight; and after micro pulverization, the polyamide is dispersed into a mixed solvent containing aromatic hydrocarbon and alcohol and subjected to the controlled swelling at a lower temperature to form the polyamide paste rheological aid. The obtained polyamide paste rheological aid serving as an additive provides excellent coating performance for a coating system, namely has high viscosity during standing and good viscosity stability, prevents the powder in the system from settling and caking, has thinner viscosity during coasting and is easy for construction; the leveling property and the flowing resistance of a coated film are well balanced; and the polyamide paste rheological aid has broad application prospect in the coating industry.
Description
Technical field
The invention belongs to the coatings additive(s) field, the polyamide paste rheological aid that particularly a kind of oligoamide and swelling thereof are made, this polyamide paste rheological aid can be used for preparing coating with control coating system rheological characteristics.
Background technology
In each stage of coating material production and use, the control of the rheological property of coating is the important factor that must consider, wherein, gives coating fluid system thixotropy and can obtain good effect.For example in coating, add some auxiliary agents, thixotropy improves coating performance, coating system is under low shear rate, promptly when leaving standstill storage or after the brushing construction, fluid has high viscosity, can prevent sagging on the execution of coating face, delay the sedimentation of pigment in the formulation for coating material and filler and prevent its gathering; Under high shear rate, promptly when the brushing construction, fluidic viscosity is lower, but convenient construction, and make coating that good mobility be arranged, do not damage the flow leveling of coating.
When the thixotropic essence of fluid is to leave standstill, the auxiliary agent swelling in solvent that adds, because faint hydrogen bond action, form physical crosslinking between polymkeric substance and pigment and be bridge and form by polar adsorption and crosslinkedly between polymkeric substance obtain a kind of reticulated structure between the swollen particles, disperse with the colloidal form, this reticulated structure is destroyed under shearing action, viscosity degradation, in case leave standstill, reticulated structure slowly recovers again, viscosity rises, so system shows thixotropy.
In order to give like this some performances of coating system, prior art discloses a lot of methods, is scattered in organic wax in the solvent as using organic bentonite, hydrogenated castor oil and derivative, oxidized polyethlene wax etc.These auxiliary rheological agents or use separately, or by composite common adding coating system, though be widely used, but still have some potential shortcomings, for example, for organobentonite, its color and luster is dark, poor transparency, thickening effectiveness is obvious, but because dope viscosity is too big, cause the levelling property variation, easily produce brush mark,, coat with lacquer liquid-solid body burden and cannot say for sure to demonstrate,prove as increasing solvent load.Must be before hydrogenated castor oil uses through activation fully, in reactivation process, temperature controlling must be precisely, if surpass overactivity temperature, when cooling, stir not enough, then hydrogenated castor oil just can not form thixotropic gel network and can separate out " crystal grain ", and activation temperature is too low and the activation time length is not enough, this situation also can occur, when " crystal grain " when occurring, its rheology control characteristic not only can reduce, and this type of " crystal grain " volume is bigger, causes coating particle to occur.For the polyethylene wax of polymer, polar group is less on its molecular chain, thus the hydrogen bond action that forms of itself and coating resin a little less than, use can not provide good anti-sag effect separately.
In addition, polyamide-based compound also is widely used as auxiliary rheological agents, comprises polyaminoester and polyureas derivative, and there are many patents in technology of preparing.In Chinese invention patent ublic specification of application (publication number CN1535309A), a kind of polyalkylene glycol hydroxyalkyl isostearoyl amine that contains has been proposed as rheology modified auxiliary agent, be applicable to surfactant system.Chinese invention patent application (200610132220.5) discloses the polymkeric substance of a class phosphinylidyne-containing amine group, it is earlier by dimeracid and diamine condensation polymer, then respectively with acrylamide or acrylic ester compound, isocyanate reaction, phosphinylidyne-containing amine group not only in the polymkeric substance that obtains, simultaneously can also there be ester, carbamate and urea groups, can be as the rheology control additive of coating.But these reaction product complex structures, composition is indeterminate, and application performance is also unclear.
Chinese invention patent application (200780047705.7) has been described a kind of lipid acid diamide compound and randomly has been diluted in powder in the hydrogenated castor oil, pass through temperature regulation, be dispersed at least a organic softening agent, form uniform dispersion, promptly activated thickener in advance, the main purpose of invention is for the final user provides a kind of property easy to operate, activates thickener in advance easily in producing each stage adding coating, the final user has save the activation act process, avoids powder to form dust.Obviously this is a kind of amide compound activatory method.
U.S. Pat Pat 5,180, the preparation method of the polymeric amide of the 802 end capped nonreactive activities of a kind of monoamine that disclose, purpose is to obtain not contain the polymeric amide of reactive hydrogen, for coating system provides thixotropic while, be unlikely to coating resin such as urethane generation chemical reaction and damage the stability of system, employed long-chain fat amine end-capping reagent cost is higher.
Also there is patent to adopt the condensation reaction products of longer chain fatty acid and diamine as the rheology of coating system, anti-heavy, anti-sag auxiliary agent, for example, U.S. Pat Pat 3,937,678, US Pat 5,939,475, Chinese invention patent application (200910036499.0) proposes with hydrogenated castor oil fatty and binary primary amine condensation, obtaining is a kind of wax, and they are actual should to belong to diamide compound, is not polymeric amide alleged in the patent application.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of preparation method of oligoamide.
Another object of the present invention is to provide the oligoamide of method for preparing.
A further object of the present invention is to provide a kind of polyamide paste rheological aid that is formed by above-mentioned oligoamide swelling, can be used as rheology control auxiliary agent, has good suspension characteristic simultaneously again.
Another purpose of the present invention is to provide a kind of preparation method of above-mentioned polyamide paste rheological aid.
Another purpose of the present invention is to provide the application of above-mentioned polyamide paste rheological aid; This polyamide paste rheological aid is applied to prepare coating.
Purpose of the present invention realizes by following technical proposals: a kind of preparation method of oligoamide; comprise following operation steps: with aliphatic dibasic acid, aliphatic polyamine compound with have the aliphatics monoprotic acid of polar group or its ester drops in the reactor; add catalyzer; under 150～200 ℃ of temperature condition, carry out acylation reaction, obtain oligoamide.
Described aliphatic dibasic acid and have the aliphatics monoprotic acid of polar group and the mol ratio of ester is an aliphatic dibasic acid: have the aliphatics monoprotic acid of polar group and ester thereof=0.05: 1～0.3: 1;
Described aliphatic dibasic acid and have the aliphatics monoprotic acid of polar group and a total reactive hydrogen in the ester thereof, with the mol ratio of the reactive hydrogen of primary amine groups in the aliphatic polyamine compound be 1: 1;
Described catalyst consumption is for to add 0.0001～0.01 mole in every mole of acylation reaction monomeric compound;
The described reaction times is 1～12 hour;
Described reaction is to carry out in organic solvent, and described organic solvent is more than one in benzene, toluene and the dimethylbenzene, and the consumption of described organic solvent is 10～50% of an acylation reaction monomeric compound weight meter;
Described aliphatic polyamine compound is the single amine or the mixed amine of 150 ℃～300 ℃ of boiling points;
Described aliphatic dibasic acid is that carbonatoms is 6～36 aliphatic dibasic acid;
Described polar group is hydroxyl, sulfydryl, sulfonic group or sulfate group; Described aliphatics monoprotic acid and the ester thereof that has polar group is aliphatic carboxylic acid saturated or the carbon-carbon double key and methyl alcohol ester or glyceryl ester;
Described catalyzer is that mol ratio is triphenyl phosphorus-tetracol phenixin of 1: 1, triphenyl phosphorus-carbon tetrabromide that mol ratio is 1: 1, triphenyl phosphorus-hexachloroacetone that mol ratio is 1: 1, triphenyl phosphorus-N-bromo-succinimide, trimethylchlorosilane, silicon tetrachloride, boron trifluoride-ether, dicyclohexylcarbodiimide, stannous octoate, dibutyl tin dilaurate or the Dibutyltin oxide that mol ratio is 1: 1.
When selecting for use the aliphatics monobasic acid ester that has polar group to participate in acylation reaction, when dropping in the reactor with aliphatic dibasic acid and aliphatic polyamine compound, except above-mentioned catalyzer, also can select sodium methylate, sodium ethylate, sodium hydride or butyllithium for use, they can increase the nucleophilicity of amine and ester acylation reaction; But when selecting the aliphatics monoprotic acid that has polar group for use, acylation reaction has enough nucleophilicities, can not use such base metal catalysts of sodium methylate, sodium ethylate, sodium hydride or butyllithium, otherwise side reaction can take place.
Described aliphatic polyamine compound is more than one in quadrol, butanediamine, hexanediamine, decamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, dodecane diamines and the octadecamethylene diamine; Described aliphatic dibasic acid is that carbonatoms is 10～36 aliphatic dicarboxylic acid; The described aliphatics monoprotic acid that has polar group is more than one in 6 hydroxycaproic acid, 6-mercaptohexanoic acid, dodecyl thiohydracrylic acid, sabinic acid, Castor Oil Fatty Acid and the hydrogenated castor oil fatty; The described aliphatics monobasic acid ester that has polar group is more than one in Viscotrol C, hydrogenated castor oil, Castor Oil Fatty Acid methyl esters, hydrogenated castor oil fatty methyl esters, sulfonated castor oil and the sulfate group Viscotrol C.
Described aliphatic dibasic acid is sebacic acid, dodecanedioic acid, Thapsic acid, docosandioic acid, unsaturated C
18Acid dimer, laurylene base succsinic acid and contain C
36Dimer (fatty acid) yl in more than one; Known contain C to preferred especially those skilled in the art
36The dimer (fatty acid) yl of carbon atom (Dimer acid) can contain starting monomer and its tripolymer of being useful on the preparation dimeracid in this dimer (fatty acid) yl, but both total content general requirements is less than 10%.Described aliphatic dibasic acid can use separately, also can mix use, preferably then is to contain C
36The dimer (fatty acid) yl of carbon atom and mixing acid other diprotic acid, and C in the mixing acid
36The molar ratio of the dimer (fatty acid) yl of carbon atom is greater than 80%.
A kind of oligoamide by method for preparing.
A kind of polyamide paste rheological aid of making by above-mentioned oligoamide swelling.
The preparation method of above-mentioned polyamide paste rheological aid comprises following operation steps: oligoamide is ground into the polymeric amide micro mist; Under 20～65 ℃ of temperature condition, the control stirring velocity is 1000 ± 50 commentaries on classics/min, the polymeric amide micro mist is added in the mixed solvent of aromatic hydrocarbons and alcohol, stirs until forming uniform dispersion; Controlled temperature is at 20～65 ℃, regulate the stirring velocity of dispersion machine, make above-mentioned dispersion be in flow state, and keep 10～1500min (the swollen time length is depended on the polarity size of mixed solvent), make dispersion swelling (activation), obtain polyamide paste rheological aid.
The median size of described polymeric amide micro mist is 5～10 μ m; Described aromatic hydrocarbons is 50～95: 50～5 with the volume ratio of alcohol; Described aromatic hydrocarbons is more than one in the solvent oil of toluene, dimethylbenzene, trimethylbenzene and high aromaticity content; Described alcohol is more than one in methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol and the phenylcarbinol.
Above-mentioned polyamide paste rheological aid is applied to prepare coating; This polyamide paste rheological aid can be added in the coating system easily, prevent sedimentation, the caking of pigment, filler in the coating storage process, avoid drippage, the sagging of coating in the coating process, improve the flow leveling of filming, in coatings industry, possesses wide application prospect; Described coating comprises solvent-borne type, UV curing (no-solvent type) and water-borne coatings.
Principle of the present invention is: aliphatic dibasic acid, aliphatic polyamine compound and have the aliphatics monoprotic acid of polar group and the reaction of ester three compounds can be operated according to common amide polycondensation reaction method, in being lower than under 200 ℃ of temperature, at first carry out the condensation polymerization reaction, by the monoprotic acid end-blocking, obtain oligoamide at last then; By controlling the mol ratio of three compounds, can regulate relative molecular weight, the fusing point of product within the specific limits.The application target of aliphatic dibasic acid is to obtain having the oligoamide of larger molecular weight, as previously mentioned, monoprotic acid and diamine condensation only can obtain diamide compound, and in the present invention, aliphatic dibasic acid is selecting for use of dimeracid particularly, can obtain to contain the oligopolymer of multiamide key, and amido linkage is far away at interval in this structure, the carbonatoms that is midfeather is more, help the formation of hydrogen bond structure, easily twine mutually between molecular chain, obtain the closeer and more stable reticulated structure of physical crosslinking point, such structure helps improving the suspension characteristic of coating system.But when all selecting diprotic acid for use as polycondensation monomer and without monoprotic acid or its ester, the polyamide molecular weight that obtains is higher, the fusing point height, generally only use in chemical industry as the matrix resin of coating and printing ink or as tackiness agent, such polymeric amide Intermolecular Forces is strong, easily crystallization is insoluble in common aromatic solvent, thereby also not easy to operate in the swelling activation step below.When the consumption of diprotic acid relatively more after a little while, the monoprotic acid of adding or its ester provide single reaction functional group in reaction, thereby play the end-blocking effect, can regulate the molecular weight of condensation product, further the polymeric amide that obtains of reaction has swellable thus.Have polar group monoprotic acid or its ester and amine condensation and can obtain amido linkage equally, hydroxyl, sulfydryl, sulfonic group or sulfate group wherein all can be used as the formation of donor or acceptor help hydrogen bond simultaneously, and such low molecular polyamides product is particularly suitable for as the rheology control and the suspension aids of coating system.So, in aliphatic dibasic acid and the aliphatics monoprotic acid of polar functionalities and the mol ratio of ester thereof of the present invention, obtaining the oligoamide of ad hoc structure by the control long-chain, its mol ratio is preferably between 0.05: 1～0.3: 1 scope; The mol ratio of the reactive hydrogen of primary amine groups is 1: 1 in their total reactive hydrogen (reaction active groups) and the aliphatic polyamine compound; There is no particular limitation for the monomeric addition sequence of three kinds of condensation reactions, can throw simultaneously to reactor, also can successively add, and adds acylation reaction catalyst then and can begin reaction.
In the above-mentioned acylation reaction, for the long-chain fat monoprotic acid of avoiding polar functionalities and or their esters in polar group be removed, bronsted acid catalyst is not selected; When selecting for use fatty monacid ester to participate in acylation reaction, also available catalyzer has: sodium methylate, sodium ethylate, sodium hydride, butyllithium etc., they can increase the nucleophilic performance of amine and ester acylation reaction.Catalyzer of the present invention there is no specific step and goes to remove them after acylation reaction is finished.
Above-mentioned condensation reaction can be carried out under condition of no solvent, also can carry out in organic solvent medium.Some can form the aromatic solvent of azeotrope with water, and for example the mixture of benzene,toluene,xylene or these solvents can make condensation reaction more complete.
If desired, in reaction process, can use devices such as water trap, remove the by product of dereaction, with fast reaction speed.
The fusing point of oligoamide of the present invention is recorded by differential scanning calorimeter (DSC), and its acid number and amine value are recorded by the method for chemistry titration.The melting range of above-mentioned polymeric amide is 80-150 ℃; Acid number≤8mgKOH/g, amine value≤8mgKOH/g, optimum is acid number≤3mgKOH/g, amine value≤3mgKOH/g.
Above-mentioned polyamide paste rheological aid can add in the coating resin under lower stirring velocity and under the common coating proportioning temperature, can be scattered in the coating system with uniform colloidal form, gives the thixotropy energy consumption suspension property of coating system excellence; High-shear disperses or disperses by grinding, and may damage these performances; Dispersion temperature too high (＞80 ℃) may cause crystallization, and makes coating produce the particulate state defective.
Polyamide paste rheological aid thixotropy in coating is represented with thixotropy index TI, measures with brookfield viscosity.TI=(viscosity that records during 6 commentaries on classics/min)/(viscosity that records during 60 commentaries on classics/min), TI is high more, it is generally acknowledged that thixotropy is high more.
Polyamide paste in coating suspension with the rate of descent D of identical time flatting silica in the coating
1Estimate:
D
1＝(1/L)×100％
In the formula: D
1Rate of descent for coating; L is the coating total height; 1 is coating placement for some time (the present invention is 24h) back upper strata stillness of night height.
Rate of descent is more little and do not form powder agglomeration, shows that then its suspension property is good.
Polyamide paste rheological aid of the present invention can obviously improve the coating system rheological characteristics, gives thixotropic behaviour, and described thixotropic behaviour is characterised in that the system pronounced shear thinning, and the viscosity dependence time slowly recovers then.Such additive provides excellent brushing performance for the coating system at place: viscosity is high and have a good viscosity stability when leaving standstill, prevent powder sedimentation, caking in the system, then viscosity is thinning during brushing, construction easily, and levelling property of filming and anti-sag performance obtain well balanced.
The present invention has following advantage and beneficial effect with respect to prior art: (1) raw material of the present invention is easy to get, and preparation process is simple; (2) gained polyamide paste rheological aid of the present invention provides excellent brushing performance as additive for coating system: viscosity is high and have a good viscosity stability when leaving standstill, prevent powder sedimentation, caking in the system, then viscosity is thinning during brushing, construction easily, levelling property of filming and anti-sag performance obtain well balanced, in coating industry, possesses wide application prospect.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 25.0g C
36Dimer (fatty acid) yl, the 6 hydroxycaproic acid of 2.2g docosandioic acid and 140g, logical N
2, be heated to 90 ℃, add the 94.4g butanediamine, constant temperature is at 95 ℃ of reaction 1h, be warming up to 120 ℃, add 0.5g catalyzer boron trifluoride diethyl etherate, be warming up to 190 ℃ of reaction 4h, slough by product under the decompression, cooling obtains light yellow wax shape polymeric amide solid, and recording acid number is 5.1mgKOH/g, and the amine value is 4.5mgKOH/g, it is 141 ℃ that the DSC method records fusing point, is ground into polymeric amide fine powder (median size is 10 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 22.1, flatting silica 24h sedimentation test: rate of descent 31.7%.
Embodiment 2
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 25.0g C
36Dimer (fatty acid) yl, 2.2g docosandioic acid, the 12-hydroxy oleate (Castor Oil Fatty Acid) of 298.5g, logical N
2, be heated to 90 ℃, add the 64.4g quadrol, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, adds 0.5g catalyzer boron trifluoride diethyl etherate, be warming up to 150 ℃ of reaction 6h, decompression is sloughed by product down, and cooling obtains light yellow wax shape polymeric amide solid, recording acid number is 4.5mgKOH/g, the amine value is 5.0mgKOH/g, and it is 137 ℃ that DSC records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 20.0, flatting silica 24h sedimentation test: rate of descent 31.3%.
Embodiment 3
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 25.0g C
36Dimer (fatty acid) yl, 1.2g sebacic acid, the sulfonated castor oil of 296.4g (saponification value is 189.3), logical N
2, be heated to 90 ℃, add the 166.9g decamethylene diamine, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, adds 0.5g catalyzer trimethylchlorosilane, be warming up to 200 ℃ of reaction 9h, decompression is sloughed by product down, and cooling obtains light yellow wax shape polymeric amide solid, it is 133 ℃ that DSC records fusing point, recording acid number is 4.8mgKOH/g, and the amine value is 5.9mgKOH/g, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 19.9, flatting silica 24h sedimentation test: rate of descent 34.7%.
Embodiment 4
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 25.0g and contain C
36Dimer (fatty acid) yl, the sabinic acid of 2.2g docosandioic acid and 216g, logical N
2, be heated to 90 ℃, add the 94.4g butanediamine, constant temperature is at 95 ℃ of reaction 1h, be warming up to 120 ℃, add the inferior tin of 0.5g octoate catalyst, be warming up to 180 ℃ of reaction 12h, slough by product under the decompression, cooling obtains light yellow wax shape polymeric amide solid, and recording acid number is 3.9mgKOH/g, and the amine value is 3.9mgKOH/g, it is 138 ℃ that the DSC method records fusing point, is ground into polymeric amide fine powder (median size is 6 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 40 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 80/20), about 1000rpm rotating speed dispersed with stirring 15min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 20.8, flatting silica 24h sedimentation test: rate of descent 36.0%.
Embodiment 5
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add the 13.2g Thapsic acid, the 12-hydroxy oleate (ricinolic acid) of 298.5g, logical N
2, be heated to 90 ℃, add the 94.4g butanediamine, constant temperature is at 95 ℃ of reaction 1h, be warming up to 120 ℃, add the inferior tin of 0.5g octoate catalyst, be warming up to 150 ℃ of reaction 10h, slough by product under the decompression, cooling obtains light yellow wax shape polymeric amide solid, and recording acid number is 2.3mgKOH/g, and the amine value is 4.4mgKOH/g, it is 145 ℃ that the DSC method records fusing point, is ground into polymeric amide fine powder (median size is 8 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 20 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 80/20), about 1000rpm rotating speed dispersed with stirring 15min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 20.8, flatting silica 24h sedimentation test: rate of descent 30%.
Embodiment 6
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add the 12-hydroxy oleate of 17.1g docosandioic acid and 298.5g, logical N
2, be heated to 90 ℃, add the 106.2g diethylenetriamine, constant temperature is at 95 ℃ of reaction 1h, be warming up to 120 ℃, add 0.5g catalyzer boron trifluoride diethyl etherate, be warming up to 190 ℃ of reaction 2h, slough by product under the decompression, cooling obtains light yellow wax shape polymeric amide solid, and recording acid number is 5.0mgKOH/g, and the amine value is 5.2mgKOH/g, it is 143 ℃ that the DSC method records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 65 ℃, add 200g toluene/7 pure mixed solvents (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 20.2, flatting silica 24h sedimentation test: rate of descent 37.1%.
Embodiment 7
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 10.0g dodecanedioic acid and 216g sabinic acid, logical N
2, be heated to 90 ℃, add the 94.4g butanediamine, constant temperature is at 95 ℃ of reaction 1h, be warming up to 120 ℃, add 0.5g catalyzer dibutyl tin laurate, be warming up to 190 ℃ of reaction 5h, slough by product under the decompression, cooling obtains light yellow wax shape polymeric amide solid, and recording acid number is 5.1mgKOH/g, and the amine value is 4.5mgKOH/g, it is 145 ℃ that the DSC method records fusing point, is ground into polymeric amide fine powder (median size is 10 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 50 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 19.6, flatting silica 24h sedimentation test: rate of descent 40.7%.
Embodiment 8
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 10.1g sebacic acid and 312.5g Castor Oil Fatty Acid methyl esters, logical N
2, be heated to 90 ℃, add the 124.5g hexanediamine, constant temperature is at 95 ℃ of reaction 1h, be warming up to 120 ℃, add 0.5g catalyzer butyllithium, be warming up to 180 ℃ of reaction 4h, slough by product under the decompression, cooling obtains light yellow wax shape polymeric amide solid, and recording acid number is 4.0mgKOH/g, and the amine value is 5.5mgKOH/g, it is 147 ℃ that the DSC method records fusing point, is ground into polymeric amide fine powder (median size is 10 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 19.1, flatting silica 24h sedimentation test: rate of descent 41.7%.
Embodiment 9
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 13.3g dodecenylsuccinic anhydride and 312.5g Castor Oil Fatty Acid methyl esters, logical N
2, be heated to 90 ℃, add the 64.4g quadrol, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, adds 0.8g catalyzer sodium ethylate, be warming up to 155 ℃ of reaction 7h, decompression is sloughed by product down, and cooling obtains yellow wax shape polymeric amide solid, recording acid number is 5.5mgKOH/g, the amine value is 6.1mgKOH/g, and it is 131 ℃ that DSC records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 18.0, flatting silica 24h sedimentation test: rate of descent 39.3%.
Embodiment 10
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 13.3g dodecenylsuccinic anhydride and 312.5g Castor Oil Fatty Acid methyl esters, logical N
2, be heated to 90 ℃, add the 156.7g triethylene tetramine, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, adds 0.5g catalyzer sodium ethylate, be warming up to 170 ℃ of reaction 6.5h, decompression is sloughed by product down, and cooling obtains yellow polymeric amide solid, recording acid number is 4.9mgKOH/g, the amine value is 5.7mgKOH/g, and it is 145 ℃ that DSC records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/7 pure mixed solvents (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 18.6, flatting silica 24h sedimentation test: rate of descent 42.3%.
Embodiment 11
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 13.3g dodecenylsuccinic anhydride and 156g 6-mercaptohexanoic acid, logical N
2, be heated to 90 ℃, add the 304g octadecamethylene diamine, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, and adding 1g mol ratio is triphenylphosphine-tetracol phenixin of 1: 1, be warming up to 190 ℃ of reaction 6.5h, decompression is sloughed by product down, and cooling obtains yellow polymeric amide solid, recording acid number is 5.5mgKOH/g, the amine value is 4.2mgKOH/g, and it is 129 ℃ that DSC records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 18.9, flatting silica 24h sedimentation test: rate of descent 40%.
Embodiment 12
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 10.1g sebacic acid and 311.2g Viscotrol C, logical N
2, be heated to 90 ℃, add the 304g octadecamethylene diamine, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, and adding 1g mol ratio is triphenylphosphine-tetracol phenixin of 1: 1, be warming up to 190 ℃ of reaction 7h, decompression is sloughed by product down, and cooling obtains yellow polymeric amide solid, recording acid number is 6.0mgKOH/g, the amine value is 4.2mgKOH/g, and it is 131 ℃ that DSC records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 18.2, flatting silica 24h sedimentation test: rate of descent 43%.
Embodiment 13
1. polyamide wax is synthetic
In the reaction flask that thermometer, prolong, water trap, whipping appts are housed, add 14.3g hexadecyl diacid and 314g hydrogenated castor oil, logical N
2, be heated to 90 ℃, add 186.8g dodecyl diamines, constant temperature is warming up to 120 ℃ at 95 ℃ of reaction 1h, adds 0.8g tetrabutyl stannic oxide, be warming up to 190 ℃ of reaction 7.5h, decompression is sloughed by product down, and cooling obtains yellow polymeric amide solid, recording acid number is 65.5mgKOH/g, the amine value is 5.1mgKOH/g, and it is 139.3 ℃ that DSC records fusing point, is ground into polymeric amide fine powder (median size is 5 μ m) through micronizer.
2. controlled swelling prepares auxiliary rheological agents
In decollator, add 50g step 1 gained polymeric amide fine powder, circulating water temperature is 45 ℃, add 200g toluene/ethanol mixed solvent (volume ratio is 90/10), about 1000rpm rotating speed dispersed with stirring 20min, swelling obtains about 250g polyamide paste rheological aid of the present invention, and solid content is about 20%.Recording thixotropy index is 19.3, flatting silica 24h sedimentation test: rate of descent 45.1%.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of an oligoamide; it is characterized in that comprising following operation steps: with aliphatic dibasic acid, aliphatic polyamine compound with have the aliphatics monoprotic acid of polar group or its ester drops in the reactor; add catalyzer; under 150～200 ℃ of temperature condition, carry out acylation reaction, obtain oligoamide.
2. the preparation method of a kind of oligoamide according to claim 1 is characterized in that:
Described aliphatic dibasic acid and have the aliphatics monoprotic acid of polar group and the mol ratio of ester is an aliphatic dibasic acid: have the aliphatics monoprotic acid of polar group and ester thereof=0.05: 1～0.3: 1;
Described aliphatic dibasic acid and have the aliphatics monoprotic acid of polar group and a total reactive hydrogen in the ester thereof, with the mol ratio of the reactive hydrogen of primary amine groups in the aliphatic polyamine compound be 1: 1;
Described catalyst consumption is for to add 0.0001～0.01 mole in every mole of acylation reaction monomeric compound;
The described reaction times is 1～12 hour;
Described reaction is to carry out in organic solvent, and described organic solvent is more than one in benzene, toluene and the dimethylbenzene, and the consumption of described organic solvent is 10～50% of an acylation reaction monomeric compound weight meter.
3. the preparation method of a kind of oligoamide according to claim 1 is characterized in that:
Described aliphatic polyamine compound is the single amine or the mixed amine of 150 ℃～300 ℃ of boiling points;
Described aliphatic dibasic acid is that carbonatoms is 6～36 aliphatic dibasic acid;
Described polar group is hydroxyl, sulfydryl, sulfonic group or sulfate group; Described aliphatics monoprotic acid and the ester thereof that has polar group is aliphatic carboxylic acid saturated or the carbon-carbon double key and methyl alcohol ester or glyceryl ester;
Described catalyzer is that mol ratio is triphenyl phosphorus-tetracol phenixin of 1: 1, triphenyl phosphorus-carbon tetrabromide that mol ratio is 1: 1, triphenyl phosphorus-hexachloroacetone that mol ratio is 1: 1, triphenyl phosphorus-N-bromo-succinimide, trimethylchlorosilane, silicon tetrachloride, boron trifluoride-ether, dicyclohexylcarbodiimide, stannous octoate, dibutyl tin dilaurate or the Dibutyltin oxide that mol ratio is 1: 1;
When the aliphatics monoprotic acid that has polar group or its ester are that catalyzer is sodium methylate, sodium ethylate, sodium hydride or butyllithium when having the aliphatics monobasic acid ester of polar group.
4. the preparation method of a kind of oligoamide according to claim 2, it is characterized in that: described aliphatic polyamine compound is more than one in quadrol, butanediamine, hexanediamine, decamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, dodecane diamines and the octadecamethylene diamine; Described aliphatic dibasic acid is that carbonatoms is 10～36 aliphatic dicarboxylic acid; The described aliphatics monoprotic acid that has polar group is more than one in 6 hydroxycaproic acid, 6-mercaptohexanoic acid, dodecyl thiohydracrylic acid, sabinic acid, Castor Oil Fatty Acid and the hydrogenated castor oil fatty; The described aliphatics monobasic acid ester that has polar group is more than one in Viscotrol C, hydrogenated castor oil, Castor Oil Fatty Acid methyl esters, hydrogenated castor oil fatty methyl esters, sulfonated castor oil and the sulfate group Viscotrol C.
5. the preparation method of a kind of oligoamide according to claim 4, it is characterized in that: described aliphatic dibasic acid is sebacic acid, dodecanedioic acid, Thapsic acid, docosandioic acid, unsaturated C
18Acid dimer, laurylene base succsinic acid and contain C
36Dimer (fatty acid) yl in more than one.
6. oligoamide by each described method preparation of claim 1～5.
7. polyamide paste rheological aid of making by the described oligoamide swelling of claim 6.
8. the preparation method of polyamide paste rheological aid according to claim 7 is characterized in that comprising following operation steps: oligoamide is ground into the polymeric amide micro mist; Under 20～65 ℃ of temperature condition, the control stirring velocity is 1000 ± 50 commentaries on classics/min, the polymeric amide micro mist is added in the mixed solvent of aromatic hydrocarbons and alcohol, stirs until forming uniform dispersion; Controlled temperature is regulated the stirring velocity of dispersion machine at 20～65 ℃, makes above-mentioned dispersion be in flow state, and keeps 10～1500min, makes the dispersion swelling, obtains polyamide paste rheological aid.
9. preparation method according to claim 8 is characterized in that: the median size of described polymeric amide micro mist is 5～10 μ m; Described aromatic hydrocarbons is 50～95: 50～5 with the volume ratio of alcohol; Described aromatic hydrocarbons is more than one in the solvent oil of toluene, dimethylbenzene, trimethylbenzene and high aromaticity content; Described alcohol is more than one in methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol and the phenylcarbinol.
10. polyamide paste rheological aid according to claim 9 is applied to prepare coating.
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| CN105705542A (en) * | 2013-10-31 | 2016-06-22 | 阿科玛法国公司 | Additives made from fatty diamides for nucleophile-sensitive cross-linkable compositions |
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| CN112521795A (en) * | 2020-12-24 | 2021-03-19 | 浙江丰虹新材料股份有限公司 | Water-based polyamide wax rheological additive with improved thermal stability and preparation method thereof |
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