CN104231191A - Preparation method of waterborne non-isocyanate polyurethane modified polyester - Google Patents
Preparation method of waterborne non-isocyanate polyurethane modified polyester Download PDFInfo
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Abstract
The invention relates to a preparation method of waterborne non-isocyanate polyurethane modified polyester and provides a preparation method of the waterborne non-isocyanate polyurethane modified polyester. The preparation method comprises the following steps: (1) preparation of unsaturated prepolymer containing a urethane bond; (2) preparation of polyester containing an unsaturated double bond; (3) graft polymerization of the prepared polyester containing the unsaturated double bond, and the prepolymer; and (4) dispersion of a graft polymer. The invention also provides an application of the prepared waterborne non-isocyanate polyurethane modified polyester in vehicle coatings.
Description
Technical field
The invention belongs to new chemical materials field, relate to the preparation method of the polyester of a kind of water-based non-isocyanate polyurethane (Nonisocyanate Polyurethane, NIPU) modification.The application that the polyester also relating to the modification prepared by described method is coated with in the car.
Background technology
The polyurethane-modified polyester coating reacting preparation by polyisocyanates and polyester polyol has excellent tensile strength, Young's modulus and good cryogenic mechanics performance, wear-resistant type and obtain wide model and apply, especially it still keeps good elasticity in very wide temperature range, is suitable for especially being applied in automobile being coated with stone-impact-proof paint.
But, there is many deficiencies in traditional polyurethane-modified polyester.First, the polyisocyanates activity of use is high, easily and environment, solvent, the water reaction that contains in resin, cause quality product exception even complete failure, therefore from raw material to process need, strictly control steam; Secondly, polyisocyanates toxicity is very large, can work the mischief in its preparation and use procedure to personnel and environment; In addition, when polyurethane-modified polyester is prepared into aqueous dispersion, the hydrolytic resistance of usual polyester is poor, and the ester group on main chain, amino-formate bond hydrolytic resistance are limited, thus limit the use of waterborne polyester.
Nineteen fifty-seven, Stephen J.Groszos etc. are at United States Patent (USP) 2,802, low molecular compound containing beta-hydroxy carbamate of proposition monocyclic carbonate and aliphatie diamine Reactive Synthesis first in 022, for the synthesis of non-isocyanate polyurethane is laid a good foundation.Since the nineties in 20th century, developed country more and more pays close attention to the research of non-isocyanate polyurethane, namely the Reactive Synthesis new polyurethane (non-isocyanate polyurethane) of polynary cyclic carbonate ester and polyamine is passed through, non-isocyanate polyurethane not only can avoid the use enjoying the isocyanic ester denounced, and because the hydroxy carbamate group generated can form intramolecular hydrogen bond, there is stable seven-members ring structure, overcome the shortcoming of carbamate not hydrolysis, and chemicals-resistant, thermotolerance and physical strength have also been obtained raising.
Such as, Oleg L.Figovsky at United States Patent (USP) 6,120, disclose the hydridization type non-isocyanate network structure formed containing the oligopolymer of multiple cyclic carbonate ester and polyfunctional primary amine low-molecular material in 905, gel content reaches more than 96%, can be used as matrix material.FIGOVSKY also cooperates with SHAPOVALOV LEONID to disclose in US 20040491268, US 60407198B1, US 201113028067 etc. to react with the diamine containing different activities amino with the compound of end containing cyclic carbonate ester and prepares Amino End Group non-isocyanate performed polymer, the hydridization type non-isocyanate having bi-material advantage concurrently is obtained by reacting again with epoxy resin, but these NIPU materials are solvent borne, a large amount of VOC (volatile organic compounds) still can be discharged in use.
In addition, Chinese patent application CN 101775137A also provides a kind of use prepares aqueous dispersions or water soluble resin method containing the prepolymer of cyclic carbonate ester key and polyamine reaction, it still needs when preparing containing ring carbonic acid prepolymer to use a large amount of organic solvents, and product is polyurethane dispersions, still can discharge a large amount of VOC in use.
Up to now, the method for the water-based non-isocyanate polyurethane modified poly ester having nontoxic and low VOCization concurrently is not yet developed in this area.
Summary of the invention
The invention provides a kind of preparation method of polyester of water-based non-isocyanate polyurethane modification of novelty, thus solve the problem of prior art.
On the one hand, the invention provides a kind of preparation method of polyester of water-based non-isocyanate polyurethane modification, the method comprises the following steps:
(1) containing the preparation of the unsaturated prepolymer of ammonia ester bond
The cyclic carbonate ester and primary amine that contain unsaturated double-bond are reacted to amine value≤5mg KOH/g at 80-180 DEG C, to obtain the unsaturated prepolymer containing ammonia ester bond;
(2) containing the preparation of the polyester of unsaturated double-bond
Use and prepare polyester containing unsaturated double-bond containing the acid of unsaturated double-bond or alcohol, the molecular weight of the polyester containing unsaturated double-bond of gained is 2000-5000, acid value≤3mg KOH/g, and second-order transition temperature is-30 ~ 10 DEG C, and hydroxyl value is 70-150mg KOH/g;
(3) gained containing the polyester of unsaturated double-bond and the graft polymerization of prepolymer
By the prepolymer of gained, and hydrophilic monomer, unsaturated monomer and initiator mixing, 120-140 DEG C add gained containing unsaturated double-bond polyester in introduce carboxyl and ammonia ester bond on its side chain, thus obtain graftomer, wherein, the prepolymer of gained, hydrophilic monomer, the weight ratio of unsaturated monomer and initiator is: (30-50): (10-30): (20-30): (0.5-5), the weight ratio of the polyester containing unsaturated double-bond of described unsaturated monomer and gained is (20-50): 100, the second-order transition temperature of the graftomer of gained is-10 ~ 10 DEG C, hydroxyl value is 70-130mg KOH/g, acid value is 20-50mg KOH/g,
(4) dispersion of graftomer
In the graftomer of gained, add solubility promoter and neutralizing agent, to obtain the polyurethane dispersions of non-isocyanate modification, its solid part is the total amount <10% of 30-55%, pH=7-8.5, VOC.
In one preferred embodiment, in step (1), the described cyclic carbonate ester containing unsaturated double-bond meets following formula I-III:
In formula, R
1h, or C linear, side chain, ring-type
1-6alkyl;
R
2h or CH
3-;
R
3represent singly-bound or C
1-C
5alkylidene group;
Described primary amine meets following formula I V:
H
2N-R
4 (IV)
In formula, R
4straight chain, side chain or alicyclic ring C
1-8the C of alkyl or hydroxyl
1-8alkyl, or substituted or unsubstituted phenyl, wherein, described substituting group is selected from: methyl, ethyl, methoxyl group and oxyethyl group.
Another preferred embodiment in, described primary amine is selected from: propylamine, n-Butyl Amine 99, positive heptyl amice, carbinolamine, Monoethanolamine MEA BASF, butanolamine, isobutyl hydramine, hexahydroaniline, aniline, benzylamine, open-chain crown ether and P-nethoxyaniline.
Another preferred embodiment in, in step (2), described alcohol comprises: the alcohol of dibasic alcohol, trivalent alcohol and more polyfunctionality; Described acid comprises: unit carboxylic acid and polycarboxylic acid.
Another preferred embodiment in, in step (2), prepare the unsaturated monomer used containing the polyester of unsaturated double-bond and comprise: MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE and (methyl) vinylformic acid.
Another preferred embodiment in, in step (2), preparing the unsaturated monomer used containing the polyester of unsaturated double-bond is MALEIC ANHYDRIDE, its consumption is 0.5-9 weight part, is 100 parts by weight to prepare the gross weight of the described monomer used containing the polyester of unsaturated double-bond.
Another preferred embodiment in, in step (3), described hydrophilic monomer be acrylic or methacrylic acid;
Described unsaturated monomer comprises: vinylbenzene, vinyl toluene, vinyl acetate, tertiary ethylene carbonate, (methyl) vinylformic acid methyl, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) isobornyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, N-methylol (methyl) acrylamide and N-hydroxyethyl (methyl) acrylamide;
Described initiator is organic peroxide evocating agent.
Another preferred embodiment in, in step (4), described solubility promoter comprises: Virahol, propylene glycol, a contracting propylene glycol, propylene glycol monomethyl ether, butyl glycol ether, propandiol butyl ether, butyl, methyl-2-pyrrolidone, N, dinethylformamide, and composition thereof;
Described neutralizing agent comprises organic amine.
Another preferred embodiment in, described organic amine comprises: ammoniacal liquor, triethylamine, dimethylethanolamine, methyldiethanolamine, ethyl diisopropylamine, trolamine, and composition thereof.
On the other hand, the application during the polyester that the invention provides water-based non-isocyanate polyurethane modification prepared by aforesaid method is coated with in the car.
Accompanying drawing explanation
According to carrying out following detailed description by reference to the accompanying drawings, object of the present invention and feature will become more obvious, in accompanying drawing:
Fig. 1 is the infrared spectrogram of prepolymer A/B-1 and raw material VEC (vinyl cyclic carbonate ester) in the embodiment of the present application 1.
Embodiment
The present inventor finds after extensive and deep research, utilize non-isocyanate polyurethane modified poly ester, overcome the defect of conventional urethane modified poly ester, namely, poisonous isocyanate-monomer is not used to achieve the object of polyurethane-modified polyester, production process environmental protection, without the need to strictly controlling moisture content; Ammonia ester bond and carboxyl are incorporated on the side chain of polyester simultaneously, namely, Graft Method introduce carboxyl by other hydrophobic chain interval away from polyester backbone, make polyester dispersions have good resistance to hydrolysis, be coated with in the aqueous automobile prepared with this modified poly ester and there is good anti-hitting property of stone and the supporting sticking power of coating.Based on above-mentioned discovery, the present invention is accomplished.
the preparation method of the polyester of water-based non-isocyanate polyurethane modification
In a first aspect of the present invention, provide a kind of preparation method of polyester of water-based non-isocyanate polyurethane modification, the method comprises the following steps:
(1) containing the preparation of the unsaturated prepolymer of ammonia ester bond;
(2) containing the preparation of the polyester of unsaturated double-bond;
(3) gained containing the polyester of unsaturated double-bond and the graft polymerization of prepolymer;
(4) dispersion of graftomer.
(1) containing the preparation of the unsaturated prepolymer of ammonia ester bond
In this step, the unsaturated prepolymer containing ammonia ester bond is obtained with the cyclic carbonate ester containing unsaturated double-bond and primary amine reaction, wherein, the described cyclic carbonate ester containing discord double bond can be (methyl) acryllic acid cyclic carbonate ester, shown in I, or vinyl cyclic carbonate ester, shown in II, or allyl ether basic ring carbonic ether, shown in III:
In formula, R
1h, or C linear, side chain, ring-type
1-6alkyl;
R
2h or CH
3-;
R
3represent singly-bound or C
1-C
5alkylidene group;
Described primary amine is aromatic amine or aliphatic amide, shown in IV:
H
2N-R
4 (IV)
In formula, R
4straight chain, side chain or alicyclic ring C
1-8the C of alkyl or hydroxyl
1-8alkyl, or substituted or unsubstituted phenyl, wherein, described substituting group is selected from: methyl, ethyl, methoxyl group and oxyethyl group.
In the present invention, described primary amine includes, but are not limited to: propylamine, n-Butyl Amine 99, positive heptyl amice, carbinolamine, Monoethanolamine MEA BASF, butanolamine, isobutyl hydramine, hexahydroaniline, aniline, benzylamine, open-chain crown ether and P-nethoxyaniline.
In the present invention, react to amine value≤5mg KOH/g at 80-180 DEG C containing the cyclic carbonate ester of unsaturated link(age) and the mixture of a kind of primary amine or two or more primary amine, available tertiary amine or an alkali metal salt (as triethylamine, N-Methylimidazole, lithium hydroxide) make catalyzer, generate the unsaturated monomer of amido-containing acid ester key, its chemical reaction process schematically as follows:
In formula, R
0represent the segment containing unsaturated link(age) in formula I, II, III, R
1and R
4as hereinbefore defined.
In the present invention, the open loop of cyclic carbonate ester and primary amine has two kinds of modes, namely in the open loop of A position with in the open loop of B position, resultant is the mixture of A, B two kinds of prepolymers, two kinds of ammonia ester bonds are all with beta-hydroxy, intramolecular hydrogen bond can be formed and form a stable seven-membered ring, thus overcome the shortcoming of traditional ammonia ester bond not hydrolysis.
In the present invention; for protection double bond also can adopt stopper in above-mentioned preparation process; described stopper comprises; but be not limited to: para benzoquinone, methylbenzoquinone, MEHQ and to Tert. Butyl Hydroquinone; consumption is generally 0.1-0.3 weight part, is 100 parts by weight with the gross weight of the monomer preparing the described unsaturated prepolymer use containing ammonia ester bond.
(2) containing the preparation of the polyester of unsaturated double-bond
Be substantially similar to the preparation of conventional polyester containing the preparation principle of the polyester of unsaturated double-bond and process, difference is exactly need to use the acid containing unsaturated double-bond or alcohol.
In the present invention, adoptable alcohol comprises dibasic alcohol, as ethylene glycol, diethylene glycol, hexylene glycol, neopentyl glycol, methyl propanediol, neopentyl glycol and cyclohexanediol; Trivalent alcohol, as TriMethylolPropane(TMP) and trimethylolethane; And the alcohol of more polyfunctionality, as tetramethylolmethane and Dipentaerythritol.
In the present invention, adoptable acid mainly comprises polycarboxylic acid, if aliphatic polycarboxylic acid is as hexanodioic acid, nonane diacid, sebacic acid and dimeracid, and less use oxalic acid and succinic acid, because there is decarboxylation problem when high temperature in low molecular diacid; Aromatic polycarboxylic acid is as phthalic anhydride, m-phthalic acid, terephthalic acid and trimellitic acid 1,2-anhydride; Alicyclic polycarboxylic acid is as cyclohexyldicarboxylic acids, HHPA and tetrahydrophthalic anhydride.
In the present invention, also can adopt unit carboxylic acid or alcohol, as cocinic acid, lauric acid, ricinolic acid and tertiary carbonic acid glycidyl ester, to adjust the snappiness of functionality and vibrin; And when using vegetable oil acid, its iodine number is less than 10, to avoid causing during follow-up grafting gel, in addition, is not particularly limited the selection of this kind of monomer.
The unsaturated monomer that the described polyester containing unsaturated double-bond of preparation uses mainly comprises: MALEIC ANHYDRIDE (also known as maleic anhydride), FUMARIC ACID TECH GRADE (also known as fumaric acid) and (methyl) vinylformic acid; but (methyl) vinylformic acid is under the hot conditions of synthesizing polyester; the protection of double bond is more difficult; therefore preferred maleic anhydride and fumaric acid; because price is low and source is convenient, more preferably maleic anhydride is as the main raw material of the described polyester containing unsaturated double-bond of synthesis.
In the present invention, being introduced in vibrin by the maleic anhydride containing insatiable hunger double bond, is in order to follow-up grafting double bond containing prepolymer A/B monomer is prepared.The consumption of maleic anhydride is generally 0.5-9.0 weight part, preferred 3-7 weight part, be 100 parts by weight to prepare the gross weight of the described monomer used containing the polyester of unsaturated double-bond, resin gel is easily there is too much in consumption when grafting, and consumption grafting is insufficient very little, be difficult to obtain stable dispersion.
In the present invention, adjust the proportioning of various monomer, the second-order transition temperature of the polyester containing unsaturated double-bond of gained is adjusted to-30 ~ 10 DEG C, and number-average molecular weight Mn controls at 2000-5000, hydroxyl value design is in 70-150mg KOH/g scope, and acid value controls to be≤3mg KOH/g.
In the present invention, the preparation of the described polyester containing unsaturated double-bond adopts scorification, carries out, N in the four-hole boiling flask with water trap, thermometer, stirring, nitrogen conduit
2the water that polycondensation generation is stroked in air-blowing enters water trap, reacts and carries out 2 hours at 160-170 DEG C, within after this every 1 hour, heats up 10 DEG C until 220 DEG C, and the refluxing xylene dehydration of admixture doses 3% is to resin acid value AV<3mg KOH/g.
(3) gained containing the polyester of unsaturated double-bond and the graft polymerization of prepolymer
In this step, the polyester containing unsaturated double-bond of preparation in above-mentioned steps (2) is cooled to 120-140 DEG C, (namely dropping includes A/B prepolymer, hydrophilic monomer, acrylic or methacrylic acid), the mixture of initiator and unsaturated monomer, 3 hours drip off, a initiator can be added, and be incubated 3 hours, make described mixture and the polyester generation graft polymerization reaction containing unsaturated double-bond.
In the present invention, generally design at 100:20 to 100:50 containing the polyester of unsaturated double-bond and the weight ratio of unsaturated monomer.
In the present invention, consisting of of described mixture: prepolymer A/B mixture 30-50 weight part, hydrophilic monomer (acrylic or methacrylic acid) 10-30 weight part, unsaturated monomer 20-30 weight part, initiator 0.5-5 weight part is 100 parts by weight with described mixture.
In the present invention, described unsaturated monomer is various Acrylic Acid Monomer well known in the art and the unsaturated monomer containing vinyl, such as general monomer, as (methyl) vinylformic acid methyl, ethyl ester, butyl ester, different monooctyl ester and isobornyl thiocyanoacetate, the monomer of hydroxyl, as (methyl) Hydroxyethyl acrylate, hydroxypropyl acrylate, N-methylol (methyl) acrylamide and N-hydroxyethyl (methyl) acrylamide, vinyl monomer, as vinylbenzene, vinyl toluene, vinyl acetate and tertiary ethylene carbonate, optimization styrene of the present invention or methyl styrene monomer, as the reactivity ratio r1=0.04 of vinylbenzene (M1) and MALEIC ANHYDRIDE (M2) copolymerization, r2=0.015, r1r2=0.006, Q, e value of MALEIC ANHYDRIDE is respectively 0.23,2.25, is short of electricity subtype monomer, usually not easily carries out polyreaction separately, cinnamic Q, e value is respectively 1.0 ,-0.8, for power supply subtype monomer, therefore easily copolymerization occurs between two monomers, graft polymerization preferentially occurs between MALEIC ANHYDRIDE and vinylbenzene, causes other monomer-grafted side chain to polyester macromolecule more subsequently because free radical chain increases.
In the present invention, described initiator is organic peroxide evocating agent, as acyl class superoxide (benzoyl peroxide, lauroyl peroxide), hydroperoxide (isopropyl benzene hydroperoxide, tertbutyl peroxide), dialkyl peroxide (tert-butyl peroxide, peroxide tertiary butyl, isopropyl peroxide), and ester class superoxide (peroxidized t-butyl perbenzoate, peroxidation trimethylacetic acid tertiary butyl ester).Because graft polymerization is carried out at higher temperatures, therefore preferably decomposition temperature is high, the initiator of long half time, as ditertiary butyl peroxide (DTBP), isopropyl benzene hydroperoxide (DCP) and peroxybenzoate (TPB).
In the present invention, the acid value of the graftomer of gained is designed to 20 ~ 50mg KOH/g, and hydroxyl value is designed to 70-130mgKOH/g, regulates kind and the consumption of vinyl monomer, can by the adjustment of the second-order transition temperature of graftomer between-10 ~ 10 DEG C.
(4) dispersion of graftomer
In this step, the graftomer obtained in step (3) is cooled to 70-80 DEG C, add the solubility promoter that amount of resin is 3 ~ 15%, neutralizing agent is added again after stirring, degree of neutralization controls at 80-100%, then under 200-1000rpm stirs, slowly deionized water is dripped, by the adjustment of solid part between 30-55% (preferred 42-45%), the polyurethane dispersions of non-isocyanate modification can be obtained, the total amount <10% of its VOC, preferred <8%, pH=7-8.5.
In the present invention, described solubility promoter is namely water-soluble, again can class two solvophilic of dissolving resin well, as Virahol, propylene glycol, a contracting propylene glycol, propylene glycol monomethyl ether, butyl glycol ether, propandiol butyl ether, butyl, methyl-2-pyrrolidone, N, dinethylformamide, and composition thereof.Described neutralizing agent mainly organic amine, as ammoniacal liquor, triethylamine, dimethylethanolamine, methyldiethanolamine, ethyl diisopropylamine, trolamine, and composition thereof.
the application of the polyester of obtained water-based non-isocyanate polyurethane modification
In a second aspect of the present invention, the application during the polyester providing the water-based non-isocyanate polyurethane modification of gained is coated with in the car.
In the present invention, modified poly ester dispersion liquid prepared by employing the present invention is as the main film forming matter be coated with in automobile, then the film coordinating water-compatible amino resin, color stuffing, auxiliary agent etc. to be formed has good anti-hitting property of stone and supporting sticking power.
Major advantage of the present invention is:
Be the polyester material that non-isocyanate polyurethane modification prepared by raw material with cyclic carbonate compound, instead of the polyurethane-modified route that traditional polyisocyanates is raw material, compared with traditional route, there is nontoxic advantage; The present invention successfully introduces hydrophilic radical in polyurethane-modified polyester, thus realizes its Water-borne modification, makes coating based on this can realize low VOCization.The present invention does not use poisonous isocyanic ester ester monomer to achieve the object of polyurethane-modified polyester, production process environmental protection, without the need to strictly controlling moisture content, the carboxyl of Graft Method introducing simultaneously, by other hydrophobic chain interval away from polyester backbone, make polyester dispersions have good resistance to hydrolysis, be coated with in the aqueous automobile prepared with this modified poly ester and there is good anti-hitting property of stone and the supporting sticking power of coating.
embodiment
The present invention is set forth further below in conjunction with specific embodiment.But, should be understood that these embodiments only do not form limitation of the scope of the invention for illustration of the present invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Except as otherwise noted, all per-cent and number are by weight.
Non-isocyanate polyurethane modified poly ester dispersion divides four steps to implement: 1) preparation is containing the unsaturated prepolymer A/B of amino key; 2) double bond containing unsaturated polyester UPE is prepared; 3) with monomers such as prepolymer A/B splits vinylformic acid (AC), grafting is carried out to unsaturated polyester, prepare graftomer UPE-g-AC; 4) UPE-g-AC is carried out neutralization dispersion.
embodiment 1
Step 1): the preparation of prepolymer A/B-1
In the four-hole boiling flask that thermometer, agitator, prolong, nitrogen conduit are housed, add vinyl cyclic carbonate ester (VEC) 119.9 grams, Monoethanolamine MEA BASF 61 grams, the Methylimidazole of 0.5 gram, toluhydroquinone (stopper) 0.25 gram, at N
2under gas shielded, in 120 DEG C of reaction 2-3h, be warming up to 150 DEG C of reaction 2-3h, then rise to 160 DEG C of reactions, to amine value≤5mg KOH/g, cooling discharge.
Step 2): the preparation of unsaturated polyester UPE-1
In the four-hole boiling flask that thermometer, agitator, point water condenser, nitrogen conduit are housed, drop into all raw materials in following table 1 except dimethylbenzene successively.
Table 1
Reaction carries out 2 hours at 160-170 DEG C, and nitrogen brushes the water that reaction generates, and within after this every 1 hour, heats up 10 DEG C until 220 DEG C, adds 11.9 grams of refluxing xylene dehydrations to resin acid value AV<3mg KOH/g.
The number-average molecular weight of gained resin is about 3000, and second-order transition temperature is about-20 DEG C, and theoretical hydroxyl number is 134mg KOH/g, and maleic anhydride content is 4.4%.
Step 3): the preparation of graftomer UPE-g-AC-1
The UPE-1 unsaturated polyester 300 grams of gained is put into agitator, reflux condensing tube, thermometer, in the four-hole bottle of constant pressure funnel, under nitrogen protection, between 130-140 DEG C, by vinylbenzene 18 grams, A/B-1 prepolymer 30 grams, 13.9 grams, vinylformic acid, the mixture of tert-butyl peroxide (DTBP) 1.35 grams dripped off at 3-3.5 hour, after being incubated half an hour, mend dropping 0.3 gram of tert-butyl peroxide initiator (being dissolved in 5 grams of propylene glycol monomethyl ethers), insulation reaction 3 hours again, obtain acid value AV and be about 30.2mgKOH/g, hydroxyl value is the resin liquid being about 147.6mg KOH/g, be cooled to 80 DEG C and enter next step operation.
Step 4): modified poly ester dispersion D-1
In step 3) in add propylene glycol monomethyl ether 25 grams in the graft resin liquid 362 grams that obtains, dimethylethanolamine 15.6 grams, after stirring, slowly deionized water 382 grams is dripped from dropping funnel, control rotating speed about 400rpm, dropwise rear continuation maintenance 30 minutes, obtain the polyester dispersions D-1 of non-isocyanate polyurethane modification.
performance measurement
This dispersion liquid solid part is 43-45%, and degree of neutralization is 95%, pH is 7-8.5, and particle diameter is 80-120nm, VOC is that 6.9%, 50 DEG C of thermmal storages are stablized for 10 days, and acid number raises and is less than 10%.
As shown in Figure 1,1783cm
-1the cyclic carbonate ester key at place disappears, at 1696 cm
-1there is the stretching vibration peak of C=O bond in ammonia ester bond in place, 1537 cm
-1there is the formation vibration peak of hydrogen bound to nitrogen in ammonia ester bond in place, demonstrates the formation of ammonia ester bond.
embodiment 2
Step 1): the preparation of prepolymer A/B-2
Reaction unit, with embodiment 1, adds methacrylic acid cyclic carbonate ester 195.3 grams, n-Butyl Amine 99 73.1 grams, the Methylimidazole of 0.38 gram, and toluhydroquinone (stopper) 0.2 gram, at N
2under gas shielded, in 80 DEG C of reaction 2-3h, be warming up to 120 DEG C of reaction 2-3h, then rise to 150 DEG C of reactions, to amine value≤5mg KOH/g, cooling discharge.
Step 2): the preparation of unsaturated polyester UPE-2
Device and technique, with embodiment 1, drop into all raw materials in following table 2 except dimethylbenzene, terminal acid value AV<3mg KOH/g successively.
The number-average molecular weight of gained resin is about 4300, and second-order transition temperature is about-25 DEG C, and theoretical hydroxyl number is 112mg KOH/g, and maleic anhydride content is 3.7%.
Step 3): the preparation of graftomer UPE-g-AC-2
Reaction unit is with embodiment 1, the UPE-2 unsaturated polyester 300 grams of gained is put into agitator, reflux condensing tube, thermometer, in the four-hole bottle of constant pressure funnel, under nitrogen protection, between 130-140 DEG C, by vinylbenzene 1.6 grams, A/B-2 prepolymer 30 grams, 32 grams, vinylformic acid, butyl acrylate 8 grams, Hydroxyethyl acrylate 8 grams, the mixture of tert-butyl peroxide (DTBP) 1.8 grams dripped off at 3-3.5 hour, after being incubated half an hour, mend dropping 0.4 gram of tert-butyl peroxide initiator (being dissolved in 5 grams of propylene glycol monomethyl ethers), insulation reaction 3 hours again, obtain acid value AV and be about 37.7mg KOH/g, hydroxyl value is about the resin liquid of 119.5mg KOH/g, be cooled to 80 DEG C and enter next step operation.
Step 4): modified poly ester dispersion D-2
In step 3) in gained graft resin liquid 384 grams in add propylene glycol monomethyl ether 27, dimethylethanolamine 20 grams, after stirring, slowly deionized water 462 grams is dripped from dropping funnel, control rotating speed about 400rpm, dropwise rear continuation maintenance 30 minutes, obtain the polyester dispersions D-2 of non-isocyanate polyurethane modification.
performance measurement
This dispersion liquid solid part is 42-44%, and degree of neutralization is 90%, pH is 7-8.5, and particle diameter is 80-120nm, VOC is that 6.8%, 50 DEG C of thermmal storages are stablized for 10 days, and acid number raises and is less than 10%.
embodiment 3
Step 1): the preparation of prepolymer A/B-3
Reaction unit is with embodiment 1, by 3-allyloxy-1,2-ring carbonic acid glycidyl ester (3-allyloxy-1,2-cyclic carbonate glycidyl ester) 165.9 grams, with Monoethanolamine MEA BASF 61 grams, the lithium hydroxide of 0.4 gram, toluhydroquinone (stopper) 0.25 gram, at N
2under gas shielded, in 120 DEG C of reaction 2-3h, be warming up to 150 DEG C of reaction 2-3h, then rise to 160 DEG C of reactions to amine value≤5, cooling discharge.
Step 2): the preparation of unsaturated polyester UPE-3
Conversion unit and technique are with embodiment 1, and proportioning raw materials is as shown in table 3 below:
Table 3
The number-average molecular weight of gained resin is about 2200, and second-order transition temperature is about 3 DEG C, and theoretical hydroxyl number is 100.9mg KOH/g, and maleic anhydride content is 4.88%.
Step 3): the preparation of graftomer UPE-g-AC-3
Equipment is with embodiment 1, UPE-3 unsaturated polyester 300 grams is dropped in four-hole boiling flask, under nitrogen protection, between 130-140 DEG C, by vinylbenzene 18 grams, the A/B-3 prepolymer of gained 30 grams, 13.9 grams, vinylformic acid, the mixture of tert-butyl peroxide (DTBP) 1.35 grams dripped off at 3-3.5 hour, after being incubated half an hour, mend dropping 0.3 gram of tert-butyl peroxide initiator (being dissolved in 5 grams of propylene glycol monomethyl ethers), insulation reaction 3 hours again, obtain acid value AV and be about 30.9mg KOH/g, hydroxyl value is about the resin liquid of 124mg KOH/g, be cooled to 80 DEG C and enter next step operation.
Step 4): modified poly ester dispersion D-3
In above-mentioned steps 3) in add propylene glycol monomethyl ether 25 in the graft resin liquid 362 grams that obtains, triethylamine 18.5 grams, after stirring, slowly deionized water 382 grams is dripped from dropping funnel, control rotating speed about 400rpm, dropwise rear continuation maintenance 30 minutes, obtain the polyester dispersions D-3 of non-isocyanate polyurethane modification.
performance measurement
This dispersion liquid solid part is 43-45%, and degree of neutralization is 95%, pH is 7-8.5, and particle diameter is that 100-150nm, VOC are about 7.3%, and 50 DEG C of thermmal storages are stablized for 10 days, and acid number raises and is less than 10%.
comparative example
Step 3 in embodiment 1) middle with hydroxyethyl methylacrylate equivalent substitution prepolymer A/B-1 (both hydroxyl values are similar to), all the other conditions are constant, prepare graftomer UPE-4, by this graftomer UPE-4 by step 4 in embodiment 1) identical proportioning raw materials, only substitute UPE-g-AC-1 with UPE-g-AC-4 and obtain dispersion D-4.
performance measurement
This dispersion liquid solid part is 43-45%, and degree of neutralization is 95%, pH is 7-8.5, and particle diameter is that 80-120nm, VOC are about 6.9%, and 50 DEG C of thermmal storages are stablized for 10 days, and acid number raises and is less than 10%.
embodiment 4:
the preparation be coated with in aqueous automobile
Raw material and proportioning see the following form 4 (for grey):
Table 4
In formula, the ratio of vibrin and aminoresin is 80:20, resin-pigment ratio is 1.1/1, solid part is about 60%, pH=8.0-9.0 is adjusted with dimethylethanolamine, VOC total content is about 7%, wherein aminoresin can be full methyl-etherified or part methyl-etherified aminoresin, also can be butyl ether or mixed etherified amino resins.
making sheet and detection
Painting deionized water in prepared is adjusted to and 40-50 second (adopts and be coated with-4 glasss of methods and measure, 23 DEG C), be sprayed on and scribble on the phosphatization plate of cathode electrodip painting in advance, spray pressure was 0.3-0.4MPa, 80-100 DEG C of preliminary drying 5-10 minute, 160 DEG C of bakings 25 minutes, obtain the middle film of 30-35 μm, detect supporting sticking power by GB/T9286-88 cross-hatching, hit performance by the anti-stone of GM9508P General Motors standard detection, the results are shown in following table 5.
Table 5
| Formula number | t-1 | t-2 | t-3 | t-4 |
| Supporting sticking power, level | 0 | 0 | 0 | 1～2 |
| Anti-stone hits, level | 7 | 7 | 7 | 6 |
Note: anti-stone hits and adopts GM9508P method B, SAE90 DEG C, model temperature-30 DEG C, air pressure 480 ± 20KPa, attack time 7-10 second, rubble amount 473ml gravel.By the evaluation of 0-9 level, 0 grade the poorest, and 9 grades best.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a preparation method for the polyester of water-based non-isocyanate polyurethane modification, the method comprises the following steps:
(1) containing the preparation of the unsaturated prepolymer of ammonia ester bond
The cyclic carbonate ester and primary amine that contain unsaturated double-bond are reacted to amine value≤5mg KOH/g at 80-180 DEG C, to obtain the unsaturated prepolymer containing ammonia ester bond;
(2) containing the preparation of the polyester of unsaturated double-bond
Use and prepare polyester containing unsaturated double-bond containing the acid of unsaturated double-bond or alcohol, the molecular weight of the polyester containing unsaturated double-bond of gained is 2000-5000, acid value≤3mg KOH/g, and second-order transition temperature is-30 ~ 10 DEG C, and hydroxyl value is 70-150mg KOH/g;
(3) gained containing the polyester of unsaturated double-bond and the graft polymerization of prepolymer
By the prepolymer of gained, and hydrophilic monomer, unsaturated monomer and initiator mixing, 120-140 DEG C add gained containing unsaturated double-bond polyester in introduce carboxyl and ammonia ester bond on its side chain, thus obtain graftomer, wherein, the prepolymer of gained, hydrophilic monomer, the weight ratio of unsaturated monomer and initiator is: (30-50): (10-30): (20-30): (0.5-5), the weight ratio of the polyester containing unsaturated double-bond of described unsaturated monomer and gained is (20-50): 100, the second-order transition temperature of the graftomer of gained is-10 ~ 10 DEG C, hydroxyl value is 70-130mg KOH/g, acid value is 20-50mg KOH/g,
(4) dispersion of graftomer
In the graftomer of gained, add solubility promoter and neutralizing agent, to obtain the polyurethane dispersions of non-isocyanate modification, its solid part is the total amount <10% of 30-55%, pH=7-8.5, VOC.
2. the method for claim 1, is characterized in that, in step (1), the described cyclic carbonate ester containing unsaturated double-bond meets following formula I-III:
In formula, R
1h, or C linear, side chain, ring-type
1-6alkyl;
R
2h or CH
3-;
R
3represent singly-bound or C
1-C
5alkylidene group;
Described primary amine meets following formula I V:
H
2N-R
4 (IV)
In formula, R
4straight chain, side chain or alicyclic ring C
1-8the C of alkyl or hydroxyl
1-8alkyl, or substituted or unsubstituted phenyl, wherein, described substituting group is selected from: methyl, ethyl, methoxyl group and oxyethyl group.
3. method as claimed in claim 2, it is characterized in that, described primary amine is selected from: propylamine, n-Butyl Amine 99, positive heptyl amice, carbinolamine, Monoethanolamine MEA BASF, butanolamine, isobutyl hydramine, hexahydroaniline, aniline, benzylamine, open-chain crown ether and P-nethoxyaniline.
4. the method for claim 1, is characterized in that, in step (2), described alcohol comprises: the alcohol of dibasic alcohol, trivalent alcohol and more polyfunctionality; Described acid comprises: unit carboxylic acid and polycarboxylic acid.
5. the method as described in claim 1 or 4, is characterized in that, in step (2), prepares the unsaturated monomer used containing the polyester of unsaturated double-bond and comprises: MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE and (methyl) vinylformic acid.
6. method as claimed in claim 5, it is characterized in that, in step (2), preparing the unsaturated monomer used containing the polyester of unsaturated double-bond is MALEIC ANHYDRIDE, its consumption is 0.5-9 weight part, is 100 parts by weight to prepare the gross weight of the described monomer used containing the polyester of unsaturated double-bond.
7. the method for claim 1, is characterized in that, in step (3), described hydrophilic monomer is acrylic or methacrylic acid;
Described unsaturated monomer comprises: vinylbenzene, vinyl toluene, vinyl acetate, tertiary ethylene carbonate, (methyl) vinylformic acid methyl, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) isobornyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, N-methylol (methyl) acrylamide and N-hydroxyethyl (methyl) acrylamide;
Described initiator is organic peroxide evocating agent.
8. the method for claim 1, it is characterized in that, in step (4), described solubility promoter comprises: Virahol, propylene glycol, a contracting propylene glycol, propylene glycol monomethyl ether, butyl glycol ether, propandiol butyl ether, butyl, methyl-2-pyrrolidone, N, dinethylformamide, and composition thereof;
Described neutralizing agent comprises organic amine.
9. method as claimed in claim 8, it is characterized in that, described organic amine comprises: ammoniacal liquor, triethylamine, dimethylethanolamine, methyldiethanolamine, ethyl diisopropylamine, trolamine, and composition thereof.
10. the application during the polyester of water-based non-isocyanate polyurethane modification prepared by the method any one of claim 1-9 is coated with in the car.
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