CN1878820A - Dispersions of sulfonic acid group-containing, unsaturated and amorphous polyesters based on defined dicidol isomers - Google Patents
Dispersions of sulfonic acid group-containing, unsaturated and amorphous polyesters based on defined dicidol isomers Download PDFInfo
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- CN1878820A CN1878820A CNA2005800012309A CN200580001230A CN1878820A CN 1878820 A CN1878820 A CN 1878820A CN A2005800012309 A CNA2005800012309 A CN A2005800012309A CN 200580001230 A CN200580001230 A CN 200580001230A CN 1878820 A CN1878820 A CN 1878820A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
Abstract
The invention relates to an aqueous dispersion based on a sulfonic acid group-containing, amorphous, unsaturated polyester based on defined Dicidol isomers and saturated and/or unsaturated dicarboxylic acids. The invention also relates to a method for producing said dispersion and to its use.
Description
The present invention relates to contain sulfonic acid (sulphur) base and based on amorphous, the unsaturated polyester ester dispersion of some tristane dimethanol (Dicidol) isomer and acid.
Unsaturated polyester resin (UP-resin) is known.They are that condensation reaction by saturated and undersaturated dicarboxylic acid or its acid anhydrides and glycol makes.Their character can change significantly, and depends on the kind and the ratio of starting raw material to a great extent.
Usually use α, beta-unsaturated acid is as the carrier of polymerizable double bond, and it mainly is toxilic acid or its acid anhydrides or fumaric acid; And unsaturated diol is inferior important.Double bond content is high more, and promptly the two key spacings on the chain molecule are more little, and then the vibrin activity is big more.The very fast polymerization of this resin, it is very big to emit big calorimetric and volumetric shrinkage, generates highly cross-linked and therefore more crisp the finished product relatively.Therefore people come active pair of key in " dilution " polyester molecule by cocondensation radical of saturated aliphatic or aromatic dicarboxylic acid.With the glycol of straight or branched as alkoxide component.Difference between the various UP resinous type not only is to be used for producing their component, also be ratio, the condensation degree of the saturated acid of decision degree of crosslinking in polymerization process to unsaturated acid, also be molar weight, acid number and OH value, be kind, monomer content and the additive of end group on the chain molecule kind (Ullmann ' sEncyclopedia of Industrial Chemistry, the A21 volume, the 217th page and below, 1992).
DE924889 for example, DE953117, DE2245110, DE2721989 discloses among EP0114208 and the EP0934988 based on the UP resin of tristane dimethanol (Dicidol) as diol component.
The objective of the invention is, from a large amount of possible scheme of prior art and variant scheme, seek new, contain sulfo group and unbodied vibrin, it is water dispersible in addition and is transparent when existing with solid form.This purpose is finished by the following method that will illustrate.
The invention provides a kind ofly based on the aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group, this vibrin is synthetic by following component:
I. alkoxide component,
The α of II.20 to 100 mole of %, the beta-unsaturated carboxylic acid component and
The other carboxyl acid component of 0 to 80 mole of %, and
III. at least a component that contains sulfo group,
This alkoxide component I comprises isomeric compound 3,8-two (methylol) three ring [5.2.1.0
2,6] decane, 4,8-two (methylol) three ring [5.2.1.0
2,6] decane and 5,8-two (methylol) three ring [5.2.1.0
2,6] tristane dimethanol (Dicidol) mixture of decane forms, every kind of shared part of isomer can be 20% to 40% in the mixture, and the summation of three kinds of isomer is 90% to 100%, and this mixture is at least 10 to 100 moles of % in the alkoxide component of polyester, and
This aqueous based dispersions has
A) content of nonvolatile substances is 20%-60%,
B) content of solvent is 0-20wt%,
C) the pH value is 5.0-9.5,
D) viscosity is 20-350mPas 20 ℃ the time,
E) mark of carbamate groups and/or urea groups is 0-15wt%,
F) sulfonic mark is 0.25-20wt%.
According to the present invention, employed alkoxide component comprises isomeric compound 3,8-two (methylol) three ring [5.2.1.0
2,6] decane, 4,8-two (methylol) three ring [5.2.1.0
2,6] decane and 5,8-two (methylol) three ring [5.2.1.0
2,6] tristane dimethanol (Dicidol) mixture of decane, every kind of shared part of isomer can be 20% to 40% in the mixture, and the summation of three kinds of isomer is 90% to 100%, and is preferred 95% to 100%, and this mixture is at least 10 weight % in the alkoxide component of polyester.The content of isomer of Dicidol mixture can analyze qualitative and quantitative assay by for example GC, or by the fractional separation quantitative analysis, method is that preliminary GC or HPLC analyze then NMR spectroscopic analysis.All corresponding isomer of Dicidol all are same being fit on the position 9, but because the mirror symmetry of above-mentioned isomer also has cis and trans isomer, so distinguish to come out under general actual service condition.
The Dicidol mixture can also contain at the most the trimerization and/or the higher poly-isomery glycol of Diels-Alder (diels-alder) reaction product of 10% other Dicidol isomer and/or cyclopentadiene.The preferred alcohols component is by 20%, 50%, and more preferably 90%, preferred especially 100% Dicidol mixture is formed, and this mixture especially preferably contains above-mentioned three kinds of isomeric compounds of 95% to 100%.
Except the Dicidol mixture, can also contain in the alkoxide component other straight chain and/or side chain, aliphatic series and/or cyclic aliphatic and/or aromatic glycol and/or polyvalent alcohol.Preferred used other alcohol comprises: ethylene glycol, 1,2-and/or 1, ammediol, glycol ether, dipropylene glycol, triglycol, Tetraglycol 99,1,2-and/or 1,4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1,3-methyl propanediol, 1,5-pentanediol, dihydroxyphenyl propane, B, C and F, norbornylene glycol, 1,4-benzyl dimethanol and 1,4-benzyl di-alcohol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, cyclohexanedimethanol, glycerol, hexylene glycol, neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP) and/or tetramethylolmethane.
The sulfo group unsaturated, amorphous polyester resin that contains of the present invention comprises at least a α as the starting acid component, β-unsaturated dicarboxylic acid.Preferred this unsaturated polyester resin contains citraconic acid, fumaric acid, methylene-succinic acid, toxilic acid and/or methylfumaric acid.
In addition, also can there be aromatic series and/or aliphatic series and/or alicyclic monocarboxylic acid and/or dicarboxylic acid and/or poly carboxylic acid, for example: phthalic acid, m-phthalic acid, terephthalic acid, 1,4-cyclohexane dicarboxylic acid, succsinic acid, sebacic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, hexanodioic acid, nonane diacid, pyromellitic acid and/or trimellitic acid, different n-nonanoic acid and 2 ethyl hexanoic acid.Preferably phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, six hydrogen terephthalic acids, trimellitic acid, hexanodioic acid and/or nonane diacid.
Carboxyl acid component can be all or part of by acid anhydrides and/or low-molecular-weight alkyl ester, and preferred methyl esters and/or ethyl ester constitute.
Generally speaking, alkoxide component is 0.5-2.0 to the mol ratio of acid constituents: 1, and preferred 0.8-1.5: 1.Special preferred reaction is 1.0-1.3 by alkoxide component to the mol ratio of acid constituents: 1 carries out.
With sulfonic acid group be attached in the unsaturated, amorphous polyester be by: the monomeric unit that will contain sulfo group is sulfoisophthalic acid and/or sulfo-succinic acid for example, be used for for example polyester condensation (scheme 1), perhaps making the unsaturated, amorphous polyester of hydroxyl-functional and isocyanate component and containing isocyanic ester is that the sulfo group component that contains of active part is reacted (scheme 2).
Polyester of the present invention has a small amount of sulfonic group of 0.25 weight % to 20 weight % usually.
As according to scheme 1 contain the sulfo group component, can use single-and many-carboxyl sulfonic acid and their salt, for example sulfoisophthalic acid, sulfo-succinic acid and their salt.Under this scheme situation, will contain the other carboxyl acid component that the sulfo group component is regarded all acid component I I as, and its content can be between 1 and 60 mole of %, preferably between 2 and 40 moles of %.
According to scheme 2, can use singly-and many-hydroxyl sulfoacid, and/or single-and many-thionamic acid, and their salt, they are connected on the polyester by for example suitable vulcabond and/or polyisocyanates.Here suitable example is: 1,4-dihydroxyl fourth sulfonic acid, N-(cyclohexyl) thionamic acid and N-(2-amino-ethyl)-2-aminoethyl sulfonic acid and their salt, and (to every mole of polyester (by means of Mn) that derives from I and II) use 0.2 to 3 mole, preferred 0.25 to the 2 mole sulfo group component that contains.
The preferred isocyanate that is used for connecting according to scheme 2 the sulfonic acid components is: about at the most 1000 gram/moles of molecular-weight average and average isocyanate functionality are 2 to 4 aliphatic series and/or cycloaliphatic polyisocyanate.They for example comprise: separately or as the simple vulcabond of mixture, as cyclohexyl diisocyanate, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, phenylene diisocyanate, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, tolylene diisocyanate, two (isocyanato-phenyl) methane, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate, as the own diester of two isocyanic acids (HDI) or 1,5-two isocyanato-s-2-methylpentane (MPDI), the heptane vulcabond, the octane vulcabond, the nonane vulcabond, as 1,6-two isocyanato-s-2,4,4-trimethyl cyclohexane or 1,6-two isocyanato-s-2,2,4-trimethyl cyclohexane (TMDI), nonane triisocyanate, as 4-isocyanato-methyl isophthalic acid, 8-octane vulcabond (TIN), the vulcabond of decane and triisocyanate, undecanoic vulcabond and triisocyanate, the vulcabond of dodecane and triisocyanate, isoflurane chalcone diisocyanate (IPDI), two (isocyanato-methylcyclohexyl) methane (H
12MDI), isocyanato-methyl cyclohexyl isocyanate, 2,5 (2,6)-two (isocyanato-methyl) dicyclos [2.2.1] heptane (NBDI), 1, two (isocyanato-methyl) hexanaphthenes of 3-(1,3-H
6-XDI) or 1, and two (isocyanato-methyl) hexanaphthenes of 4-(1,4-H
6-XDI) and/or their cuts.
Another kind of possibility is to use polyisocyanates, and it can obtain by reacting with difunctional reactant thing (for example glycol, diamines, list-and/or two-hydroxyl sulfoacid, list-and/or bis-amino sulfonic acid etc.).Another kind of preferred polyisocyanates is the trimerization by simple vulcabond, allophanate-modified, biuret reaction and/or urethane-modified (urethanization) preparation, and its per molecule has the compound more than two isocyanate groups, these simple vulcabond for example are as IPDI, HDI and/or H
12MDI, with the reaction product of polyvalent alcohol (for example glycerol, TriMethylolPropane(TMP), tetramethylolmethane) or multifunctional polyamine, or by simple vulcabond, as IPDI, HDI and H
12Three isocyanuric acid esters that the trimerization of MDI obtains.The useful representative of aromatic polyisocyanate comprises, tetramethylene eylylene diisocyanate (TMXDI for example, tetramethylenexylylene diisocyanate), 2,4-two isocyanato-toluene and/or itself and 2, the cuts of 6-two isocyanato-toluene, the cuts that also has 4,4 '-two isocyanato-ditans and/or itself and 2,4 '-two isocyanato-ditans.
Therefore, the present invention also provide water base, contain sulfo group, the preparation method of unsaturated, amorphous polyester.In scheme 1, with starting ingredient I to III at 150 to 270 ℃, preferred 160 to 230 ℃ temperature, preferably in inert atmosphere, preferably in nitrogen or rare gas, more preferably in nitrogen, the oxygen level of rare gas element is lower than 50ppm, preferably be lower than 20ppm, carry out (partly) in single hop or multistage operation continuous or rhythmic reaction of initial pure I, starting acid II and sulfonic acid component III, this resin (this resin neutralizes under the needs situation) combines with water subsequently.
In scheme 2, at first at 150 to 270 ℃, preferred 160 to 230 ℃ temperature, preferably in inert atmosphere, preferably in nitrogen or rare gas, more preferably in nitrogen, the oxygen level of rare gas element is lower than 50ppm, preferably be lower than 20ppm, (partly) in single hop or multistage operation continuously or rhythmic reaction makes starting ingredient I and II reaction by initial pure I and starting acid II.Then in the preferred temperature that is lower than 100 ℃, under 70 ℃ of conditions, and contain the reaction of sulfomonomer unit and vulcabond or polyisocyanates, suitably under the situation by suitable secondary solvent.If desired, make the compound that contains sulfo group and di-isocyanate reaction to obtain to contain the preadduct of isocyanate group in advance.Used suitable secondary solvent is lower boiling inert solvent, it does not form miscibility gap with water at least in wide range, have and be lower than 100 ℃ boiling point under the atmospheric pressure, thereby and can be when needed, easily remove by distillation, its residual quantity is dropped to less than 2 weight %, particularly less than 0.5 weight %, based on final dispersion.The suitable example of these solvents comprises: acetone, methyl ethyl ketone and tetrahydrofuran (THF).In principle high boiling solvent as just-butyleneglycol, two-just-butyleneglycol and N-Methyl pyrrolidone also are suitable, it stays the dispersion of water-dilutable then.
Be this resin subsequently and the combining of water, if desired, neutralize earlier.
Resin according to the present invention's preparation can neutralize with organic and/or mineral alkali, for example sodium hydroxide, potassium hydroxide, ammonia or organic amine.Preferred use primary, the second month in a season and/or tertiary amine, for example ethamine, propylamine, dimethylamine, dibutylamine, hexahydroaniline, benzylamine, morpholine, piperidines and trolamine.Preferred especially sodium hydroxide and ammonia, and volatile tertiary amine, especially dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, triethylamine, tripropyl amine and Tributylamine.
Degree of neutralization be preferably in the stoichiometry and required dosis neutralisata 50% to 130%.
The present invention contains acid number that the sulfo group unsaturated, amorphous polyester can have between 1 and 200 milligram of KOH/ gram, preferably between 1 and 100, more preferably between 10 and 50 milligrams of KOH/ grams, and the OH value restrains between 1 and 200 milligram of KOH/, preferably between 1 and 100, more preferably between 10 and 50 milligrams of KOH/ grams.
In a preferred embodiment (1), the sulfo group unsaturated polyester that contains of the present invention is by alkoxide component, with fumaric acid and/or toxilic acid (acid anhydride), isophorone diisocyanate (IPDI) and/or hexamethylene diisocyanate (HDI) and/or two (isocyanato-methylcyclohexyl) methane (H
12MDI) and N-(2-amino-ethyl)-and 2-aminoethyl sulfonic acid constitutes, and this alkoxide component contains at least 90%, and is preferred 95%, more preferably 100% isomeric compound 3,8-two (methylol) three ring [5.2.1.0
2,6] decane, 4,8-two (methylol) three ring [5.2.1.0
2,6] decane and 5,8-two (methylol) three ring [5.2.1.0
2,6] the Dicidol mixture of decane.
In other preferred embodiment (2), this polyester is except that containing just like the starting ingredient described in (1), also contain other acid, it is selected from: hexanodioic acid, dodecanedioic acid and/or phthalic acid (acid anhydride), α, the ratio of beta-unsaturated acid and additional acid may change between 2: 1 to 1: 4.Preferred ratio is about 1: 1 to 1: 2.Usually, the acid number of these polyester is 1 to 200, and is preferred 1 to 100, and more preferably 10 to 50 milligrams of KOH/ grams, and OH value is 1 to 200 are preferred 1 to 100, and more preferably 10 to 50 milligrams of KOH/ restrain.
In preferred embodiment (3), the sulfo group unsaturated polyester that contains of the present invention is by alkoxide component and fumaric acid and/or toxilic acid (acid anhydride) and sulfoisophthalic acid and/or sulfo-succinic acid formation, this alkoxide component contains at least 90%, preferred 95%, more preferably 100% isomeric compound 3,8-two (methylol) three ring [5.2.1.0
2,6] decane, 4,8-two (methylol) three ring [5.2.1.0
2,6] decane and 5,8-two (methylol) three ring [5.2.1.0
2,6] the Dicidol mixture of decane.
In other preferred embodiment (4), this polyester is except that containing just like the starting ingredient described in (3), also contain other acid, it is selected from: hexanodioic acid, dodecanedioic acid and/or phthalic acid (acid anhydride), α, the ratio of beta-unsaturated acid and additional acid may change between 2: 1 to 1: 4.Preferred ratio is about 1: 1 to 1: 2.
According to the present invention, the dispersion that contains the sulfo group unsaturated, amorphous polyester also can contain auxiliary agent and additive, they are selected from: inhibitor, organic solvent, tensio-active agent, neutralizing agent, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, the color brightening agent, photosensitizers and light trigger, influence additive such as the thixotropic agent and/or the thickening material of rheological property, flowing regulator, anti, softening agent, defoamer, static inhibitor, lubricant, wetting agent and dispersion agent, sanitas also comprises for example mycocide and/or biocide, thermoplastic additive, dyestuff, pigment, matting agent, fire retardant, interior remover, filler and/or propelling agent.
The present invention also provides the purposes of the aqueous based dispersions that contains the sulfo group unsaturated, amorphous polyester.
These aqueous based dispersions
-in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup, sealing agent and/or insulating material as main ingredient, basic components or annexing ingredient.
-in water base filler compound, priming paint, surfacer, priming coat, finish paint and lacquer materials as main ingredient, basic components or annexing ingredient.
-in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup and/or sealing agent and insulating material as main ingredient, basic components or annexing ingredient, wherein have other polymkeric substance, these polymkeric substance are selected from alone or in combination: urethane, polyester, polyacrylic ester, polyolefine, natural resin, Resins, epoxy, silicone oil, silicone resin, aminoresin, fluoropolymer and their derivative.
The present invention also provides with water base amorphous unsaturated polyester resin manufacturing of sulfo group and/or the accurately machined goods of containing.
Illustrate the aqueous based dispersions that contains the sulfo group unsaturated, amorphous polyester according to of the present invention in more detail with following embodiment, but the application's scope be not construed as limiting:
Embodiment
Use starting ingredient Dicidol with isomer proportion near 1: 1: 1.
Under the highest 210 ℃ temperature, place nitrogen atmosphere to react the Dicidol of 1.25 moles hexanodioic acids and 3.675 moles, be less than 5 milligrams of KOH/ grams until acid number.Add 1.25 moles of fumaric acid and 0.05 weight % quinhydrones monomethyl ether (in fumaric acid) then.Stir 2 hours after-applied vacuum of 20 millibars, restrain less than 5 milligrams of KOH/ until acid number.After the cooling polyester is dissolved in the acetone soln, obtains the solution of concentration 60%.
In the presence of 1.2 gram dibutyl tin dilaurates, in reflux temperature the isophorone diisocyanate of 1128 this polyester liquids of gram and 444 grams was reacted 3 hours, be less than about 1.2% until NCO content.
For above-mentioned affixture provides the aqueous solution of the concentration 50% of 432 gram N-(2-amino-ethyl)-2-aminoethyl sulfonic acid sodium salts, and, be less than 0.1% until NCO content in the reflux temperature reaction.
Under violent stirring, add deionized water, and after other 30 minutes, acetone is removed in distillation under slight vacuum condition.Obtaining a kind of stable storing like this, not containing solvent and solid content is about 33% muddy dispersion.
Feature:
Viscosity
D-200: 260mPas, pH value: 7.1
Feature after the storage:
| 8 all room temperatures | 50 ℃ of 2 weeks | 50 ℃ of 8 weeks | |
| Viscosity D-200 | 75mPa·s | 70mPa·s | 50mPa·s |
| pH | 7.0 | 6.8 | 6.4 |
| Vision | Muddiness is stable | Muddiness is stable | Muddiness is stable |
Claims (44)
1. one kind based on the aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group, and this vibrin is synthetic by following component:
I: alkoxide component,
The α of II:20 to 100 mole of %, the beta-unsaturated carboxylic acid component and
The other carboxyl acid component of 0 to 80 mole of %, and
III: at least a component that contains sulfo group,
This alkoxide component I comprises isomeric compound 3,8-two (methylol) three ring [5.2.1.0
2,6] decane, 4,8-two (methylol) three ring [5.2.1.0
2,6] decane and 5,8-two (methylol) three ring [5.2.1.0
2,6] the tristane dimethanol mixture of decane, every kind of shared part of isomer can be 20% to 40% in the mixture, and the summation of three kinds of isomer is 90% to 100%, and this mixture is at least 10 to 100 moles of % in the alkoxide component of polyester, and
This aqueous based dispersions has
A) content of nonvolatile substances is 20%-60%,
B) content of solvent is 0-20wt%,
C) the pH value is 5.0-9.5,
D) viscosity is 20-350mPas 20 ℃ the time,
E) mark of carbamate groups and/or urea groups is 0-15wt%,
F) sulfonic mark is 0.25-20wt%.
2. the described aqueous based dispersions of claim 1, wherein alkoxide component I comprises at the most the trimerization and/or the higher poly-isomery glycol of the diels-Alder reaction product of the other isomer of 10% tristane dimethanol and/or cyclopentadiene.
3. the aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group described in or two in the aforementioned claim, wherein
Alkoxide component I contain other straight chain and/or side chain, aliphatic series and/or cyclic aliphatic and/or aromatic glycol and/or polyvalent alcohol.
4. the described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group of claim 3, it contains the ethylene glycol as other alcohol, 1,2-and/or 1, ammediol, glycol ether, dipropylene glycol, triglycol, Tetraglycol 99,1,2-and/or 1, the 4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1, the 3-methyl propanediol, 1, the 5-pentanediol, cyclohexanedimethanol, glycerol, hexylene glycol, trimethylolethane, TriMethylolPropane(TMP) and/or tetramethylolmethane, dihydroxyphenyl propane, B, C and F, the norbornylene glycol, 1,4-benzyl dimethanol and 1,4-benzyl di-alcohol, 2,4-dimethyl-2-ethyl hexane-1, the 3-glycol.
5. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein at least 20% of the alkoxide component I isomer by the tristane dimethanol constitutes.
6. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein at least 50% of the alkoxide component I isomer by the tristane dimethanol constitutes.
7. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein at least 90% of the alkoxide component I isomer by the tristane dimethanol constitutes.
8. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein 100% of the alkoxide component I isomer by the tristane dimethanol constitutes.
9. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein this carboxyl acid component II is all or part of is made of acid anhydrides and/or alkyl ester.
10. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, it comprises citraconic acid, fumaric acid, methylene-succinic acid, toxilic acid and/or methylfumaric acid as α, beta-unsaturated carboxylic acid component I I.
11. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, it comprises fumaric acid and/or toxilic acid (acid anhydride) as α, beta-unsaturated carboxylic acid component I I.
12. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein this other carboxyl acid component comprises monocarboxylic acid aromatic and/or aliphatic and/or cyclic aliphatic and/or dicarboxylic acid and/or poly carboxylic acid.
13. the described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group of claim 12, it comprises: phthalic acid, m-phthalic acid, terephthalic acid, 1,4-cyclohexane dicarboxylic acid, succsinic acid, sebacic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, hexanodioic acid, nonane diacid, pyromellitic acid and/or trihemellitic acid, their acid anhydrides and/or methyl ester, and different n-nonanoic acid and/or 2 ethyl hexanoic acid.
14. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, it comprises hexanodioic acid and/or dodecanedioic acid and/or phthalic acid (acid anhydride) the other carboxyl acid component as this unsaturated, amorphous polyester.
15. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, its comprise single-and/or many-carboxylate radical close sulfonic acid and/or their salt as component III.
16. the described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group of claim 15, it comprises sulfoisophthalic acid and/or sulfo-succinic acid and/or its salt.
17. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein use hydroxyl-and/or the reaction product of thionamic acid and vulcabond and/or polyisocyanates as component III.
18. the aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group described in the aforementioned at least claim wherein uses 1,4-dihydroxyl fourth sulfonic acid, N-(cyclohexyl) thionamic acid and/or N-(2-amino-ethyl)-2-aminoethyl sulfonic acid and/or their salt.
19. at least one the described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group wherein uses aromatic series, aliphatic series and/or cycloaliphatic diisocyanates as vulcabond in the aforementioned claim.
20. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein use isoflurane chalcone diisocyanate and/or the own diester of two isocyanic acids and/or 4,4 '-methylene-bis (cyclohexyl diisocyanate) is as vulcabond.
21. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, the alkoxide component I of the unsaturated, amorphous polyester that it comprises and the mol ratio of acid constituents II are 0.5 to 2.0: 1.
22. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, the alkoxide component I of the unsaturated, amorphous polyester that it comprises and the mol ratio of acid constituents II are 0.8 to 1.5: 1.
23. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, the alkoxide component I of the unsaturated, amorphous polyester that it comprises and the mol ratio of acid constituents II are 1.0 to 1.3: 1.
24. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, the acid number that has are between 1 and 200 milligram of KOH/ gram, preferably between 1 and 100, more preferably between 10 and 50 milligrams of KOH/ grams.
25. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, the OH value that has are between 1 and 200 milligram of KOH/ gram, preferably between 1 and 100, more preferably between 10 and 80 milligrams of KOH/ grams.
26. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, it comprises auxiliary agent and additive.
27. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, auxiliary agent and additive that it comprises are selected from: inhibitor, organic solvent, tensio-active agent, neutralizing agent, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, color brightening agent, influence additive such as the thixotropic agent and/or the thickening material of rheological property, defoamer, wetting agent, dispersion agent, sanitas also comprise for example mycocide and/or biocide etc.
28. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein the alkoxide component of unsaturated, amorphous polyester comprises at least 90% tristane dimethanol isomer, and this acid constituents is made of fumaric acid and/or toxilic acid (acid anhydride).
29. the described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group of claim 28, wherein this amorphous unsaturated polyester also comprises hexanodioic acid, dodecanedioic acid and/or phthalic acid (acid anhydride) in addition as acid constituents, make α, the ratio of beta-unsaturated acid and other acid is 3: 1 to 1: 4, is preferably 1: 1 to 1: 2.
30. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein this contains being neutralized to the small part acidic group of sulfo group unsaturated, amorphous polyester.
31. at least one the described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group wherein uses amine and/or inorganic hydroxide solution to neutralize in the aforementioned claim.
32. at least one described aqueous based dispersions that contains the amorphous unsaturated polyester resin of sulfo group in the aforementioned claim, wherein degree of neutralization is between 0.3 and 1.2, preferably between 0.5 and 1.0, more preferably between 0.6 and 1.0.
33. as at least one described water base, preparation method of containing sulfo group, unsaturated, amorphous polyester in the claim 1 to 32,
A) at 150 to 270 ℃, under preferred 160 to the 230 ℃ temperature, in inert atmosphere, make those starting ingredients carry out (partly) continuous or rhythmic reaction, and in water, disperse product, if desired, neutralization earlier;
B) at 150 to 270 ℃, under preferred 160 to the 230 ℃ temperature, preferably in inert atmosphere, make starting ingredient I and II carry out (partly) continuous or rhythmic reaction, and make product subsequently, under 70 ℃ of conditions in the preferred temperature that is lower than 100 ℃, with contain sulfomonomer unit and vulcabond or polyisocyanates the reaction, by suitable secondary solvent, and make this resin and water combination subsequently in the time of suitably, neutralize earlier in the time of suitably.
34. the preparation method of the described aqueous based dispersions of claim 33 wherein is dispersed in the amorphous unsaturated sulfopolyester that contains in this melt or with organic secondary solvent and is dispersed in the water.
35. the preparation method of claim 33 and 34 described aqueous based dispersions wherein should distill by organic secondary solvent.
36. in the aforementioned claim at least one described aqueous based dispersions in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup, sealing agent and/or insulating material as the purposes of main ingredient, basic components or annexing ingredient.
37. in the aforementioned claim at least one described aqueous based dispersions in water base filler compound, priming paint, surfacer, priming coat, finish paint and lacquer materials as the purposes of main ingredient, basic components or annexing ingredient.
38. the described aqueous based dispersions of at least one item is used for the purposes of metal, plastics, timber, leather, cardboard, paper, textiles and glass in the aforementioned claim.
39. the described aqueous based dispersions of at least one item as the purposes of main ingredient, basic components or annexing ingredient, wherein exists other oligopolymer and/or polymkeric substance in the aforementioned claim in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup, sealing agent and/or insulating material.
40. in the aforementioned claim at least one described aqueous based dispersions in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup, sealing agent and/or insulating material as the purposes of main ingredient, basic components or annexing ingredient, wherein
Have other oligopolymer and/or polymkeric substance alone or in combination, it is selected from: urethane, polyester, polyacrylic ester, polyethers, polyolefine, natural resin, Resins, epoxy, silicone oil, silicone resin, aminoresin, fluoropolymer and their derivative.
41. the described aqueous based dispersions of at least one item as the purposes of main ingredient, basic components or annexing ingredient, wherein exists other auxiliary agent and additive in the aforementioned claim in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup, sealing agent and/or insulating material.
42. in the aforementioned claim at least one described aqueous based dispersions in water-based paint, tackiness agent, gel coat, the printing ink that comprises printing-ink or ink, lustering agent, tinting material, pigment paste, filler compound, makeup, sealing agent and/or insulating material as the purposes of main ingredient, basic components or annexing ingredient, wherein
Other auxiliary agent and additive are selected from: inhibitor, organic solvent, tensio-active agent, neutralizing agent, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, the color brightening agent, photosensitizers and light trigger, influence additive such as the thixotropic agent and/or the thickening material of rheological property, flowing regulator, anti, softening agent, defoamer, static inhibitor, lubricant, wetting agent and dispersion agent, sanitas also comprises for example mycocide and/or biocide, thermoplastic additive, dyestuff, pigment, matting agent, fire retardant, interior remover, filler and/or propelling agent.
43. one kind contains the amorphous unsaturated polyester resin of sulfo group, this vibrin is synthetic by following component:
I: alkoxide component,
The α of II:20 to 100 mole of %, the beta-unsaturated carboxylic acid component and
The other carboxyl acid component of 0 to 80 mole of %,
III: at least a component that contains sulfo group,
This alkoxide component I comprises isomeric compound 3,8-two (methylol) three ring [5.2.1.0
2,6] decane, 4,8-two (methylol) three ring [5.2.1.0
2,6] decane and 5,8-two (methylol) three ring [5.2.1.0
2,6] the tristane dimethanol mixture of decane, every kind of shared part of isomer can be 20% to 40% in the mixture, and the summation of three kinds of isomer is 90% to 100%, and this mixture is at least 10 to 100 moles of % in the alkoxide component of polyester, and
This aqueous based dispersions has
A) content of nonvolatile substances is 20%-60%,
B) content of solvent is 0-20wt%,
C) the pH value is 5.0-9.5,
D) viscosity is 20-350mPas 20 ℃ the time,
E) mark of carbamate groups and/or urea groups is 0-15wt%,
F) sulfonic mark is 0.25-20wt%.
44. with each the described or desired water base amorphous unsaturated polyester resin manufacturing of sulfo group and/or accurately machined goods of containing in the aforementioned claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200410051862 DE102004051862A1 (en) | 2004-10-26 | 2004-10-26 | Dispersions of sulphonic acid-containing, unsaturated and amorphous polyesters based on certain dicidole isomers |
| DE102004051862.9 | 2004-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1878820A true CN1878820A (en) | 2006-12-13 |
Family
ID=35124419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800012309A Pending CN1878820A (en) | 2004-10-26 | 2005-09-02 | Dispersions of sulfonic acid group-containing, unsaturated and amorphous polyesters based on defined dicidol isomers |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1878820A (en) |
| DE (1) | DE102004051862A1 (en) |
| WO (1) | WO2006045662A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951818A (en) * | 2014-04-15 | 2014-07-30 | 中科院广州化学有限公司 | Sulphonic acid type water-based unsaturated polyester and application of sulphonic acid type water-based unsaturated polyester in coating |
| CN104629665A (en) * | 2015-01-27 | 2015-05-20 | 安徽环瑞电热器材有限公司 | Heat-resisting, antiflaming and environment-friendly glue and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2017016073A (en) | 2015-06-09 | 2018-02-21 | Ppg Ind Ohio Inc | Stain resistant, soft touch coating compositions and coatings formed therefrom. |
| CN110016127B (en) * | 2019-04-26 | 2021-08-10 | 永悦科技股份有限公司 | Synthetic method of water-based unsaturated polyester quartz resin |
| CN110591591B (en) * | 2019-09-05 | 2020-12-01 | 深圳市柳鑫实业股份有限公司 | Insulating medium adhesive film, preparation method thereof and multilayer printed circuit board |
| CN116004090B (en) * | 2023-02-27 | 2023-09-29 | 上海正欧实业有限公司 | Wear-resistant epoxy floor coating and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54143494A (en) * | 1978-04-28 | 1979-11-08 | Mitsubishi Petrochem Co Ltd | Unsaturated polyester resin composition |
| DE3935495A1 (en) * | 1989-10-25 | 1991-05-02 | Bayer Ag | METHOD FOR THE PRODUCTION OF UNSATURATED, URETHANIZED POLYESTER RESINS, THE POLYESTER RESINS AVAILABLE BY THIS METHOD AND THEIR USE AS OR FOR THE PRODUCTION OF COATING AGENT (S) |
| IT1260587B (en) * | 1991-03-07 | 1996-04-16 | Sir Soc Italiana Resine Spa | POLYESTER RESINS WATER SOLUBLE UNSATURES SUITABLE FOR THE PREPARATION OF WATER-BASED PAINTS, AND PAINTS PREPARED WITH SUCH RESINS. |
| NL1002153C2 (en) * | 1996-01-23 | 1997-08-04 | Dsm Nv | Radiation curable powder paint binder composition. |
| DE10212706A1 (en) * | 2002-03-21 | 2003-10-02 | Degussa | Unsaturated, amorphous polyester based on certain dicidol isomers |
| DE10242265A1 (en) * | 2002-09-12 | 2004-03-25 | Degussa Ag | Adhesion-improving additive made from an unsaturated, amorphous polyester |
| DE10261006A1 (en) * | 2002-12-24 | 2004-07-08 | Degussa Ag | Dispersions of amorphous, unsaturated polyester resins based on certain dicidol isomers |
| DE10261005A1 (en) * | 2002-12-24 | 2004-07-08 | Degussa Ag | Dispersions of amorphous, urethanized unsaturated polyester resins based on certain dicidol isomers |
-
2004
- 2004-10-26 DE DE200410051862 patent/DE102004051862A1/en not_active Withdrawn
-
2005
- 2005-09-02 CN CNA2005800012309A patent/CN1878820A/en active Pending
- 2005-09-02 WO PCT/EP2005/054334 patent/WO2006045662A1/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951818A (en) * | 2014-04-15 | 2014-07-30 | 中科院广州化学有限公司 | Sulphonic acid type water-based unsaturated polyester and application of sulphonic acid type water-based unsaturated polyester in coating |
| CN103951818B (en) * | 2014-04-15 | 2015-10-07 | 中科院广州化学有限公司 | A kind of sulfonic acid type water-based unsaturated polyester and the application in coating thereof |
| CN104629665A (en) * | 2015-01-27 | 2015-05-20 | 安徽环瑞电热器材有限公司 | Heat-resisting, antiflaming and environment-friendly glue and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006045662A1 (en) | 2006-05-04 |
| DE102004051862A1 (en) | 2006-04-27 |
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