EP3849962A1 - Polyasparaginsäureester-zusammensetzungen und verfahren zur reinigung - Google Patents
Polyasparaginsäureester-zusammensetzungen und verfahren zur reinigungInfo
- Publication number
- EP3849962A1 EP3849962A1 EP18765668.1A EP18765668A EP3849962A1 EP 3849962 A1 EP3849962 A1 EP 3849962A1 EP 18765668 A EP18765668 A EP 18765668A EP 3849962 A1 EP3849962 A1 EP 3849962A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyaspartic
- general formula
- acid ester
- purified
- polyaspartic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 126
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 61
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 41
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000608 Polyaspartic Polymers 0.000 claims description 53
- 238000004821 distillation Methods 0.000 claims description 38
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 26
- 229920000768 polyamine Polymers 0.000 claims description 22
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011552 falling film Substances 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 abstract description 16
- 239000000047 product Substances 0.000 description 10
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 10
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 9
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 9
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 8
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 8
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 6
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- JWTVQZQPKHXGFM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diamine Chemical compound CC(C)(N)CCC(C)(C)N JWTVQZQPKHXGFM-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000005700 Putrescine Substances 0.000 description 5
- -1 aspartic acid ester Chemical class 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- PZVANPGBOPAOIK-UHFFFAOYSA-N (1,3,3-trimethylcyclohexyl)methanamine Chemical compound CC1(C)CCCC(C)(CN)C1 PZVANPGBOPAOIK-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HMJBXEZHJUYJQY-UHFFFAOYSA-N 4-(aminomethyl)octane-1,8-diamine Chemical compound NCCCCC(CN)CCCN HMJBXEZHJUYJQY-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RPYFJVIASOJLJS-UHFFFAOYSA-N [3-(aminomethyl)-2-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1CC2C(CN)C(CN)C1C2 RPYFJVIASOJLJS-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N activated carbon Substances [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229940009098 aspartate Drugs 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-L aspartate group Chemical class N[C@@H](CC(=O)[O-])C(=O)[O-] CKLJMWTZIZZHCS-REOHCLBHSA-L 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 150000001510 aspartic acids Chemical class 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- GPCKFIWBUTWTDH-UHFFFAOYSA-N pentane-3,3-diamine Chemical compound CCC(N)(N)CC GPCKFIWBUTWTDH-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 description 1
- 238000010518 undesired secondary reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
Definitions
- the present invention relates to a process for the purification of polyaspartic ester compositions and the provision of polyaspartic esters containing 0.01 to ⁇ 2 wt.% Fumarcic aciddialkylester.
- Polyaspartic acid esters are used in two-component coating compositions which contain a polyisocyanate component as binder. Such coating compositions are suitable for the production of high-quality coatings which can be adjusted to be hard, elastic, resistant to abrasion and solvents.
- An advantage over primary amines is the moderate reactivity of the amine functions contained in the polyaspartic esters over isocyanates.
- EP0403921, EP0639628, EP0667362, EP0689881, US5,214,086, US6,605,684, EP0573860, EP0699696, EP0596360, EP0893458, DE19701835, DE102006002153, EP1767559, WO2001007504, WO2001007399, WO2004033517, US6458293, EP1426397 and US5,243,012 describe by way of example low-viscosity polyaspartic esters, which secondary
- polyaspartic esters are also called aspartates and are particularly suitable for producing low-solvent or -amideer coating compositions which show rapid curing.
- the reaction of maleic or fumaric acid esters with primary amines is carried out using ratios such that each primary amino group has at least one and preferably exactly one olefinic double bond.
- an undesired secondary reaction may take place in which dialkyl fumarate (dialkyl fumarate) is formed as a secondary component.
- dialkyl fumarate dialkyl fumarate
- a typical manufacturing process of a polyaspartic acid ester requires a storage time of 4-6 weeks after most of the reactants have reacted with each other. During this time, the so-called maturation of the product, which manifests itself by stabilizing the viscosity occurs.
- dialkyl fumarate Due to the fact that sales continue to increase within this time, the content of dialkyl fumarate also decreases. This storage over several weeks leads to significant logistics costs within the production. Furthermore, although the product is only after storage delivered to customers, it still contains substantial amounts of dialkyl fumarate which can cause sensitization. After completion of the reaction, polyaspartic esters thus prepared usually contain residues of from 3 to 20% by weight of unreacted fumaric and / or maleic acid esters.
- fumaric and / or maleic acid esters can be separated by distillation. Conditions under which the separation can be carried out successfully, does not name the document.
- DE102006002153A1 likewise describes the preparation of aspartic acid esters which contain several percent by weight of diethyl fumarate as raw material, but also after storage.
- Example 3 it is mentioned that the excess diethyl fumarate was completely removed by thin film distillation. Again, the required distillation conditions are not discussed.
- this document describes positive technical effects of a content of 2 to 10% by weight of diethyl fumarate in the aspartic acid ester, such as low viscosity coupled with good pot life and final hardness, it should be noted that such a high diethyl fumarate content may also be present has the above-mentioned adverse effects.
- polyaspartic esters having less than 2 percent by weight of free dialkyl fumarates.
- a content of less than 0.01% by weight brings here no further advantage in terms of processing conditions and can be realized technically only with considerable effort.
- the object of the present invention is to provide a method for purifying polyaspartic ester compositions for providing polyaspartic esters which can be easily applied in common applications with minimal health risk.
- This process should be particularly suitable for those polyaspartic esters which have a low platinum-cobalt color number. This problem could be solved by the inventive method for the purification of
- Polyaspartic acid ester compositions for providing purified polyaspartic acid esters containing ⁇ 2% by weight fumaric acid dialkyl ester.
- the present invention relates to a process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I)
- X is an m-valent, optionally one or more
- Heteroatom-containing organic radical is, as it can be obtained by removal of primary amino groups from a corresponding, aromatic, (cyclo) aliphatic or araliphatically bound primary amino groups having polyamine in the molecular weight range 60 to 6000 g / mol, and the other isocyanate-reactive and / or may contain inert functional groups at temperatures up to 100 ° C,
- R 1 and R 2 represent the same or different organic radicals each having 1 to 18
- Carbon atoms, m is an integer> 1, characterized in that the purified polyaspartic acid ester contains from 0.01 to ⁇ 2 wt.% Fumarcic aciddialkylester.
- a preferred object of the present invention is the above-mentioned process for purifying polyaspartic ester compositions of the general formula (I) in which
- X is an m-valent organic radical optionally containing one or more heteroatoms, as obtained by removal of primary amino groups from polyetherpolyamines having aliphatically bonded primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-
- Diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane is obtained,
- R 1 and R 2 represent identical or different alkyl radicals each having 1 to 8 carbon atoms
- n is an integer> 1, characterized in that the purified polyaspartic acid ester contains a proportion of 0.01-0.2% by weight of fumaric acid dialkyl ester.
- a further preferred subject matter of the present invention is the abovementioned process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I),
- X is an m-valent organic radical, as obtained by removal of primary amino groups from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 1 , 5-diamino-2-methylpentane can be obtained
- R 1 and R 2 represent identical or different alkyl radicals selected from the group
- m is 2, characterized in that the purified polyaspartic acid ester contains a proportion of 0.01 to 0.2 percent by weight of fumaric acid dialkyl ester.
- Another preferred object of the present invention is the above-mentioned process for purifying polyaspartic ester compositions containing polyaspartic acid esters of the general formula (I) in which
- X is an m-valent organic radical, as can be obtained by removal of primary amino groups from 2,4 'and / or 4,4'-diaminodicyclohexylmethane, R 1 and R 2 are ethyl radicals,
- a further subject matter of the present invention is a process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I)
- X is an m-valent, optionally containing one or more heteroatoms organic radical, as he by removal of primary amino groups from a corresponding, aromatic, (cyclo) aliphatic or araliphatic bound primary amino groups having polyamine in the molecular weight range 60 to 6000 g / mol and which may contain further isocyanate-reactive and / or inert at temperatures up to 100 ° C functional groups,
- R 1 and R 2 represent the same or different organic radicals each having 1 to 18
- a polyaspartic ester composition comprising polyaspartic acid esters of the general formula (I) and purified in at least one further step, characterized in that the purified polyaspartic ester contains from 0.01 to ⁇ 2% by weight of fumaric acid dialkyl ester.
- a preferred object of the present invention is the above-mentioned process for purifying polyaspartic ester compositions of the general formula (I) in which
- X is an m-valent organic radical optionally containing one or more heteroatoms, as obtained by removal of primary
- Amino groups of polyether polyamines having aliphatically bonded primary amino groups 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5-diamino-2, 5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1, 6-diaminohexane, 1,11-diaminounodecane, 1,12-diaminododecane, 1-amino
- Diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane is obtained,
- R 1 and R 2 represent identical or different alkyl radicals each having 1 to 8 carbon atoms
- a further preferred subject matter of the present invention is the abovementioned process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I), is an m-valent organic radical, as obtained by removal of primary amino groups from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4- and / or 4,4'-diaminodicyclohexylmethane, 1.5 - Diamino-2-methylpentane can be obtained
- a polyaspartic ester composition comprising polyaspartic esters of the general formula (I) be reacted and purified in a further step, characterized in that the purified polyaspartic acid ester contains a proportion of 0.01 to 0.2 percent by weight Fumarkladialkylester.
- a further preferred subject matter of the present invention is the abovementioned process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I),
- X is an m-valent organic radical, as can be obtained by removal of primary amino groups from 2,4'- and / or 4,4'-diaminodicyclohexylmethane,
- R 1 and R 2 are ethyl radicals
- m is 2, characterized in that substituted maleic and / or fumaric acid esters of the general formula (II), wherein the radicals Rl and R2 have the abovementioned meanings, with primary polyamines of the general formula (III), wherein X and m have the meanings mentioned above, to a polyaspartic acid ester composition containing polyaspartic acid ester of the general formula (I) and purified in a further step, characterized in that the purified polyaspartic ester contains a proportion of 0.01 to 0.1 percent by weight of fumaric acid dialkyl ester.
- maleic and / or Fumarkladialkylester of formula (II) are used in which for Rl and R2 are identical or different alkyl radicals each having 1 to 18 carbon atoms, preferably identical or different alkyl radicals each having 1 to 8 carbon atoms and all particularly preferred for each alkyl radicals such as methyl, ethyl, propyl, iso-propyl, butyl or iso-butyl radicals. Particularly preferred is diethyl maleate.
- diesters may be mentioned for compounds of the general formula (II): dimethyl maleate, diethyl ester, di-n-butyl ester, the corresponding fumaric acid esters or the corresponding methyl-substituted in the 2- and / or 3-position Maleic acid or fumaric acid ester.
- Polyamines of the general formula (III) which can be used for the process according to the invention are selected from the following group: all known polyamines having primary amino groups which correspond to the general formula (III).
- the following compounds may be mentioned by way of example: ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,5-diamino-2,5-dimethylhexane, 1,5-diamino-2-methylpentane (Dytek ®A, Fa DuPont), 1,6-diaminohexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,1-diaminoundecane, 1,1-diaminododecane or triaminononane , Etheramines, such as 4,9-dioxadodecane-l, 12-diamine, 4,7,
- Tricyclodecanbismethylamine (TCD-diamine) or bis (aminomethyl) norbornane, amino-functional siloxanes, e.g. Diaminopropylsiloxane G10 DAS (from Momentive), fatty alkyl based amines, e.g. Fentamine from Solvay, dimer fatty acid diamines such as priamines from Croda.
- TCD-diamine Tricyclodecanbismethylamine
- amino-functional siloxanes e.g. Diaminopropylsiloxane G10 DAS (from Momentive)
- fatty alkyl based amines e.g. Fentamine from Solvay
- dimer fatty acid diamines such as priamines from Croda.
- polyamines of the general formula (III) selected from the group consisting of polyether polyamines having aliphatically bonded primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
- Diamino-dicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane is particularly preferred.
- polyamines of the general formula (III) selected from the group: 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4- and / or 4,4'-diaminodicyclohexylmethane, 1 , 5-diamino-2-methylpentane and very particularly preferred is the use of 2,4- and / or 4,4'-diaminodicyclohexylmethane.
- aromatic polyamines such as 2,4- and / or 2,6-diaminotoluene or 2,4'- and / or 4,4'-diaminodiphenylmethane or their polynuclear homologues.
- relatively high molecular weight polyether polyamines having aliphatically bonded primary amino groups such as those sold under the name Jeffamine®.
- m is an integer> 1 and preferably 2.
- polyaspartic acid ester composition containing polyaspartic acid ester of the general formula (I) can be stored or matured for several weeks and / or worked up by the inventive method for purification.
- Polyaspartic acid ester compositions contain from 70 to 98% by weight, preferably from 80 to 98% by weight and more preferably from 85 to 98% by weight of polyaspartic acid ester of the general formula (I).
- the purified polyaspartic acid ester is the product which is obtained by the process according to the invention for purifying polyaspartic ester compositions comprising polyaspartic acid esters of the general formula (I). It preferably contains from 0.01 to ⁇ 2 wt.%, Preferably 0.01 to 0.2 wt.% And particularly preferably 0.01 to 0.1 wt.% Fumarkladialkylester.
- purified polyaspartic esters which have a platinum-cobalt color number ⁇ 100, preferably ⁇ 50 and particularly preferably ⁇ 30, and a proportion of 0.01 to ⁇ 2 wt.%, preferably 0.01 to 0.2 wt.% and particularly preferably 0.01 to 0.1 wt.% of fumaric acid dialkyl ester.
- Another object of the present invention is the above-mentioned method of purification, characterized in that containing polyaspartic acid ester compositions
- Polyaspartic acid ester of the general formula (I) with a platinum-cobalt color number ⁇ 100 are purified.
- purified polyaspartic esters for coatings it is preferred if they have a platinum cobalt color number ⁇ 100, more preferably ⁇ 50.
- the measurement of the platinum-cobalt color number is carried out in accordance with DIN EN ISO 6271: 2016-05.
- formula (I) is not to be expected, so that preference is given to purifying those polyaspartic ester compositions comprising polyaspartic esters of the general formula (I) by the process according to the invention which already have a platinum-cobalt color number ⁇ 100, preferably ⁇ 50 and more preferably ⁇ 30 have.
- Another object of the present invention is the above-mentioned method for purification, wherein the polyaspartic acid ester compositions containing polyaspartic acid ester of the general formula (I) are purified by distillation.
- Another object of the present invention is the above-mentioned method for
- polyaspartic ester compositions containing polyaspartic acid ester of the general formula (I) are purified by distillation at a pressure below 20 mbar and a temperature below 180 ° C.
- Another object of the present invention is the above-mentioned method for purification, wherein the polyaspartic acid ester compositions comprising polyaspartic acid ester of the general formula (I) is purified by distillation, characterized in that
- distillation is carried out at a pressure between 0.005 and 2 mbar and
- the distillation is carried out at a pressure between 0.005 and 2 mbar, preferably between 0.005 and 0.8 mbar, more preferably between 0.005 and 0.2 mbar.
- Another object of the present invention is the above-mentioned method for purification, characterized in that the time during which the polyaspartic acid ester composition containing polyaspartic acid ester of the general formula (I), is exposed to temperatures above 100 ° C, less than 2 hours. In a further preferred embodiment, therefore, the time during which the
- Polyaspartic acid ester compositions containing polyaspartic esters of the general formula (I) exposed to temperatures above 100 ° C are limited to less than 2 hours, preferably less than 30 minutes, more preferably less than 10 minutes.
- Another object of the present invention is the abovementioned process for purification, characterized in that the bottom effluent comprising the purified polyaspartic acid ester is cooled directly after leaving the distillation apparatus to temperatures below 100 ° C, wherein the average residence time of the bottom effluent between exit from the distillation apparatus and entering a cooler below 5 minutes.
- the bottoms effluent is therefore cooled directly after leaving the distillation apparatus to temperatures below 100 ° C, preferably below 80 ° C.
- "directly after leaving the distillation apparatus” is understood to mean that the mean residence time of the bottoms effluent between exit from the distillation apparatus and entry into a cooler is less than 5 minutes, preferably less than 2 minutes and particularly preferably less than 1 minute.
- At least the last stage of the distillation is characterized by the conditions given above.
- Suitable apparatuses for the distillation according to the invention are, for example, falling-film evaporators, thin-film evaporators and / or short-path evaporators. Preference is given to the use of thin film evaporators and / or short path evaporators, since these allow a particularly gentle distillation.
- Another object of the present invention is the above-mentioned method for purification, characterized in that the distillation is carried out using falling film evaporator, thin film evaporator and / or short path evaporator.
- Another object of the present invention is the above-mentioned method for purification, characterized in that the distillation in two stages using a Combination of thin-film evaporator and subsequent short-path evaporator is performed.
- the distillation is carried out in two stages, that is, in two connected in series evaporators wherein the purified polyaspartic ester is obtained in each case at the bottom of the evaporator.
- a further subject of the present invention are polyaspartic ester compositions containing compounds of the general formula (I)
- X is an m-valent, optionally one or more
- Heteroatom-containing organic radical as obtained by removal of primary amino groups from a corresponding, aromatic, (cyclo) aliphatic or araliphatically bonded primary amino groups containing polyamine in the molecular weight range 60 to 6000 g / mol, and the other, reactive toward isocyanate groups and / or may contain inert functional groups at temperatures up to 100 ° C,
- R 1 and R 2 represent the same or different organic radicals each having 1 to 18
- Another object of the present invention are polyaspartic acid ester compositions containing compounds of general formula (I), in which
- X is an m-valent organic radical optionally containing one or more heteroatoms, as obtained by removal of primary
- Amino groups of polyether polyamines having aliphatically bonded primary amino groups 1,2 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, l, 5-diamino-2-methylpentane, 2.5 diamino-2.5 dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminounodecane, 1,12-diaminododecane, 1-amino-
- R 1 and R 2 represent identical or different alkyl radicals each having 1 to 8 carbon atoms
- a further subject of the present invention are polyaspartic ester compositions containing compounds of the general formula (I) in which X is an m-valent organic radical, as obtained by removal of primary amino groups from 3,3'-dimethyl-4,4 ' diamino-dicyclohexylmethane, 2,4- and / or 4,4'-diaminodicyclohexylmethane, 1,5-diamino-2-methylpentane can be obtained,
- R 1 and R 2 represent identical or different alkyl radicals selected from the group
- m is 2, characterized in that a proportion of 0.01-0.2% by weight of fumaric acid dialkyl ester is contained and a platinum Cobalt color number ⁇ 30 is present.
- Another object of the present invention are polyaspartic acid ester compositions containing compounds of general formula (I), in which X is an m-valent organic radical, as can be obtained by removal of primary amino groups from 2,4- and / or 4,4'-diaminodicyclohexylmethane,
- R 1 and R 2 are ethyl radicals
- m 2 characterized in that a proportion of 0.01 to 0.1 wt.% Fumarcicredialkylester is present and a platinum-cobalt color number ⁇ 30 is present.
- the starting substance was tetraethyl-N, N '- (methylenedicyclohexane-4, l-diyl) bis-DL-aspartate (CAS No. 136210-30-5) which had a platinum-cobalt color number of 15 and a content of
- the quantitative determination of the content of diethyl fumarate in the samples was carried out by means of a GC method with an internal standard.
- a GC Agilent with a fused silica capillary and a FID detector was used.
- the temperature of the injector (split outlet) was 180 ° C, helium was used as the carrier gas.
- the limit of quantification of this method was 300 ppm.
- Polyaspartic acid ester A was first purified by distillation, so that the content of
- Fumaric acid dialkyl ester (FADE) in the purified polyaspartic acid ester was 0.07% by weight. Samples of this purified polyaspartic acid ester were then annealed at 70 ° C, at 100 ° C and at 130 ° C. At the beginning and after 2 h and after 5 h, the annealed samples were examined for their content of FADE. The results of the heat treatment are summarized in the following Table 1. The percentages are each weight percent of FADE in the sample.
- Example 2 200 kg of the polyaspartic acid ester A are distilled as in Example 2. Now, however, the bottom effluent is passed directly after leaving the evaporator in a heat exchanger and cooled there to 70 ° C, before the product is stored for storage in a steel container. After 2 hours, a sample is examined for its content of FADE. This is 0.07 wt.
- Percent and the platinum-cobalt color number of the sample is 30.
- Example 3 200 kg of the polyaspartic acid ester A are distilled as in Example 3, with the difference that this time a pressure of 1 mbar is set. A sample of the stored product is examined after 2 hours for its content of FADE. This is 0.7 percent by weight and the platinum-cobalt color number of the sample is 28.
- Example 2 Cooling of the sump drain. In contrast to Example 2, this time a pressure of 0.5 mbar is set and the heating power is increased, so that the temperature of the bottom outlet is 175 ° C.
- the sample after 2 h has a FADE content of 0.37% by weight.
- a discoloration of the product shows.
- the platinum-cobalt color number is 240.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
Description
Claims
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EP17191793.3A EP3456706A1 (de) | 2017-09-19 | 2017-09-19 | Polyasparaginsäureester-zusammensetzungen und verfahren zur reinigung |
PCT/EP2018/074885 WO2019057627A1 (de) | 2017-09-19 | 2018-09-14 | Polyasparaginsäureester-zusammensetzungen und verfahren zur reinigung |
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EP18765668.1A Pending EP3849962A1 (de) | 2017-09-19 | 2018-09-14 | Polyasparaginsäureester-zusammensetzungen und verfahren zur reinigung |
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US (1) | US10968165B2 (de) |
EP (2) | EP3456706A1 (de) |
CN (1) | CN111065620A (de) |
WO (1) | WO2019057627A1 (de) |
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JP2022524587A (ja) * | 2019-03-19 | 2022-05-09 | コベストロ・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・アンド・コー・カーゲー | 環状エーテルをベースとする、第二級アミン基を含有するバインダー |
EP4137524A1 (de) | 2021-08-17 | 2023-02-22 | Covestro Deutschland AG | Neue zweikomponenten-beschichtungssysteme enthaltend polyasparaginsäureester |
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GB573154A (en) | 1942-06-26 | 1945-11-08 | American Cyanamid Co | Improvements in or relating to n-substituted aspartic acid esters and methods of preparing same |
ATE113622T1 (de) | 1989-06-23 | 1994-11-15 | Bayer Ag | Verfahren zur herstellung von überzügen. |
US5214086A (en) | 1991-09-04 | 1993-05-25 | Basf Corporation | Coating compositions which may be ambient cured |
US5243012A (en) | 1992-06-10 | 1993-09-07 | Miles Inc. | Polyurea coating compositions having improved pot lives |
DE4237468A1 (de) | 1992-11-06 | 1994-05-11 | Bayer Ag | Alkoxysilan- und Aminogruppen aufweisende Verbindungen |
DE4327853A1 (de) | 1993-08-19 | 1995-02-23 | Bayer Ag | Verfahren zur Herstellung von Überzügen |
EP0667362A1 (de) | 1994-02-09 | 1995-08-16 | Bayer Corporation | Polyharnstoff-Beschichtungszusammensetzungen mit verlängerter Verarbeitungszeit |
DE4415778A1 (de) | 1994-05-05 | 1995-11-09 | Bayer Ag | Verfahren zur Herstellung von Überzügen |
US5489704A (en) * | 1994-08-29 | 1996-02-06 | Bayer Corporation | Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings |
ES2148877T3 (es) * | 1996-07-02 | 2000-10-16 | Bayer Ag | Procedimiento para la fabricacion de mono- y poliesteres del acido aspartico. |
DE19701835A1 (de) | 1997-01-21 | 1998-07-23 | Huels Chemische Werke Ag | Kalthärtende, lösemittelarme oder lösemittelfreie Zweikomponenten-Polyurethan-Polyharnstoff-Massen |
US6399736B1 (en) | 1997-03-11 | 2002-06-04 | Huntsman Petrochemical Corporation | Method of preparing spray elastomer systems |
DE19731540A1 (de) | 1997-07-23 | 1999-01-28 | Herberts Gmbh | Überzugsmittel und deren Verwendung bei Verfahren zur Mehrschichtlackierung |
EP1208135B1 (de) * | 1999-07-23 | 2003-10-01 | Bayer Corporation | In-situ herstellung von polyasparaginestermischungen |
KR100636757B1 (ko) * | 1999-07-23 | 2006-10-20 | 바이엘 코포레이션 | 폴리아스파르트산 에스테르 혼합물의 동일반응계내 제조방법 |
US6737500B1 (en) * | 1999-07-23 | 2004-05-18 | Bayer Polymers Llc | In-situ preparation of polyaspartic ester mixture |
US6458293B1 (en) | 1999-07-29 | 2002-10-01 | Bayer Corporation | Polyurea coatings from dimethyl-substituted polyaspartic ester mixtures |
US6774207B2 (en) * | 2002-09-26 | 2004-08-10 | Bayer Polymers Llc | Polyaspartate resins with good hardness and flexibility |
DE10246708A1 (de) | 2002-10-07 | 2004-04-15 | Bayer Ag | Zweikomponenten-Systeme für die Herstellung elastischer Beschichtungen |
US6790925B2 (en) | 2002-12-05 | 2004-09-14 | Bayer Polymers Llc | In-situ preparation of polyaspartic ester mixtures |
US6984715B2 (en) * | 2003-10-03 | 2006-01-10 | Bayer Materialscience Llc | Process for preparing aspartates |
US20070066786A1 (en) | 2005-09-22 | 2007-03-22 | The Hanson Group, Llc | Methods of preparing and using polyurea elastomers |
DE102006002153A1 (de) | 2006-01-17 | 2007-07-19 | Bayer Materialscience Ag | Polyasparaginsäureester-haltige Bindemittel |
CN101024618B (zh) * | 2007-02-12 | 2010-08-18 | 江苏省化工研究所有限公司 | 一种天门冬氨酸酯的制备方法 |
EP2083025A1 (de) | 2008-01-24 | 2009-07-29 | Bayer MaterialScience AG | Medizinische Klebstoffe für die Chirurgie |
CN107805207B (zh) * | 2017-10-18 | 2020-01-31 | 万华化学集团股份有限公司 | 一种聚天门冬氨酸酯的制备方法 |
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2017
- 2017-09-19 EP EP17191793.3A patent/EP3456706A1/de not_active Ceased
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2018
- 2018-09-14 WO PCT/EP2018/074885 patent/WO2019057627A1/de unknown
- 2018-09-14 EP EP18765668.1A patent/EP3849962A1/de active Pending
- 2018-09-14 CN CN201880060623.4A patent/CN111065620A/zh active Pending
- 2018-09-14 US US16/648,366 patent/US10968165B2/en active Active
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EP3456706A1 (de) | 2019-03-20 |
CN111065620A (zh) | 2020-04-24 |
WO2019057627A1 (de) | 2019-03-28 |
US10968165B2 (en) | 2021-04-06 |
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