WO1991009897A2 - Process for preparing crosslinked polymers - Google Patents
Process for preparing crosslinked polymers Download PDFInfo
- Publication number
- WO1991009897A2 WO1991009897A2 PCT/EP1990/002209 EP9002209W WO9109897A2 WO 1991009897 A2 WO1991009897 A2 WO 1991009897A2 EP 9002209 W EP9002209 W EP 9002209W WO 9109897 A2 WO9109897 A2 WO 9109897A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- poly
- acylalkyleneimine
- groups
- carbon atoms
- Prior art date
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Classifications
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives thereof
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
Definitions
- the invention relates to a new process for the preparation of crosslinked polymers from linear polymers containing hydroxyl groups and to polymers containing new hydroxyl groups as starting materials for this process.
- Crosslinked polymers are used today in many fields of technology, for example as materials (thermosets, rubber), as coating agents and as carrier materials (gelling agents).
- Crosslinked polymers of this type can belong to a wide variety of substance classes, it being possible to distinguish essentially two construction principles: firstly, there is the possibility of building up the polymeric networks in one step from low-molecular-weight compounds, and secondly one of those which have already been prepared linear polymers and crosslink them with suitable honorary reagents or in some other way.
- crosslinked polymers can be obtained by crosslinking certain hydroxyl-containing soluble polyalkyleneimines in a suitable manner.
- the invention relates to a process for the preparation of crosslinked polymers, in which one reagent has several for reaction having groups capable of hydroxyl groups is reacted with a soluble poly-N-acylalkyleneimine in which at least some of the N-acyl groups have hydroxyl groups as substituents.
- Poly-N-acylalkyleneimines are understood to mean polymers of the general formula A
- alkylene group generally represents an optionally substituted chain of 2 or 3 carbon atoms.
- cyclic imino ethers are also referred to as delta-2-0xazolines or 5,6-dihydro-4H-0xazines, and consequently the term polyiminoethers (polyoxazolines or polyoxazines) is also introduced for the polymers.
- Soluble poly-N-acylalkyleneins which carry hydroxyl groups in the radical R 1 or in some of these radicals are now used for the process according to the invention. They can be obtained, for example, by saponification of poly-N-acylalkyleneimines which contain acetoxy groups as substituents in the acyl radical (A. Levy and M. Litt, J. polym. Sei. AI, 6, 1883-1894 (1968) and US Pat. No. 3,483 145).
- the labeling of these polymers as soluble is to be understood qualitatively and is not restricted to a specific solvent. It is only intended to distinguish these polymers from crosslinked polymers, which are generally not soluble in solvents, but rather can swell at best.
- Soluble poly-N-acylalkyleneimines are preferably used, which can be prepared by copolymerizing 1 to 100 mol% of at least one cyclic imino ether of the formula I with 99 to 0 mol% of at least one cyclic imino ether of the formula II, the Formulas I and II have the following appearance:
- R alkyl or alkenyl with 1 to 12 carbon atoms, or aryl;
- M direct bond or double-bonded group with 1 to 12 C atoms, selected from alkylene, alkenylene, arylene and alkarylene groups, which may optionally contain ether oxygens in its chain, where R and M are represented by further hydroxyl groups and / or can be substituted by alkoxy groups having 1 to 3 carbon atoms;
- R * to - each independently of one another are H, alkyl or aryl having 1 to 8 C atoms;
- poly-N-acylalkyleneimines which, by copolymerization of 15.1 to 100 mol%, in particular 20 to 98 mol%, of at least one cyclic imino ether of the formula I with 84.9 to 0 mol%, in particular 80 to 2 Mol% of at least one cyclic imino ether of the formula II can be prepared.
- cyclic imino ethers of the formula I are:
- the iminoethers can also be polymerized by methods known per se, for example according to DE 12 06 585, US 3,458,456 or the earlier application DE-P 39 00859.2.
- the poly-N-acylalkyleneimines formed during the polymerization are not insoluble, even in the case of higher molar proportions.
- poly-N-acylalkyleneimines which are prepared from cyclic imino ethers in whose formula I and / or II at least 4 of the radicals R * to R6 are hydrogen atoms and the others consist of C 1 -C 3 -alkyl .
- formula I and / or formula II Z preferably the meaning of a direct bond, ie the monomers are delta-2-0xazo.ine.
- those with the following substitution patterns are particularly preferred:
- Poly-N-acylalkyleneimines in which all of the radicals R 1 to R ⁇ are hydrogen are very particularly preferred.
- poly-N-acylalkyleneimines are copolymers, they can be prepared in a customary manner by choosing the polymerization conditions with a more or less random distribution of the monomers in the chain or else as block polymers. All forms are suitable for the process according to the invention, but the statistical polymers are preferred in most cases.
- the molecular weight of the poly-N-acylalkyleneimines can be chosen within wide limits, for example between 1,000 and 1,000,000, preferably between 3,000 and 50,000.
- poly-N-acylalkyleneimines which, by copolymerization, from 15.1 to 100 mol%, preferably 20 to 98 mol%, of a cyc- Tables of Iminothers of formula I with 84.9 to 0 mol%, preferably 80 to 2 mol% of a cyclic imino ether of formula II are prepared, with the exception of polyacylalkylimines according to the earlier application DE-P 39 00 859.2, which contains 20% by weight. -% and more contain monomer units that carry acyl residues of an unsaturated al phatic carboxylic acid with 16 to 22 carbon atoms.
- the explanations given above for the poly-N-acylalkylenimines apply.
- Particularly preferred compounds are those which carry acyl groups of 2-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxyoctanoic acid, 12-hydroxystearic acid or 9,10- (hydroxy, methoxy) stearic acid, and those where R? represents an alkyl radical having 1 to 21 carbon atoms, preferably 2 to 17 carbon atoms, or a phenyl radical.
- the reagents required for crosslinking are preferably relatively low molecular weight compounds which carry at least two functional groups which can react with hydroxyl groups. Examples of such groups are anhydride groups and acid chloride groups. The reactivity of these groups essentially determines the reaction conditions of the process. The amount of crosslinking reagent in relation to the hydroxyl groups present determines the degree of crosslinking, the upper limit of which is otherwise determined by the density of the hydroxyl groups in the poly-N-acylalkyleneimine.
- Preferred crosslinking reagents for the process according to the invention are polyisocyanates and aminoplast precondensates, but phenol-formaldehyde precondensates are also suitable, for example.
- the polyisocyanates can be compounds of the formula III A (-NC0) n (III)
- A represents an aliphatic, aromatic or araliphatic group with 4 to 40 C atoms and n free valences on different C atoms and n has one of the values 2, 3 or 4.
- These polyisocyanates are compounds which are well known in chemical engineering and are usually prepared from the corresponding amines using COCI2. They preferably contain 6 to 26 carbon atoms in the molecular part A. With regard to the details, reference is made to the information in manuals such as Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, volume 23, p. 586 (1984).
- polyisocyanates examples include N, N'N '' -Tris- (omega-isocyanatohexyl) biuret; 2,2,4-trimethylhexamethylene-1,6-di-isocyanate; 1,6-hexamethylene diisocyanate; 2,4-tolylene diisocyanate; 4,4'- and / or 2,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate.
- Diisocyanates are particularly preferred in the context of the invention. Instead of the polyisocyanates of the formula III, so-called masked polyisocyanates can be used with equal success.
- the reaction between the isocyanates III and the poly-N-acylalkyleneimines proceeds smoothly under the conditions customary for the reaction of alcohols with isocyanates, that is to say at temperatures between about room temperature and about 160 ° C. and reaction times of about 1 to 10 hours. Depending on the reactivity of the isocyanates and the alcohol component, these conditions can also be significantly exceeded or fallen short of.
- the reaction can be carried out in the presence of suitable aprotic solvents, for example aromatic hydrocarbons, chlorinated hydrocarbons, esters or ketones, it being generally carried out with the exclusion of moisture.
- the crosslinking is preferably carried out without solvent.
- the catalysts customary for the reaction of alcohols with isocyanates especially tin compounds such as dibutyltin dilaurate or tertiary amines such as 1,4-diazabicyclo [2,2,2] octane, can be added.
- the progress of the reaction can be followed by determining the unreacted isocyanate, for example by reaction with excess dibutyla in in toluene and back titration with HC1.
- amino plast precondensates which are also preferred as crosslinking reagents, are condensation products of formaldehyde with various amides, preferably urea and / or melamine, which may be etherified with lower alcohols.
- the reaction between the aminoplast precondensates and the poly-N-acylalkyleneimines does not follow a fixed stoichiometry.
- the ratio of the reactants can therefore be freely selected within wide limits depending on the desired properties of the end product.
- Weight ratios of 1 to 0.2 are customary for hydroxyl group contents above 15 mol% in poly-N-acylalkyleneimine; 0.7 to 0.25 are preferred (in each case precondensate to poly-N-acylalkyleneimine), but these values can also be exceeded or fallen below if necessary.
- the end products of the process are highly elastic to hard materials which can swell in solvents with a low degree of crosslinking. They are particularly suitable as materials and, if necessary, can also be made smooth in molds. Their suitability as coating agents for solid surfaces, where they produce resistant and firmly adhering coatings, is also outstanding.
- Poly-N-acylalkyleneimines suitable according to the invention were prepared by cationic polymerization of cyclic imino ethers of the formula I and cyclic imino ethers of the formula II in bulk with the addition of methyl p-toluenesulfonic acid as the catalyst.
- the iminoethers were mixed in the intended ratio at room temperature or just above their melting point, and a small amount of methyl p-toluenesulfonic acid as catalyst was then added with stirring and the mixture was heated at 160 ° C. for 30 minutes.
- imino ethers with a lower boiling point were used, the polymerization was carried out correspondingly longer below the boiling point, but in any case until the reaction was complete.
- Tables 1 and 2 give the details of the iminoethers used for the polymerization based on mostly technical carboxylic acids. They were produced analogously to the information in the older patent applications EP 88 118090.5, DE-P 39 14 133 and DE-P 39 14155.
- the polymerizations were generally carried out in batch sizes of approximately 100 g. They supplied solid products at room temperature which could be used for the process according to the invention without further purification.
- the polymers were characterized by the molecular weight (determined as the weight average with the aid of gel permeation chromatography against the polystyrene standard).
- Table 3 shows the details of the polymerizations and the molecular weights of the resulting products.
- Table 1 Cyclic iminoethers of the formula I.
- the crosslinking process was carried out on deep-drawn iron sheets, in order in this way to produce a hot-hardened coating on the sheets.
- the aqueous dispersions were produced in such a way that initially 33% solutions of the polymers in isopropanol were prepared, which were then mixed with 2.5 times the amount of water (based on polymer) with stirring. Isopropanol and water were then removed from the mixture under vacuum until a 55% dispersion remained in water.
- the coated sheets were heated in a forced-air oven at 160 ° C. for 25 minutes in order to crosslink the films.
- the pendulum hardness of the paint films was determined in accordance with the German standard DIN 53 157. The results, shown in Table 1 below, showed that films of good hardness were formed.
- This crosslinking reaction was also carried out here on reaction mixtures which had been applied as films to iron sheets with the aid of a doctor blade, in order in this way to produce adherent coatings.
- the mixture consisted of equivalent amounts of poly-N-acylalkyleneimine (based on hydroxyl groups) and 4,4'-diphenylmethane diisocyanate (MDI) or a diisocyanate blocked with caprolactam (Grillbond IL6 (Ems- Chemistry), equivalent weight 238).
- MDI 4,4'-diphenylmethane diisocyanate
- Grillbond IL6 Ems- Chemistry
- the properties of the coating film were determined in the form of the pendulum hardness in accordance with DIN 53157, the deepening (reverse) in accordance with US standard ASTM-D 2795-69 and the cross cut in accordance with the German standard DIN 53 151.
- the cross-cut was assessed visually with a rating between 0 (best adhesion) and 4 (poor adhesion).
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19893943111 DE3943111A1 (en) | 1989-12-27 | 1989-12-27 | METHOD FOR PRODUCING CROSSLINKED POLYMERS |
DEP3943111.8 | 1989-12-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1991009897A2 true WO1991009897A2 (en) | 1991-07-11 |
WO1991009897A3 WO1991009897A3 (en) | 1991-08-22 |
Family
ID=6396511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1990/002209 WO1991009897A2 (en) | 1989-12-27 | 1990-12-17 | Process for preparing crosslinked polymers |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0507790A1 (en) |
JP (1) | JPH05502685A (en) |
DE (1) | DE3943111A1 (en) |
WO (1) | WO1991009897A2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4226805A1 (en) * | 1992-08-13 | 1994-02-17 | Henkel Kgaa | Binder mixtures for stoving enamels |
DE10160097A1 (en) * | 2001-12-07 | 2003-06-26 | Sandler Ag | New modified poly-2-oxazolines, their production and their use as sorbents and liquid absorbers |
-
1989
- 1989-12-27 DE DE19893943111 patent/DE3943111A1/en not_active Withdrawn
-
1990
- 1990-12-17 WO PCT/EP1990/002209 patent/WO1991009897A2/en not_active Application Discontinuation
- 1990-12-17 EP EP19910900773 patent/EP0507790A1/en not_active Withdrawn
- 1990-12-17 JP JP50123690A patent/JPH05502685A/en active Pending
Non-Patent Citations (1)
Title |
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Keine Entgegenhaltungen * |
Also Published As
Publication number | Publication date |
---|---|
DE3943111A1 (en) | 1991-07-04 |
WO1991009897A3 (en) | 1991-08-22 |
JPH05502685A (en) | 1993-05-13 |
EP0507790A1 (en) | 1992-10-14 |
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