CA2577944A1 - Modified aminotriazine resin and method for the production thereof - Google Patents
Modified aminotriazine resin and method for the production thereof Download PDFInfo
- Publication number
- CA2577944A1 CA2577944A1 CA002577944A CA2577944A CA2577944A1 CA 2577944 A1 CA2577944 A1 CA 2577944A1 CA 002577944 A CA002577944 A CA 002577944A CA 2577944 A CA2577944 A CA 2577944A CA 2577944 A1 CA2577944 A1 CA 2577944A1
- Authority
- CA
- Canada
- Prior art keywords
- aminotriazine
- resin
- modified
- aminotriazine resin
- melt
- 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.)
- Abandoned
Links
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 229920005989 resin Polymers 0.000 title claims abstract description 159
- 239000011347 resin Substances 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 41
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000005690 transetherification reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 9
- -1 melamine Chemical compound 0.000 abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- YSKUZVBSHIWEFK-UHFFFAOYSA-N ammelide Chemical compound NC1=NC(O)=NC(O)=N1 YSKUZVBSHIWEFK-UHFFFAOYSA-N 0.000 description 3
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FSQQTNAZHBEJLS-OWOJBTEDSA-N (e)-4-amino-4-oxobut-2-enoic acid Chemical class NC(=O)\C=C\C(O)=O FSQQTNAZHBEJLS-OWOJBTEDSA-N 0.000 description 1
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a modified aminotriazine resin, particularly melamine formaldehyde resin, which has a high reactivity and can be obtained by reacting a modified aminotriazine resin melt with at least one aminotriazine, particularly melamine, which is in the form of a solid and/or a suspension, at a temperature ranging from 130 to 250 ~C and with a dwell time of 30 to 600 s.
This makes it possible to produce aminotriazine resins that have an increased reactivity during molar mass build-up inside the extruder and during the final curing, and even in the event of high aminotriazine contents, are stabile and capable of being stored.
This makes it possible to produce aminotriazine resins that have an increased reactivity during molar mass build-up inside the extruder and during the final curing, and even in the event of high aminotriazine contents, are stabile and capable of being stored.
Description
Modified aminotriazine resin and method for the production thereof The invention relates to a modified aminotriazine resin as claimed in claim 1, a process for the production thereof as claimed in claim 10 and the use thereof as claimed in claim 14.
Aminotriazine resins are condensates of an aminotriazine with a carbonyl compound. The industrially most important aminotriazine resins are melamine-formaldehyde resins.
Aminotriazine resins in which the primary aminotriazine condensates are modified, for example, with alcohols or polyols contain ether groups in their structure; they are referred to as modified aminotriazine resins. WO
03/046053 Al or WO 03/106558 Al discloses, for example, modified aminotriazine resins which have a sufficiently high melt viscosity so that they can be processed by thermoplastic methods, such as, for example, extrusion or injection molding.
Such resins are usually obtained by a method in which a modified aminotriazine resin is prepared in liquid form, said resin is then concentrated to give a resin melt and the resin melt is then converted by reaction at elevated temperature in extruders, kneaders or the like.
The thermoplastically processable modified aminotriazine resins thus obtained have several disadvantages.
They exhibit relatively low reactivity in the conversion in the extruder, in which as large an increase as possible in the molar mass of the resins should take place. In order to achieve an increase in - la -the molar mass at a sufficient rate, high extrusion temperatures are necessary in the case of the known resins. High extrusion temperatures are disadvantageous since the extrusion process is difficult to control and there is the danger of spontaneous curing of the resins in the extruder.
A further disadvantage of the known aminotriazine resins is their slow curing during the final shaping.
High curing temperatures, long residence times and relatively large amounts of curing catalysts are required in order to bring about final curing.
Furthermore, modified aminotriazine resin solutions having a molar formaldehyde:aminotriazine ratio of not less than 2:1 could be prepared to date in a stable manner at room temperature. Higher proportions of aminotriazine cannot be realized or can be realized only by a very complicated reaction procedure. In general, the product or the aminotriazine is precipitated from the resin solutions on cooling to room temperature, with the result that the further processing is very complicated. The higher the formaldehyde content, the more undesired emissions of methanol and formaldehyde occur both during the processing of the resins and from the end product. A
further disadvantage is the easy combustability of the resins, which is likewise higher the higher the formaldehyde content and the degree of modification of the resins.
Accordingly, an object of the present invention was to find an aminotriazine resin which does not have said disadvantages.
This object is achieved by an aminotriazine resin as claimed in claim 1.
The present invention relates to a modified aminotriazine resin, in particular melamine- formaldehyde - 2a -resin, which is obtainable by reacting a modified aminotriazine resin melt with at least one aminotriazine present in the form of a solid and/or a suspension, in particular melamine, at a temperature of from 130 to 250 C and in a residence time of from 30 to 600 s.
The advantage of the aminotriazine resin according to the invention is that it exhibits increased reactivity during the increase of molar mass in the extruder and during the final curing. In this way, a major part of the undesired cleavage products which are otherwise released only during processing and in the end product are removed in the extruder itself. Furthermore, the aminotriazine resins according to the invention can also be prepared in a stable and simple manner with high aminotriazine contents.
Suitable aminotriazines for the preparation of the modified aminotriazine resin melt are, for example, melamine, guanamines, oxoaminotriazines, such as, for example, ammeline or ammelide, or substituted melamines. Melamine is preferably used. For the preparation of the modified aminotriazine resin melt, certain proportions of urea and/or dicyandiamide can be used in addition to the aminotriazine.
Suitable carbonyl compounds for the preparation of the modified aminotriazine resin melt are, for example, formaldehyde, acetaldehyde, isobutyraldehyde, acetone, methyl ethyl ketone, glyoxylic acid, glyoxylic acid methyl ester hemiacetal, glyoxal, glutardialdehyde or diethyl ketone. A preferably used carbonyl compound is formaldehyde.
In the modified aminotriazine resin, the primary condensates of carbonyl compound and aminotriazine are partly or completely etherified with C1-Cq-alcohols. The partly or completely etherified condensates can be partly or completely transetherified in a further reaction step, the transetherification preferably being - 3a -effected with aliphatic C9-C18-alcohols or aromatic alcohols, diols or polyols or mixtures thereof.
A modified aminotriazine resin in the context of the present invention is also one which, in addition to or instead of the etherification and/or transetherification with alcohols, diols and polyols, is obtained, for example, by incorporating by condensation or subsequently adding other customary modifiers, such as, for example, caprolactam, sulfites, sulfonamides, carbamates, salts of maleic or fumaric acid monoamides, epoxides, bisepoxides or isocyanates.
Furthermore, fillers and/or reinforcing fibers, further polymers and stabilizers, UV absorbers and/or auxiliaries may be present in the modified aminotriazine resin.
Particularly preferably, the modified aminotriazine resin melt is formed from a condensate of the components melamine and formaldehyde.
It usually has a molar carbonyl compound:aminotriazine ratio of from 2:1 to 3.5:1, higher carbonyl contents up to 6:1 also being possible.
Advantageously, the reaction of the modified aminotriazine resin melt with at least one aminotriazine takes place at a temperature of from 190 to 250 C. This ensures that the aminotriazine metered in reacts particularly rapidly with the aminotriazine resin melt.
The required amount of aminotriazine is dependent on a plurality of parameters:
1) which carbonyl:aminotriazine ratio is to be present in the end product and 2) the carbonyl:aminotriazine ratio possessed by the starting aminotriazine resin melt.
Aminotriazine resins are condensates of an aminotriazine with a carbonyl compound. The industrially most important aminotriazine resins are melamine-formaldehyde resins.
Aminotriazine resins in which the primary aminotriazine condensates are modified, for example, with alcohols or polyols contain ether groups in their structure; they are referred to as modified aminotriazine resins. WO
03/046053 Al or WO 03/106558 Al discloses, for example, modified aminotriazine resins which have a sufficiently high melt viscosity so that they can be processed by thermoplastic methods, such as, for example, extrusion or injection molding.
Such resins are usually obtained by a method in which a modified aminotriazine resin is prepared in liquid form, said resin is then concentrated to give a resin melt and the resin melt is then converted by reaction at elevated temperature in extruders, kneaders or the like.
The thermoplastically processable modified aminotriazine resins thus obtained have several disadvantages.
They exhibit relatively low reactivity in the conversion in the extruder, in which as large an increase as possible in the molar mass of the resins should take place. In order to achieve an increase in - la -the molar mass at a sufficient rate, high extrusion temperatures are necessary in the case of the known resins. High extrusion temperatures are disadvantageous since the extrusion process is difficult to control and there is the danger of spontaneous curing of the resins in the extruder.
A further disadvantage of the known aminotriazine resins is their slow curing during the final shaping.
High curing temperatures, long residence times and relatively large amounts of curing catalysts are required in order to bring about final curing.
Furthermore, modified aminotriazine resin solutions having a molar formaldehyde:aminotriazine ratio of not less than 2:1 could be prepared to date in a stable manner at room temperature. Higher proportions of aminotriazine cannot be realized or can be realized only by a very complicated reaction procedure. In general, the product or the aminotriazine is precipitated from the resin solutions on cooling to room temperature, with the result that the further processing is very complicated. The higher the formaldehyde content, the more undesired emissions of methanol and formaldehyde occur both during the processing of the resins and from the end product. A
further disadvantage is the easy combustability of the resins, which is likewise higher the higher the formaldehyde content and the degree of modification of the resins.
Accordingly, an object of the present invention was to find an aminotriazine resin which does not have said disadvantages.
This object is achieved by an aminotriazine resin as claimed in claim 1.
The present invention relates to a modified aminotriazine resin, in particular melamine- formaldehyde - 2a -resin, which is obtainable by reacting a modified aminotriazine resin melt with at least one aminotriazine present in the form of a solid and/or a suspension, in particular melamine, at a temperature of from 130 to 250 C and in a residence time of from 30 to 600 s.
The advantage of the aminotriazine resin according to the invention is that it exhibits increased reactivity during the increase of molar mass in the extruder and during the final curing. In this way, a major part of the undesired cleavage products which are otherwise released only during processing and in the end product are removed in the extruder itself. Furthermore, the aminotriazine resins according to the invention can also be prepared in a stable and simple manner with high aminotriazine contents.
Suitable aminotriazines for the preparation of the modified aminotriazine resin melt are, for example, melamine, guanamines, oxoaminotriazines, such as, for example, ammeline or ammelide, or substituted melamines. Melamine is preferably used. For the preparation of the modified aminotriazine resin melt, certain proportions of urea and/or dicyandiamide can be used in addition to the aminotriazine.
Suitable carbonyl compounds for the preparation of the modified aminotriazine resin melt are, for example, formaldehyde, acetaldehyde, isobutyraldehyde, acetone, methyl ethyl ketone, glyoxylic acid, glyoxylic acid methyl ester hemiacetal, glyoxal, glutardialdehyde or diethyl ketone. A preferably used carbonyl compound is formaldehyde.
In the modified aminotriazine resin, the primary condensates of carbonyl compound and aminotriazine are partly or completely etherified with C1-Cq-alcohols. The partly or completely etherified condensates can be partly or completely transetherified in a further reaction step, the transetherification preferably being - 3a -effected with aliphatic C9-C18-alcohols or aromatic alcohols, diols or polyols or mixtures thereof.
A modified aminotriazine resin in the context of the present invention is also one which, in addition to or instead of the etherification and/or transetherification with alcohols, diols and polyols, is obtained, for example, by incorporating by condensation or subsequently adding other customary modifiers, such as, for example, caprolactam, sulfites, sulfonamides, carbamates, salts of maleic or fumaric acid monoamides, epoxides, bisepoxides or isocyanates.
Furthermore, fillers and/or reinforcing fibers, further polymers and stabilizers, UV absorbers and/or auxiliaries may be present in the modified aminotriazine resin.
Particularly preferably, the modified aminotriazine resin melt is formed from a condensate of the components melamine and formaldehyde.
It usually has a molar carbonyl compound:aminotriazine ratio of from 2:1 to 3.5:1, higher carbonyl contents up to 6:1 also being possible.
Advantageously, the reaction of the modified aminotriazine resin melt with at least one aminotriazine takes place at a temperature of from 190 to 250 C. This ensures that the aminotriazine metered in reacts particularly rapidly with the aminotriazine resin melt.
The required amount of aminotriazine is dependent on a plurality of parameters:
1) which carbonyl:aminotriazine ratio is to be present in the end product and 2) the carbonyl:aminotriazine ratio possessed by the starting aminotriazine resin melt.
This gives (at a predetermined throughput) the amount of aminotriazine which has to be metered in. (The addition of the aminotriazine shifts the carbonyl:aminotriazine ratio, i.e. reduces it.) The amount of aminotriazine metered in is preferably chosen so that, in the resulting aminotriazine resin, the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines is from 0.1 to 1.5 units smaller than the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines in the modified aminotriazine resin melt.
In the resulting aminotriazine resin, the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines is particularly preferably from 0.3 to 1.0 unit smaller than the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines in the modified aminotriazine resin melt. Aminotriazine resins which have this molar ratio are readily processable and the reaction is technically readily controllable. This formulation defines the amount of aminotriazine metered in.
In the modified aminotriazine resin, the molar carbonyl:aminotriazine ratio is preferably less than 2:1, particularly preferably less than 1.6:1.
It has not been possible to date to prepare modified aminotriazine resins having such high aminotriazine contents in stable form in a conventional manner. They exhibit particularly low emissions, advantageous flame-retardant properties and a very fast curing rate.
The invention furthermore relates to a process for the preparation of a modified aminotriazine resin, characterized in that - a modified aminotriazine resin melt is prepared, - the modified aminotriazine resin melt is then converted by reaction in at least one extruder or kneader, at least one aminotriazine, in particular melamine, being metered in as a solid and/or as a suspension before and/or during the reactive conversion into the modified aminotriazine resin melt, whereupon the modified aminotriazine resin is discharged.
The modified aminoplast resin melt is prepared, for example, as described in WO 03/046053 or in WO
03/106558 or by concentration of modified aminoplast resin solutions in thin-film evaporators according to WO 04/056900 Al.
The aminotriazine metered into the aminotriazine resin melt surprisingly reacts with the aminotriazine resin melt, and a clear resin strand which can be further processed in a conventional manner is obtained.
The aminotriazine metered in acts as a crosslinking center, as a flame-retardant component and also as a scavenger for the carbonyl compounds used. Furthermore, readily volatile cleavage products are liberated in the reactive incorporation of the aminotriazine, so that the modified aminotriazine resins according to the invention have lower emissions than the modified aminotriazine resins which can be prepared using conventional methods.
Advantageously, the solid aminotriazine is in the form of small lumps or in the form of powder.
At least one aminotriazine is preferably metered into at least one extruder or kneader.
In the resulting aminotriazine resin, the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines is particularly preferably from 0.3 to 1.0 unit smaller than the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines in the modified aminotriazine resin melt. Aminotriazine resins which have this molar ratio are readily processable and the reaction is technically readily controllable. This formulation defines the amount of aminotriazine metered in.
In the modified aminotriazine resin, the molar carbonyl:aminotriazine ratio is preferably less than 2:1, particularly preferably less than 1.6:1.
It has not been possible to date to prepare modified aminotriazine resins having such high aminotriazine contents in stable form in a conventional manner. They exhibit particularly low emissions, advantageous flame-retardant properties and a very fast curing rate.
The invention furthermore relates to a process for the preparation of a modified aminotriazine resin, characterized in that - a modified aminotriazine resin melt is prepared, - the modified aminotriazine resin melt is then converted by reaction in at least one extruder or kneader, at least one aminotriazine, in particular melamine, being metered in as a solid and/or as a suspension before and/or during the reactive conversion into the modified aminotriazine resin melt, whereupon the modified aminotriazine resin is discharged.
The modified aminoplast resin melt is prepared, for example, as described in WO 03/046053 or in WO
03/106558 or by concentration of modified aminoplast resin solutions in thin-film evaporators according to WO 04/056900 Al.
The aminotriazine metered into the aminotriazine resin melt surprisingly reacts with the aminotriazine resin melt, and a clear resin strand which can be further processed in a conventional manner is obtained.
The aminotriazine metered in acts as a crosslinking center, as a flame-retardant component and also as a scavenger for the carbonyl compounds used. Furthermore, readily volatile cleavage products are liberated in the reactive incorporation of the aminotriazine, so that the modified aminotriazine resins according to the invention have lower emissions than the modified aminotriazine resins which can be prepared using conventional methods.
Advantageously, the solid aminotriazine is in the form of small lumps or in the form of powder.
At least one aminotriazine is preferably metered into at least one extruder or kneader.
The aminotriazine metered in is thus well distributed and incorporated into the aminotriazine resin melt.
The extruder used is, for example, a twin-screw extruder. It is also possible to operate two extruders or kneaders in series.
The aminotriazine metered in can be metered in gravimetrically in the form of a solid. The aminotriazine is preferably added as a suspension.
Suspension media which may be used are, for example, water, alcohols, such as, for example, butanol or methanol, diols or polyols, such as, for example, simulsols, caprolactone derivatives, polyester polyols, oligoester polyols, trimethylolpropane or mixtures of these components. Concentrated resin solutions having a higher viscosity are possible as further suspension media. In order to obtain a pumpable and meterable suspension, the suspension can be stirred and heated.
The solids content of the suspension is from about 30 to about 90% by weight, preferably from about 40 to 80%
by weight.
It is particularly advantageous to use the modified aminotriazine resin melt and/or at least a part of the transetherification agents and/or modifiers used for the modification as suspension media.
An advantage of the addition of the aminotriazine as a suspension is the better meterability in comparison with the addition in the form of a solid.
Suitable aminotriazines for metering into the modified aminotriazine resin melt are, for example, melamine, oxoaminotriazines, such as, for example ammeline or ammelide, guanamines or substituted melamines. At least one aminotriazine metered in is preferably melamine.
The extruder used is, for example, a twin-screw extruder. It is also possible to operate two extruders or kneaders in series.
The aminotriazine metered in can be metered in gravimetrically in the form of a solid. The aminotriazine is preferably added as a suspension.
Suspension media which may be used are, for example, water, alcohols, such as, for example, butanol or methanol, diols or polyols, such as, for example, simulsols, caprolactone derivatives, polyester polyols, oligoester polyols, trimethylolpropane or mixtures of these components. Concentrated resin solutions having a higher viscosity are possible as further suspension media. In order to obtain a pumpable and meterable suspension, the suspension can be stirred and heated.
The solids content of the suspension is from about 30 to about 90% by weight, preferably from about 40 to 80%
by weight.
It is particularly advantageous to use the modified aminotriazine resin melt and/or at least a part of the transetherification agents and/or modifiers used for the modification as suspension media.
An advantage of the addition of the aminotriazine as a suspension is the better meterability in comparison with the addition in the form of a solid.
Suitable aminotriazines for metering into the modified aminotriazine resin melt are, for example, melamine, oxoaminotriazines, such as, for example ammeline or ammelide, guanamines or substituted melamines. At least one aminotriazine metered in is preferably melamine.
In a preferred embodiment, a mixture of different aminotriazines is metered in. It is thus possible to prepare different resin types having advantageous properties. The higher the chosen proportion of oxoaminotriazines, the greater is the curing rate of the resulting resin.
It is furthermore preferred if, in addition to or instead of a mixture of different aminotriazines, a mixture of at least one aminotriazine and a compound present in encapsulated form is metered in. The compound present in encapsulated form contains phosphorus and/or nitrogen and/or boron in chemically bonded form. The compound is, for example, an inorganic or organic phosphorus, nitrogen and/or boron compound and preferably has both flame-retardant and proton-liberating activity. For example, ammonium polyphosphate, melamine polyphosphate, phosphoric acid esters and phosphonic acid esters based on the reaction of phosphorus pentoxide or phosphorus trioxide with pentaerythritol or dipentaerythritol, and the ammonium and melamine salts thereof serve as the encapsulated compound, it being possible to use a modified aminoplast resin as capsule wall material. Modified aminotriazine resins having even better flameproof properties and even higher reactivity and curing rate are obtainable thereby since, in addition to its flame-retardant activity, the encapsulated compound also acts as a curing catalyst.
After the reactive conversion of the modified aminotriazine resin melt to which at least one aminotriazine has been added in the extruder or kneader, the modified aminotriazine resin obtained is compounded, for example granulated and discharged.
Granulators usually used are pelletizers, granulating mills, hot die face cutting granulators or tableting apparatuses.
It is furthermore preferred if, in addition to or instead of a mixture of different aminotriazines, a mixture of at least one aminotriazine and a compound present in encapsulated form is metered in. The compound present in encapsulated form contains phosphorus and/or nitrogen and/or boron in chemically bonded form. The compound is, for example, an inorganic or organic phosphorus, nitrogen and/or boron compound and preferably has both flame-retardant and proton-liberating activity. For example, ammonium polyphosphate, melamine polyphosphate, phosphoric acid esters and phosphonic acid esters based on the reaction of phosphorus pentoxide or phosphorus trioxide with pentaerythritol or dipentaerythritol, and the ammonium and melamine salts thereof serve as the encapsulated compound, it being possible to use a modified aminoplast resin as capsule wall material. Modified aminotriazine resins having even better flameproof properties and even higher reactivity and curing rate are obtainable thereby since, in addition to its flame-retardant activity, the encapsulated compound also acts as a curing catalyst.
After the reactive conversion of the modified aminotriazine resin melt to which at least one aminotriazine has been added in the extruder or kneader, the modified aminotriazine resin obtained is compounded, for example granulated and discharged.
Granulators usually used are pelletizers, granulating mills, hot die face cutting granulators or tableting apparatuses.
The modified aminotriazine resins obtainable by the process according to the invention have a variety of uses.
They can be used, for example, as injection molding resins. It is also possible to process the aminotriazine resins according to the invention with a substrate material to give a composite material. For example, fibers, tiles, woven fabrics, wood and/or polymers can be used as substrate materials.
Furthermore, the aminotriazine resins according to the invention can be used for the production of shaped articles, such as pipes, sheets, profiles or fibers.
The modified aminotriazine resins according to the invention have increased reactivity with respect to an increase in molar mass compared with the conventional modified aminotriazine resins having the same molar carbonyl:aminotriazine ratio. The aminotriazine metered in acts as a crosslinking center and accelerates the crosslinking both in the extruder and during t.he final curing. Accordingly, the addition of a separate curing catalyst can be dispensed with in certain applications.
Below, the invention is explained with reference to examples.
1 Preparation of the modified aminotriazine resin having high reactivity Modified aminotriazine resin melts as described in WO
04/056900 Al were prepared. The starting composition of the modified aminotriazine resin melts, the amount of aminotriazine added in the extruder, the amount of added capsules and of polyol as modifier or suspension medium and the composition of the modified aminotriazine resins according to the invention as end product in granular form after the reactive conversion are stated in table 1. Melamine or oxoaminotriazines were used as aminotriazine added in the extruder.
Table 1 states the amount in % by weight of melamine powder having the customary particle size distribution which was added and the amount in % by weight of melamine which was added in the amount of polyol in which it was suspended.
The experimental parameters for the reactive conversion of the aminotriazine resin melts and the properties of the resulting modified aminotriazine resins having high reactivity are shown in table 2.
In examples Cl, 2 and 3, modified aminotriazine resins having a formaldehyde:aminotriazine ratio of 2:1 were prepared. In comparative example Cl, no aminotriazine was added during the extrusion. In examples 2 and 3, the formaldehyde:aminotriazine ratio of 2:1 in the end product was achieved by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 2.5:1 with melamine or oxoaminotriazines.
In examples C4 and 5, modified aminotriazine resins having a formaldehyde:melamine ratio of 2.5:1 were prepared. In comparative example C4, no aminotriazine was added during the extrusion. In example 5, the formaldehyde:melamine ratio of 2.5:1 in the end product was achieved by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 3:1 with melamine.
They can be used, for example, as injection molding resins. It is also possible to process the aminotriazine resins according to the invention with a substrate material to give a composite material. For example, fibers, tiles, woven fabrics, wood and/or polymers can be used as substrate materials.
Furthermore, the aminotriazine resins according to the invention can be used for the production of shaped articles, such as pipes, sheets, profiles or fibers.
The modified aminotriazine resins according to the invention have increased reactivity with respect to an increase in molar mass compared with the conventional modified aminotriazine resins having the same molar carbonyl:aminotriazine ratio. The aminotriazine metered in acts as a crosslinking center and accelerates the crosslinking both in the extruder and during t.he final curing. Accordingly, the addition of a separate curing catalyst can be dispensed with in certain applications.
Below, the invention is explained with reference to examples.
1 Preparation of the modified aminotriazine resin having high reactivity Modified aminotriazine resin melts as described in WO
04/056900 Al were prepared. The starting composition of the modified aminotriazine resin melts, the amount of aminotriazine added in the extruder, the amount of added capsules and of polyol as modifier or suspension medium and the composition of the modified aminotriazine resins according to the invention as end product in granular form after the reactive conversion are stated in table 1. Melamine or oxoaminotriazines were used as aminotriazine added in the extruder.
Table 1 states the amount in % by weight of melamine powder having the customary particle size distribution which was added and the amount in % by weight of melamine which was added in the amount of polyol in which it was suspended.
The experimental parameters for the reactive conversion of the aminotriazine resin melts and the properties of the resulting modified aminotriazine resins having high reactivity are shown in table 2.
In examples Cl, 2 and 3, modified aminotriazine resins having a formaldehyde:aminotriazine ratio of 2:1 were prepared. In comparative example Cl, no aminotriazine was added during the extrusion. In examples 2 and 3, the formaldehyde:aminotriazine ratio of 2:1 in the end product was achieved by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 2.5:1 with melamine or oxoaminotriazines.
In examples C4 and 5, modified aminotriazine resins having a formaldehyde:melamine ratio of 2.5:1 were prepared. In comparative example C4, no aminotriazine was added during the extrusion. In example 5, the formaldehyde:melamine ratio of 2.5:1 in the end product was achieved by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 3:1 with melamine.
In the examples C8 and 9, modified aminotriazine resins having a formaldehyde:melamine ratio of 3:1, which contain the transetherification agent Simulsol BPPE, were prepared. In comparative example C8 no aminotriazine was added during the extrusion. In example 9, the formaldehyde:melamine ratio of 3:1 in the end product was achieved by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 3.5:1 with melamine, suspended in Simulsol BPPE.
In example 6, a modified aminotriazine resin having a very low formaldehyde:melamine ratio of 1.5:1 was prepared. It was obtained by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 2:1 with melamine.
In example 7, a modified aminotriazine resin having a formaldehyde:melamine ratio of 1.71:1, which contains the encapsulated compound Exolit AP462, was prepared.
It was obtained by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 2:1 with melamine and Exolit AP462.
The extrusion was effected under a devolatilizing vacuum PEXtr and at an average temperature of barrels 2-8 of the extruder of T02_$, a melt temperature of TMelt and a screw speed nEXtr. The feed into the extruder is stated as m' Extr_in and the output from the extruder is stated as m' EXtr_oõt.
The extruded stand of the modified aminotriazine resin according to the invention was cooled after extrusion and granulated. Tg designates the glass transition temperature of the granules and rl the melt viscosity measured isothermally at 130 C.
In example 6, a modified aminotriazine resin having a very low formaldehyde:melamine ratio of 1.5:1 was prepared. It was obtained by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 2:1 with melamine.
In example 7, a modified aminotriazine resin having a formaldehyde:melamine ratio of 1.71:1, which contains the encapsulated compound Exolit AP462, was prepared.
It was obtained by reactive conversion of a modified aminotriazine resin melt having a formaldehyde:melamine ratio of 2:1 with melamine and Exolit AP462.
The extrusion was effected under a devolatilizing vacuum PEXtr and at an average temperature of barrels 2-8 of the extruder of T02_$, a melt temperature of TMelt and a screw speed nEXtr. The feed into the extruder is stated as m' Extr_in and the output from the extruder is stated as m' EXtr_oõt.
The extruded stand of the modified aminotriazine resin according to the invention was cooled after extrusion and granulated. Tg designates the glass transition temperature of the granules and rl the melt viscosity measured isothermally at 130 C.
Table 2 also mentions the content of methanol in % by weight, based on the total weight of the extrudates.
This is determined by means of gas chromatography after acidic total hydrolysis of the methoxy groups of the resin. The methanol content corresponds to the methanol which can potentially be released, and it is for this reason that as low a methanol content as possible is desired in the resin.
The curing time in s, stated in table 2, designates the duration which is required to reach 10 Pa=s at 180 C
(dynamic mechanical analysis DMA).
From tables 1 and 2, it is evident that those modified aminotriazine resins which were prepared by reactive conversion with addition of aminotriazines are more reactive, potentially have lower emissions and have a higher viscosity in comparison with the resins having the same formaldehyde:aminotriazine ratio which were prepared in a conventional manner under similar and in some cases more stringent extrusion conditions but without addition of aminotriazines. It can also be seen that an additional improvement in said properties can be achieved on addition of oxoaminotriazines and encapsulated compounds, such as Exolit AP462.
This is determined by means of gas chromatography after acidic total hydrolysis of the methoxy groups of the resin. The methanol content corresponds to the methanol which can potentially be released, and it is for this reason that as low a methanol content as possible is desired in the resin.
The curing time in s, stated in table 2, designates the duration which is required to reach 10 Pa=s at 180 C
(dynamic mechanical analysis DMA).
From tables 1 and 2, it is evident that those modified aminotriazine resins which were prepared by reactive conversion with addition of aminotriazines are more reactive, potentially have lower emissions and have a higher viscosity in comparison with the resins having the same formaldehyde:aminotriazine ratio which were prepared in a conventional manner under similar and in some cases more stringent extrusion conditions but without addition of aminotriazines. It can also be seen that an additional improvement in said properties can be achieved on addition of oxoaminotriazines and encapsulated compounds, such as Exolit AP462.
Starting composition of the Addition in the extruder (o by Composition of modified aminotriazine resin after modified aminotriazine resin weight, based on amount of the reactive conversion in the extruder melts aminotriazine resin melt) Addition [% by weight] Content of [% by weight]
Ex. Molar Modifier Content Aminotriazine Capsules3 Suspension Aminotriazine Modifier Capsules3 Molar ratiol No. ratio1 polyol2 of medium polyol2 F:aminotriazine F:M [o by melamine polyolz wt.] by wt. ] cNn C1 2.0:1 - 58.9 - - - 64.2 - - 2.0:1 2 2.5:1 - 53.4 13.3 (M) - - 66.0 - -2.0:1 o 3 2.5:1 53.4 13 (OAT) - - 66.0 - - 2.0:1 C4 2.5:1 - 53.4 - - - 58.2 - - 2.5:1 3.0:1 - 48.9 8.9 (M) - - 59.4 - - 2.5:1 6 2.0:1 - 58.9 19.6 (M) - - 73.5 - - 1.5:1 7 2.0:1 - 58.9 10.0 (M) 12.2 - 61.5 - 10 1.71:1 C8 3.0:1 13.12 42.5 - - - 46.3 14.3 - 3.0:1 WO 2006/024544 13a - PCT/EP2005/009513 -9 3.5:1 - 45.0 7.5 (M)9 - 16.239 47.5 14.3 - 3.0:1 Table 1 1 M...melamine F...formaldeh de OAT...oxoaminotriazines y (mixture of 73% of ammeline, 25% of ammelide, 2% of cyanuric acid) 2 Simulsol BPPE
3 Exolit AP462 9 Melamine added in suspension in polyol Ln tD
iP
iP
N
O
N
I
Ex. Molar Modifier Content Aminotriazine Capsules3 Suspension Aminotriazine Modifier Capsules3 Molar ratiol No. ratio1 polyol2 of medium polyol2 F:aminotriazine F:M [o by melamine polyolz wt.] by wt. ] cNn C1 2.0:1 - 58.9 - - - 64.2 - - 2.0:1 2 2.5:1 - 53.4 13.3 (M) - - 66.0 - -2.0:1 o 3 2.5:1 53.4 13 (OAT) - - 66.0 - - 2.0:1 C4 2.5:1 - 53.4 - - - 58.2 - - 2.5:1 3.0:1 - 48.9 8.9 (M) - - 59.4 - - 2.5:1 6 2.0:1 - 58.9 19.6 (M) - - 73.5 - - 1.5:1 7 2.0:1 - 58.9 10.0 (M) 12.2 - 61.5 - 10 1.71:1 C8 3.0:1 13.12 42.5 - - - 46.3 14.3 - 3.0:1 WO 2006/024544 13a - PCT/EP2005/009513 -9 3.5:1 - 45.0 7.5 (M)9 - 16.239 47.5 14.3 - 3.0:1 Table 1 1 M...melamine F...formaldeh de OAT...oxoaminotriazines y (mixture of 73% of ammeline, 25% of ammelide, 2% of cyanuric acid) 2 Simulsol BPPE
3 Exolit AP462 9 Melamine added in suspension in polyol Ln tD
iP
iP
N
O
N
I
Conditions in the reactive conversion of the modified Properties of the modified aminotriazine resins aminotriazine resin melts in the extruder after the reactive conversion in the extruder Ex. T02-1 TMelt TMax PExtr nExtr m' extr-iõ m' Extr-out Tg rl [ Pa = s] Curing Content Appearance No. [ C] [ C] [ C] [mbar] [rpm] [kg/h] [kg/h] [ C] isothermally time of at 130 C DMA5 at methanol 180 C by M1 ~
[s] wt.]
C1 225 220 245 400 330 10.7 9.6 81 1500 300 19.2 Clear 2 223 221 240 950 330 8.4 9.1 82 1800 250 18.4 Clear tD
3 220 215 230 950 330 8.4 9.1 82 2300 220 18.1 Opaque C4 230 222 250 400 330 11.4 10.4 72 450 420 22.7 Clear N
225 220 245 950 330 8.5 9.2 74 600 350 21.8 Opaque N
6 216 205 230 950 330 8.6 10.6 85 4900 210 16.2 Opaque 7 144 142 150 950 330 5.7 7.0 85 12 000 180 15.5 White C8 235 222 250 400 330 9.3 8.3 50 50 580 20.2 Clear 9 230 220 245 950 330 8.5 9.3 55 150 450 19.1 Opaque WO 2006/024544 - 14a - PCT/EP2005/009513 Table 2 Determination of the curing time, time to reach 10 Pa=s at 180 C
~
N
Ln tD
iP
iP
N
N
j N I
N
[s] wt.]
C1 225 220 245 400 330 10.7 9.6 81 1500 300 19.2 Clear 2 223 221 240 950 330 8.4 9.1 82 1800 250 18.4 Clear tD
3 220 215 230 950 330 8.4 9.1 82 2300 220 18.1 Opaque C4 230 222 250 400 330 11.4 10.4 72 450 420 22.7 Clear N
225 220 245 950 330 8.5 9.2 74 600 350 21.8 Opaque N
6 216 205 230 950 330 8.6 10.6 85 4900 210 16.2 Opaque 7 144 142 150 950 330 5.7 7.0 85 12 000 180 15.5 White C8 235 222 250 400 330 9.3 8.3 50 50 580 20.2 Clear 9 230 220 245 950 330 8.5 9.3 55 150 450 19.1 Opaque WO 2006/024544 - 14a - PCT/EP2005/009513 Table 2 Determination of the curing time, time to reach 10 Pa=s at 180 C
~
N
Ln tD
iP
iP
N
N
j N I
N
2 Production of a pure resin sheet from the modified aminotriazine resin A pressed sheet having the dimensions 100 x 100 x 3 mm was produced from the modified aminotriazine resins, prepared in 1, of experiments Cl, 2, 6, 7, C8, 9. A
laminate press served as a mold therefor. The granules were milled and the powder was then introduced into the stainless steel mold heated to 100 C and was melted for about 8 min at this temperature.
Thereafter, the compression mold was heated to 180 C, placed for 30 min in the press at 180 C and pressed at 80 bar. Thereafter, the test specimen was cooled in the press to 70 C for a duration of about 15 min.
The pure resin sheet was removed from the mold at 70 C.
Test bars were produced from this pure resin sheet and were used for carrying out mechanical tests and fire tests in experiments A to F.
The fire test UL-94 is a test for determining the flammability of materials. Classification is effected according to fire classes V-0, V-1, V-2, n.p. V-0 is the highest and therefore best fire class, i.e. the fire behavior fulfills all test criteria. n.p. means not passed, i.e. the fire behavior is poor. The UL-94 test is carried out according to ASTM 2863, vertically.
Furthermore, the time required for curing, the emissions during processing and the volume contraction as a measure of the shrinkage of the resin on curing were determined.
The properties of the pure resin sheet are shown in table 3.
laminate press served as a mold therefor. The granules were milled and the powder was then introduced into the stainless steel mold heated to 100 C and was melted for about 8 min at this temperature.
Thereafter, the compression mold was heated to 180 C, placed for 30 min in the press at 180 C and pressed at 80 bar. Thereafter, the test specimen was cooled in the press to 70 C for a duration of about 15 min.
The pure resin sheet was removed from the mold at 70 C.
Test bars were produced from this pure resin sheet and were used for carrying out mechanical tests and fire tests in experiments A to F.
The fire test UL-94 is a test for determining the flammability of materials. Classification is effected according to fire classes V-0, V-1, V-2, n.p. V-0 is the highest and therefore best fire class, i.e. the fire behavior fulfills all test criteria. n.p. means not passed, i.e. the fire behavior is poor. The UL-94 test is carried out according to ASTM 2863, vertically.
Furthermore, the time required for curing, the emissions during processing and the volume contraction as a measure of the shrinkage of the resin on curing were determined.
The properties of the pure resin sheet are shown in table 3.
With respect to the fire tests, table 3 shows that the modified aminotriazine resins according to the invention have improved fire behavior in comparison with the conventional resins. In experiments A and E, which were carried out with conventional comparative resins to which no aminotriazine was added, the fire test was not passed. In experiments B, C and F, which were carried out using the aminotriazine resins according to the invention, fire classes V-1 and V-2 were reached. In experiment D, carried out using a resin according to the invention additionally containing the encapsulated compound AP462, it was possible to achieve the best fire class V-0.
It is furthermore evident from table 3 that no deterioration in the mechanical properties, such as tensile strength and elongation at break, occurs in comparison with the conventional modified aminotriazine resins as a result of the reactive conversion of the resin melts with aminotriazines.
The reactivity of the modified aminotriazine resins according to the invention is substantially increased in comparison with the conventional resins having the same formaldehyde:melamine ratio. This is evident from a substantially shorter curing time of the resins according to the invention.
The modified aminotriazine resins according to the invention exhibit lower emissions than the comparable conventional resins.
Even in the case of the volume contraction as a measure of the shrinkage of the resin during curing, there are substantially lower values for the aminotriazine resins according to the invention than in the case of the conventional aminotriazine resins. Particularly low values are to be observed in experiment D, carried out using an aminotriazine resin containing the - 16a -encapsulated compound Exolit AP462.
It is furthermore evident from table 3 that no deterioration in the mechanical properties, such as tensile strength and elongation at break, occurs in comparison with the conventional modified aminotriazine resins as a result of the reactive conversion of the resin melts with aminotriazines.
The reactivity of the modified aminotriazine resins according to the invention is substantially increased in comparison with the conventional resins having the same formaldehyde:melamine ratio. This is evident from a substantially shorter curing time of the resins according to the invention.
The modified aminotriazine resins according to the invention exhibit lower emissions than the comparable conventional resins.
Even in the case of the volume contraction as a measure of the shrinkage of the resin during curing, there are substantially lower values for the aminotriazine resins according to the invention than in the case of the conventional aminotriazine resins. Particularly low values are to be observed in experiment D, carried out using an aminotriazine resin containing the - 16a -encapsulated compound Exolit AP462.
3 Production of natural fiber composites The modified aminotriazine resin according to the invention, of experiments Cl, 2, 6, 7, C8, 9 from 1, was sprinkled onto a flax fiber web having a weight per unit area of 300-350 g/mz using a powder scattering unit, a resin coat of about 30% of the total weight being achieved. The powder-coated nonwoven was then subjected to precondensation in an IR field at 190 C
for 2 min after which shapes measuring 300 x 200 mm were punched out. 6 layers of powder-coated nonwovens were then placed one on top of the other with the powder-coated side facing upward, and this precondensed fiber composite was placed in an evacuable down-stroke press heated to 180 C. After a preheating time of 30 sec, pressing was effected to 400 kN for 20 sec in the first pressing stage, the vacuum simultaneously being set at 200 mbar absolute pressure. Thereafter venting was effected for 20 sec in vacuo. In the second pressing stage, the fiber composite was pressed until a degree of curing of 95%, measured by means of ultrasound, was reached. The cured composite material was removed while hot at 180 C.
With the composite materials thus obtained, the same tests as with the pure resin sheet from 2 were carried out in experiments Al to Fl. The properties of the composite materials produced are shown in table 4.
All advantages of the modified aminotriazine resins according to the invention in comparison with the conventional resins having the same formaldehyde:aminotriazine ratio are also to be observed in the case of the fiber composites produced from the resins.
for 2 min after which shapes measuring 300 x 200 mm were punched out. 6 layers of powder-coated nonwovens were then placed one on top of the other with the powder-coated side facing upward, and this precondensed fiber composite was placed in an evacuable down-stroke press heated to 180 C. After a preheating time of 30 sec, pressing was effected to 400 kN for 20 sec in the first pressing stage, the vacuum simultaneously being set at 200 mbar absolute pressure. Thereafter venting was effected for 20 sec in vacuo. In the second pressing stage, the fiber composite was pressed until a degree of curing of 95%, measured by means of ultrasound, was reached. The cured composite material was removed while hot at 180 C.
With the composite materials thus obtained, the same tests as with the pure resin sheet from 2 were carried out in experiments Al to Fl. The properties of the composite materials produced are shown in table 4.
All advantages of the modified aminotriazine resins according to the invention in comparison with the conventional resins having the same formaldehyde:aminotriazine ratio are also to be observed in the case of the fiber composites produced from the resins.
Properties of the pure resin sheets - resin test specimens without reinforcing fibers Experiment Ex. No. Molar ratio6 UL-94 Tensile Elongation Curing time Mass loss Volume F:M 3mm sheet strength at break at 180 C during contraction processing (emissions) [--] [MPa] [,--] [s] [o by wt.] ]
~
A Cl 2.0:1 n.p 35 1.5 300 4.0 10.1 B 2 2.0:1 V-2 35 1.7 250 3.1 9.5 cn (from 2.5:1 tD
.P~
+ M) C 6 1.5:1 (from V-1 30 1.5 210 2.2 8.2 2.0:1 + M) D 7 1.71:1 V-0 35 1.4 180 1.8 6.5 (from 2.0:1 + M + C) E V8 3.0:1 + P n.p 25 2.5 580 11.0 12.2 F 9 3.0:1 + P V-2 30 2.0 450 9.0 11.0 - 18a -(from 3.5:1 + P + M) Table 3 6 M...Melamine F...Formaldehyde C...Capsules (Exolit AP462) P...Polyol (Simulsol BPPE) ~
N
Ln J
tD
iP
iP
N
I
O
N
I
N
N
tp -Properties of the fiber composites - resin test specimens with natural fiber reinforcement Experiment Ex. No. Molar Fiber UL-94 Tensile Elongation Curing Mass loss Volume ratio' content 3mm sheet strength at break time at during contraction F:M 180 C processing (emissions) [o] [--] [MPa] [o] [sec] [o by wt.] [o]
~
Al Cl 2.0:1 70 n.p 7900 3.1 350 2.1 2.5 N
Ln Bl 2 2.0:1(from 70 V-2 8100 3.3 280 1.7 2.2 1O
.P~
2.5:1 + M) C1 6 1.5:1 70 V-2 8000 3.5 230 1.4 1.6 ( f r om 2.0:1 + M) Dl 7 1.71:1 70 V-0 8200 3.7 200 0.9 0.8 (from 2.0:1 + M
+ C) - 19a -El C8 3.0:1 + P 70 n.p. 6000 4.5 650 3.0 3.5 F1 9 3.0:1 + P 70 V-2 6500 4.8 480 2.8 2.9 (from 3.5:1 + P
+ M) Table 4 ~
M...Melamine F...Formaldehyde C...Capsules (Exolit AP462) P...Polyol (Simulsol BPPE) ~
.P~
O
O
O
~
A Cl 2.0:1 n.p 35 1.5 300 4.0 10.1 B 2 2.0:1 V-2 35 1.7 250 3.1 9.5 cn (from 2.5:1 tD
.P~
+ M) C 6 1.5:1 (from V-1 30 1.5 210 2.2 8.2 2.0:1 + M) D 7 1.71:1 V-0 35 1.4 180 1.8 6.5 (from 2.0:1 + M + C) E V8 3.0:1 + P n.p 25 2.5 580 11.0 12.2 F 9 3.0:1 + P V-2 30 2.0 450 9.0 11.0 - 18a -(from 3.5:1 + P + M) Table 3 6 M...Melamine F...Formaldehyde C...Capsules (Exolit AP462) P...Polyol (Simulsol BPPE) ~
N
Ln J
tD
iP
iP
N
I
O
N
I
N
N
tp -Properties of the fiber composites - resin test specimens with natural fiber reinforcement Experiment Ex. No. Molar Fiber UL-94 Tensile Elongation Curing Mass loss Volume ratio' content 3mm sheet strength at break time at during contraction F:M 180 C processing (emissions) [o] [--] [MPa] [o] [sec] [o by wt.] [o]
~
Al Cl 2.0:1 70 n.p 7900 3.1 350 2.1 2.5 N
Ln Bl 2 2.0:1(from 70 V-2 8100 3.3 280 1.7 2.2 1O
.P~
2.5:1 + M) C1 6 1.5:1 70 V-2 8000 3.5 230 1.4 1.6 ( f r om 2.0:1 + M) Dl 7 1.71:1 70 V-0 8200 3.7 200 0.9 0.8 (from 2.0:1 + M
+ C) - 19a -El C8 3.0:1 + P 70 n.p. 6000 4.5 650 3.0 3.5 F1 9 3.0:1 + P 70 V-2 6500 4.8 480 2.8 2.9 (from 3.5:1 + P
+ M) Table 4 ~
M...Melamine F...Formaldehyde C...Capsules (Exolit AP462) P...Polyol (Simulsol BPPE) ~
.P~
O
O
O
Claims (13)
1. A modified aminotriazine resin, in particular melamine-formaldehyde resin, obtainable by reacting a modified aminotriazine resin melt with at least one aminotriazine present in the form of a solid and/or a suspension, with the exception of aminotriazines from the group consisting of the salts of melamine or guanamines with C1-C18-aliphatic carboxylic acids, where, in the aminotriazine resin, the molar ratio of the sum of the carbonyl compounds to the sum of the amino-triazines is from 0.1 to 1.5 units less than the molar ratio of the sum of the carbonyl compounds to the sum of the aminotriazines in the modified aminotriazine resin melt.
2. The modified aminotriazine resin as claimed in claim 1, characterized in that the solid is used in the form of small lumps or in pulverulent form.
3. The modified aminotriazine as claimed in claim 1 or 2, characterized in that the reaction is effected at a temperature of from 130 to 250°C.
4. The modified aminotriazine resin as claimed in at least one of the preceding claims, characterized in that the reaction is effected at from 190 to 250°C.
5. The modified aminotriazine resin as claimed in at least one of the preceding claims, characterized in that the reaction has a residence time of from 30 to 600 s.
6. The modified aminotriazine resin as claimed in claim 6, characterized in that, in the aminotriazine resin, the molar ratio is from 0.3 to 1.0 unit smaller than the molar ratio in the modified aminotriazine resin melt.
7. The modified aminotriazine resin as claimed in at least one of the preceding claims, characterized in that the molar carbonyl:aminotriazine ratio in the aminotriazine resin is less than 2:1.
8. The modified aminotriazine resin as claimed in at least one of the abovementioned claims, characterized in that the molar carbonyl:aminotriazine ratio in the aminotriazine resin is less than 1.6:1.
9. A process for the preparation of a modified aminotriazine resin, characterized in that a) a modified aminotriazine resin melt is prepared, b) the modified aminotriazine resin melt is then converted by reaction in at least one extruder or kneader, c) at least one aminotriazine, in particular melamine, being metered in as a solid and/or as a suspension before and/or during the reactive conversion to the modified aminotriazine resin melt, d) whereupon the modified aminotriazine resin with is discharged.
10. The process as claimed in claim 9, characterized in that at least one aminotriazine is metered into at least one extruder or kneader.
11. The process as claimed in either of claims 9 and 10, characterized in that at least one aminotriazine is added as a suspension, the modified aminotriazine resin melt and/or at least a part of the transetherification agent and/or modifier used for modifying the aminotriazine resin melt serving as a suspension medium.
12. The process as claimed in at least one of claims 19 to 11, characterized in that a mixture of different aminotriazines and/or a mixture of at least one aminotriazine and a compound present in encapsulated form are metered in.
13. The use of a modified aminotriazine resin as claimed in at least one of claims 1 to 8 as an injection molding resin, for the production of composite materials or of shaped articles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200410043213 DE102004043213A1 (en) | 2004-09-03 | 2004-09-03 | Modified aminotriazine resin and a process for its preparation |
| DE102004043213.9 | 2004-09-03 | ||
| PCT/EP2005/009513 WO2006024544A1 (en) | 2004-09-03 | 2005-09-01 | Modified aminotriazine resin and method for the production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2577944A1 true CA2577944A1 (en) | 2006-03-09 |
Family
ID=35423307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002577944A Abandoned CA2577944A1 (en) | 2004-09-03 | 2005-09-01 | Modified aminotriazine resin and method for the production thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1791878A1 (en) |
| CA (1) | CA2577944A1 (en) |
| DE (1) | DE102004043213A1 (en) |
| WO (1) | WO2006024544A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722779B2 (en) | 2007-10-12 | 2014-05-13 | Borealis Agrolinz Melamine Gmbh | Thermoplastically processible aminoplastic resin, thermoset microfibre non-wovens, and process and plant for their production |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355797B2 (en) * | 1998-01-30 | 2002-03-12 | Agrolinz Melamin Gmbh | Process for cooling melamine |
| BR0012789A (en) * | 1999-07-27 | 2002-04-30 | Agrolinz Melamin Gmbh | Process for preparing melamine |
| AT411685B (en) * | 2002-06-14 | 2004-04-26 | Agrolinz Melamin Gmbh | COMPOSITIONS FOR THE MANUFACTURE OF AMINO CLASSIC PRODUCTS |
| DE10361878A1 (en) * | 2003-12-19 | 2005-07-14 | Ami-Agrolinz Melamine International Gmbh | Flame retardant mixture for lignocellulosic composites |
-
2004
- 2004-09-03 DE DE200410043213 patent/DE102004043213A1/en not_active Withdrawn
-
2005
- 2005-09-01 CA CA002577944A patent/CA2577944A1/en not_active Abandoned
- 2005-09-01 EP EP05791755A patent/EP1791878A1/en not_active Withdrawn
- 2005-09-01 WO PCT/EP2005/009513 patent/WO2006024544A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722779B2 (en) | 2007-10-12 | 2014-05-13 | Borealis Agrolinz Melamine Gmbh | Thermoplastically processible aminoplastic resin, thermoset microfibre non-wovens, and process and plant for their production |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006024544A1 (en) | 2006-03-09 |
| EP1791878A1 (en) | 2007-06-06 |
| DE102004043213A1 (en) | 2006-03-09 |
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| FZDE | Discontinued |