CN1251119A - Polymeric amines - Google Patents
Polymeric amines Download PDFInfo
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- CN1251119A CN1251119A CN 98803601 CN98803601A CN1251119A CN 1251119 A CN1251119 A CN 1251119A CN 98803601 CN98803601 CN 98803601 CN 98803601 A CN98803601 A CN 98803601A CN 1251119 A CN1251119 A CN 1251119A
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Abstract
Polymeric amines that have N-substituted 2,5-pyrrolediyl groups incorporated in the backbone wherein the N-substituted 2,5-pyrrolediyl group may be represented by general formula (I), wherein R independently represents a hydrogen atom or a hydrocarbyl group and wherein B represents the substituent containing at least one primary amino group.
Description
The present invention relates to have that the N-that is introduced in the skeleton replaces 2, the novel polymeric amine of 5-pyrroles's subunit.The invention still further relates to the preparation method of this type of novel polymeric amine, curable resin combination and laminated product, particularly laminated wood goods.
Have 2 in the skeleton, the polymeric amines of 5-pyrroles's subunit (being the pyrroles unit) is known.For example at EP-A-0, gang's pyrrole derivative of ethylene/alpha-olefin/carbon monoxide terpolymer has been described in 400,903.These polymeric amines in Knorr-Paal type reaction promptly by making linear alpha-olefin-carbon monoxide polymkeric substance and ammonia or amine (be selected from C
1～C
50The benzylamine of primary alkyl amine, benzylamine and replacement) reaction and make.At EP-A-0, can find the content of relevant other polymeric amines in 400,903.
According to EP-A-0,400,903, wherein disclosed polymeric amines is suitable for makes the characteristic plastics.Yet if polymeric amines has useful functional group in curable resin composition and other a large amount of purposes, situation can be more favourable so.
Another example of Knorr-Paal type reaction can find in WO93/19114.Under the sort of situation, alkene-carbon monoxide polymkeric substance and the reaction of amino acid or derivatives thereof, generation has the polymeric amines that carboxyl functional group maybe can be transformed into the functional group of carboxyl.Do not find that as yet these polymeric amines have special purpose.This may have less desirable suitability owing to carboxy-functionalized polymeric amines, and for example they are not suitable for the fast setting thermosetting material.Therefore need expansion to have the polymeric amines of the functional group different with carboxyl functional group.Amine reactant in the reaction of Knorr-Paal type needs not to be monoamine.For example at EP-A-0, in 372,602, alkene-carbon monoxide polymkeric substance and polyamines reaction.Yet these polymeric amines are crosslinked, thereby for example have less suitability in the curable resin composition.
Be surprisingly found out that the novel polymeric amine has bigger suitability than above-mentioned polymeric amines.Therefore, the invention provides have that the N-that is introduced in the skeleton replaces 2, the polymeric amines of 5-pyrroles's subunit, wherein pyrroles's nitrogen-atoms replaces with the group with primary amino functional group.2 of N-replacement, 5-pyrroles's subunit can be represented by general formula (I):
Wherein R represents hydrogen atom or alkyl independently, and wherein B represents to contain the substituting group of at least one primary amino.
Substituent B generally is the substituting group with 1～100 coupled atom of at least one primary amino.Suitably, these atoms are carbon atoms, but the group that replaces also can contain one or more nitrogen, sulphur or Sauerstoffatom in its skeleton.Preferably, substituent B has coupled single primary amino, and it has more more Knorr-Paal reactive behavior than ethylamine.Can test or measure this different reactive behavior by the method described in this specification sheets embodiment 5.
Substituent B can have other functional group, as long as these groups also have the Knorr-Paal reactive behavior more lower than ethylamine.More preferably, substituent B has coupled sterically hindered primary amino.
Word " solid " steric hindrance generally refers to atom or group bigger than hydrogen atom on adjacent atom.For example, 1, in the 2-propylene diamine, it is sterically hindered that the amino on 2 is formed the methyl of the 3rd carbon atom of propane skeleton, and the amino on 1 is not by sterically hindered.
These sterically hindered substituting groups can be represented by following general formula:
Wherein X is 99 at the most, the preferred alkylene or the hydridization alkylene of 20 atoms at the most, and R ' and R " each represents 20 at the most, preferred alkyl or the hydridization alkyl or the R of 10 atoms at the most independently " are hydrogen atoms.
The suitable example of substituent B comprises: the amino butyl of 1-amino-ethyl, 1-or 2-aminopropyl, 1-, 2-or 3-, 2-amino-2-methyl propyl group, 4-amino-2-oxa-amyl group, 7-amino-2,4-diaza octyl group, 4-amino-3,5-di-tert-butyl-phenyl and polyethers substituting group be NH for example
2-CH (CH
3)-(O-CHR-CH
2)
n-O-CHR-.
Each R in the general formula (I) can be hydrogen atom or alkyl independently.Suitable alkyl comprises the aryl of phenyl and replacement; Methyl and other alkyl of 12 carbon atoms at the most; And methoxyl group and other alkoxyl group of 12 carbon atoms at the most.
2 of N-replacement, the R in 5-pyrroles's subunit preferably or is hydrogen atom or is respectively hydrogen atom and methyl.
Except 2 of N-replacement, beyond 5-pyrroles's subunit, the novel polymeric amine also comprises 2 of alkylidene group replacement or unsubstituted and N-replacement, and 5-pyrroles's subunit does not have functional group or has one is not the functional group of primary amino.
Novel polymeric amine of the present invention thereby can represent by following general formula :-(A-CO-)
l-(2,5-NPy-)
m-(2,5-Py-)
n(II) wherein each A represents alkylidene group that replace or unsubstituted independently; L, m and n are the integers of representing the number of repeating unit p jointly, wherein 1≤m≤p, preferred 2≤m≤p, 0≤l+n＜p and p 〉=3; Each 2,5-NPy represent that N-replaces 2,5-pyrroles's subunit, wherein pyrroles's nitrogen-atoms replaces with the group with primary amino functional group, and each 2,5-Py represent there is not functional group or have one be not the N-of the functional group of primary amino replace 2,5-pyrroles's subunit.
Repeating unit " (A-CO-) " is corresponding to the repeating unit of the alkene that is used to prepare the novel polymeric amine-carbon monoxide polymkeric substance as can be seen.In random olefin-carbon monoxide polymkeric substance,, find that each alkylidene group can have 2～10,000 carbon atom independently in skeleton in 495,286, US-A-2,846,406 or US-A-4,024,326 for example at US-A-2.Yet as mentioned below, that each A of this repeating unit preferably replaces or unsubstituted 1,2-or 1, the 3-alkylidene group, be more preferably replacement or unsubstituted 1, the 2-alkylidene group.
At last, repeating unit (2, be aforesaid 2 5-Py), 5-pyrroles's subunit, wherein pyrroles's nitrogen-atoms has for example a hydrogen atom, (replacement that is determined on a case-by-case basis) alkyl, (replacement that is determined on a case-by-case basis) aryl, (replacement that is determined on a case-by-case basis) alkenyl, the for example second month in a season or uncle's aminoalkyl group, acidic group or preferred (N-pyrroles) alkyl.The latter is corresponding to the novel polymeric amine, and some polymer molecules can not formed as EP-A-0 by coupling thus, the insoluble polymer system in 372,602.For example, can have 3 this (N-pyrroles) alkyl at the most, but, actual number depends on the molecular weight of polymkeric substance to a great extent.
Integer m, l and n can change in wide region, are at most p as long as m+l+n amounts to.Integer p is preferably greater than 10, and for example scope is 30～70.Suitably, the scope of l is 0≤l＜0.9p, and the scope of m is 0.1p＜m≤p.More suitably, the scope of l is 0.2p≤l≤0.5p, and the scope of m is 0.5p≤m≤0.8p.Integer n equals p-(1+m), and it can be 0～0.9p, is at most 0.3p suitably.
The invention still further relates to the method for preparing novel polymeric amine of the present invention.Therefore, provide its preparation method by the primary amine reaction that makes alkene-carbon monoxide polymkeric substance and general formula (III): H
2NCH
2-B (III) wherein B has implication same as described above, and reaction conditions should make and form 2,5-pyrroles's subunit and can the functional group that be connected on the substituent B not being had a negative impact.
The example of suitable primary amine can be known by inference simply by the example of above-mentioned suitable substituents B.Therefore, when B was the 1-amino-ethyl, primary amine was a 1.More generally, suitable amine comprises α-alkyl-α, ω-diamino hydro carbons, and wherein one or more carbon atoms can be replaced by heteroatoms, and condition is that to have more last (ω) carbon atom that active amino connects be methylene radical.
Alkene-carbon monoxide the polymkeric substance that is used to prepare the novel polymeric amine can be to replace fully that (alkene: the mol ratio of carbon monoxide equals 1: 1, and alkene is 1, the 2-addition), replace fully partly that (alkene: the mol ratio of carbon monoxide equals 1: 1, but some alkene additions are not 1, the 2-addition) or random (for example as US-A-2, disclosed carbonyl content in 846,406) with about 30～50mol%.For the latter, should see that theoretical yield is subjected to as 1, the restriction that the carbonyl of 4-dicarbapentaborane body distributes in polymer chain.Preferably, alkene-carbon monoxide is to replace fully or half complete alternative.
When for example vinyl-acetic ester, ethyl propenoate and N-vinyl pyrrolidone, alpha-olefin or internal olefin prepared alkene-carbon monoxide polymkeric substance by ethene, (replacement) vinylbenzene, ethylenically unsaturated hydrocarbons, it can be a homopolymer; When different alkene is used to its preparation, can also be " multipolymer ".Polymkeric substance is by the olefin production with 2～14 carbon atoms, especially by the alpha-olefin preparation (not having magnetism with bigger olefin production polymkeric substance) with 2～8 carbon atoms.Preferably, alkene-carbon monoxide polymkeric substance is carbon monoxide and homopolymer or the multipolymer that is selected from ethene, propylene and cinnamic alkene.It particularly preferably is the fully alternately homopolymer of ethene and carbon monoxide or vinylbenzene and carbon monoxide; Fully or the partly homopolymer fully alternately of propylene and carbon monoxide; The complete alternating copolymer of ethylene/styrene and carbon monoxide; Complete or the half complete alternating copolymer of ethylene/propene and carbon monoxide or propylene/styrene and carbon monoxide.
Particularly when alkene-carbon monoxide polymkeric substance be that alpha-olefin can mainly be introduced into section rule format or section irregular form when having the alternately homopolymer of alpha-olefin of 3 or more a plurality of carbon atoms.Use the advantage of irregular homopolymer of section or multipolymer to be, in addition its viscosity be lower than all similar viscosity of (section rule) homopolymer of others.
The molecular weight ranges of alkene-carbon monoxide polymkeric substance is 200～500,000 dalton.For as curable resin or the application scenario in curable resin composition, polymkeric substance has molecular weight ranges 500～20 suitably, 000 dalton.Preferably, polymkeric substance has molecular weight ranges 1,000～5, and 000 dalton, more preferably scope is 2,000～3,500 dalton.In the context of this patent file, molecular weight refers to number-average molecular weight.
The advantage that use has low-molecular-weight relatively alkene-carbon monoxide polymkeric substance is, is that they can be liquid under the temperature of using always in its technological process in 10-80 ℃ temperature range.
The synthetic of (preferably) alkene-carbon monoxide polymkeric substance is not a part of the present invention.At the patent specification of quoting as proof with at for example EP-A-0,121,965, EP-A-0,181,014, EP-A-0,516,238 and EP-A-0,522,635 and its incidental European search report in can find relevant information in the file mentioned.
Alkene-carbon monoxide polymkeric substance also can be on it grafting polymer of vinyl monomer.Resulting graftomer can have higher water tolerance and can bring benefit in others (expense).
Can use any method that is used to form graft copolymer, with vinyl monomer-grafted to polymkeric substance.This comprises is exposed under the energy-rich radiation suitable monomers and mixture of polymers; In the presence of polymkeric substance, heat suitable monomers, or in the presence of radical initiator and polymkeric substance, make the suitable monomers reaction.Any other method that is used for the graft copolymerization polymkeric substance all is applicable to enforcement the present invention.
The free radical elicitation procedure is the most preferred method of preparation graftomer.Being used for thus, method formation grafted suitable monomers comprises for example mono-olefin class such as vinylbenzene and derivative thereof, monoene belongs to unsaturated ester class such as vinyl-acetic ester, the vinyl ester of halogenated acid such as α-vinyl chloroacetate, allyl group and methacrylic compound such as chlorallylene, the ester of alkenyl alcohol such as β-allyl ethyl alcohol, acrylic acid haloalkyl ester such as methyl, α-Qing Jibingxisuanwanjizhi, fumarate such as DEF, monoene belongs to for example vinyl cyanide of unsaturated nitrile, the acid amides of above-mentioned acid such as acrylamide, alkyl oxide such as vinyl methyl ether, vinyl sulfide such as vinyl β-ethoxyethyl group sulphur, the mixture of the unsaturated hydro carbons of diolefinic such as 1,3-butadiene and above-claimed cpd.Preferred monomer is vinylbenzene, acrylate, methacrylic ester, vinyl ester and vinyl halide.Vinylbenzene is most preferred.
Radical initiator can or water miscible or oil-soluble.Water-soluble radical initiator comprises for example Potassium Persulfate, ammonium peroxydisulfate, Sodium persulfate, hydrogen peroxide and water-soluble azo initiator.The oil soluble radical initiator for example comprise benzoyl peroxide, t-butylperoxyl benzoate and 2,2 '-azo two (isopropyl cyanide).Water soluble starter for example Potassium Persulfate or azo initiator is preferred.In every 100g total monomer, the concentration of free radical initiator is about 0.01～about 0.5g.
The redox initiation process that comprises oxygenant (for example Potassium Persulfate or potassium bromate) and reductive agent (for example pyrosulphite hydrogen sodium) or tertiary amine (for example triethylamine) also can be used to the initiation grafting polyreaction, especially when low temperature.
The method for preparing graftomer is included in the monomer that is used to form the polymer graft part and exists down, and polymkeric substance is contacted with initiator.Preferably, by being used to form in the oil phase that the grafted monomer is incorporated into polymeric dispersions, in dispersion, adding initiator then and finish this method.Can use more a spot of stirring for example by stirring or mixing.
The polymeric dispersions that wherein adds grafted monomer preferably forms by polymkeric substance is mixed with water and tensio-active agent.Usually, dispersion contains more water by weight than polymkeric substance, but, can add the solids content of polymkeric substance aliquots containig with the product that increases final formation in addition in emulsion process.
Can use can be in water any tensio-active agent of dispersed polymeres, condition is that this material does not influence grafting.Preferably, tensio-active agent is non-ionic, and generally include for example polyalkylene glycol and polyalkylene glycol alkyl oxide, polyalkylene glycol alkyl phenyl ether, polyalkylene glycol fatty acid ester, fatty acid esters of sorbitan, alkylpolyglycosides, lipid acid two alkanolamides etc.Usually, tensio-active agent is equivalent to the polymkeric substance that about 3～15wt% is used to form emulsion, but can use the tensio-active agent that is used for polymkeric substance and grafted monomer are all joined any amount of emulsion.
When heating, the carbonyl of the primary amine of general formula (III) and alkene-carbon monoxide polymkeric substance can react at an easy rate.Temperature of reaction can be selected from room temperature to about 120 ℃.This can use higher temperature, but should avoid too high temperature, because may have a negative impact and/or may cause being connected functional group reactions on the substituent B to alkene-carbon monoxide polymkeric substance.Preferably, be reflected in 50～90 ℃ the temperature range and carry out.
It is favourable forcing reaction to stop.For example, when about 95% the transformation efficiency that reaches based on the primary amine meter of general formula (III), reaction can be terminated.If the hyperactivity of primary amine and functional group thereof, work can avoid crosslinked so like this.Though can not determine the reaction times accurately, this area professional just can easily find by a limited number of simple experiment.Be determined on a case-by-case basis, the functional group of the primary amine of general formula (III) is protected by the reaction with the compound that primary amino is kept perfectly, and removes from functional group in Knorr-Paal reaction back.
The practice useful in the Knorr-Paal reaction process is to use solvent, even to have the polymkeric substance of preferable range molecular weight under temperature of reaction be liquid or dissolve in the liquid primary amine.The solvent that can be used comprises for example toluene.Preferably do not use solvent.
The present invention also relates to the purposes of novel polymeric amine of the present invention.These novel polymeric amines can be used as curable resin, for example ought remain with unconvertedly 1, when the 4-dicarbapentaborane is whole, or are used to wherein polymeric amines as in the curable resin composition of solidifying agent.
Particularly importantly the novel polymeric amine is used for water-based resin composition to form the tackiness agent in coating and the woodwork gummed prescription.The water soluble of polymeric amines own is for example when adding carboxyl functional group or after the amino seasonization at them.From the HSE viewpoint, water-based resin composition is better than the resin combination based on volatile organic compounds.And these solubility polymerization amines water dispersion polyketone in the water for example of helping to form stable emulsion or other polymkeric substance.
Can for example use acid carry out seasonization as lactic acid, citric acid, tartrate, acetate or toluenesulphonic acids.Yet this is not exhaustive inventory, because can use many other acid.
Therefore, the present invention also relates to based on as the curable resin composition of the novel polymeric amine of curable resin and/or solidifying agent and these curable resin compositions purposes in mixture, coating and room temperature or thermofixation woodwork gummed prescription as tackiness agent.
PCT/EP95/04324 reported resin combination the laminated wood goods for example in the preparation of glued board, shaving board, MDF, OSB and stoplog as the purposes of tackiness agent.These resin combinations comprise one or more alkene-carbon monoxide polymkeric substance (be determined on a case-by-case basis and have different molecular weight), as one or more polyamines classes of solidifying agent hexamethylene-diamine and look particular case and one or more curing catalysts of existing for example.They also can comprise thinner and annexing ingredient such as viscosity modifier, fire retardant, secretion agent, antioxidant, UV stablizer and tinting material.As shown in PCT/EP95/04324, these resin combinations with based on urea-or the curable resin of phenolic aldehyde compare and sit pretty.
Find now based on the resin combination of novel polymeric amine key property for example working life, handle the composition before being better than aspect easiness and the intensity.
Be a key property of curable resin composition, particularly water-based resin composition working life.For example in coating and woodwork gummed prescription, if tackiness agent premature setting when placing, this is undesirable.In the experiment of carrying out for the end of the year 1996, illustrated the excellent working life of resin combination of the present invention.In this experiment, monitored the performance of uncured woodwork gummed prescription.After three months, do not find to change on viscosity or other performance! Yet when using, such curing that the woodwork prescription prepares seemingly again.
Handle the viscosity that easiness especially also relates to curable resin composition.For some application need high viscosity, for example when curable resin composition is used as paste, and other is used for some, and it should be a water-dilutable, for example when it is sprayed.The advantage of this curable resin composition is, can adjust its viscosity to be fit to its purposes, and for example the water by using relatively small amount is as thinner.In fact, just can realize for example low viscosity of 1～10Pas during also greater than 50wt% in solids content, this makes the water rapid evaporation.
In habitual curable resin composition, there is the problem of excessively infiltrating.Curable resin penetrates in the woodwork, and does not increase the total intensity of cured article.Therefore, the shortage that causes cohesive force owing to starved.Generally speaking, use other and curable resin costliness to compensate this loss.Yet the viscosity of this resin combination no longer needs the additional resin composition with highly filled combining.
At last, the solidification rate of resin combination of the present invention is easy to be adjusted to adapt to solidification rate used in the universal method.And curable resin composition of the present invention provides excellent cohesive strength and the high dimensional stability of cured article and the excellent water resistance of adherend.Resin combination of the present invention has for example demonstrated and has been highly suitable for glued board.Thus, the limit long duration test of high quality glued board comprises in the long-time immersion boiling water (72 hours) at least.After this test, detect the cohesive force of woodwork if any.As be shown in the examples, the glued board that makes with resin combination of the present invention successfully passes through this test.
Curable resin composition can to PCT/EP95/04324 in disclosed similar.Therefore, they can comprise one or more alkene-carbon monoxide polymkeric substance (be determined on a case-by-case basis and have different molecular weight), novel polymeric amine and look particular case and one or more polyamines classes that are used as solidifying agent of existing hexamethylene-diamine and look particular case and one or more curing catalysts of existing for example.They also can comprise thinner and annexing ingredient such as viscosity modifier, fire retardant, secretion agent, antioxidant, UV stablizer and tinting material.
The amount of these components can easily be determined by normal experiment by this area professional.Usually, the molar ratio range of primary amine group is 0.25～8.0 in carbonyl in alkene-carbon monoxide polymkeric substance and the solidifying agent, and suitable scope is 0.5～4.0.
If any, an amount of scope of curing catalysts is based on 0.1～15.0wt% of alkene-carbon monoxide polymkeric substance.If for example use weak acid (promptly when test, the pKa scope is 2～5.5) in 20 ℃ of water, in right amount scope be in same datum 0.2～10.0,0.5～8.0wt% particularly.This type of sour example comprises Whitfield's ointment, lactic acid, oxalic acid and propanedioic acid.Use Cr, Cu, Ni and Fe salt and salicylic mixture can obtain good result.
The existence of thinner with and performance depend on the use of curable resin composition and required viscosity.Preferable absorbent is a water.The water yield that can use is based on 0.2～200wt% of alkene-carbon monoxide polymkeric substance meter.
Curable resin composition also can comprise claimed not only the having the carbonyl functional group but also have the polymeric amine of amido functional group of the application.In the case, independent alkene-carbon monoxide polymkeric substance is unique selection.Therefore, the performance of alkene-carbon monoxide polymkeric substance and polyamines is incorporated in the single polymkeric substance.So curable resin composition has been found and has also had excellent performance.
The invention still further relates to laminated product, particularly laminated wood goods, comprise the mutual agglutinating of tackiness agent (wooden) parts that obtain by means of by the cure curable resin combination, also relate to the product that comprises laminated wood goods of the present invention.This series products can be made into and is similar to the claimed product of PCT/EP95/04324.
Kind and shape for the woody part part that is used to produce the laminated wood goods are not particularly limited.Timber can be high or low density timber, and it can be fallen leaves or needle timber.The example of suitable species is oak, chestnut, ash, maple wood, teak, okoume, mahogany, meranti and pine.Use beech, birch, dragon spruce and poplar can obtain good result.When using habitual wood gluing prescription, except used usually pre-treatment, wood chip is without any need for other pre-treatment.For example, generally be enough to make the required type of the woody part part suitable laminated wood goods that will produce on size and dimension by using machinery and/or chemical process.Suitably, timber is used with the form of slab, veneer, log, thin layer, wood chip or paper pulp.Can use two or more kinds of woody part part or the combination of form, so that for example improve the outward appearance of laminated wood goods.
Timber can be pretreated to improve its weather resistance.This type of pretreated example is to use 150-220 ℃ of pressurized superheated steam, heats down at normal pressure 100-220 ℃ then.Another pre-treatment is to carry out salt with for example chromium, copper, mercury, arsenic salt or its mixture to soak.
Another of the present composition may purposes be to be the tackiness agent interlayer of polymer-based carbon matrix, timber and metal composite etc. as solid ingredient.Therefore, it can be used to apply for example used natural and synthon in the structural composite material of reinforcing filler.For example, many technical rubber goods such as tire, flexible pipe and travelling belt contain the weaving strongthener to strengthen intensity and dimensional stability.Have only when the cohesive force between fiber (generally being polyester (PET) or aromatic polyamide fibre) and rubber is fine, these mixtures could be used well.
By the following examples explanation the present invention, but the present invention is not limited in these embodiment.In these embodiments, use as EP-A-0, the alkene-carbon monoxide polymkeric substance for preparing among 522,635 the embodiment 10, its molecular weight is 2000 dalton, alkene: the mol ratio of carbonyl is 1: 1, and is obtained by ethene and the propylene mol ratio with 28: 72.Embodiment 1 (synthesizing of polymeric amine)
With 1 of 1000g alkene-carbon monoxide polymkeric substance and 370.5g, the 2-propylene diamine mixes.With mixture heating up to 80 ℃ also stirring, the transformation efficiency of primary amino reaches till 95% (240 minutes, by being measured by the potentiometric titration of 7300mmol/kg amine～3830mmol/kg) on the 1-position.Embodiment 2 (curable resin composition)
Curable resin composition by at 80 ℃ with about 50% available amino end protonated make of acetate with above-mentioned polymeric amine.Add entry to obtain 40% solid solution (with the amount of reaction water compensation water).With the mixture cool to room temperature, and add 1000g alkene-carbon monoxide polymkeric substance and 24g Whitfield's ointment (catalyzer).At last, add entry to obtain 50% solid curable resin composition.
Embodiment 1 and 2 can carry out according to single still synthetic method.Embodiment 3a (wood gluing test EN-314)
With the prescription of embodiment 2 with 100g/m
2Single glue-line is coated on the thick 20 * 20cm birch plywood of 2mm.Use the 3rd block of plate of intermediary these plates that superpose, outer field wood grain each other in the same way and the wood grain of interlayer be the intersection direction with it.Under 1.2MPa and 200 ℃ with lamination pressurization 2 minutes.With the triplex cool to room temperature that so forms.Be cut into the sample that is suitable for glued board standard method of test EN-314 then.In this test, sample was immersed in the boiling water through 72 hours, it was carried out shearing test when cooling down when but still very wet then.Triplex should be higher than under the level of shear of 1.0MPa by producing the timber fracture destroyed.The sample that is used for above-mentioned test produces wood failure when the shearing resistance reading is 1.5～2.0Mpa.Embodiment 3b (wood gluing test EN-204)
EN-204 judges the universal testing method of timber with the colloid amount.In this test, the equidirectional beech slab of wood grain soaked 6 hours through boiling water, and then carried out remaining shearing resistance test.In the at room temperature wet test, reading should be greater than 4.0MPa after the hot water effect.
In compare test, use the prescription of following 3 kinds of prescription: I, embodiments of the invention 2; II, identical with I uses based on the 13 weight part wheat-flours and the 20 weight part coconut shell powder of per 100 weight part curable resins and fills; With III, Dynosol S-576 (tm), a kind of high-quality external application resol.
The beech slab is with the gummed dosage that provides in following table gummed, and pressurization 10 minutes under 140 ℃ and 2.0MPa.Sample is exposed in the boiling water 6 hours.The results are shown in the following table:
| Prescription | I | I | II | II | III | III | III |
| Gummed dosage g/m 2 | 50 | 80 | 65 | 100 | 65 | 100 | 150 |
| Virgin resin amount g/m 2 | 25 | 40 | 25 | 38 | 20 | 31 | 46 |
| Filler g/m 2 | 16 | 25 | 15 | 23 | 35 | ||
| Hygrometric state shearing resistance MPa behind the boiling water | 5.7 | 5 | 4.1 | 5.7 | 3.8 | 7 | 6.2 |
As can be seen, curable resin system of the present invention has been passed through EN-204 and EN-314 test from these numerals, thereby it can be with low dosage and best commercially available prod competition.Embodiment 4 (as formulation for coating material)
With the curable resin composition of embodiment 2 with 100g/m
2Single paint line is coated on the Bar steel plate (Q-plate QD-36).Then, at 120 ℃ it was solidified 15 minutes.Thickness coating sheet material with brown, glossy coating 15～20 μ m.Its performance is as follows: forward impact is by 80 times, according to ASTM D 2794-84.Reverse impact is by 80 times, according to ASTM D 2794-84.Solvent resistance is cleaned by 100 MEK.By bonding gitterschnitt, according to ASTM D 2395-83.Embodiment 5 (the active evaluation of diamine reactant)
In order to measure the electromotive force of the two primary diamines of the present invention, use following experimental technique.2mol is normal 2,5, and 8-triketone in the ninth of the ten Heavenly Stems (being actually 10g) and the normal diamines of 1mol mix in toluene (40g), subsequently mixture are refluxed.In regular time intervals, from mixture, shift out sample and pass through titration determination amine transformation efficiency.The suitable amine of the present invention demonstrates high initial transformation efficiency, but the amine transformation efficiency is less than or equal to 50% after refluxing 3 hours.Representational data are: transformation efficiency (%) the quadrol 86 hexanediamines 84 dodecane diamines 85 m-xylylene amine 892-methyl isophthalic acids after diamines refluxed 3 hours, 5-pentamethylene diamine 82 Triethylenetetramine (TETA) 98N-methyl diethylenetriamine 981,2-propylene diamine 49 (suitable) isophorone diamine 32 (suitable) 1,3-pentamethylene diamine 49 (suitable) embodiment 6 (as the evaluation of tackiness agent interlayer)
(TOYOBA at 1018 dawn gathers (ethylene glycol terephthalate) tire line to trevira to estimate curable resin composition of the present invention with so-called H-tension test (ASTM D2138); Having toughness is 11.4g/d) with the effect that cohesive force produced of rubber (CARIFLEX S-1712DF, according to ASTM D3185, method 2B mixes).In this test, (coating) ultimate fibre is embedded into the two ends of following sulfureted block rubber.After the sulfuration, the fiber of embedding is pulled out from rubber matrix.Required power is measuring of bound stress.
Curable resin composition of the present invention prepares in the mode identical with embodiment 2, and but, the alkene-carbon monoxide polymkeric substance that joins in the polymeric amine is obtained by ethene and the propylene mol ratio with 1: 1.
Fiber is used by former state or applies with several coating solution.Do not adopt specific varnish coating device, by they being immersed in the bath with the manual coated fiber of coating.In order to remove excessive material, with cloth with fiber wiping gently.Prepare mould and pressurization behind the applying coatings at once.
At ASTM D 2138-3, vulcanize in the mould described in the H-test.145 ℃ and 35 the crust under in the plasticator of not preheating, vulcanized 50 minutes.Follow cooling die in cooling bath.The coating condition guarantees the sulfuration of this special SBR sizing material at least 90%.
Go up the evaluation sample at INSTRON tensile testing machine (the right angle extruder rate is 100mm/min, has the 2g load cell).Estimate cohesive strength as follows: pull out the required power of a branch of PET fiber divided by the insert length in rubber matrix.
When applying coatings not, every millimeter embeds fiber on the staple length-rubber bound power size metering is 2 N/mm.When coating resin of the present invention, this cohesive force almost is doubled to 3.4N/mm.Only use carbon monoxide-olefin copolymer, the situation of observing does not have any improvement.
Claims (10)
1, have that the N-that is incorporated in the skeleton replaces 2, the polymeric amines of 5-pyrroles's subunit, wherein N-replace 2,5-pyrroles's subunit can be represented by general formula (I):
Wherein R represents hydrogen atom or alkyl independently, and wherein B represents to contain the substituting group of at least one primary amino.
2, the polymeric amines of claim 1, wherein substituent B is the substituting group with 1～100 atom, it has at least one coupled sterically hindered primary amino.
3, the polymeric amines of claim 1, wherein substituent B is represented by following general formula:
Wherein X is 99 at the most, the preferred alkylene or the hydridization alkylene of 20 atoms at the most, and R ' and R " each represents 20 at the most, preferred alkyl or the hydridization alkyl or the R of 10 atoms at the most independently " are hydrogen atoms.
4, each polymeric amines in the claim 1～3, wherein substituent B is the 1-amino-ethyl.
5, each polymeric amines in the claim 1～4, represent by general formula (II) :-(A-CO-)
1-(2,5-NPy-)
m-(2,5-Py-)
n(II) wherein each A represents alkylidene group that replace or unsubstituted independently; L, m and n are the integers of representing the number of repeating unit p jointly, wherein 1≤m≤p, preferred 2≤m≤p, 0≤l+n＜p and p 〉=3; Each 2,5-NPy represent that N-replaces 2,5-pyrroles's subunit, wherein pyrroles's nitrogen-atoms replaces with the group with primary amino functional group, and each 2,5-Py represent there is not functional group or have one be not the N-of the functional group of primary amino replace 2,5-pyrroles's subunit.
6, the polymeric amines of claim 5, each A of wherein said repeating unit are that replace or unsubstituted 1,2-or 1,3-alkenyl, be more preferably replacement or unsubstituted 1,2-alkenyl.
7, claim 5 or 6 polymeric amines, wherein repeating unit (2, be as defined above 2 5-Py), 5-pyrroles's subunit, wherein pyrroles's nitrogen-atoms has a hydrogen atom, an alkyl, an aryl, an alkenyl, uncle's aminoalkyl group or (N-pyrroles) alkyl preferably.
8, the preparation method of each polymeric amines in the claim 1～7, by making the primary amine reaction of alkene-carbon monoxide polymkeric substance and general formula (III):
H
2NCH
2-B (III) wherein B as above defines, and reaction conditions should make and form 2,5-pyrroles's subunit and can the functional group that be connected on the substituent B not being had a negative impact.
9, based on the curable resin composition of each polymeric amines in the claim 1～7 purposes as curable resin and/or solidifying agent.
10, laminated product comprises by means of obtaining the mutual agglutinating assembly of solidified tackiness agent by the curable resin composition that solidifies claim 9.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97200868 | 1997-03-24 | ||
| EP97309094.7 | 1997-11-12 | ||
| EP97200868.4 | 1997-11-12 | ||
| EP97309094 | 1997-11-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1251119A true CN1251119A (en) | 2000-04-19 |
Family
ID=26146280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98803601 Pending CN1251119A (en) | 1997-03-24 | 1998-03-23 | Polymeric amines |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1251119A (en) |
| ID (1) | ID22652A (en) |
| PL (1) | PL335814A1 (en) |
-
1998
- 1998-03-23 CN CN 98803601 patent/CN1251119A/en active Pending
- 1998-03-23 PL PL33581498A patent/PL335814A1/en unknown
- 1998-03-23 ID IDW991078A patent/ID22652A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ID22652A (en) | 1999-12-02 |
| PL335814A1 (en) | 2000-05-22 |
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