CN101531727A - Post-crosslinking wax and method for producing the same - Google Patents
Post-crosslinking wax and method for producing the same Download PDFInfo
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- CN101531727A CN101531727A CN200910126529A CN200910126529A CN101531727A CN 101531727 A CN101531727 A CN 101531727A CN 200910126529 A CN200910126529 A CN 200910126529A CN 200910126529 A CN200910126529 A CN 200910126529A CN 101531727 A CN101531727 A CN 101531727A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/544—Silicon-containing compounds containing nitrogen
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- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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Abstract
The invention relates to a cross-linkable wax which contains at least one amino functional silicon compound and at least one carboxy functional wax and optionally an organo functional silicon compound and/or the salts thereof, and to aqueous wax compositions. The invention further relates to methods for producing the same and to the use thereof.
Description
Technical field
The present invention relates to contain the silicon compound of at least a amino-functional and wax and the silicon compound of organic functional optionally and/or the crosslinkable wax of its salt of at least a carboxyl-functional, and aqueous Wax composition.In addition, the present invention relates to be used to method for preparing it and uses thereof.
Background technology
Wax is the common name of many products, and it can have different molecular structures and different sources, but they have general character in (for example machinery-physicals) aspect their technical characteristic.The animal and plant wax that natural origin is for example arranged is wherein also mentioned from oil (for example fully refined wax (Tafelparaffine) and Microcrystalline Wax) and from the montanin wax of brown coal.The animal and plant cerul is in the ester of lipid acid and long chain aliphatic.Typical vegetable wax is the carnauba wax that is derived from palm, Jojoba oil (Jojoba
L) can also be considered as liquid wax.Typical synthetic wax is water miscible polyoxyethylene glycol, according to the polyethylene wax of the synthetic preparation of alkene and Poly Propylene Wax and the Fischer-Tropsch wax by Fischer-Tropsch synthetic (Fischer-Tropsch-Synthese) preparation.About the wax type that exists on wax field, the market with and acquisition and preparation method's detailed summary can be referring to UllmannEnzyklopadie.
In first production phase of synthetic wax (for example polyethylene wax, Poly Propylene Wax and Fischer-Tropsch wax), this synthetic wax is usually based on pure hydrocarbon compound.Their general molecular weight ranges is 500-5000, is under special circumstances at the most 10000 (according to by the osmometry determining molecular weight).
These waxes are called as so-called paraffinum durum (Hartparaffine), and its fusing point is generally 85 ℃-120 ℃; The fusing point of Poly Propylene Wax is typically about 160 ℃.The manufacturer of synthetic wax for example is Clariant AG, Honeywell Inc., BASF AG, Evonik Degussa GmbH, ShellAG or also has die Sasol Ltd..
In order these paraffinum durums to be incorporated into range of application widely, for some application purpose, the nonpolar paraffinum durum that needs not have functional group provides hydroxyl, carboxyl and carbonic ether (Carbonester) group to polymeric matrix (main polymer chain) in oxidising process, to improve the polarity of this compound.Usually, described oxidation is in solid phase, perhaps in dispersion agent (for example water) or carry out in the fusion liquid phase.
For example, DE 3112163 A1 have put down in writing the method that is used at flowing bed reactor oxidic polyethylene in solid phase.US 3,463, and 767 also disclose the method for oxidic polyethylene in solid phase.In open source literature DE2 035706A1, put down in writing in liquid, aqueous oxidation in mutually, wherein disclose and be used for the method that oxidation contains the homopolymer and the multipolymer of ethene.Oxidation is open in DE102 33 464 A1 in the fusion liquid phase.
By functional group's oxidisability being inserted into the range of application that to expand wax in the wax.The polarity of raising through processing wax has been expanded its purposes as the plastics lubricant, its in printing-ink (Druckfarbe) and paint vehicle application and it is processed from aqueous phase in addition.Described oxidized petroleum waves (it also is called the wax oxide compound with the free burial ground for the destitute) also can easily be distributed in the water by proper auxiliary agent (for example emulsifying agent).In addition, described carboxyl can easily further react with alkali reaction compound (for example calcium hydroxide, sodium hydroxide or lithium hydroxide) and obtain metallic soap.In this case, relate to so-called partly-hydrolysed wax, the further change of properties that it causes the further change of properties of wax and causes wax coating thus.
The sign of wax is usually by " German grease (the Deutschen Gesellschaft f ü rFettwissenschaft of science association; (DGF)) " disclosed analytical procedure is carried out.For example, melting behavior and dropping point (Tropfpunkt) are measured according to DGF M-III-3, hardness and penetration number (Penetrationszahl) are measured according to DGF M-III-9b, and acid number, saponification value and hydroxyl value (Hydroxylzahl) are pressed titration measuring according to DGF M-IV-2.The viscosity of wax is measured with rotational viscosimeter in the temperature of 120 ℃ or 150 ℃ with the melt liquid state.The parameter that is used to characterize wax in addition is density and molecular weight.Density based on the paraffinum durum of polyethylene or Fischer-Tropsch wax is about 0.92-0.96g/cm
3, wherein the molecular weight of measuring according to osmotic method is generally 500-5000, is at the most 10000 under special circumstances.
Preferably, wax processes from aqueous dispersion.In the spoken language, this aqueous dispersion or aqueous compositions are corruptly called the wax emulsion.This wax emulsion for example is used for producing the fruit coating, as nursing agent, be used for textile auxiliary agent, be used for being used for papermaking emulsion, be used for moisture printing-ink and paint vehicle system and be used to be used for interim etch-proof emulsion.
For above-mentioned wax being distributed in the water, more precisely be that the wax water that becomes can be disperseed, the wax with particular polarity need be provided.This polarity is regulated by the oxidisability of wax usually.Usually also need emulsifying agent in addition, so that this wax is water dispersible.Usually, described emulsifying agent is the oligomeric or polymeric compounds of possess hydrophilic property group and lipophilic group.Described lipophilic group is made of long straight chain or branched alkyl chain or alkyl chain usually.Depend on hydrophilic radical, relate to nonionic, negatively charged ion or cationic emulsifier system.Usually, the nonionic system comprises that poly alkyl ether, negatively charged ion system as hydrophilic radical comprise that functional hydrophilic radical of carboxylate radical and cationic system generally include ammonium salt.In principle, emulsifying agent is anchored on the polymer-wax by its lipophilic group, makes polymkeric substance or wax be equipped with hydrophilic radical and make it to be dispersed in the water in this way by emulsifying agent.Also can carry out modification to polymkeric substance itself in principle, so that it has the carboxylate functionality or the ammonium functional group of sufficient amount, these functional groups make this polymkeric substance to be dispersed in the water.Do not need to use in addition emulsifying agent like this.At this moment, through the polymkeric substance of modification can with alkali metal hydroxide, alkaline earth metal hydroxides or amine or with acid (for example formic acid or acetate) reaction, and be distributed in the water then.
Zhi Bei emulsifier system has various defectives according to structure in this way.For example, must use the nonionic emulsifying agent that improves concentration under the situation mostly, make this wax become softer thus.This emulsifying agent plays the effect of similar tenderizer (Weichmacher).In addition, prepared coating is mostly to moisture-sensitive.Nonionic emulsifying agent also causes spreading from the teeth outwards, can allow surperficial deliquescing and greasy (schmierig) and make middle layer adhesivity variation thus.
If use alkali metal hydroxide or alkaline earth metal hydroxides as anionic emulsifier, although cere is hard relatively on the one hand, but on the other hand but to moisture-sensitive, because alkali metal hydroxide and/or alkaline earth metal hydroxides are retained in the cere as nonvolatile component, and can be through water dissolution.By in the negatively charged ion system, using amine (making up individually or with oleic acid),, discharge unacceptable amine to environment on the other hand although suppressed this defective and realized higher water tolerance by its volatility.Its behavior is similarly in cationic system, and it is amino also with corresponding yogurtization that wherein emulsifying agent and/or emulsifying polymers or wax have primary amino, secondary amino group and/or uncle.Usually, discharging volatile acid (for example acetate or formic acid) when cationic system is dry also reaches in the environment thus.
Except the amount of used emulsifier system and emulsifying agent, itself also depends on the molecular weight of used wax the hardness of formed cere or tolerance.
Summary of the invention
Task of the present invention is, develop a kind of can the dispersion easily or the spoken emulsive wax easily of going up, it is after particularly being applied by aqueous composition, crosslinked to increase structure and/or by crosslinked increase molecular weight with can be cross-linked into the polymer cere after applying.
In order to address the above problem, the present invention proposes according to the crosslinkable wax of claim 1 or 21 and according to the preparation method of the above-mentioned crosslinkable wax of claim 12.In addition, theme of the present invention also is according to the Wax composition of claim 10 or 22 and they are according to the wax of the also with good grounds claim 24 of preparation of claim 18 or 19 and/or the purposes of Wax composition.Other favourable expansion embodiment is the theme of each relevant dependent claims.
According to first inventive aspect, theme of the present invention is a kind of crosslinkable wax, it contains the silicon compound of at least a amino-functional, the silicon compound and the wax of at least a carboxyl-functional and silicon compound and/or its salt of organic functional optionally that particularly contain aminoalkyl group, Diaminoalkyl or triamino alkyl.Another inventive aspect relates to the Wax composition that comprises crosslinkable wax and water.
In this crosslinkable wax, be interpreted as wax according to carboxyl-functional of the present invention as the wax of carboxyl-functional, it also is called the wax oxide compound hereinafter with the free burial ground for the destitute, they have the acid number above 15mg KOH/g wax, particularly surpass 20mg KOH/g, especially preferably have acid number above 30mg KOH/g wax.In particularly preferred embodiments, the wax of described carboxyl-functional has the acid number that is higher than 45mgKOH/g wax.In order to improve the carboxylic group number or in order to improve the acid number of crosslinkable wax, described crosslinkable wax can contain oleic acid in addition.Oleic content should be at most 40 weight % in crosslinkable wax, is in particular at the most 20 weight % and preferred 10 weight % at the most, with respect to the gross weight of crosslinkable wax and all auxiliary agents and additive.Particularly preferably, described crosslinkable wax does not contain oleic acid.Be suitable as carboxyl-functional wax be general natural wax (for example carnauba wax and ceresine), mineral wax derivative (for example through the fully refining wax (Tafelparaffine) of oxidation with through the Microcrystalline Wax (Mikrowachse) of oxidation, acid montanin wax, montanin wax derivative the montanin wax of partial esterification (for example partly-hydrolysed or)), the mixture of the Fischer-Tropsch wax of derivative of fatty acid, oxidation and the polyolefin-wax of oxidation and above-mentioned wax, wherein said wax and/or wax mixture should have above-mentioned acid number and should have free carboxy.Especially, the dropping point of this wax or wax mixture is lower than 115 ℃, preferably is lower than 110 ℃.Certainly, in dispersion or emulsification are under the situation that contains aqueous phase under the pressure, the higher dropping point of described wax or wax mixture also is possible in autoclave.
The wax of described carboxyl-functional (randomly with oleic mixture in) can be for example at 120 ℃-150 ℃ the temperature and the silicon compound of amino-functional, particularly with the organosilane of amido-containing group, reacts.The silicon compound of the amino-functional of this interpolation has at least one amino, and it can exist with primary amino, secondary amino group or uncle's amine-format.This can be the silicon compound that contains aminoalkyl group, Diaminoalkyl or triamino alkyl.Particularly preferably be the functional silicon compound of primary amino and/or secondary amino group, wherein more particularly preferably be the functional silicon compound of primary amino.According to a particularly preferred embodiment, only in crosslinkable wax, add the silicon compound of amino-functional with primary amino.
The reaction of the wax of common described amine and carboxyl-functional and increase structure and/or by with crosslinked its molecular weight that increases of the carboxyl-functional of wax, at least one amido linkage of ammonium salt structure for example in these cases from first forming.For the suitable functional silicon compound of especially preferably primary amino of intramolecularly amido linkage between the wax of the silicon compound that is formed on amino-functional and carboxyl-functional, it can easily form amino-functional with the free carboxy functional response of wax especially.
Wherein said crosslinkable wax preferably contains the silicon compound of at least one amino-functional, and it can represent at least a aminosilane of general formula I a or Ib, its salt and/or deutero-siloxanes thus,
A
1 mSiY
1 n(Ia) (Y
1*)
3Si-A
1*-Si(Y
1*)
3 (Ib)
A wherein
1And/or A
1*Can represent the aminoalkyl group, Diaminoalkyl or the triamino alkyl that do not replace or replace independently of each other, m=1 or 2 and n=1,2 or 3 wherein, m+n=4 wherein,
. especially, A among the formula Ia
1Be identical or different, and can represent the amino-functional group of general formula III a and/or IIIb
R
10 h*NH
(2-h*)[(CH
2)
h(NH)]
j[(CH
2)
1(NH)]
c-(CH
2)
k- (IIIa)
0≤h≤6 wherein; h
*=0,1 or 2, j=0,1 or 2; 0≤1≤6; C=0,1 or 2; 0≤k≤6, and R
10Can represent benzyl, vinyl benzyl, aryl, vinyl, formyl radical group and/or have straight chain, branching and/or the cyclic alkyl group of 1-8 carbon atom, and/or
[NH
2(CH
2)
e]
2N(CH
2)
d- (IIIb)
0≤e≤6 and 0≤d≤6 wherein, especially, e and/or d represent integer, and/or
. especially, A among the formula Ib
1*Be identical or different, and can represent two amino-functional groups of general formula III c,
-(CH
2)
i-[NH(CH
2)
f]
gNH[(CH
2)
f*NH]
g*-(CH
2)
i*-(IIIc)
Wherein i, i
*, f, f
*, g or g
*Be identical or different, wherein i and/or i
*=0-8, wherein i and/or i
*Represent integer independently of each other, f and/or f
*=1,2 or 3, g and/or g
*=0,1 or 2, and/or
.Y
1And/or Y
1*Can be identical or different independently of each other under each situation, and can comprise one of following groups :-OH ,-OM ,-OR
1,-R
1,-O (CO) R
1,-N (R
1)
2,-Cl ,-Br ,-J (iodine) and/or-OSi (R
1)
a(OR
1)
bA=0,1,2 or 3 and b=0,1,2 or 3 and a+b=3, wherein R wherein
1Be identical or different independently of each other, and can represent hydrogen, under each situation, have straight chain, side chain and/or cyclic alkyl, thiazolinyl, alkynyl and/or alkylaryl, aryl and/or the heteroaryl of 1-18 carbon atom, they under each situation be replace or be unsubstituted, wherein M comprises metallic cation, particularly alkali metal cation, for example Na
+, K
+Or Li
+And other conventional monovalence or divalent metal.Can consider cycloalkyl or cycloalkenyl group and/or cycloalkynyl radical especially as cyclic alkyl, thiazolinyl and/or alkynyl.
Especially, Y in formula Ia and/or Ib
1And/or Y
1*Can represent independently of each other-OH ,-ONa ,-OK ,-OR
1,-R
1,-O (CO) R
1, R wherein
1Can be identical or different independently of each other, and can represent hydrogen, have the alkyl of straight chain, ring-type and/or the side chain of 1-4 carbon atom, wherein R
1Especially preferably can represent methyl, ethyl, propyl group, isopropyl group.
Particularly preferably, the silicon compound of described amino-functional can be represented aminosilane or aminoalkyl group silane, and wherein the aminoalkyl group organoalkoxysilane is particularly preferred.Particularly preferred aminosilane is 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-aminopropyl methyldiethoxysilane, 2-amino-ethyl-3-TSL 8330 and/or the functional propyl trimethoxy silicane of triamino.Exemplary compounds also has 2-aminopropyl-3-TSL 8330,2-amino-propyl group-3-aminopropyltriethoxywerene werene, 2-amino-ethyl-2-amino-ethyl-3-aminopropyl-Trimethoxy silane, 2-amino-ethyl-3-aminopropyltriethoxywerene werene, 2-amino-ethyl-3-amino-propyl group methyl dimethoxysilane, 2-amino-ethyl-3-aminopropyl methyldiethoxysilane, the functional propyl trimethoxy silicane of triamino, two (3-trimethoxy-silylpropyl) amine, two (3-triethoxysilylpropyltetrasulfide) amine, N-benzyl-N-(2-amino-ethyl)-3-aminopropyl-Trimethoxy silane-hydrochloride, N-benzyl-N-(2-amino-ethyl)-3-aminopropyl-Trimethoxy silane-hydrogen acetate, N-(normal-butyl)-3-TSL 8330, N-vinyl benzyl-N (2-amino-ethyl)-3-aminopropyl polysiloxane and/or N-(2-amino-ethyl)-3-aminopropyl methyl-dimethoxy silane.The silicon compound of particularly preferred amino-functional is Dynasyla
AMMO, Dynasyla
AMEO, Dynasyla
1505, Dynasyla
DAMO and/or Dynasyla
TRIAMO.
According to an embodiment, described crosslinkable wax can contain silicon compound and/or its salt of organic functional, and the silicon compound of wherein said organic functional can be represented the organofunctional silane of general formula I I, its salt and/or by its deutero-siloxanes,
(R
2)
o(X
1)
pSiY
2 q (II)
-X wherein
1Be identical or different, and X
1Can comprise oxygen base, carboxyl, carboxyalkyl, silyl, alkyl silyl, alkoxysilyl, siloxy-, particularly-O-SiO
3/2Group, silyl alkyl, alkoxysilylalkyl, alkyl silyl alkyl, haloalkyl; Can comprise omega-halogenated alkyl groups, fluoro-alkyl and/or perfluoroalkyl more especially; Epoxy group(ing), ω-glycidoxyalkyl, ester group, end capped isocyanate group, cyanate radical close alkyl, isocyanato-alkyl, ω-methacryloxy alkyl, acrylate-based, methacrylate based, sulfydryl, ω-mercaptoalkyl, itrile group and/or phosphine groups, and/or
-Y wherein
2Be identical or different, and Y
2Can comprise-OH ,-OM ,-OR
1,-O (CO) R
1,-OSi (R
1)
a(OR
1)
b, a=0,1,2 or 3 and b=0,1,2 or 3 wherein, wherein a+b=3 ,-Cl ,-Br ,-J and/or-N (R
1)
2Group, wherein R
1Be identical or different straight chain, side chain and/or cyclic alkyl, thiazolinyl, alkynyl and/or alkylaryl, aryl and/or the heteroaryl that also can represent hydrogen, under each situation, have 1-18 carbon atom independently of one another, they under each situation be replace or be unsubstituted, wherein M is a metallic cation.
-o=0,1 or 2 wherein, p=0 or 1 and q=1,2,3 or 4, wherein o+p+q=4 and
-R
2Can be identical or different independently of one another, and can represent hydrogen, under each situation, have 1-18 carbon atom, preferred 1-8 carbon atom, straight chain, side chain and/or cyclic alkyl, thiazolinyl, alkynyl and/or alkylaryl, aryl and/or heteroaryl, they under each situation be replace or be unsubstituted
Especially, R
1Can represent to have the alkyl of straight chain, ring-type and/or the side chain of 1-4 carbon atom, wherein R
1Especially preferably can represent methyl, ethyl, propyl group, sec.-propyl.
The silicon compound of preferred organic functional comprises organofunctional silane, its salt and/or deutero-siloxanes thus, and wherein preferred trialkoxy silane (for example alkyltrialkoxysilaneand) can be contained by general formula I I type, wherein Y
2Can represent to have the alkoxyl group of 1-4 carbon atom, particularly methoxyl group and/or oxyethyl group, q can equal 3 and R
2Can represent to have the alkyl of 1-5 carbon atom, particularly have the alkyl of 2-4 carbon atom, especially preferably have the alkyl of 3 carbon atoms.
The preferred embodiment of the alkyltrialkoxysilaneand of general formula I I and/or aryl trialkoxy silane is isobutyl-Trimethoxy silane (Dynasyla
IBTMO), isobutyl-triethoxyl silane, propyl trimethoxy silicane (Dynasyla
PTMO), propyl-triethoxysilicane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane (Dynasyla
MTMS), Union carbide A-162, octyl group Trimethoxy silane, octyltri-ethoxysilane, hexadecyl Trimethoxy silane, phenyltrimethoxysila,e and/or phenyl triethoxysilane.
The silicon compound of the organic functional of same preferred general formula I I is the trialkoxy silane of general formula I I, wherein X
1Can represent haloalkyl, glycidoxyalkyl, mercaptoalkyl, acryloxyalkyl and/or thiazolinyl.Particularly preferred compound for example is the 3-r-chloropropyl trimethoxyl silane, 3-glycidyl propyl trimethoxy silicane
GLYMO), 3-glycidoxy triethoxyl silane
GLYEO), 3-sulfydryl propyl trimethoxy silicane
MTMO), 3-methacryloxypropyl trimethoxy silane
MEMO).According to a particularly preferred embodiment, can use the thiazolinyl trialkoxy silane, for example vinyltrimethoxy silane
VTMO) or vinyltriethoxysilane.
In order to regulate or change the performance of crosslinkable wax, the haloalkyl that can contain general formula I I in crosslinkable wax in addition is functional, the functional silane of silicon compound, particularly fluorine of organic functional.The particularly preferred fluorine functional silane of general formula I I can contain as X
1Have a R
3-Y
3 r-(CH
2)
s-group, R wherein
3Can comprise have singly the fluoridizing of 1-13 carbon atom, the widow fluoridizes or fluoridized alkyl or singly fluoridize, the widow fluoridizes or fluoridized aryl, Y wherein in addition
3Can represent CH
2-, O-, aryl-S-group and r can equal 0 or 1 and s can equal the integer (s=0-12) of 0-12.With the fluorine functionalized silicon compound crosslinkable wax is carried out modification and be specially adapted to crosslinkable wax and/or hydrophobization and/or oleophobicization that can thus obtained cere.
Particularly preferred fluoro-alkyl trialkoxy silane is corresponding to following formula CF
3((CF
2) (
0 to 12)(CH
2)
(0 to 12)) Si (O alkyl)
3, for example 3,3,4,4,5,5,6,6,7,7,8,8,8-13 fluoro-1,1,2,2-tetrahydrochysene octyltri-ethoxysilane
F8261).
For the wax for preparing the carboxyl-functional that described crosslinkable wax uses should have maximum 5000 molecular weight, it is measured according to osmotic method.Preferred wax can be polyethylene wax oxide compound or Fischer-Tropsch oxide compound (Fischer-Tropsch-Oxidat), and wherein this wax should have 5000 osmotic method molecular weight at the most.
According to the present invention, described crosslinkable wax under the situation that improves molecular weight, is crosslinkable particularly at first forming ammonium official energy and optionally forming subsequently under the situation of amido linkage and/or siloxane bond.If the osmotic method molecular weight by maximum 5000 sets out, it all relates to the wax of pure carboxyl-functional in all cases before the silicon compound with amino-functional forms amido linkage so.Therefore, crosslinkable wax of the present invention has significantly higher molecular weight after the crosslinking reaction process.
Crosslinkable wax of the present invention solid-state down be anti-storage.Advantageously, the carboxyl in wax (HOOC-group) is excessive on a small quantity with respect to amido functional group for the storage stability of this crosslinkable wax, should be the mol ratio of 1:1 under the unavoidable situation.Preferably, the pH value of crosslinkable wax should be the pH value of 7-7.5, is preferably 6.5-7.5.This can realize in the following way: make the wax of described carboxyl-functional have the acid number above the wax of this carboxyl-functional of 15mg KOH/g, preferably surpass 20mg KOH/g, more preferably surpass 30mg KOH/g and especially preferably above the acid number of the wax of this carboxyl-functional of 45mgKOH/g.Generally speaking, the wax that should utilize described carboxyl-functional aspect the contained carboxyl with respect to the silicon compound of employed amino-functional and the ammonia that optionally adds and/or excessive processing of amine of optionally adding.
Except the silicon compound of amino-functional, described crosslinkable wax can also contain ammonia and/or amine, for example 2-amino-2-methyl-1-propanol (AMP) and/or 2-dimethylamino-2-methyl-1-propanol (DMAMP80).
Theme of the present invention also is to contain the crosslinkable wax of with good grounds above-mentioned definition and the Wax composition of water.Preferably, the content of water can be for more than or equal to 50 weight % in this Wax composition, and wherein water-content is that 100 weight % determine based on Overall Group's compound of other auxiliary agent that optionally contains and/or additive.Especially, water-content can be for more than or equal to 30 weight % in the said composition, are preferably greater than especially or equal 20 weight %.Alternatively, the silicon compound of the wax of the silicon compound of amino-functional, carboxyl-functional and organic functional optionally and/or other definite ingredients ground can be 50 weight % at the most in this Wax composition, based on this Overall Group's compound meter, wherein maximum 30 weight % or lower content are preferred.
Theme of the present invention also is to be used to produce the method for wax, especially for the method for producing according to the crosslinkable wax of above-mentioned definition, and can thus obtained wax, wherein the silicon compound of the wax of the silicon compound of at least a amino-functional and at least a carboxyl-functional and at least a organic functional optionally is especially in the temperature that improves, especially at 120 ℃-150 ℃.Reaction each other.Preferably, described compound is at 100 ℃-180 ℃, preferred 120 ℃-150 ℃, melt in be mixed with each other and/or homogenize each other.
According to a kind of method modification, the wax of carboxyl-functional also can be after its preparation, for example after oxidation finishes and reaches required acid number, still with fused solution immediately with the silicon compound reaction of amino-functional of the present invention.This method steps can be compared with the preparation of partly-hydrolysed wax, for example VESTOWA
AS 1550 E (Degussa) wherein use alkali metal hydroxide or alkaline earth metal hydroxides.According to this method modification, in this procedure, be noted that described viscosity may by with the silicon compound of amino-functional, particularly partly-hydrolysed with aminosilane, and increase slightly, and this may influence curing schedule and for example makes lozenge or granulation.Formed reaction water should be removed from this reaction mixture, for example by processing under the decompression slightly, for example by holding in the palm processing at 50-300, perhaps by purging with nitrogen is lasting.Preferably, described wax should adiabatic drying ground storage, can aminosilane be hydrolyzed to silanol and under the crosslinked situation condensation take place subsequently in wax thus by atmospheric moisture.
The silicon compound of used in the method amino-functional can preferably include at least a according to the general formula I a of above-mentioned definition or the aminosilane of Ib, its salt and/or the mixture of deutero-siloxanes and/or these compounds thus.The silicon compound of the organic functional of at least a interpolation optionally can preferably be represented the organofunctional silane, its salt of general formula I I as defined above and/or the mixture of deutero-siloxanes or these compounds thus.
In order to prepare the crosslinkable wax of anti-storage, can preferable separation remove the water that depends on method and contain and/or form.
In order to prepare the Wax composition that contains crosslinkable wax of the present invention, described crosslinkable wax comprises the silicon compound of the wax of the silicon compound of at least a amino-functional and at least a carboxyl-functional and at least a organic functional according to above-mentioned definition optionally especially, described crosslinkable wax can be dispersed in the hot water, perhaps spoken going up is emulsified in it in hot water in fact, with can optionally cool off, particularly can cool off the mixture of gained, wherein particularly can obtain according to Wax composition of the present invention.
For example, can be in first step by the silicon compound of the wax of carboxyl-functional and amino-functional thermotonus at 120 ℃-150 ℃.Then, under violent stirring (for example by arm stirrer), the melt that for example is in 105 ℃ of-130 ℃ of temperature can be incorporated in the hot water that is in about 95 ℃ of water temperatures.Slowly be cooled to after about 70 ℃, can reduce stirring velocity (for example under the situation of using conventional arm stirrer) also with this Wax composition, wax emulsion or wax dispenser in other words, in water-bath under the strong refrigerative situation or under the situation of using cooling coil further cool to room temperature.Conform with the point of destination, can be in being distributed to hot water before or after the Wax composition of cooling gained or emulsion in addition and ammonia and/or conventional amine for example AMP (2-amino-2-methyl-2-propyl alcohol) or DMAMP 80 (2-dimethylamino-2-methyl-1-propanol) react.
According to another inventive aspect, theme of the present invention is the preparation method of Wax composition and the Wax composition that can obtain according to this method, wherein in first method steps with the wax of at least a carboxyl-functional, especially under elevated temperature, with the reaction of ammonia and/or amine, and in step subsequently with the silicon compound of at least a amino-functional with optionally exist under the condition of water and disperse with the silicon compound of at least a organic functional.
Especially, the wax of described carboxyl-functional usually can be optionally with oleic acid and amine or only negatively charged ion takes place and disperse with amine (for example 2-amino-2-methyl-1-propanol or 2-dimethylamino-2-methyl-1-propanol), carry out emulsification perhaps on spoken language.
Can be in step subsequently add the silicon compound of amino-functional or contain silicon compound (for example aminosilane) and the silicon compound of organic functional optionally or the composition of its hydrolysis and/or condensation product of amino-functional to this wax emulsion that in first method steps, prepares or wax dispenser.This composition that contains the silicon compound of amino-functional is available on the market, and can be for example at Degussa with trade(brand)name
HS or Hydrosil
TMBuy.The composition that conforms with purpose is to be adjusted to the pH value to be about 11 alkaline compositions, for
HS 2627 types (moisture amino/alkyl functional siloxanes co-oligomer does not contain alcohol) and
HS 2776 types (the moisture diamino/alkyl functional siloxanes co-oligomer that does not have alcohol).Also can use for example to be adjusted to the pH value and to be about 4 acidic composition, for
HS 2909 types (aqueous no alcohol/alkyl functional siloxanes co-oligomer) or
HS 2907 types (the siloxanes co-oligomer of aqueous nothing alcohol amino/vinyl functional).These acid adjustings
The HS-composition should be before being used for the inventive method, also promptly with before the wax emulsion for preparing or wax dispenser in first method steps mix, is adjusted to and is higher than 7 pH value.This can easily realize by adding amine (for example 2-amino-2-methyl-1-propanol and 2-dimethylamino-2-methyl-1-propanol) in advance, conform with the point of destination and at room temperature carry out under with the arm stirrer agitation condition.Directly use acidity to regulate
The HS-composition is feasible, as long as handle with cationic wax emulsion (its pH value is for being lower than 7) in first method steps.
Usually, in first method steps, can disperse almost in later step, to exist under the condition of water than silicon compound arbitrarily with amino-functional by the wax emulsion of the wax of at least a carboxyl-functional and ammonia and/or amine preparation or wax dispenser.Preferably, can use the silicon compound of amino-functional as aqueous dispersion.
Especially, wax emulsion that in first method steps, prepares or wax dispenser and
The ratio of mixture of HS type composition extends through the wax emulsion of 0.1-99.9 weight % and 99.9 weight %-0.1 weight %'s
The ratio of mixture of HS type composition is 100 weight % meters based on Wax composition of the present invention all, and said composition can optionally contain extra auxiliary agent and additive.Wherein, be interpreted as the wax emulsion that in first method steps, prepares in this wax emulsion.Except the wax of carboxyl-functional, it can optionally contain oleic acid and ammonia and/or amine.Preferred compositions can be based on the wax emulsion of 10-80 weight % and 90-20 weight %
The HS composition particularly preferably is the wax emulsion of 20-70 weight % and 80-30 weight %
HS composition, perhaps the wax emulsion of 40-60 weight % and 60-40 weight %
The ratio of mixture of HS type, wherein the summation of Wax composition is 100 weight % under each situation.
Certainly, the use of the silicon compound of amino-functional is not limited to use
HS can use the comparable composition that contains the silicon compound of amino-functional usually in the methods of the invention.It is known to those skilled in the art that to allow the silicon compound of described wax emulsion or wax dispenser and amino-functional exist under the condition of water, particularly with
The HS composition, according to the method process and add the different amts of compound, can be by stirring together by conventional arm stirrer, for example at room temperature, mix or react.
Based on the favourable physical and mechanical property of wax of the synthetic carboxyl-functional for preparing, for example dropping point, hardness, lubrication and hydrophobic interaction preferably use the wax of the carboxyl-functional of synthetic preparation to prepare crosslinkable wax and Wax composition.Particularly preferably be the Fischer-Tropsch wax and the polyolefin-wax of oxidation, for example according to the polyethylene wax of Ziegler process (Ziegler).
By Wax composition as defined above of the present invention being applied on base material and/or the substrate surface and drying, described base material for example is fabric, line, yarn, leather, fruit, mineral, concrete, plastics, plastic optical fibre, can obtain cere.
Therefore, theme of the present invention is that also this wax or Wax composition are used to handle and/or the purposes of modification base material and/or substrate surface, especially for the purposes of preparation cere.Crosslinkable wax or Wax composition are specially adapted to the purposes in the fabric field; especially for the preparation line; the chemical enhancement process (Hochveredelung) of fabric; improve the sewability of fabric; be used for the wrinkle resistant processing (Knitterfestausr ü stung) of fabric; be used for from smooth emulsion (Selbstglanzemulsion); be used for leather nursing; in leather care products or be used to prepare leather care products; as forming agent and releasing agent; water-based printing ink and/or paint vehicle system; be used for interim corrosion protection or be used for interim corrosion protection agent; be used to prepare the fruit coating, be used to apply mineral; concrete; plastics; the plastics work in-process; plastic grain and/or plastic optical fibre.Wherein be interpreted as especially by material and/or yarn natural and/or the synthon preparation as fabric.
Specific embodiments
Following embodiment is used to explain crosslinkable wax of the present invention, Wax composition and method, but be not to limit the invention to these embodiment.The wax parameter of concrete physics-machinery is measured according to following method.Dropping point is measured according to DGF M-III-3, and hardness and penetration number (Penetrationszahl) are measured according to DGF M-III-9b, and acid number is pressed titration measuring according to DGF M-IV-2.
Embodiment
Embodiment 1 (according to the present invention)
The Wax composition that contains polyethylene wax oxide compound (VESTOWAX AO 1570, Degussa, acid number are 43mg KOH/g wax) and oleic acid and 2-dimethylamino-2-methyl-1-propanol:
With the wax (VESTOWAX AO 1570) of 100g carboxyl-functional and 10g oleic acid (99%, Aldrich) in the fusion marmite 125 ℃ of temperature fusions.Then, under by the arm stirrer agitation condition, in 125 ℃ in about 20 seconds processes, add by the 17.2g3-aminopropyltriethoxywerene werene (99%, Dynasyla
AMEO) and 5.5g2-dimethylamino-2-methyl isophthalic acid-propyl alcohol (80%, the Aldrich) mixture of Zu Chenging.This wax melt is poured into water temperature under by the effect of arm stirrer violent stirring be in 95 ℃ the hot water.Slowly be cooled to after 70 ℃, the reduction stirring velocity also is under the refrigerative condition Wax composition to be cooled fast to room temperature in the water-bath.Gained Wax composition (emulsion) be finely divided (feinteilig) with the blueing look.Be in application to after surperficial the going up, dry this Wax composition is to form clarifying film.
Embodiment 2 (according to the present invention)
Contain polyethylene wax oxide compound (osmotic method molecular weight 1500,102 ℃ of dropping points, hardness 4mm * 10 as the wax of carboxyl-functional
-1, acid number 65mg KOH/g wax) Wax composition:
In the fusion marmite in the wax of 125 ℃ of fusion 200g carboxyl-functionals.Then, use under the situation of arm stirrer in 125 ℃ added in the process at about 20 seconds 52g3-aminopropyl Union carbide A-162 (
AMEO).This wax melt adds water temperature under by arm stirrer violent stirring condition be in 95 ℃ the 1000ml hot water.Slowly be cooled to after 70 ℃, reducing stirring velocity, and be in the water-bath under the cooling conditions the rapid cool to room temperature of this emulsion.The Wax composition of gained is very finely divided and is the blueing look.This Wax composition is applied on the surface, and drying obtains clarifying cere.
Embodiment 3 (according to the present invention)
The preparation partly-hydrolysed polyethylene wax oxide compound of aminosilane
A) by polyethylene wax (osmotic method molecular weight 1500,118 ℃ of dropping points, acid number 0mgKOH/g wax, penetration number 1mm * 10
-1, density is 0.94g/cm
3) set out.
B) at 21 Glass Containerss with the built-in glass filter (Glasfritte) that is used for introducing air (with air throughput) with 151/h, by arm stirrer with 3-5 revolutions per second of agitation condition under, allow 500g from the oxidation by air under the 0.1 weight % Zinic stearas condition of interpolation of a) polyethylene wax.Oxidizing temperature at first kept 30 minutes at 170 ℃, kept 8 hours at 140 ℃ for remaining step of reaction then.Then, after air is introduced end and when introducing nitrogen, finish reaction.In order to discharge the water that during reaction forms, the guiding drying nitrogen passed through the gained mixture other 2 hours 140 ℃ of temperature.The acid number of prepared polyethylene wax oxide compound is a 55mg KOH/g wax.
C) the polyethylene wax oxide compound that makes according to step b) of 200g 125 ℃ in the fusion marmite under slow agitation condition by arm stirrer with 37.5g 3-aminopropyl methyldiethoxysilane
1505) reaction is about 2 minutes.Prepared crosslinkable wax is preserved under the condition of isolated moisture.The true qualities of wax are yellow.
D) but detect emulsifying property
With 100g from c) crosslinkable wax in the fusion marmite in 125 ℃ of temperature and 5g oleic acid (99%, Aldrich) and the 2.8g 2-dimethylamino-2-methyl-1-propanol (80%, Aldrich) fusion together, and stir by arm stirrer.Then, add 1g trifluoro octyltri-ethoxysilane
F8261).Immediately this melt is poured into the 500ml temperature after the interpolation under by arm stirrer violent stirring situation is in 95 ℃ the water.Slowly be cooled to after 70 ℃, the reduction stirring velocity also is under the refrigerative condition Wax composition to be cooled fast to room temperature in the water-bath.
Prepared Wax composition is finely divided, and dry and form clarifying film on sheet glass.
Embodiment 4 (not being) according to the present invention
The wax emulsion, the polyethylene wax oxide compound that it has from embodiment 2 does not use only using 2-dimethylamino-2-methyl-1-propanol under the silicon compound condition of amino-functional to prepare.
In the fusion marmite in the polyethylene wax oxide compound of 125 ℃ of fusion 200g carboxyl-functionals.Using under the arm stirrer condition, this temperature added in the process at about 20 seconds 35g diethylin-2-methyl isophthalic acid-propyl alcohol (80%, Aldrich).Allow this wax melt under by arm stirrer violent stirring condition, flow in 95 ℃ of hot water of 1000ml.Slowly be cooled to after 70 ℃, reducing stirring velocity, and be in the water-bath under the cooling conditions the rapid cool to room temperature of this emulsion.The emulsion of gained is very finely divided.Dry from the teeth outwards this emulsion obtains clarifying layer.
Embodiment 5 (according to the present invention)
With non-of the present invention wax emulsion and 50ml 40% emulsion of 100ml from embodiment 4
HS 2627 in container in room temperature by mixing.The Wax composition of gained is very finely divided.This Wax composition is applied to the surface goes up and be dried to clarification.
Embodiment 6
Detect water tolerance and scratch resistance
A) water tolerance
Under each situation with 2cm
3The Wax composition from embodiment 1-5 (emulsion) at room temperature be applied on the sheet glass that specification is 5cm * 2cm by transfer pipet.After 2 hour time of drying, on wax coating, applied 0.5cm as drop in room temperature
3Distilled water, and the outward appearance of the treated wax coating of visual evaluation 30 minutes.Under the not water-proof situation of cere, cere will dissolve and form significantly muddy therein.
B) adhesivity and hardness and scratch resistance
To deposit 7 days in room temperature through the sheet glass that applies, and detect then.Described detection is undertaken by sharp keen cutter.Applying under the big supporting power situation, detecting the situation that the coating of the sheet glass for preparing is scraped off in a) by this cutter.
Estimate: 1=can not scrape off (infeasible) from substrate of glass, has formed hard cere and this cutter and only can deviate from chip by cere, and 4=can easily separate cere with sheet glass.
Table 1
Detect the water tolerance (a) and the scratch resistance (b) of cere
| The test number that carries out | Emulsion from embodiment | According to the present invention | The outward appearance on surface | Adhesive power/hardness/scratch resistance |
| 1 | 1 | Be | Keep clarification | 2 |
| 2 | 2 | Be | Keep clarification | 1 |
| 3 | 3 | Be | Keep clarification | 2 |
| 4 | 4 | Not | Become muddy | 4 |
| 5 | 5 | Be | Keep clarification | 3 |
Find that generally speaking embodiments of the invention 1-3 and 5 Wax composition form water-proof and hard cere, and form firmly and not water-proof cere from the Wax composition of embodiment 4.
Claims (26)
1. wax is characterized in that, this wax is crosslinkable and contains silicon compound and the wax of at least a carboxyl-functional and silicon compound and/or its salt of organic functional optionally of at least a amino-functional.
2. the wax of claim 1 is characterized in that, the silicon compound of described amino-functional is represented the aminosilane of at least a general formula I a or Ib, its salt and/or deutero-siloxanes thus,
A
1 mSiY
1 n(Ia) (Y
1*)
3Si-A
1*-Si(Y
1*)
3 (Ib)
-A wherein
1And/or A
1*Aminoalkyl group, Diaminoalkyl or triamino alkyl that expression does not independently of each other replace or replaces,
-Y
1And/or Y
1*Be identical or different independently of each other under each situation, and comprise one of following groups :-OH ,-OM ,-OR
1,-R
1,-O (CO) R
1,-N (R
1)
2,-Cl ,-Br ,-J and/or-OSi (R
1)
a(OR
1)
b, a=0,1,2 or 3 and b=0,1,2 or 3 and a+b=3, wherein R wherein
1Be identical or different independently of each other, and expression hydrogen, the straight chain that under each situation, has 1-18 carbon atom, side chain and/or cyclic alkyl, thiazolinyl, alkynyl and/or alkylaryl, aryl and/or heteroaryl, they under each situation be replace or be unsubstituted, wherein M comprises metallic cation
-m=1 or 2 and n=1,2 or 3, wherein m+n=4 wherein.
3. claim 1 or 2 wax is characterized in that the silicon compound of described organic functional is represented the organofunctional silane of general formula I I, its salt and/or by its deutero-siloxanes,
(R
2)
o(X
1)
pSiY
2 q (II)
-X wherein
1Be identical or different, and X
1Comprise the oxygen base, carboxyl, carboxyalkyl, silyl, the alkyl silyl, alkoxysilyl, siloxy-, silyl alkyl, alkoxysilylalkyl, the alkyl silyl alkyl, haloalkyl, epoxy group(ing), ω-glycidoxyalkyl, ester group, end capped isocyanate group, cyanate radical closes alkyl, the isocyanato-alkyl, ω-methacryloxy alkyl, acrylate-based, methacrylate based, sulfydryl, ω-mercaptoalkyl, itrile group and/or phosphine groups
-Y wherein
2Be identical or different, and Y
2Comprise-OH ,-OM ,-OR
1,-O (CO) R
1,-OSi (R
1)
a(OR
1)
b, a=0,1,2 or 3 and b=0,1,2 or 3 wherein, a+b=3 wherein ,-Cl ,-Br ,-J and/or-N (R
1)
2Group, wherein R
1Be identical or different independently of one another and represent hydrogen, under each situation, have straight chain, side chain and/or cyclic alkyl, thiazolinyl, alkynyl and/or alkylaryl, aryl and/or the heteroaryl of 1-18 carbon atom, they under each situation be replace or be unsubstituted, wherein M is a metallic cation
-o=0,1 or 2 wherein, p=0 or 1 and q=1,2,3 or 4, wherein o+p+q=4 and
-R
2Be identical or different independently of one another, and expression hydrogen, the straight chain that under each situation, has 1-18 carbon atom, side chain and/or cyclic alkyl, thiazolinyl, alkynyl and/or alkylaryl, aryl and/or heteroaryl, they under each situation be replacement or be unsubstituted.
4. the wax of one of claim 1-3 is characterized in that,
A among the-Shi Ia
1Be identical or different, and the amino-functional group of expression general formula III a and/or IIIb
R
10 h*NH
(2-h*)[(CH
2)
h(NH)]
j[(CH
2)
1(NH)]
c-(CH
2)
k- (IIIa)
0≤h≤6 wherein; h
*=0,1 or 2, j=0,1 or 2; 0≤1≤6; C=0,1 or 2; 0≤k≤6, and R
10Expression benzyl, vinyl benzyl, aryl, vinyl, formyl radical group and/or have straight chain, branching and/or the cyclic alkyl group of 1-8 carbon atom, and/or
[NH
2(CH
2)
e]
2N(CH
2)
d- (IIIb)
0≤e≤6 and 0≤d≤6 wherein, and/or
A among the-Shi Ib
1*Be identical or different, and two amino-functional groups of expression general formula III c,
-(CH
2)
i-[NH(CH
2)
f]
gNH[(CH
2)
f*NH]
g*-(CH
2)
i*- (IIIc)
Wherein i, i
*, f, f
*, g or g
*Be identical or different, wherein i and/or i
*=0-8, f and/or f
*=1,2 or 3, g and/or g
*=0,1 or 2, and/or
Y among-Shi Ia and/or the Ib
1And/or Y
1*Independently of each other expression-OH ,-ONa, OK ,-OR
1,-R
1,-O (CO) R
1, R wherein
1Be identical or different independently of each other, and expression hydrogen, under each situation, have the alkyl of straight chain, ring-type and/or the side chain of 1-4 carbon atom, especially, R
1Expression methyl, ethyl, propyl group, isopropyl group.
5. the wax of one of claim 1-4, it is characterized in that the silicon compound of described amino-functional is represented 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-aminopropyl methyldiethoxysilane, 2-amino-ethyl-3-TSL 8330 and/or the functional propyl trimethoxy silicane of triamino.
6. the wax of one of claim 1-5 is characterized in that, the wax of described carboxyl-functional has the acid number above 15mg KOH/g wax.
7. the wax of one of claim 1-6 is characterized in that, described wax contains oleic acid.
8. the wax of one of claim 1-7 is characterized in that, the wax of described carboxyl-functional is that the osmotic method molecular weight mostly is 5000 polyethylene wax oxide compound or Fischer-Tropsch oxide compound most.
9. the wax of one of claim 1-8 is characterized in that, it is crosslinkable under the situation that forms amido linkage and/or siloxane bond.
10. Wax composition is characterized in that, it comprises wax and the water of one of claim 1-9.
11. the Wax composition of claim 10 is characterized in that, water-content is more than or equal to 50 weight %.
12. be used to prepare the method for the wax of one of claim 1-9, wherein make silicon compound and the wax of at least a carboxyl-functional and silicon compound reaction each other under elevated temperature of at least a organic functional optionally of at least a amino-functional.
13. the method for claim 12 is characterized in that, uses the wax of the fused carboxyl-functional of prepared fresh.
14. the method for claim 12 or 13 is characterized in that, the wax of described carboxyl-functional has the acid number that is higher than 15mg KOH/g.
15. the method for one of claim 12-14, it is characterized in that, the silicon compound of described amino-functional is represented at least a according to claim 2, the general formula I a of 4 and/or 5 definition or the aminosilane of Ib, its salt and/or deutero-siloxanes, the perhaps mixture of these compounds thus.
16. the method for one of claim 12-14 is characterized in that, the silicon compound of described organic functional is represented according to the organofunctional silane of the general formula I I of claim 4 definition, its salt and/or deutero-siloxanes, the perhaps mixture of these compounds thus.
17. the method for one of claim 12-16 is characterized in that, water sepn that contained and/or formed is removed.
18. be used to prepare method, wherein will be dispersed in the hot water according to the wax of one of claim 1-9 or 12-17 and cooling optionally through fused according to the Wax composition of claim 10 or 11.
19. be used to prepare method according to the Wax composition of claim 10 or 11, the wax that wherein makes at least a carboxyl-functional in first method steps is in elevated temperature and ammonia and/or amine reaction, and in step subsequently with the silicon compound of at least a amino-functional with optionally exist under the condition of water and disperse with the silicon compound of at least a organic functional.
20. the method for claim 19 is characterized in that, uses 2-amino-2-methyl-1-propanol and/or 2-dimethylamino-2-methyl-1-propanol as amine.
21. the wax that can obtain according to the method for one of claim 12-17.
22. the Wax composition that can obtain according to the method for one of claim 18-20.
23. cere, can by will according to claim 10,11 or the Wax composition of one of 18-20 be applied on base material and/or the substrate surface and dry the acquisition.
24. be used to handle and/or the purposes of modification base material and/or substrate surface according to the wax of one of claim 1-22 or Wax composition.
25. the purposes of claim 24 is used to prepare cere.
26. the purposes of claim 24; be used for the preparation of line; the wrinkle resistant processing of the chemical enhancement process of fabric, the sewability of improving fabric, fabric, be used for from smooth emulsion, be used for leather nursing; in leather care products; as releasing agent, be used for water-based printing ink and/or paint vehicle system, be used for interim corrosion protection; be used to prepare the fruit coating, be used to apply mineral, concrete, plastics, plastics work in-process, plastic grain and/or plastic optical fibre.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008000595.9 | 2008-03-11 | ||
| DE102008000595A DE102008000595A1 (en) | 2008-03-11 | 2008-03-11 | Postcrosslinking wax and process for its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101531727A true CN101531727A (en) | 2009-09-16 |
Family
ID=40651321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910126529A Pending CN101531727A (en) | 2008-03-11 | 2009-03-10 | Post-crosslinking wax and method for producing the same |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN101531727A (en) |
| DE (1) | DE102008000595A1 (en) |
| WO (1) | WO2009112329A1 (en) |
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| CN102190802A (en) * | 2011-03-23 | 2011-09-21 | 南京天诗实验微粉有限公司 | Preparation method of cross-linked polymer wax micropowder |
| CN102939341A (en) * | 2010-04-12 | 2013-02-20 | 赢创德固赛有限公司 | Alkyl- and amino-functionalized siloxanes comprising bis(alkoxysilyl)amine for the mass hydrophobization of inorganic building materials |
| CN105671954A (en) * | 2016-03-30 | 2016-06-15 | 江阴芗菲服饰有限公司 | Mark-resistant ramie textile fabric coated by aid of air knives |
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| WO2012064705A1 (en) * | 2010-11-10 | 2012-05-18 | Agrium Advanced Technologies | Cross-linked modified waxes for controlled release fertilizers |
| MY181825A (en) * | 2010-11-10 | 2021-01-08 | Agrium U S Inc | Cross-linked polyols for controlled release fertilizers |
| EP3572462A1 (en) | 2018-05-25 | 2019-11-27 | Sasol Wax GmbH | Wax composition comprising linear hydrocarbons, branched hydrocarbons and oxidized hydrocarbons, aqueous dispersion thereof, method to produce such wax composition and dispersion and use thereof as carnauba wax replacement |
| CN110241619B (en) * | 2019-06-11 | 2021-11-30 | 浙江梅盛实业股份有限公司 | Waterproof post-treatment liquid and waterproof post-treatment process for artificial leather |
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| US3463767A (en) | 1967-12-04 | 1969-08-26 | Allied Chem | Process for emulsifying high molecular weight polyethylene |
| DE2035706C3 (en) | 1970-07-18 | 1975-09-11 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of oxidation products of ethylene polymers |
| US4250068A (en) * | 1978-05-15 | 1981-02-10 | Glass Containers Corporation | Composition for coating glass containers |
| DE3112163A1 (en) | 1981-03-27 | 1982-10-14 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING EMULSIBLE POLYETHYLENE BY OXIDATION OF POLYETHYLENE IN THE FLUID BED REACTOR |
| US5240660A (en) * | 1991-05-17 | 1993-08-31 | Allied-Signal Inc. | Abrasion resistant polyester yarn and cordage |
| JP2000273285A (en) * | 1999-03-24 | 2000-10-03 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| DE10233464B4 (en) | 2002-07-24 | 2007-03-29 | Degussa Ag | Process for the preparation of an initiator for the oxidation of hydrocarbons |
-
2008
- 2008-03-11 DE DE102008000595A patent/DE102008000595A1/en not_active Withdrawn
-
2009
- 2009-02-17 WO PCT/EP2009/051843 patent/WO2009112329A1/en active Application Filing
- 2009-03-10 CN CN200910126529A patent/CN101531727A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102939341A (en) * | 2010-04-12 | 2013-02-20 | 赢创德固赛有限公司 | Alkyl- and amino-functionalized siloxanes comprising bis(alkoxysilyl)amine for the mass hydrophobization of inorganic building materials |
| CN102190802A (en) * | 2011-03-23 | 2011-09-21 | 南京天诗实验微粉有限公司 | Preparation method of cross-linked polymer wax micropowder |
| CN102190802B (en) * | 2011-03-23 | 2013-06-26 | 南京天诗新材料科技有限公司 | Preparation method of cross-linked polymer wax micropowder |
| CN105671954A (en) * | 2016-03-30 | 2016-06-15 | 江阴芗菲服饰有限公司 | Mark-resistant ramie textile fabric coated by aid of air knives |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102008000595A1 (en) | 2009-09-17 |
| WO2009112329A1 (en) | 2009-09-17 |
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Application publication date: 20090916 |