CN105593304B - Purposes of the mixture of organic functional modified polysiloxanes and amide in the preparation of polyurethane flexible foam - Google Patents

Purposes of the mixture of organic functional modified polysiloxanes and amide in the preparation of polyurethane flexible foam Download PDF

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CN105593304B
CN105593304B CN201480048412.0A CN201480048412A CN105593304B CN 105593304 B CN105593304 B CN 105593304B CN 201480048412 A CN201480048412 A CN 201480048412A CN 105593304 B CN105593304 B CN 105593304B
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CN105593304A (en
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S·施米茨
R·胡贝尔
M·格洛斯
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
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    • C08G2110/005—< 50kg/m3
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
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Abstract

The present invention relates to mixture, it includes：(a) organic functional modified polysiloxanes and (b) amide compound and (c) organic solvent, optionally combined with additional blending ingredients, purposes of the mixture in the preparation of polyurethane flexible foam is further related to, and is related to preparing the method for polyurethane flexible foam.

Description

The mixture of organic functional modified polysiloxanes and amide is in polyurethane flexible foam Preparation in purposes
The present invention relates to the fields of polyurethane, especially flexible polyurethane foams (flexible polyurethane Foams field).The present invention is more particularly directed to the mixtures of organic functional modified polysiloxanes and amide and organic solvent to exist Purposes in the preparation of flexible polyurethane foams, and the method for preparing flexible polyurethane foams.
Polysiloxane-polyxyalkyl-blockpolymer (hereinafter referred to as polyether silicone) is used to prepare polyurethane foam Foam.They can be such that uniform and fine pore structure is formed, and so that foam is stablized during preparation process.However according to preparation Method and further used raw material, the degree of the hole obtained in some cases fine (cell fineness) are It is inadequate.For example, often obtaining tending to relatively rough microcellular structure using the polyalcohol with high polypropylene oxide content (cellular structure).Mechanical correlative factor may also lead to irregular and/or coarse microcellular structure, such as make When with when low pressure mixing head or even being under atmospheric pressure simply to stir raw material.
Similarly, using certain foaming agent (such as, specifically, liquid CO2Or dichloromethane) polyether silicone is obtained It obtains the microcellular structure with fine hole and proposes extra high requirement.Due to its beneficial ecological balance, in the recent period in western countries In, liquid CO2Technology becomes more and more important.In liquid CO2In technology, except through between used water and isocyanates Chemical reaction formed CO2, by the CO of pressurization2As foamed gas.The technology is for example described in EP-A-0 645 226.
However, introducing the technology (with the pressurization CO for excluding reaction mixture generation2Spontaneous foaming) for steeping More stringent requirements are proposed for the hole Formation and characteristics of component used in foam formulation.This can virtually completely explain, because Isocyanate-water reaction (slowly occurring within time several seconds so far) is only resulted in mutually is saturated liquid with gas slowly, and therefore Cause to be slowly formed bubble, indicates the cream time of described foam.
Hole is may also lead to using volatility dichloromethane to be roughened.Particularly, (it mainly gives birth in Asia low density foam Production) preparation for siloxanes stabilize property have high request.As foaming agent is using horizontal increase, reaction mixture becomes Must be more not sticky, therefore strong gel-type catalyst and a large amount of stabilizer are added into the reaction mixture, to realize foot Enough horizontal holes stabilize.
(in no CO2Under/dichloromethane) usually slowly foaming process establish gained foam morphological properties-hole count With the basis of barrel hole size distribution-, and several seconds of several points are compressed to, that is, make raw material by foaming machines and subsequent coating The mixing head of the pressurization of device is down to the interval needed for the environmental pressure of an atmospheric pressure.CO2Foaming is generated with by sprayer Shaving foam the case where resemblance be, pass through liquid CO2Foam is spontaneously formed with its evaporation.The foam of the type produces Raw defect is uneven, part roughening hole in foaming structure, but can be remarkably contributing to using suitable foam stabiliser Reduce these defects.However, problem is often, in particular according to environmental parameter (such as pressure, material temperature, in formulation The middle solid used), it is fit closely stabilizer even from the prior art, such as in US-A-5 357 018 or US-A-5 Recorded in 321 051, complete flawless foam can not be generated.
In principle, improve polyether silicone is strictly the method for keeping pore structure finer using level, but for carrying The amount of polyether silicone used in height, range are limited, are firstly because the satellite phenomenon of the overstabilization then occurred, It can lead to the hole of a high proportion of closure, and the contraction of foam is even resulted in extreme case, secondly because associated Unfavorable economy.
In principle, it is to enhance hole fineness itself using additive in polyether silicone and/or flexible foam formulation It is known.
EP-A-0 900 811 describes cyclic carbonate in flexible foam formulation as hole fineness reinforcing agent Purposes.But cyclic carbonate only with effectively, and also have from preparing under the amount of polyether silicone same order The shortcomings that foam is deflated in the form of volatile matter.
EP-A-0 976 781 describes the combined use of the salt of polyether silicone and organic acid.It sends out really at low concentrations The enhancing of hole fineness is given birth to, but the solubility of salt is relatively limited, needs to use water as cosolvent.Therefore as use Combination is still limited to the polyether silicone of hydrolysis.Water additionally aids the foamable reaction with isocyanates, and depending on being used Concentration, the presence of water may have to be allowed in the estimation for preparing people.
EP-A-1 029 878 is related to preparation of the improved polysiloxane-polyxyalkyl-blockpolymer in polyurethane foam The middle purposes as additive, wherein the improvement is in a mixture that Si-C- is not used only and uses Si-O-C- The silicone-polyether block copolymer of connection, to realize the specific combination of activity and hole fineness.
US-A-4 520 160 describes the method for preparing polyether silicone in the presence of fatty alcohol.The latter prevents Gelling during the method.The product of gained is preferably used as emulsifier in cosmetic applications, or in elastomer preparation As stabilizer, but it is not used in the preparation of flexible foam.
US-A-20020132867 is related to purposes of the fatty alcohol as the component of mixture of polyether silicone.The fatty alcohol It is the branched alcohol selected from Guerbet and Ziegler alcohol, the processing of especially branched oxo and different tridecanol.However, wherein not Refer to the use of the compound comprising amide.
According to US-A-20020132867, in the mixture using polyether silicone and isooctadecanol and other fatty alcohols Under, recorded test generates the foam of trepanning, for its pore structure, it is said that it is equal with the foam that test obtains compared with Or it is more excellent.
The problem to be solved in the present invention is the enhancing for preparing flexible polyurethane foams, while providing effective hole fineness.
Then, it was surprisingly found now that (independent with corresponding polyether silicone in the preparation of flexible polyurethane foams Or combined with conventional component of mixture) compare, certain polyether silicones and certain compounds comprising amide groups and organic The mixture of solvent has significantly more effectively influence for the enhancing of hole fineness.The mixture of the present invention, which to prepare, to be had The flexible polyurethane foams of the pore structure of ad hoc rules and the hole fineness of enhancing are possibly realized.
The theme of the problem to be solved in the present invention through the invention solves.What is be directed to is：
It is used as the mixture of additive in the preparation of flexible polyurethane foams, the mixture includes having for (a) general formula I The compound of the functional modified polysiloxanes of machine and (b) at least one formula (III), and (c) organic solvent, preferably a contracting dipropyl Glycol and/or propylene glycol：
Wherein group
R1It is each independently alkyl group or aryl group,
R2Each independently with R1And/or R3Identical, condition is at least one R2Group has R3Meaning,
R3It is each independently the polyether group of Formula II：
-(Y)e[O(C2H4-dR'dO)m(CxH2xO)pZ]w (II)
Condition is
E=0-1,
W=1-3,
D=1-3,
M >=0,
X=2-4 particularly can be by being used alone or in combination C2H4O-、C3H6O- and C4H8O- units obtain, and
P >=0, and
Y be have it is branched or without branched alkyl,
R' is selected from C1-C18Monovalent hydrocarbon, be optionally C1-C18Monovalent aromatic alkyl,
Z be hydrogen group or the monovalent organic group comprising carboxyl groups,
The sum of m+p is equal to 1-200, wherein be the arrangement that lower target structure block can have any desired with m and p,
When b is>When 6 to 8 numerical value, a is the numerical value of 1-100,
When b is>When 3 to 6 numerical value, a is the numerical value of 1-200,
When b is the numerical value of 0-3, a is the numerical value of 1-300,
B=0-8, such as 1-8,
Wherein
R is m valence organic groups, preferably alkyl, and as m=1-7, R is preferably the alkyl with 1-30 carbon atom, more excellent Choosing is the alkyl for having 8-20 carbon atom, and as m=2 or 3, and R is preferably the alkyl with 2-6 carbon atom, more excellent Choosing is saturated hydrocarbyl,
R' is H or organic group, preferably with or without oxygen or nitrogen-atoms, particularly with or without hydroxyl or The C of amino1-C12Alkyl, aryl or alkylaryl group or R' are-X-Z groups, and are identical or not when every place occurs With,
M=1-5, it is preferable that m=1,2 or 3,
Z is OH or NHR ", and is identical or different when every place occurs, and wherein R "=H or alkyl especially have The alkyl of 1-30 carbon atom, R " are preferably H,
X is the bivalent organic group at least two carbon atoms, preferably alkyl, preferably wherein w=2-5-(CH2)w- Group, more preferable ethylidene,
Wherein polysiloxane compound and the mass ratio of the compound of formula (III) is more than 1:10, preferably not less than 1:4, more Preferably not less than 1:2, and more preferably 1:1.5 to 1:0.125.
Subscript e and b, which are respectively equal to 1, to be characterized in that for the polysiloxanes of the highly useful general formula I of the purpose of the present invention With equal to 0.Therefore, SiC structures are herein related to.Alternatively, similarly it is preferable to use the polysiloxanes of general formula I, It is characterized in that subscript e=0.Therefore, SiOC structures are herein related to.
The suitable amide of formula (III) preferably can react acquisition by aliphatic acid or aliphatic ester and alkanolamine.
The mixture of the present invention provides the particularly effective enhancing of hole fineness in the preparation of flexible polyurethane foams.More Particularly, it is compared with corresponding polyether silicone (individually or with conventional component of mixture combining), they provide hole essence The notable more effective enhancing of fineness.These benefits also by use certain foaming agents (especially liquid CO2Or dichloromethane) To realize, the extra high requirement of pore structure proposition with fine hole is obtained generally for polyether silicone.
As a mixture simultaneously applied component (a) to (c) for the purpose of the present invention is it is particularly advantageous that because with Some individually add (such as amide compound (b) is added by polyol component) and compare, for the enhancing of hole fineness, It generates significantly higher effect.Therefore, including the mixture of component (a) to (c) is applied to the purpose of the present invention.
Including the mixture of the present invention of component (a) to (c) preferably comprises no less than >=40 weight %, preferably >=50 weight Measure the said components (a) and (b) of %.The mixture of the present invention also may include other components, preferably water and other surface-active Agent.They also can be free of water and other surfactant.
The preferred mixture of the present invention is also optionally including water and component (a) to (c).
In addition to component (a) and (b), mixture specifically preferred according to the invention further comprises as a contracting dipropyl two of component (c) Alcohol and/or propylene glycol, and the water being optionally present and at least one other surfactant being optionally present.However, can be special Preferably there is no dipropylene glycol and/or propylene glycol as component (c), but water and other surfactant is not present.
In addition to component (a) and (b), the other preferred mixtures of the present invention further comprise as a contracting dipropyl two of component (c) Alcohol and/or propylene glycol and water and at least one other surfactant.
Similarly, the mixture, which can be gone up, utilizes non-reacted polyethers (preferably having relatively high molecular weight), benzene diformazan The antifreezing agent of acid esters, animal and plant oil and/or liquid form, as other component of mixture.
The mixture of the present invention is particularly suitable for preparing heat cure flexible polyurethane foams.The preferred mixture of the present invention It is particularly useful as heat cure flexible polyurethane foams stabiliser solution, and includes：
>=30 weight % to≤68 weight %, preferably >=35 weight % are to≤65 weight %, and more preferably >=40 weight The polyether silicone for meeting formula (I) for measuring % to≤62 weight %, wherein the polyether silicone of 40 weight % to 60 weight % contain Amount be it is particularly preferred,
>=1 weight % to≤70 weight %, preferably >=2 weight % are to≤50 weight %, and more preferably >=5 weight % To the compound for including amide groups for meeting formula (III) of≤40 weight %, the compound of wherein formula (IV) be it is particularly preferred,
>=1 weight % to≤70 weight %, preferably >=10 weight % are to≤60 weight %, and more preferably >=20 weight The organic solvent of % to≤55 weight %, preferably propylene glycol and/or dipropylene glycol, especially dipropylene glycol are measured,
Valuably >=1 weight % to≤70 weight %, preferably >=10 weight % extremely≤60 weight %, and more preferably >= The water of 20 weight % to≤55 weight %,
Valuably >=1 weight % to≤10 weight %, preferably >=2 weight % are to≤8 weight %, and more preferably >=4 weight Measure the other organic surface active agent of % to≤6 weight %, such as optimizing alkyl benzene sulfonate, particularly, using including water Solvent combination, or meet the ratio of the compound comprising amide groups of formula (III)>60 weight %.The mixture of the present invention It also can be free of water and without other organic surface active agent.
Optionally, mixture of the invention (mixture especially heat cure flexible polyurethane foams stabiliser solution) It also may include other additive as annexing ingredient.In each case, the ratio of component used in selecting so that each group The toatl proportion divided is no more than 100 weight %.
Currently preferred mixture includes：
>=35 weight % extremely≤65 weight %, the preferably polyether silicone for meeting formula (I) of 40-50 weight %,
The compound for including amide groups for meeting formula (III) of >=1 weight % to≤50 weight %, wherein formula (IV) Compound be it is particularly preferred,
>=1 weight % to≤10 weight %, preferably >=2 weight % extremely≤8 weight %, and the alkane of more preferable 5 weight % Base benzene sulfonate,
>=30 weight % to≤50 weight %, preferably >=35 weight % extremely≤45 weight %, and more preferable 40 weight % Water, and
The organic solvent of >=1 weight % to≤20 weight %, preferably >=3 weight % to≤15 weight %, preferably propylene glycol And/or dipropylene glycol, especially dipropylene glycol.
Other mixture specifically preferred according to the invention includes：
>=35 weight % extremely≤65 weight %, the preferably polyether silicone for meeting formula (I) of 40-50 weight %,
The compound for including amide groups for meeting formula (III) of >=1 weight % to≤50 weight %, wherein formula (IV) Compound be it is particularly preferred,
>=5 weight % to≤70 weight %, preferably >=10 weight % are to≤60 weight %, and more preferably 20-40 weights Measure the organic solvent of %, preferably propylene glycol and/or dipropylene glycol, especially dipropylene glycol.The preferred mixture It is preferred that not aqueous and other organic surface active agent.
Now, the other useful organic surface active agent being optionally present can be more specifically described.They can be more specific Ground is selected from anionic surfactant, cationic surface active agent, nonionic surface active agent and/or amphoteric surface and lives Property agent, wherein the organic surface active agent is preferably anionic surfactant.The present invention mixture preferably include One or more surfactants, selected from anionic, nonionic, cationic, both sexes (both sexes, amphoteric ion) table Face activating agent and its mixture.
Anionic, cationic, nonionic and both sexes (amphoteric ion) type and classification of these surfactants Exemplary lists provided in the 3rd, 929, No. 678 United States Patent (USP) and the 4th, 259, No. 217 United States Patent (USP), the U.S. is special It is sharp to be respectively all added herein by quoting.
Anionic surfactant：The composition of the present invention preferably comprises anionic surfactant.These can be wrapped Salt is included, sodium, potassium, ammonium and the substitution of such as anion sulfate, sulfonate, carboxylate and sarcosine salt form surfactant are included Ammonium salt (such as mono-, two- and triethanolamine salt).Anion sulfate and sulfonate surfactant are preferred.
Including sulfonate surfactant or sulfated surfactant (it is preferably linear as described herein or Branched alkylbenzene sulfonate and alkyl ethoxy sulfate), it may even live with cationic as described herein The surfactant system of the combination of property agent is particularly preferred.
Other anionic surfactant include isethionate, such as acyl isethinate, N- acyl group ox sulphurs Hydrochlorate, methyl tauride (methyl tauride) fatty acid amide, alkyl succinate and sulfosuccinate, Monoester (the especially saturated or unsaturated C of sulfosuccinate12-C18Monoester), two fat of sulfosuccinate (especially It is saturated or unsaturated C6-C14Diester), N- acyl sarcosinates.Similarly, resin acid and hydrogenated resin acid (such as rosin, Hydrogenated rosin) and in the form of animal ester oil existing for resin acid and hydrogenated resin acid or derivative thus be also suitable.
Anion sulfate acid salt form surfactant：These include linear or branched, primary and secondary alkyl sulfate, alkyl Ethoxy sulfate, fatty oleyl glycerine sulfate, alkylphenol ethylene oxide ether sulfates, C5-C17Acyl group-N- (C1-C4- Alkyl -) and N- (C1-C2Hydroxy alkyl) gucosamine sulfate and alkyl polysaccharide sulfate, such as alkyl glucosan The sulfate (compound of nonionic non-sulfuric acid salinization described herein) of glycosides.
Alkyl sulfate surfactant is preferably selected from linear or branched primary C10-C18Alkyl sulfate, preferably branch C11-C15Alkyl sulfate and straight chain C12-C14Alkyl sulfate.
Alkyl ethoxy sulfate surfactant preferably is selected from per molecule 0.5-20mol ethylene oxide ethoxylations C10-C18Alkyl sulfate.Alkyl ethoxy sulfate surfactant more preferable per molecule 0.5-7mol, preferably 1-5mol The C of ethylene oxide ethoxylation11-C18, most preferably C11-C15Alkyl sulfate.
Anion sulfoacid salt form surfactant：Anion sulfoacid salt form surfactant includes linear C5-C20Alkylbenzene Salt, alkyl ester sulfonate, the primary or secondary C of sulfonate6-C22Alkylsulfonate, C6-C24Alkene sulfonate, arylsulphonate are (especially Unsubstituted and alkyl-substituted benzene-and naphthalene sulfonate), sulfonate polycarboxylic acids, alkyl glycerol sulfonate, fatty acyl group Monoester (the especially saturated or unsaturated C of glycerol sulfonate, sulfosuccinate12-C18Monoester), sulfosuccinate Two fat (especially saturated or unsaturated C6-C14Diester), fatty oleyl glycerine sulphonic acid ester and their any desired Mixture.
Anionic carboxylic acid salt form surfactant：Suitable anionic carboxylic acid salt form surfactant includes alkyl ethoxy Carboxylate, alkyl polyethoxy polycarboxylate surfactant and soap (alkyl carboxyl), it is especially certain as described herein Secondary soap (seccondary soaps).
Suitable alkyl ethoxy carboxylate includes formulaAlkylethoxy Yl carboxylic acid salt, wherein R are C6-C18The distribution of alkyl, x 0-10, and ethoxylate so that wherein x is the amount of 0 material Less than 20 weight %, and M is cation.Suitable alkyl polyethoxy polycarboxylate surfactant includes formula RO (CHR1- CHR2-O)-R3Those of, wherein R is C6-C18Alkyl, x are 1-25, R1And R2It each is selected from hydrogen, methyl acid groups, pendent succinic acid Group, hydroxysuccinimidyl acid groups and their mixture, and R3It is substituted or unsubstituted selected from hydrogen, with 1-8 carbon atom Hydrocarbon and their mixture.
Suitable soap surfactant includes secondary soap surfactant, and it includes the carboxyl units for being connected to secondary carbon.It is preferred that Secondary soap surfactant be selected from 2- methyl-1s-undecanoic acid, 2- ethyl -1- capric acid, 2- propyl -1- n-nonanoic acids, 2- butyl -1- it is pungent The water-soluble substances of the water soluble salt of acid and 2- amyl -1- enanthic acid.
Sarcosinate surfactant：Other suitable anionic surfactant is formula R-CON (R1)CH2COOM's Sarcosinate, wherein R are linear or branched C5-C17 alkyl or alkenyls, R1For C1-C4Alkyl, and M be alkali metal from Son.Preferred example is the myristyl-and oleoyl methyl sarcosinates of sodium-salt form.
The anionic surfactant can be more preferably from alkyl sulfate, arylsulphonate, aliphatic alcohol sulfate, secondary Alkyl sulfate, paraffin sulfonate, alkyl ether sulfate, alkyl polyglycol ether sulfate, fatty alcohol ether sulphate, alkylbenzene Sulfonate, alkylphenol ether sulfate, alkylphosphonic, phosphoric acid is mono-, two-, three esters, alkyl ether phosphate, ethoxylated fat Alcohol phosphate, phosphonate ester, sulfosuccinic acid diesters, sulfosuccinic acid monoesters, ethoxylation sulfosuccinic acid monoesters, sulfosuccinic Amide, alpha-alkene sulfonate, alkyl carboxylate, alkyl ether carboxy acid salt, alkyl polyethylene carboxylic acid salt, aliphatic acid isethionic acid Salt, fatty acid methyl taurate, fatty acid sarcosine metal salt, arylsulphonate, naphthalene sulfonate, alkyl glycerol base ether Sulfonate, polyacrylate and/or alpha-sulfo fatty acid ester.
Cationic surface active agent：The cationic surface active agent for being suitable as surface active agent composition includes quaternary ammonium Surfactant.The quaternary surfactant is preferably mono- C6-C16, preferably-C6-C10N- alkyl-or-alkenyl ammonium surface are lived Property agent, wherein remaining nitrogen position is replaced by methyl, hydroxyethyl or hydroxypropyl.Similarly, mono-alkoxylated and double alcoxyls Base amine surfactant is also preferred.
Cationic ester surfactant is cationic surface active agent workable in addition suitable one kind.
Cationic ester surfactant is preferably the dispersible compound of water with surfactant properties, and it includes at least One ester (i.e. COO-) key and at least one positively charged group.
Suitable cationic ester surfactant (including choline ester surfactants) is in such as United States Patent (USP) 4228042, it discloses in 4239660 and 4260529.
In a preferred aspect, the ester bond in the surfactant molecule and positively charged group by spacer group every It opens, the spacer group is made of the chain (chain length of i.e. three atoms) comprising at least three atoms, preferably three to eight atoms, More preferable three to five atoms, most preferably three atoms.Formed spacer group chain atom be selected from carbon, nitrogen and oxygen atom and they Arbitrary mixing, condition is that the carbon atom bonding of arbitrary nitrogen in the chain or oxygen atom only and in the chain connects.Therefore, packet is excluded Spacer group containing such as-O-O- (i.e. peroxide) ,-N-N- and-N-O- keys, but include comprising such as-CH2-O-CH2- With-CH2-NH-CH2The spacer group of key.The spacer group chain includes only carbon atom in a preferred aspect, and most preferably Ground, the chain are hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactant：Workable cationic mono-alkoxylated amine surfactant is preferred With general formula V：
Wherein R1For with 6-18 carbon atom, preferably 6-16 carbon atom, the alkyl of most preferably 6-14 carbon atom or Alkenyl units；R2And R3It is each independently the alkyl with one to three carbon atom, preferably methyl, most preferably R2And R3It is Methyl；R4Selected from hydrogen (preferably), methyl and ethyl；X–It is anion, such as chlorion, bromide ion, methylsulfate or sulfate radical Deng to provide electroneutral；Z is alkoxy, especially ethyoxyl, propoxyl group or butoxy；And n be 0-30, preferably 2-15, most It is preferred that 2-8.
Preferably, the Z in Formula VnR4The n=1 of group, and ZnR4Group is the hydroxyl alkane with not more than 6 carbon atoms Base, simultaneously-OH- separated from quaternary nitrogen atoms by not more than 3 carbon atoms.Particularly preferred ZnR4Group is-CH2CH2OH、- CH2CH2CH2OH、-CH2CH(CH3) OH and-CH (CH3)CH2OH, wherein CH2CH2OH is particularly preferred.Preferred R1Group is Linear alkyl.The linear R of 8-14 carbon atom1Group is preferred.
Also workable cationic mono-alkoxylated amine surfactant preferably has Formula IV：
Wherein R1 is C10-C18Alkyl and their mixing, especially C10-C14Alkyl, preferably C10And C12Alkyl, and X It is any suitable anion to provide charge balance, preferably chlorion or bromide ion.Ethyoxyl-(the CH of Formula II2CH2O-) single First (EO) also can be replaced butoxy, isopropoxy [CH (CH3)CH2O] and [CH2CH(CH3) O] unit (i-Pr) or positive third oxygen The mixture of base unit (Pr) or EO and/or Pr and/or i-Pr units.
The bis-alkoxylated amine surfactant of cation：The bis-alkoxylated amine surfactant of cation is preferably logical Formula VII：
Wherein R1For with 8-18 carbon atom, preferably 10-16 carbon atom, the alkyl of most preferably 10-14 carbon atom Or alkenyl units；R2For the alkyl with one to three carbon atom, preferably methyl；R3And R4It can be independently varied, and each free From hydrogen (preferably), methyl and ethyl, X-is anion, chlorion, bromide ion, methylsulfate or sulfate radical etc., to fill Divide and electroneutral is provided.Z can be independently varied when every place occurs, and be respectively selected from C1-C4Alkoxy, especially ethyoxyl (i.e.-CH2CH2O-), propoxyl group, butoxy and their mixing；N is 1-30, preferably 1-4, and most preferably 1, and at every place It is identical or different when appearance.
The preferred bis-alkoxylated amine surfactant of cation has Formula VIII：
Wherein R1It is C when every place occurs10-C18Alkyl and their mixing, preferably C10、C12、C14Alkyl and theirs is mixed It closes.X is any suitable anion to provide charge balance, preferably chlorion.About above-mentioned general formula cation bis-alkoxy Change amine structure, in preferred compound, R1Derived from (cocoyl) C12-C14 alkyl fatty acids.
The other suitable bis-alkoxylated amine surfactant of cation includes the compound of Formula IX：
Wherein R1For C10-C18Alkyl, preferably C10-C14Alkyl, independently p is 1-3, and q is 1-3, R2For C1-C3Alkane Base, preferably methyl, and X is anion, preferably chloride or bromide.
Other compounds of the above-mentioned type include wherein ethyoxyl-(CH2CH2O-) unit (EO) is by butoxy-(Bu), different Propoxyl group-[CH (CH3)CH2O] and [CH2CH(CH3) O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr And/or those of the mixing replacement of i-Pr units.
The cationic surfactant can be more preferably from ester quaternary ammonium compound, preferably two (tallow fatty acid amide groups Ethyl) methyl polyethoxy ammonium methyl sulphate, diamidoamine quaternary ammonium compound, alkoxy alkyl quaternary ammonium compound, preferably Five ethoxyl methyl ammonium methyl sulphate of cocoyl and/or trialkyl quat, preferably cetyl trimethyl ammonium chloride.
Nonionic surface active agent：Substantially any nonionic surface active agent is all suitable herein.Second Oxygroup and propoxylated surfactants are preferred.
Preferred alkoxy-based surface-active agent can be selected from following type：The nonionic condensates of alkyl phenol, nonionic second Oxygroup alcohol, non-ionic ethoxylated/propoxylated fatty alcohol, non-ionic ethoxylated/propoxylation condensation with propylene glycol Object and non-ionic ethoxylated condensation product with propylene oxide/ethylenediamine adduct.
Alkoxylated alcohol surfactant：Aliphatic alcohol and 1-25mol oxyalkylenes (especially ethylene oxide, ring Ethylene Oxide, epoxy butane, Epoxydodecane or styrene oxide) condensation product also similarly purpose for use in the present invention. The alkyl chain of aliphatic alcohol can be straight chain or branched, primary or secondary, and generally comprise 6-22 carbon atom.Particularly preferably Be every mole with the alkyl containing 8-20 carbon atom alcohol and 2-10mol ethylene oxide condensation product.
Nonionic polyhydroxy fatty acid amide surfactant：It is suitble to the polyhydrony fatty acid acyl being used in the present invention Amine has R2CONR1The structural formula of Z, wherein：R1For H, C1-C4Alkyl, 2- hydroxyethyls, 2- hydroxypropyls, ethyoxyl, propoxyl group Or mixtures thereof, preferably C1-C4Alkyl, more preferable C1Or C2Alkyl, most preferably C1Alkyl (i.e. methyl)；And R2For C5-C31Hydrocarbon Base, preferably straight chain C5-C19Alkyl or alkenyl, more preferable straight chain C9-C17Alkyl or alkenyl, most preferably straight chain C11-C17Alkyl or alkene Or mixtures thereof base；And Z is the polyhydroxy alkyl for having linear hydrocarbyl chain, and wherein at least 3 hydroxyls are connected directly to described Chain or its alkoxy derivative (preferably ethoxylation or propoxylation).Z derives from reduction preferably in reductive amination process Sugar；More preferable Z is glycidyl (glycityl).
Nonionic fatty acid amide surfactant：Suitable fatty acid amide surfactant includes that of following formula A bit：R6CON(R7)2, wherein R6For with 7-21, the alkyl of preferably 9-17 carbon atom, and each R7Selected from hydrogen, C1-C4 Alkyl, C1-C4Hydroxy alkyl and-(C2H4O)xH, wherein x are 1-3.
Nonionic alkyl polysaccharide surfactant：Suitable alkyl polysaccharide for this respect in United States Patent (USP) 4,565, It is disclosed in 647, there is the hydrophobic grouping comprising 6-30 carbon atom and polysaccharide (such as polysaccharide glycosides), a comprising 1.3-10 The hydrophilic radical of sugar unit.
Preferred alkyl polyglycoside has following formula：R2O(CnH2nO)t(glycosyl)x, wherein R2Selected from alkyl, alkyl phenyl, hydroxyl Base alkyl, hydroxy-alkylphenyl and their mixture, wherein the alkyl includes 10-18 carbon atom；N is 2 or 3；T is 0- 10, and x is 1.3-8.The glycosyl is preferably derived from glucose.
The nonionic surface active agent can be particularly preferably from alcohol ethoxylate, fatty alcohol polyglycol ether, fat Sour ethoxylate, fatty acid polyethylene glycol ester, glyceride mono-alkoxylate, alkanolamide, fatty acid alkanol amides, ethoxy Base alkanolamide, fatty acid alkanol amides base-ethoxylate, imidazoline, ethylene oxide-propylene oxide block copolymer, Alkyl phenol ethoxylate, alkyl glucoside, ethoxylated sorbitan sugar alcohol ester and/or amine alkoxide.
Amphoteric surfactant：It includes oxide surfactant to be suitble to amphoteric surfactant used herein With alkyl both sexes carboxylic acid (alkylamphocarboxylic acid).
Suitable amine oxide includes having formula R3(OR4)xNO(R5)2Those of compound, wherein R3Selected from including 8-26 Alkyl, hydroxy alkyl, acylamidopropoyl and the alkyl phenyl and their mixture of a carbon atom；R4It is comprising 2-3 Or mixtures thereof alkylidene or hydroxy alkylidene of carbon atom；X is 0-5, preferably 0-3；And each R5It is former comprising 1-3 carbon The alkyl or hydroxy alkyl of son or the polyethylene oxide for including 1-3 ethylene oxide group.Preferably C10-C18Alkyl two Methyl amine oxide and C10-C18Acylamidoalkyl dimethylamine oxide.
Other suitable amphoteric surfactant can be broadly described as secondary or tertiary amine derivative, heterocycle secondary and tertiary aminess The derivative of derivative or quaternary ammonium salt, quaternary alkylphosphonium salt or tertiary sulfonium compound.Glycine betaine and sulfobetaines (sultaine) table Face activating agent is preferred amphoteric surfactant.
Suitable glycine betaine is with formula R (R ')2N+R2Those of COO-compounds, wherein R are C6-C18Alkyl, each R1 Usually C1-C3Alkyl and R2For C1-C5Alkyl.Preferred glycine betaine is C12-C18Dimethylamoniohexanoate and C10-C18Acyl Base acylamidopropane (or ethane) dimethyl (or diethyl) glycine betaine.Similarly, complicated beet alkali surface activator is suitble to For purposes of the present invention.
The amphoteric surfactant can be more preferably selected from both sexes acetate, both sexes diacetin, glycinate, both sexes Propionate, sulfobetaines, amine oxide and/or glycine betaine.
The mixture of the present invention can be used for preparing flexible polyurethane foams, specifically refer to (routine) flexible polyether foam, And flexible polyester foam, viscoelastic foam and high resiliency (cold curing) foam, but especially (routine) flexible polyether foam, Because they provide the particularly effective enhancing of hole fineness.These benefits are especially by using certain foaming agents (especially liquid CO2 Or dichloromethane) realize, obtaining the pore structure with fine hole generally for polyether silicone proposes extra high want It asks.
The logical formula (I) polyether silicone of the present invention is especially polysiloxanes-polyoxy containing modified polyalkylene oxide units Change alkene copolymer.
In principle, it is generally used for preparing or mixtures thereof arbitrary structures of flexible polyurethane foams and be included entirely within.
In particular benefit from the polyether silicone for meeting formula (I), (it preferably has certain for the cooperation of component of mixture (a)-(c) Horizontal increases to nucleation) use；That is, if be used alone, satisfactory pore structure is preferably provided.Ability Field technique personnel can come to confirm this in several hand tests.
Number for siloxane unit and it is connected to the possible mode of polyoxyalkylene, polysiloxanes can essentially appoint Desired mode of anticipating changes.
In polysiloxane-polyxyalkyl-blockpolymer described in multiple publications.
Such as DE-A-1570647 records the polyether silicone of so-called SiOC- connections.The preparation of such polyether silicone Especially described in DE-A-10 12 602, DE-A-10 40 251, DE-A-11 20 147 and US-A-3 115 512.
The preparation of the polysiloxane-polyxyalkyl-blockpolymer of so-called SiC- connections is in such as USA-A-2 846 Described in 458, and file DE-A-12 20 615 in a review and DE-A-11 53 166 is disclosed for objection.
The polyether silicone that general formula I can particularly preferably be used, on condition that R at least one2With R3It is identical, and m>P is right It should be in particularly preferred embodiment.
It is below and particularly preferred：The polysiloxanes of general formula I based on 100 parts by weight, the amide of general formula III is with 0.1- The amount of 200 parts by weight, especially 10-150 parts by weight uses.
Can suitable formula for example be obtained with reacting for carboxylic acid (being preferred from aliphatic acid or aliphatic ester) by alkanolamine (III) amide.
What the preparation of amide of principle above formula (III) itself was known to those skilled in the art, and can be according to this Method known to field is implemented.Amide can (be for example DE 1802500 at present by methods known in the art；DE 1802503, DE 1745443, DE 1745459 and US 3578612) it obtains.For example, corresponding carboxylic acid can be used as raw material herein, And it is formed by removing water amide occurs.Carboxylate (such as methyl ester) can be similarly used, remove in the described situation Methanol.It will also be preferred glyceride.The carboxylic acid that can be used for preparing the amide of formula (III) includes such as monocarboxylic acid, dicarboxylic acids, three Carboxylic acid, tetrabasic carboxylic acid, such as based on aliphatic or aromatic hydrocarbon or their derivative.Preferred acid is at most 40 carbon atom Straight chain saturation or unsaturated fatty acid, such as butyric acid (butyric acid, butanoic acid), caproic acid (caproic Acid, hexanoic acid), sad (caprylic acid, octanoic acid), capric acid (capric acid, Decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (ten Eight alkanoic acids), arachidic acid (arachic acid), behenic acid (behenic acid), lignoceric acid (lignoceric acid), palmitoleic acid ((Z)- Palmitoleic acid), oleic acid ((Z)-palmitoleic acid), elaidic acid ((Z) -9- octadecenoic acids), cis- vaccenic acid ((Z) - 11- octadecadienoic acids), linoleic acid ((9Z, 12Z) -9,12 octadecadienoic acid), alpha-linolenic acid ((9Z, 12Z, 15Z) -9, 12,15- octatecatrienoic acids), gamma-Linolenic acid ((6Z, 9Z, 12Z)-GAMMA-Linolenic acid), bishomo-γ-linolenic acid ((8Z, 11Z, 14Z) -8,11,14- eicosatrienoic acids), arachidonic acid (5Z, 8Z, 11Z, 14Z) -5,8,11,14- 20 Carbon tetraenoic acid), sinapic acid ((Z) -13- docosenoic acids), nervonic acid ((Z) -15- tetracosenoic acids), ricinoleic acid, hydroxyl Base stearic acid and undecenoic acid (undecenylic acid) and their mixture, such as vegetable seed oleic acid, soybean fat Acid, fatty acid sunflower, Fatty Acid In Peanut and floating oil fatty acid.The shape in the oligomerization of unsaturated fatty acid can also be used At dimerization and oligomeric fatty acids.The amine of amide suitable for preparing formula (III) has at least one primary or secondary amine functional group with acyl Amination, and optionally including one or more hydroxyls.Suitable amine includes for example：Ethylenediamine, diethylenetriamines (DETA), trien (TETA), tetren (TEPA), dipropylenetriamine, tri propylidene tetramine, four Asias third Five amine of base, five inferior propyl hexamine, six propylidene heptyl amices and more advanced homologue, 1,2- based on ethylenediamine or trimethylene diamine Trimethylene diamine, 4,4 '-diamino-dicyclohexyl methanes, 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane, 4,4- are sub- Methyl diphenylene diamines, trimethyl methylene diamine, neopentane diamines, eight methylene diamines, gathers at isophorone diamine Ether amines (such as polyetheramine D 2000 (BASF), polyetheramine D 230 (BASF), polyetheramine T 403 (BASF), polyetheramine T 5000 Corresponding Jeffamin types, piperazine, aminoethylpiperazine, bis- (amino-ethyl) piperazines (BASF) or from Huntsman, 1,3- diaminopropanes, 3- (Cyclohexylamino) propylamine, 3- (methylamino) propylamine, N, bis- (3- aminopropyls) methylamines of N-, (3- (2- aminoethylaminos) propyl amine), dipropylenetriamine, N, bis- (3- aminopropyls) ethylene diamines of N '-.
The suitable hydroxylamine at least one OH functional groups includes for example：Ethanol amine, Propanolamine, alkylethanolamine, Aryl ethanolamines, alkyl propanols amine, such as：Diethanol amine, monoethanolamine, diisopropanolamine (DIPA), isopropanolamine, methyl-iso-propanol Amine, diglycolamine (2- (2- amino ethoxies) ethyl alcohol), dimethylethanolamine, N- (2- hydroxyethyls) aniline, 1- (2- hydroxyl second Base) piperazine, 2- (2- amino ethoxies) ethyl alcohol, 3- amino -1- propyl alcohol, 5- amino -1- amylalcohols, butylethanolamine, ethyl hexanol Amine, N- methylethanolamines, aminopropyl monomethyl-ethanolamine, 2- amino-2-methyls propyl alcohol, trishydroxymethylaminomethane (THMAM Or TRIS), N- (2- amino-ethyls) ethanol amine (AEEA).The ethoxy of corresponding alcoxylates, especially amine can also be used Glycolylate and/or propoxylate, such as the alkylamine with ethoxy or hydroxypropyl unit such as N- ethoxy hexamethylenes Base diamines, N- ethoxys isophorone diamine, N- hydroxyethyl piperazines, bis- (ethoxy) toluenediamines.
The amide of the formula (III) of the present invention can also be the amide with OH or NH functional groups being obtained commercially, such as obtain From Evonik Industries：DC 212S、DO 280 SE、DU 185 SE、KSM、C 212、IPP 240、SPA、IM AO、IM AN orIM R 40, and 154、1301、40-CO、1281、COMF、M-10, And ethoxylation diglycollic amide, such as derived from Stepan'sC-4l、C-5、 1301, or derived from Sasol'sMAL andDC。
Entire flexible polyurethane foams formulation is particularly preferably based on for the purpose of the present invention, with 0.01-13 weights % is measured, for the total amount of preferably 0.1-13 weight % using the mixture of the present invention, mixture of the invention includes the poly- of (a) general formula I Siloxanes and (b) meet the compound comprising amide groups and (c) at least one organic solvent, especially dipropyl of general formula III Glycol.
The mixture of the present invention includes that the polysiloxanes of (a) general formula I meets the change for including amide groups of general formula III with (b) Object and (c) at least one organic solvent, especially dipropylene glycol are closed, it is of the invention based on the polyol component of 100 parts by weight The ratio of the mixture is preferably more than 0.05 to 20 mass parts, more preferable 0.2-10 mass parts, and more preferably 0.5-5 matter Measure part.
In the mixture by formula in the preparation process (being typically hydrosilylation technique) of used silicon compound (III) amide may be beneficial as solvent.This avoids additional separating steps, and/or to the present invention composition It is middle to introduce undesirable solvent.
The amide of formula (III) is preferably at least a kind of compound of formula (IIIa)
Wherein m, R, R ' and X respectively freely defined in formula (III).
By the amide of formula (III), mixture of the invention preferably comprises at least a kind of compound of formula (IV)
Wherein R is as above-mentioned defined in formula (III), and in the described situation, the amide of the formula (IV) is preferably by making Aliphatic acid reacts to obtain with diethanol amine.
The present invention also provides the sides for using the organic functional modified polysiloxanes of general formula I to prepare flexible polyurethane foams Method,
Wherein group
R1It is each independently alkyl group or aryl group,
R2Each independently with R1And/or R3Identical, condition is at least one R2Group has R3Meaning,
R3It is each independently the polyether group of Formula II：
-(Y)e[O(C2H4-dR'dO)m(CxH2xO)pZ]w (II)
Condition is
E=0-1,
W=1-3,
D=1-3,
M >=0,
X=2-4 particularly can be by being used alone or in combination C2H4O-、C3H6O- and C4H8O- units obtain, and
P >=0, and
Y be have it is branched or without branched alkyl,
R' is selected from C1-C18Monovalent hydrocarbon, be optionally C1-C18Monovalent aromatic alkyl,
Z be hydrogen group or the monovalent organic group comprising carboxyl groups,
The sum of m+p is equal to 1-200, wherein be the arrangement that lower target structure block can have any desired with m and p,
When b is>When 6 to 8 numerical value, a is the numerical value of 1-100,
When b is>When 3 to 6 numerical value, a is the numerical value of 1-200,
When b is the numerical value of 0-3, a is the numerical value of 1-300,
B=0-8, such as 1-8,
Condition is the subscript e=0 as b ≠ 0,
The polysiloxanes of its formula of I is used in mixed way with the compound of organic solvent and at least one formula III,
Wherein
R is m valence organic groups, preferably alkyl, and as m=1-7, R is preferably the alkyl with 1-30 carbon atom, more excellent Choosing is the alkyl for having 8-20 carbon atom, and as m=2 or 3, and R is preferably the alkyl with 2-6 carbon atom, more excellent Choosing is saturated hydrocarbyl,
R' is H or organic group, preferably with or without oxygen or nitrogen-atoms, particularly with or without hydroxyl or The C of amino1-C12Alkyl, aryl or alkylaryl group or R' are-X-Z groups, and R' be when every place occurs it is identical or Different,
M=1-5, it is preferable that m=1,2 or 3,
Z is OH or NHR ", and is identical or different when every place occurs, and wherein R "=H or alkyl especially have The alkyl of 1-30 carbon atom, R " are preferably H,
X is the bivalent organic group at least two carbon atoms, preferably alkyl, preferably wherein w=2-5-(CH2)w- Group, more preferable ethylidene,
The wherein described polysiloxane compound and the mass ratio of the compound of formula (III) are more than 1:10, preferably not less than 1: 4, more preferably no less than 1:2, and more preferably 1:1.5 to 1:0.125.
The method of flexible polyurethane foams is prepared using the mixture of the present invention described in more detail above.With mixture Form simultaneously applied component (a) to (c) for the purpose of the present invention is it is particularly advantageous that because individually adding with some (such as amide compound (b) is added by polyol component) is compared, and for the enhancing of hole fineness, generates significantly higher Effect.Therefore, including the mixture of component (a) to (c) is applied to the purpose of the present invention.
Flexible polyurethane foams prepare can also be usual mode and implement as recorded in the prior art.Itself is right It is well known for those skilled in the art, and particularly including at least one polyol component and at least one isocyanates group Divide reaction in the presence of one or more catalysts, the catalyst is for being catalyzed isocyanate-polyol and/or isocyanide The trimerization of the reaction of acid esters-water and/or isocyanates, meanwhile, be also preferably added water, physical blowing agent, fire retardant, and/or Other additives, and at the same time method as shown above is gathered by using the organic functional modified of general formula I in the present invention Siloxanes carries out, and the polysiloxanes of formula of I is with the shape of the mixture of the compound with organic solvent and at least one formula III Formula uses.
In the method for the invention, it can particularly preferably use liquid CO 2 or dichloromethane as foaming agent.Therefore The carbon dioxide or dichloromethane wherein to pressurize is used as the method for the present invention of foaming agent corresponding to the particularly preferred of the present invention Embodiment.
For the method for the present invention, the further preferably polysiloxanes of the general formula I based on 100 parts by weight, with 0.1-200 weight Part, especially the amount of 10-150 parts by weight utilizes the amide of general formula III.
It is also particularly that entire flexible polyurethane foams formulation is based on, with 0.01-13 weight %, preferably 0.1-13 weight The amount for measuring % uses the mixture of polysiloxanes (a) and amide compound (b) and at least one organic solvent.
It can be in amide of the upper and lower polyol component used herein preferably with formula (III) in mixture of the method for the present invention Compound and silicone compounds (I) are different.
Include that there are two or more isocyanic acids for the suitable polyalcohol of use beneficial in the context of the present invention The arbitrary organic substance and its product of ester reactive group.Preferred polyalcohol includes being commonly used for preparing polyurethane foam The arbitrary polyester polyol and polyether polyol of (particularly, flexibel polyurethane or polyisocyanurate foam).By multifunctional Change alcohol or amine and obtains polyether polyol with reacting for oxyalkylene.It (is typically phthalic acid that polyester polyol, which is based on polybasic carboxylic acid, Or terephthalic acid (TPA)) ester with polyalcohol (be typically glycol).Property required by foam means to remember in for example following documents The purposes of the suitable polyalcohol carried：US 2007/0072951 A1、WO 2007/111828 A2、US 2007/0238800、 96 12759 A2 of US 6359022 B1 or WO.The polyalcohol based on vegetable oil is preferably used, is similarly recorded in various In patent document, such as WO 2006/094227, WO 2004/096882, US 2002/0103091,2006/116456 and of WO EP 1678232, and for example in file US-Re-28 715 and US-A-3 346 557, US-A-3 823 201, US-A-3 850 861, US-A-4 454 255, US-A-4 458 038, US-A-4 550 194, US-A-4 390 645 and US-A-4 The polymer polyatomic alcohol being described in detail in 431 754.
It is used to prepare the arbitrary isocyanates of polyurethane foam (particularly, flexibel polyurethane or polyisocyanurate foam) Compound can be used as isocyanate component.Preferably have two or more isocyanate functional groups' using one or more Organic isocyanate.The isocyanates being suitble to for the purpose of the present invention includes for example arbitrary multifunctional organic isocyanate, example Such as 4,4 '-methyl diphenylene diisocyanates (MDI), toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate (HMDI) Or isophorone diisocyanate (IPDI).(it claims MDI with the more highly condensed analog of average functionality with 2-4 Make " polymeric MDI " (" crude MDI ")) mixture be particularly suitable.The example of suitable isocyanates is in EP 1 712 578 A1, EP 1 161 474,058,383 200,7/0,072,951 1 678 232 A2 and WO 2005/ of A1, EP of A1, US of WO It is referred in 085310.
Preferred amine for being catalyzed isocyanate-water reaction is selected from triethylamine, dimethylcyclohexylam,ne, tetramethyl second two Amine, 4-methyl hexamethylene diamine, five methyl diethylentriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethyl piperazine Piperazine, DMIZ 1,2 dimethylimidazole, N, N- dimethyl hexadecyl amines, sila morpholine (silamorpholine), N-ethylmorpholine, three (dimethylaminopropyl) hexahydro -1,3,5- triazines, N, N- dimethylaminoethanols, N '-(3- dimethylaminopropyls)-N, N- Diisopropanolamine (DIPA), dimethyl amino ethoxy ethanol and bis- (dimethyl aminoethyl) ethers.Evonik Industries AG are carried For such amine or amine catalyst, for example, it is entitledSMP、33 orZE 4。
It is preferred that the metal salt that can be used as carboxylic acid is preferably potassium, tin, zinc or bismuth salt, more preferable tin (II) salt.Preferably use At least one tin (II) salt of 2 ethyl hexanoic acid, ricinoleic acid or 3,5,5 Trimethylhexanoic acid.Evonik Industries AG The catalyst of offer includes tin (II) salt of 2 ethyl hexanoic acid, such as entitled29.Organotin also can be used Object (such as dibutyl tin laurate) is closed, especially when being related to the preparation of HR foams.
The present invention also provides the composition suitable for preparing flexible polyurethane foams, it includes at least one polyol component, It is catalyzed the catalyst that polyurethane or isocyanurate-bond are formed, the foaming agent, the other additive that may be present that are optionally present And isocyanate component, and mixture of the invention as described above.
The present invention also provides can obtain flexible polyurethane foams by method as described above.
The obtained polyurethane foam of method of these polyurethane foams and/or the present invention be highly suitable for furniture (such as Mould furniture foam) and mattress industry, automotive industry (such as the head rest of automotive seat, automobile seat cushion, for automobile interior The continuous light sheet material for including soft/flexible bulk PU foams), bag making industry, shoes industry and textile industry, also at home and Technical field (such as packaging material).
Another part of subject of the present invention is that the mixture of the present invention is used to prepare the purposes of flexible polyurethane foams, For enhancing hole fineness especially in the preparation of flexible polyurethane foams.
Working Examples
In 27x 27cm opening wooden cases (the high 27cm of wall), made by the way that the various formulations with following components foam Standby flexible polyurethane foams：Formulation I includes very small amount of stabilizer (0.6 part), and formulation II includes larger numbers of Stabilizer (10 parts) and dichloromethane, select these formulations to create extreme condition, and compare hole knot under these conditions Structure：
Formulation I：
Formulation II：
1) Amine catalyst derived from Evonik Industries
2) Silicone stabilizer derived from Evonik Industries
3) Metallic catalyst derived from Evonik Industries
4)TDI 80：Inferior cresyl vulcabond, 80%2,4- isomers and 20%2,6- isomers
The used foam stabiliser for stablizing the foam of gained is silicone-polyether copolymers, silicone-polyether copolymerization Object can be obtained the siloxanes hydrosilylation reactions containing Si -- H by the polyethers caused with allyl, and silicon Ketone-copolyether has trade nameBF 2470, corresponding to the SiC- type polyethers silica for meeting formula (I) Alkane.
In the embodiment of the present invention II to V, VII to X and XII to XV, what it is by the stabilizer and a small amount of formula IV includes The fatty alcohol of amide groups mixes, and does not use the fatty alcohol comprising amide groups in comparing test I and VI.In embodiment XVI, The alcohol comprising amide groups is not mixed with stabilizer, but the alcohol comprising amide groups is added separately into preparation together with polyalcohol Object.The ratio of polyether silicone and component of mixture/amide blend is 1:1.
After foam curing, the foam levels of gained are cut, and above the foam substrate at the height of 15cm, to section The pore structure of upper discovery is assessed.The standard of assessment is by the number/cm in hole and the systematicness of the pore structure obtained.According to Table of grading assesses the foam obtained by Formula II, thus compares pore structure and standard foam.In the table, grade 1 indicates Very coarse pore structure, and class 5 indicates the pore structure of maximum fineness.
In addition, being caused by making 8 liters/min of fluid pass through foam sample (a diameter of 2cm of revolution feeding line) by measuring Dynamic pressure measure the open cell content of obtained foam.Measured dynamic pressure is lower (in terms of the mm of fluid column), institute The open cell content of the foam of acquisition is bigger.
A) component of mixture：Dipropylene glycol
B) component of mixture:75% water, 12.5% sodium alkyl benzene sulfonate, 12.5% propylene glycol
The fatty alcohol for including amide groups of amide=formula IV
Obviously use the fatty alcohol comprising amide groups as the component in flexible foam stabilizer for the poly- ammonia that is obtained The fine hole content of ester foam has surprising positive effect.See that the fatty alcohol comprising amide groups of increase ratio generates Increased fine hole content.Two to three hole/cm are increased, this represent considerable improvement.Similarly see grade point Increase up to 1.5 points, this represent the obviously enhancings of the fineness of pore structure.
Test XVI shows to enhance hole fineness, and the component is mixed into polyalcohol and also generates positive effect.
Also using liquid, pressurization CO2Machine test as foaming agent (corresponds toNovaflexTMOr BeamechTMMethod) in confirm hole fineness enhancing effect.
It will be corresponding to the formula of formulation I 4.05 parts of water and 2 parts of CO2In NovaflexTMIt foams in equipment.It reuses Above-mentioned 2470 stabilizers of BF referred to.For CO2Foaming, does not recommend the stabilizer usually, because its caused pore structure is insufficient It is enough.In the embodiment of the present invention (XVIII to XXI), with the ratio different relative to component of mixture using amide (formula IV Include the fatty alcohol of amide groups).Component of mixture is used only in comparing embodiment (XVII).The amount of used stabilizer is 0.9 part (including component of mixture and amide).The ratio of polyether silicone and component of mixture/amide blend is 1:1.
It is then checked for the pore structure obtained for foam, and based on indefectible, slight unordered, unordered or severe disorder amount Table is classified.
A) component of mixture：Dipropylene glycol
Even if it follows that using the fatty alcohol comprising amide groups corresponding to inventive mixture with liquid CO2As Foaming agent also causes under conditions of foaming the hole fineness to enhance.The pore structure of the foam obtained in embodiment XVIII to XXI is non- Chang Hao is considerably better than the pore structure of embodiment XVII.

Claims (15)

1. being used as the mixture of additive in the preparation of flexible polyurethane foams, the mixture includes the organic of (a) general formula I The compound of at least one formula (IV) of functional modified polysiloxanes and (b), and (c) dipropylene glycol and/or propylene glycol：
Wherein group
R1It is each independently alkyl group or aryl group,
R2Each independently with R1And/or R3Identical, condition is at least one R2Group has R3Meaning,
R3It is each independently the polyether group of Formula II：
-(Y)e[O(C2H4-dR'dO)m(CxH2xO)pZ]w (II)
Condition is
E=0-1,
W=1-3,
D=1-3,
M >=0,
X=2-4, and
P >=0, and
Y be have it is branched or without branched alkyl,
R' is selected from C1-C18Monovalent hydrocarbon, be optionally C1-C18Monovalent aromatic alkyl,
Z be hydrogen group or the monovalent organic group comprising carboxyl groups,
The sum of m+p is equal to 1-200, wherein be the arrangement that lower target structure block can have any desired with m and p,
When b is>When 6 to 8 numerical value, a is the numerical value of 1-100,
When b is>When 3 to 6 numerical value, a is the numerical value of 1-200,
When b is the numerical value of 0-3, a is the numerical value of 1-300,
B=0-8,
Condition is the subscript e=0 as b ≠ 0,
Wherein
R is monovalent organic group,
And the amide of wherein formula (IV) is obtained by making aliphatic acid be reacted with diethanol amine,
The wherein polysiloxane compound of formula (I) and the mass ratio of the compound of formula (IV) is more than 1:10,
And the polysiloxanes of the wherein general formula I based on 100 parts by weight, compounds of formula IV is with the amount of 0.1-200 parts by weight In the presence of.
2. the mixture of claim 1, it is characterised in that the mixture includes the said components (a) and (b) of >=40 weight %.
3. the mixture of claims 1 or 2, which is characterized in that the polyether silicone of general formula I is selected from R at wherein at least one2With R3 Identical compound, on condition that m>p.
4. the mixture of claims 1 or 2, the mixture include：
The polyether silicone for meeting formula (I) of >=30 weight % to≤68 weight %,
The compound for including amide groups for meeting formula (IV) of >=1 weight % to≤70 weight %,
The propylene glycol and/or dipropylene glycol of >=1 weight % to≤70 weight %.
5. the mixture of claims 1 or 2, the mixture include：
The polyether silicone for meeting formula (I) of >=30 weight % to≤68 weight %,
The compound for including amide groups for meeting formula (IV) of >=1 weight % to≤70 weight %,
The propylene glycol and/or dipropylene glycol of >=1 weight % to≤70 weight %,
The water of >=1 weight % to≤70 weight %,
The organic surface active agent of >=1 weight % to≤10 weight %, wherein using the solvent combination comprising water, or meets The ratio of the compound comprising amide groups of formula (IV)>60 weight %.
6. the mixture of claims 1 or 2, the mixture include：
The polyether silicone for meeting formula (I) of >=40 weight % to≤55 weight %,
The compound for including amide groups for meeting formula (IV) of >=2 weight % to≤50 weight %,
The alkylbenzene sulfonate of >=1 weight % to≤10 weight %,
The water of >=30 weight % to≤50 weight %, and
The propylene glycol and/or dipropylene glycol of >=1 weight % to≤10 weight %.
7. the mixture of claims 1 or 2, wherein in formula (IV), R is the alkyl for having 1-30 carbon atom.
8. the method for preparing flexible polyurethane foams using the organic functional modified polysiloxanes of general formula I,
Wherein group
R1It is each independently alkyl group or aryl group,
R2Each independently with R1And/or R3Identical, condition is at least one R2Group has R3Meaning,
R3It is each independently the polyether group of Formula II：
-(Y)e[O(C2H4-dR'dO)m(CxH2xO)pZ]w (II)
Condition is
E=0-1,
W=1-3,
D=1-3,
M >=0,
X=2-4, and
P >=0, and
Y be have it is branched or without branched alkyl,
R' is selected from C1-C18Monovalent hydrocarbon, be optionally C1-C18Monovalent aromatic alkyl,
Z be hydrogen group or the monovalent organic group comprising carboxyl groups,
The sum of m+p is equal to 1-200, wherein be the arrangement that lower target structure block can have any desired with m and p,
When b is>When 6 to 8 numerical value, a is the numerical value of 1-100,
When b is>When 3 to 6 numerical value, a is the numerical value of 1-200,
When b is the numerical value of 0-3, a is the numerical value of 1-300,
B=0-8,
Condition is the subscript e=0 as b ≠ 0,
The polysiloxanes of its formula of I is used in mixed way with the compound of organic solvent and at least one formula IV,
The organic solvent be dipropylene glycol and/or propylene glycol,
Wherein
R is monovalent organic group,
And the amide of wherein formula (IV) is obtained by making aliphatic acid be reacted with diethanol amine,
The wherein described polysiloxane compound and the mass ratio of the compound of formula (IV) are more than 1:10,
And the polysiloxanes of the wherein general formula I based on 100 parts by weight, compounds of formula IV is with the amount of 0.1-200 parts by weight In the presence of.
9. the method for claim 8, which is characterized in that the polyether silicone of general formula I, the feature of the polyether silicone is used to exist In R at least one2With R3It is identical, on condition that m>p.
10. the method for claim 8 or 9, which is characterized in that the carbon dioxide of pressurization or dichloromethane are used as foaming agent.
11. the method for claim 8 or 9, which is characterized in that be based on entire flexible polyurethane foams formulation, the poly- silicon of formula (I) The dosage of the mixture of the compound and at least one organic solvent of oxygen alkane and formula (IV) is 0.01-13 weight %.
12. the method for claim 8 or 9, wherein in formula (IV), R is the alkyl for having 1-30 carbon atom.
13. flexible polyurethane foams can be obtained by the method for any one of claim 8-12.
14. the mixture of any one of claim 1-7 is used to prepare the purposes of flexible polyurethane foams.
15. the purposes of claim 14, the mixture is used to enhance the fineness in hole.
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