CN101868493A - Novel compounds for fabric treatment - Google Patents
Novel compounds for fabric treatment Download PDFInfo
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- CN101868493A CN101868493A CN200880117329A CN200880117329A CN101868493A CN 101868493 A CN101868493 A CN 101868493A CN 200880117329 A CN200880117329 A CN 200880117329A CN 200880117329 A CN200880117329 A CN 200880117329A CN 101868493 A CN101868493 A CN 101868493A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M15/37—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The application relates to new compounds with switchable properties of structure : where R1 is a group selected from alkyl, branched alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, alkaryl, alkoxy, aryl, aralkyl, alkenyl, alkynyl or fluorocarbon groups containing 1 to 50 carbon atom(s), ''X'' is a hydrophilic polymer chain or segment, ''Y'' is a hydrophobic or oleophobic polymer chain or segment; ''z'' is a chain containing an organofunctional group which is an amide, quaternary ammonium, phosphate or sulfate group; R2 is same as R1, or is Hydrogen, hydroxyl group or a spacer that links said compound of the formula (I) with another compound of the same formula; and a, b, c, d and e are integers from 1 to 4,000; the application further relates to a process for making said compounds, and also to a method of treating fabric with an aqueous dispersion of the new compound.
Description
Technical field
The present invention relates to have compound of convertible (switchable) surface property and the method for preparing these compounds.
The present invention is developed out and is mainly used in fabric treating and will be described about this application hereinafter.But, will be appreciated that to the invention is not restricted to this specific application area.
Background technology
In whole specification sheets, should think never to admit that to any discussion of prior art these prior aries are parts well-known or that form conventional, well-known general knowledge in this area.
The fabric person of being to use of demonstration water outlet and scolding property of oil highly welcomes.Water and scolding property of oil mean that usually fabric block water and oil penetrate into the ability in the fiber.Paid great effort and prepared fabric face with competent water and scolding property of oil and improved and competent decontamination.Can utilize some treatment processs that in these performances any given to fabric, but verified for any valuable time span, providing all these performances to fabric is difficulties relatively.A kind of method of handling fabric of giving this two specific character simultaneously is to utilize such multipolymer, and this multipolymer contains hydrophobic or oleophobic siloxanes fluorohydrocarbon (fluorocarbon) base is scolded oil and water segment (segments) and hydrophilic decontamination segment.
The for example cotton and wool of natural fiber demonstrates lower water and scolding property of oil, but when they became contaminated really, they were cleaned easily, so demonstrates easy soil release characteristics.On the other hand, synthetic textiles, particularly polyester demonstrate lower soil-removing action level during washing, but these fabrics are not contaminated so easily as cotton or wool.The surface energy that it is believed that cotton and other hydrophilic fabrics is very high, so cotton is easily by particulate soil for example carbon black and contamination by dust.On the other hand, cotton same high surface energy makes it relatively easily to clean, and discharges in water because dirt is easier.Synthetic textiles for example polyester has low surface energy, therefore compares them with cotton and attracts the ability of particulate soil much lower.Yet when tarnishing, it becomes and is difficult to remove these dirts from these fabrics, because their low surface energy prevents or postpone the release of dirt.
Therefore, preparation has the trend of the fabric of natural/synthon blend and tends to increase the weight of described problem, and spot that absorb is difficult to wash off because these blends are contaminated easily.As mentioned above, the fluorohydrocarbon class has been applied to fabric and has attempted by provide limited protection (because their oleophobic performance) to solve this problem at oily pollutant.But they tend to worsen detergency ability, because the aqueous cleaning medium matrix of moist curing suitably, and therefore can not remove crude removal.On the other hand, adopt the processing of hydrophilic soil release polymer to tend to improve decontamination.
Yet, fabric opposing and repel water and oil base dirt, more particularly the high surface energy particulate soil for example the sooty ability be very limited.
A kind of basic physicals of any material is its surface energy.This performance is usually with mJ/m
2Express.The size that depends on this performance, material can be classified as has high surface energy or low surface energy.This performance depends on the composition of matrix usually; For example, have the polarity hydrophilic radical matrix on hydroxyl, carboxylic acid, amino or the like surface for example that contains signal portion, have high surface energy usually.On the contrary, the nonpolar hydrophobic grouping that contains signal portion is the surface of silicone, fluorinated groups or the like for example, demonstrates lower surface energy usually.Known when making polar liquid for example water contacts with the surface of matrix, have only the surface tension of described liquid to be lower than the surface energy of described matrix, the just spontaneously wetting described surface of described liquid.On the contrary, if the surface tension of described liquid is higher than the surface energy of described matrix, then spontaneous wetting can not take place easily, described liquid keeps converging on the stromal surface.
Wish (stainable) surface that porous maybe can be stained, for example fabric face demonstrates high contact angle to prevent absorption or to stain to multiple liquid.Wish that also these surfaces change at the change of their environment, for example in cleaning or conditioning medium, to strengthen dirt and greasiness removal.
What highly wish will be the surface that reversibly changes at its environment, thereby described surface is anti-that stain and be easy to clean and keep this ability for many uses circulations.
US6899923B2 (MILLIKEN ﹠amp; CO, 2005) disclosed the method for giving durable scolding property and soil release characteristics to matrix, wherein apply described matrix with composition, said composition comprises hydrophilic stain remover, hydrophobicly scolds dirty agent and hydrophobic crosslinking agent, then heats described matrix to remove excessive liquid from the matrix that applies; Randomly further heat the matrix that applies.
In another way, US6818253B2 (MILLIKEN ﹠amp; CO, 2004) provide and handled matrix to obtain the method for durable repellency and improved durable decontamination quality, wherein apply mixture to textile substrates, this mixture has fluorocarbon polymer and hydrophilic soil release polymer, ratio is 1: 1-5: 1, and pH is 4-7, carries out drying then.It is said that described hydrophilic soil release polymer is a cationic property.
As can be seen aforesaid method be carry out in order and comprise a plurality of stages, therefore use, more especially bother very much for the user for daily life.
On the other hand, US5446114A (SILTECH INC, 1995) has disclosed by the silicone of siliceous hydrogen (silanic hydrogen) and the fluoric compound and the reaction between the allyl alcohol alcoxylates that contain vinyl and has prepared fluorizated dimethicone copolyol (dimethiconecopolyol).On the silicone backbone hydrophilic and existence hydrophobic side chain make these polymkeric substance be to the surface particularly fabric give the good candidate of convertible performance.The inventor will find that a major limitation of these polymkeric substance is that these polymkeric substance can not be delivered on the fabric effectively by water-bearing media.
Therefore, have the needs to such compound, this compound exhibits goes out convertible performance and can be delivered on the fabric effectively by water-bearing media.
In this case, the inventor finds that compound must have some organo-functional groups in order effectively to be deposited on the fabric face.During washing or rinsing processing, these compounds that have convertible performance and contain organo-functional group will deposit on the fabric face and effectively and combine with fabric face, scold the low and high surface energy segment of dirty and decontamination benefit to coexist thereby allow simultaneously to be respectively applied for.Therefore this treated fabric will show low interfacial energy in air (hydrophobic) and water (hydrophilic) environment, and will have to minimize in empty G﹠W and adhere to and promote the potential that spot and dirt discharge from its surface.
The present invention relates to demonstrate compound and their purposes in fabric treating of self-adaptation (convertible) surface energy properties.
This surface energy properties is providing the relative high contact angle that moves forward and backward for liquid when contacting with fabric.Especially, fabric face demonstrates about at the most 20mJ/m
2Low surface energy, measure and by the Fowkes Equation for Calculating, in about 25 ℃ temperature by goniometry.The automatic surface of this uniqueness can the change ability and then such surface is provided, and water and oil are scolded in this surface, and this surface will show stain resistance highly and the soil release characteristics in water-bearing media.In addition, depend on exposed environments, the surface energy situation of this uniqueness is repeatably and reversible.
Goal of the invention
An object of the present invention is to overcome or improve at least one shortcoming of prior art.
An object of the present invention is to provide and demonstrate convertible performance and can be delivered to compound on the fabric face by water-bearing media.
Summary of the invention
According to main aspect of the present invention, provide the compound of general formula (I):
Wherein R1 is the group that is selected from alkyl, branched-chain alkyl, cycloalkyl, multi-ring alkyl (polycycloalkyl), Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, thiazolinyl, alkynyl or fluorocarbon based (fluorocarbongroups), contain 1-50 carbon atom, " X " is hydrophilic polymer chains (chain) or segment (segment), and " Y " is hydrophobic or oleophobic polymer chain or segment; " Z " is the chain that contains organo-functional group, and described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt (phosphate) or vitriol (sulfate) group; R2 is identical with R1, or hydrogen, hydroxyl or spacer groups (spacer) that another compound of the compound of described formula (I) and same structure formula is coupled together; With a, b, c, d and e be the integer of 1-4000.
According to a further aspect in the invention, provide the method for preparation according to the compound of described main aspect; Comprise and make the have general formula compound of (II)
Wherein R1 is straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, thiazolinyl, alkynyl or fluorocarbon based, contains 1-50 carbon atom; " r " is that integer and " s " of 1-1000 is the integer of 4-16000,
Step with following all substances reaction:
(a) hydrophilic polymer, it has reactive group, and it covalently is attached to described Compound I I by the Si-H key,
(b) hydrophobic or oleophobic polymkeric substance, it has reactive group, and it covalently is attached to described Compound I I by the Si-H key,
(c) contain the compound of organo-functional group, described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt or sulfate group, and described compound further has reactive group, and it covalently is attached to the compound of described formula II by the Si-H key; With
(d) when the described R2 in described formula (I) compound is described spacer groups; The spacer groups compound is selected from α, the ω diene; α, the ω diine; α, the end capped polymkeric substance that is selected from polysiloxane or polyethers of ω alkene-alkynes or dialkylene or diynyl;
Described method is implemented in the presence of organic solvent or silicone fluid in the presence of catalyzer and randomly.
According to a further aspect in the invention, provide the method for using according to the compound treatment fabric of main aspect of the present invention, comprise the step that described fabric is contacted with the aqueous dispersion of described compound.
Embodiment
Will be appreciated that general formula (I) is the exemplary configuration of described compound.Therefore for the situation of the product of random grafting/copolymerization in the actual product, recurring group will be a random distribution.
Preferred described hydrophilic polymer chains or segment have polyalkylene oxide, poly(propylene oxide), polyvinyl alcohol, glycan (polysaccharide) or polyacrylic acid unit in compound of the present invention.More preferably, described hydrophilic polymer chains or segment contain polyethylene oxide and poly(propylene oxide) unit, thereby their surface energy is quite high, usually at 35-50mJ/m
2Scope.
Preferred described hydrophobic or oleophobic polymer chain or segment contain PFPE, fluorohydrocarbon (fluorocarbon), polystyrene or polymethylmethacrylate unit in compound of the present invention.The polymer chain that contains fluorohydrocarbon or PFPE residue is highly preferred, because because their extremely low surface energies (are generally 12-34mJ/m
2), they provide fully high hydrophobicity and oleophobic property degree.
Described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt or sulfate group.In addition, preferably all described groups all are quaternary ammonium groups, because the existence of these groups allows described compound deposition of the enhanced to the fabric face in water-bearing media.
Preferably, each R1 group is methyl, ethyl, propyl group, butyl or the tertiary butyl in formula (I) compound; More preferably be methyl all.
A, b, c, d and e preferable range separately is 10-1000 in the The compounds of this invention.
The functional silicone of silicon hydrogen
Contain the silicone (linear or cyclic) of silicon hydrogen (Si-H), it, can be represented by following general formula to prepare compound of the present invention as " base polymer ":
Wherein R1 is straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, thiazolinyl, alkynyl or the fluorocarbon based that contains 1-50 carbon atom; " r " is that integer and " s " of 1-4000 is the integer of 4-16000.
Preferably " r " is that 100-1000 and " s " are 40-4000.
Preferred each R1 group is methyl, ethyl, propyl group, butyl or the tertiary butyl.Further preferred all R1 groups all are methyl.
Described silicon hydrogen (Si-H) and described hydrophilic polymer, hydrophobic or oleophobic polymkeric substance and described respective reactivity radical reaction with compound of the organo-functional group that contains nitrogen, oxygen, phosphorus or sulphur.These reactants are by Si-H key and the reaction of described basic compound and covalently be attached to base polymer.When comprising described spacer groups compound in the reaction mixture, the reactive site reaction of some silicon hydrogen and described spacer groups compound, described spacer groups compound further with another molecular reaction of formula (I) compound (this is because the difunctionality person's character), form three-dimensional crosslinking structure.
Hydrophobic or oleophobic polymkeric substance or segment
Preferred polymkeric substance contains PFPE, fluorohydrocarbon, polystyrene or polymethylmethacrylate unit.Further preferred polymkeric substance is selected from the fluorohydrocarbon that contains vinyl, has following structure C H2=CH-(CF2) n-CF3 or CH2=CHCH2OCH2CH2 (CF2) nCF3, wherein n=1-20.
Hydrophilic polymer
Preferred hydrophilic polymer contains polyalkylene oxide, poly(propylene oxide), polyacrylic acid, polyvinyl alcohol or glycan residue.Preferred described hydrophilic polymer contains polyalkylene oxide and poly(propylene oxide) residue.Further preferred described hydrophilic polymer have structure C H2=CHCH2-O-((EO) a-(PO) b-(EO)-H, wherein EO be-(CH2CH2O)-and PO be-(CH2-CH (Me)-O)-and a, b and c be the integer of 1-20.
Compound with organo-functional group
Described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt or sulfate group.Quaternary ammonium group preferably.Necessary is that described compound with above-mentioned organo-functional group also has reactive group for example vinyl, allyl group or propargyl; Thereby described compound can with the silicon H-H reaction that exists on the silicone backbone of above (II) expression, be converted into the season amino group then.
The spacer groups compound
When using in the building-up process at The compounds of this invention, by dual functional spacer groups, basic polymer chain is covalently connected together each other.These dual functional spacer groups prevent that over-drastic is three-dimensional cross-linked, and help to form appropriately crosslinked elastomer compounds on the contrary.Preferred spacer groups compound is selected from dialkylene polyethers, α, ω diene, α, ω diine, α, the end capped polysiloxane of ω alkene-alkynes or dialkylene or diynyl.α, the suitable example of ω diene is 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-12 carbon diene, 1,13-14 carbon diene and 1,19-20 carbon diene.α, the suitable example of ω diine is 1,3-diacetylene or 1,5-hexadiyne, and α, ω alkene-alkynes is hexene-5-alkynes preferably.
Preferred described spacer groups is based on siloxanes.The end capped polysiloxane of dialkylene that can be used as spacer groups can be represented by following general formula:
Wherein R1 is straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, alkenyl or alkynyl or the fluorocarbon based that contains 1-50 carbon atom; Wherein p is mean value and is the number of value for 2-10000.
Preferred dialkylene terminated polyether can be represented by following general formula:
The R=divalent moiety
Wherein " n " and " m " is the integer of 1-10.Suitable divalent moiety is selected from-(CH2)-; Or-CH (Me)-or the like.
Catalyzer
Carry out under the preferred described existence that is reflected at suitable addition catalyst.These are selected from metal complex or their compound or are in free or machine made metal.Transition metal for example platinum, palladium and rhodium is particularly preferred.The complex compound that preferred catalyzer is Platinic chloride, platinum and unsaturated compound is platinum (O)-1 for example, 3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound; Platinum (O)-2,4,6,8-tetramethyl--2,4,6,8-tetrem thiazolinyl cyclotetrasiloxane complex compound; Pt0 (1,5cyclooctadine) be Pt (COD)]; Platinum phosphine (phospine) complex compound; Carbon carries platinum; At inorganic carrier platinum and the platinum black on the silicon-dioxide for example.For example palladium, rhodium complex also are suitable (for example Wilkinson ' s catalyzer RhCl[(C6H5) P for other metals of described reaction] 3).Preferred catalyzer is for example metal complex or the free or machine made metal of compound of platinum, palladium, rhodium of transition metal.Preferred catalyzer is the complex compound of Platinic chloride and platinum and unsaturated compound.Described catalyzer can be in heterogeneous form, for example on charcoal, perhaps preferably is in homogeneous phase form (for example Karstedt catalyzer).Most preferably use platinum (O)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound.
Solvent and swelling agent
Reaction between the functional silicone base polymer of silicon hydrogen and other reactants is randomly carried out in the presence of solvent, and described solvent is selected from water, silicone fluid, polar organic compound, nonpolar organic compound or their mixture.Typically, based on the weight of all reactants, described solvent exists with the amount of 20-99.89%wt.More preferably, the amount of described solvent is 20-80wt%, is more preferably 20-50wt%.When described solvent is polar organic compound or nonpolar organic compound, should preferably uses to produce and contain＜amount of 40wt% solid product.Preferably described solvent does not remove from composition.The silicone fluid that can be used as described solvent includes but not limited to alkyl and/or aryl siloxanes for example methylsiloxane and the alkyl and/or the aryl siloxanes that contain functional group.Volatile methyl siloxane (VMS) preferably.The VMS compound is corresponding to averaged unit formula (CH
3)
jSiO
(4-j)/2, wherein j has the mean value of 2-3.Described VMS compound contains the siloxane unit that connects by the Si-O-Si key.
The example of this silicone fluid is polydimethylsiloxane, poly-di-ethyl siloxane, polymethy ethylsiloxane, PSI and poly-diphenyl siloxane.
When silicone fluid during as herein solvent, the gained compound is the form of silicone gel (siliconegel).
Useful in this article polar organic compound comprises single hydroxyl alcohol for example ethanol and Virahol; Two pure and mild triols are propylene glycol, 2-methyl isophthalic acid for example, ammediol HOCH
2CH (CH
3) CH
2OH, 1,2-hexylene glycol CH
3(CH
2)
3CH (OH) CH
2OH, and glycerine; Glyceryl ester is triacetin (triacetin), glycerin tripropionate (propionic acid glycerine) and tributyrin (butyric acid glycerine) for example; With polyglycol polyoxyethylene glycol and polypropylene glycol, particularly polypropylene glycol (PPG) 14 butyl ether C for example
4H
9[OCH (CH
3) CH
2]
14OH.
Nonpolar organic compound also can be used as described solvent.Described nonpolar organic compound comprises aromatic hydrocarbon, aliphatic hydrocrbon, alcohol, aldehyde, ketone, amine, ester, ether, glycol, glycol ethers, haloalkane or aromatic halide.
Representational compound is for example methyl alcohol, ethanol, 1-propyl alcohol, hexalin, benzylalcohol, sec-n-octyl alcohol, ethylene glycol, propylene glycol and a glycerine of alcohol; Aliphatic hydrocrbon is pentane, hexanaphthene, heptane, VarnishMaker ' s ﹠amp for example; Painter ' s (VM﹠amp; P) solvent and mineral turpentine; Haloalkane is chloroform, tetracol phenixin, tetrachloroethylene, chloric ethane and chlorobenzene for example; Aromatic hydrocarbon is benzene, toluene, ethylbenzene and dimethylbenzene for example; Ester is ethyl acetate, isopropyl acetate, methyl aceto acetate, pentyl acetate, isobutyl isobutyrate, jasmal and Wickenol 111 for example; Ether is ether, n-butyl ether, tetrahydrofuran (THF) and 1 for example, the 4-dioxane; Glycol ethers is glycol monomethyl methyl ether, ethylene glycol monomethyl ether acetate, diglycol monotertiary butyl ether and propylene glycol list phenyl ether for example; Ketone is acetone, methyl ethyl ketone, pimelinketone, Pyranton, Methyl amyl ketone and diisobutyl ketone for example; Petroleum hydrocarbon is vaseline, mineral oil, gasoline, naphtha, kerosene, gas oil (gas oil), heavy oil and crude oil for example; Lubricating oil is spindle oil and turbine oil for example; With fatty oil for example Semen Maydis oil, soybean oil, sweet oil, rapeseed oil, Oleum Gossypii semen, sardine oil, menhaden fish oil and whale oil.
Appropriate organic solvent is such organic solvent, its under processing and the working conditions of expection not with silicone mutually any component generation chemical reaction and during its end-use that is suitable for expecting uses.
Depend on reactant, temperature of reaction is 5 ℃-200 ℃, preferably about 80-120 ℃, and most preferably 110 ℃.Reaction times can change between 1 minute and 48 hours.
Compound of the present invention is synthetic by the method that may further comprise the steps, and this step is to make the have general formula compound of (II)
Wherein R1 is straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, thiazolinyl, alkynyl or the fluorocarbon based that contains 1-50 carbon atom; " r " is that integer and " s " of 1-1000 is the integer of 4-16000,
React with following all substances:
(a) hydrophilic polymer, it has reactive group, and it covalently is attached to described Compound I I by the Si-H key,
(b) hydrophobic or oleophobic polymkeric substance, it has reactive group, and it covalently is attached to described Compound I I by the Si-H key,
(c) contain the compound of organo-functional group, described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt or sulfate group, and described compound further has reactive group, and it covalently is attached to the compound of described formula II by the Si-H key; With
(d) when the described R2 in described formula (I) compound is described spacer groups; The spacer groups compound is selected from α, the ω diene; α, the ω diine; α, the end capped polymkeric substance that is selected from polysiloxane or polyethers of ω alkene-alkynes or dialkylene or diynyl;
Described method is implemented in the presence of organic solvent or silicone fluid in the presence of catalyzer and randomly.
General synthesis strategy
A kind of exemplary synthesis strategy is as follows:
To explain the present invention in more detail by means of following non-limiting example now.
Embodiment 1
Synthesizing of The compounds of this invention
In the present embodiment, do not use the spacer groups compound; Therefore it obtains linear compound.
Prepare described compound by 3 elementary reaction methods
Stage 1:
SyntheticFormula (II)
Compound, R1=methyl wherein, it is used as and contains silicon hydrogen The silicone base polymer
In two mouthfuls of round-bottomed flasks with 50g octamethylcyclotetrasiloxane (being also referred to as D4) and can be commercially available and 15g polymethyl hydrogen siloxane (CAS number: 63148-57-2) mix from GE-Bayer Silicones.Add 1g Tulsion catalyzer in this mixture, it is an acidic catalyst (ThermaxIndia, T63MP, a sulfonic acid polystyrene resin).Reaction mixture was stirred 4 hours at 120 ℃.With viscosity formula (II) the compound cool to room temperature that obtains.Filter catalyzer by the Whatman filter paper.Under vacuum, steam unreacted D at 125 ℃
4The product that obtains is the form of colourless viscous oil.
Stage 2:
The epoxy-functional of the compound that obtains in the stage 1
With 1g polyalkylene glycol mono allyl ethers is CH
2=CHCH
2-O-(EO) x-(PO) y-H (wherein EO be-(CH2CH2O)-and PO be-(CH2-CH (Me)-O)-, x and y are the integer of 1-20 independently of one another) (can be used as Polyglykol 20-10 is commercially available from Clariant) and 0.5g " allyl group; 1H; 1H; 2H; 2H-perfluoro capryl ether " they are that (Apollo Scientific UK) is dissolved in the 50ml toluene (AR level) and joins in moisture free reflux CH2=CHCH2OCH2CH2 (CF2) nCF3, remains under the nitrogen atmosphere.Remove 25ml toluene to guarantee to remove fully the moisture in the reaction medium by component distillation.With a platinum catalyst (platinum (O)-1,3-divinyl tetramethyl--sily oxide complex solution (can derive from Aldrich; CAS 68478-92-2)) add in the reaction mixture and with mixture about 30 minutes in stirring at room.The compound in 2.5g stage 1 and the mixture of 1ml toluene (AR level) are added in the reaction mixture, and reaction is maintained at about 110 ℃ of about 2-3 hours.Progress by TLC and FT-IR monitoring reaction." Si-H " group percentage ratio is reduced to approximately～75%.Residue Si-H group and allyl glycidyl ether (can derive from Aldrich; CAS 106-92-3) reaction.After reaction finishes, under vacuum, remove excessive toluene and excessive allyl glycidyl ether.The structure of the compound that is obtained by the stage 2 provides below.
Stage 3:
Quaternized
After removing allyl glycidyl ether fully, will be from product toluene (50ml) homogenize again in stage 2.The solution of this product in toluene is transferred in the 250ml round-bottomed flask.Add 3ml tert-butylamine (Aldrich CAS number: 109-73-9,99.5%) subsequently.Reaction mixture was stirred 10 hours at 90 ℃.Use the progress of NMR (nucleus magnetic resonance) spectrum monitoring reaction.After reaction is finished, under vacuum, remove excessive tert-butylamine and toluene.The hydroxy amino compound that obtains is dissolved in the toluene again.The solution of hydroxy amino compound in toluene is transferred in the 250ml round-bottomed flask.Add 5ml methyl iodide (CAS number: 74-88-4,99.5%) subsequently.Reaction mixture was stirred 4-5 hour at 70 ℃.Sticky product is dissolved in the ethanol (concentration-85g/l).The product that obtains will have can following expression structure:
In this case, R2 is identical with R1, promptly-and CH3 (methyl) group.
Embodiment 2 (contrast)
In a comparative example, defer to stage 1 and the 2 preparation compounds of embodiment 1 by (only).This causes having the compound of epoxy-functional.
Embodiment 3
Repeat said process, use the end capped polysiloxane of divinyl as spacer groups in wherein synthesizing in the stage 4.
Stage 1:
The functional polysiloxane of synthesizing methyl hydrogen
Described in the stage 1 of embodiment 1.
Stage 2:
The synthetic end capped polysiloxane of divinyl (VTP) multipolymer
In two mouthfuls of flasks of 50ml, 20g octamethylcyclotetrasiloxane (being also referred to as D4) is mixed with 4g divinyl tetramethyl--sily oxide (can obtain from Aldrich).Interpolation 0.3gTulsion catalyzer in mixture (Thermax, T63MP).Reaction mixture was stirred 4 hours at 120 ℃.With the end capped polysiloxane copolymer of the divinyl that obtains (VTP) multipolymer cool to room temperature.Filtration catalizer.Under vacuum, steam unreacted D4 at 125 ℃.The product that obtains is colourless viscous oil.It is used as the spacer groups compound.
The end capped polysiloxane of divinyl (VTP) multipolymer
Stage 3:
The functional intermediate of synthesizing epoxy
With 1g polyalkylene glycol mono allyl ethers is CH
2=CHCH
2-O-(EO) a-(PO) b-H (wherein EO be-(CH2CH2O)-and PO be-(CH2-CH (Me)-O)-, a and b are the integer of 1-20 independently of one another) (Polyglykol 20-10, Clariant) and 0.5g " allyl group; 1H; 1H; 2H; 2H-perfluoro capryl ether " be CH2=CHCH2OCH2CH2 (CF2) 5CF3 (Apollo Scientific, UK) and the end capped polysiloxane of divinyl (in the stage 2 synthetic) be dissolved in the 50ml toluene (AR level) and join in moisture free reflux, remain under the nitrogen atmosphere.Remove 25ml toluene to guarantee to remove fully the moisture in the reaction medium by component distillation.With a platinum catalyst (platinum (0)-1,3-divinyl tetramethyl--sily oxide complex solution (can derive from Aldrich; CAS 68478-92-2)) add in the reaction mixture and with mixture about 30 minutes in stirring at room.The compound in 2.5g stage 1 and the mixture of 1ml toluene (AR level) are added in the reaction mixture, and reaction is maintained at about 110 ℃ of about 2-3 hours.Progress by TLC and FT-IR monitoring reaction." Si-H " group percentage ratio is reduced to approximately～75%.
Residue Si-H group and allyl glycidyl ether (Aldrich; CAS 106-92-3) reaction.After reaction finishes, under vacuum, remove excessive toluene and excessive allyl glycidyl ether.
Stage 4:
Quaternized
The process of back is identical with 1 stage 3 of embodiment.The final product that obtains can be represented by following structure.
Embodiment 4
Use the contact angle research of the compound of embodiment 1 and 2
The cotton block of 10cm * 10cm (100% cotton, can commerce obtain) was soaked 15-20 minute in the 2wt% solution of the described compound of 50ml.Described sample immerses in the distilled water then, soaked 15 minutes, from wherein shift out and make its baking oven 90 ℃ of dryings.After this, press described sample.Cut the 12cm * 6cm band of treated fabric and apply tackiness agent it is bonded on the slick glass slide by angle to fabric.Then described microscope slide is placed on the platform of the goniometer that photographic camera is housed.By using syringe to be placed on a water on the fabric and taking pictures.By the shape analysis of standard drop, be determined at the contact angle that drips in water in air on the fabric face.Record is passed in time and is duplicated described value in the variation of contact angle and the table 1 below.Experiment is carried out three times.
Table 1
Time/second is at the contact angle of contact angle after 6 seconds of 0 time
Hydrophobic hydrophilic
The fabric 120 26 that applies with the compound of embodiment 1
115 23
120 24
The fabric 120 26 that applies with the compound of embodiment 1
110 21
120 28
The fabric 00 that applies with the compound of embodiment 2
0 0
0 0
As can be seen, compound for preparation among the embodiment 1 is very high at the contact angle of 0 time, the hydrophobicity that shows height, and its demonstrate gradually reduce and be reduced at last～25 °, this shows that treated fabric is transformed into wetting ability character from hydrophobic nature gradually.Therefore, this treated fabric (promptly when treated fabric contacts with air) in air will show the spot of scolding of height, and it will show the wettability of height when it is contacted with water.When with water-bearing media, when more particularly the aqueous detergent medium contacts, this will make described fabric can discharge dirt.
On the other hand, demonstrate almost nil contact angle with the fabric sample of the compound treatment of embodiment 2 (comparative example), this means described fabric of 0 time be highly-hydrophilic and therefore demonstrate high degree of wetting.Such fabric season will be polluted by airborne particulate soil easily.
Provide compound with the embodiment that illustrates that is interpreted as compound and provides, described compound exhibits goes out convertible performance and can be delivered on the fabric face by water-bearing media.
Though described the present invention, skilled person will appreciate that the present invention can embody with a lot of other forms with reference to specific embodiments.
Claims (15)
1. the compound of general formula (I):
Wherein R1 is the group that is selected from alkyl, branched-chain alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, thiazolinyl, alkynyl or contains the fluorocarbon based of 1-50 carbon atom, " X " is hydrophilic polymer chains or segment, and " Y " is hydrophobic or oleophobic polymer chain or segment; " Z " is the chain that contains organo-functional group, and described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt or sulfate group; R2 or hydrogen identical, hydroxyl or the spacer groups that another compound of the compound of described formula (I) and phase cotype is coupled together with R1; With a, b, c, d and e be the integer of 1-4000.
2. the compound of claim 1, wherein said group is a quaternary ammonium.
3. claim 1 or 2 compound, wherein said hydrophilic polymer chains or segment have polyalkylene oxide, poly(propylene oxide), polyacrylic acid, polyvinyl alcohol or glycan unit.
4. the compound of claim 3, wherein said hydrophobic or oleophobic polymer chain or segment have PFPE, fluorohydrocarbon, polystyrene or polymethylmethacrylate unit.
5. each compound of aforementioned claim, wherein each described R1 is methyl, ethyl, propyl group, butyl or tertiary butyl groups.
6. the compound of claim 5, wherein each described R1 is a methyl group.
7. each compound of aforementioned claim, each integer of 10-1000 naturally of wherein said a, b, c, d and e.
8. the method for compound of preparation claim 1 comprises making the have general formula compound of (II)
Wherein R1 is straight or branched alkyl, cycloalkyl, multi-ring alkyl, Heterocyclylalkyl, alkaryl, alkoxyl group, aryl, aralkyl, thiazolinyl, alkynyl or the fluorocarbon based that contains 1-50 carbon atom; " r " is that integer and " s " of 1-1000 is the integer of 4-16000,
Step with following all substances reaction:
(a) hydrophilic polymer, it has reactive group, and it covalently is attached to described Compound I I by the Si-H key,
(b) hydrophobic or oleophobic polymkeric substance, it has reactive group, and it covalently is attached to described Compound I I by the Si-H key,
(c) contain the compound of organo-functional group, described organo-functional group is acid amides, quaternary ammonium, phosphoric acid salt or sulfate group, and described compound further has reactive group, and it covalently is attached to the compound of described formula II by the Si-H key; With
(d) when the described R2 in described formula (I) compound is described spacer groups; The spacer groups compound is selected from α, the ω diene; α, ω diine, α, the end capped polymkeric substance that is selected from polysiloxane or polyethers of ω alkene-alkynes or dialkylene or diynyl;
Described method is implemented in the presence of organic solvent or silicone fluid in the presence of catalyzer and randomly.
9. the method for claim 8, wherein said hydrophilic polymer has polyalkylene oxide, poly(propylene oxide), polyvinyl alcohol, glycan or polyacrylic acid unit.
10. the method for claim 9, wherein said hydrophilic polymer has structure C H2=CHCH2-O-((EO) a-(PO) b-(EO)-H; Wherein EO be-(CH2CH2O)-and PO be-(CH2-CH (CH3)-O)-and a, b and c be the integer of 1-20.
11. each described method of aforementioned claim 8-10, wherein said hydrophobic or oleophobic polymkeric substance contains PFPE, fluorohydrocarbon, polystyrene or polymethylmethacrylate unit.
12. the method for claim 11, wherein said fluorohydrocarbon have structure C H2=CH-(CF2) n-CF3, or CH2=CHCH2OCH2CH2 (CF2) nCF3, wherein n=1-20.
13. each described method of claim 8-12, the wherein said compound that contains organo-functional group has quaternary ammonium group.
14. each described method of aforementioned claim 8-13, wherein said reactive group is selected from vinyl, allyl group or propargyl.
15. the method with each compound treatment fabric among the claim 1-7 comprises the step that described fabric is contacted with the aqueous dispersion of described compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN2293MU2007 | 2007-11-21 | ||
| IN2293/MUM/2007 | 2007-11-21 | ||
| PCT/EP2008/063442 WO2009065664A1 (en) | 2007-11-21 | 2008-10-08 | Novel compounds for fabric treatment |
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| CN101868493A true CN101868493A (en) | 2010-10-20 |
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| CN200880117329A Pending CN101868493A (en) | 2007-11-21 | 2008-10-08 | Novel compounds for fabric treatment |
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| EP (1) | EP2212374A1 (en) |
| CN (1) | CN101868493A (en) |
| MX (1) | MX2010005404A (en) |
| RU (1) | RU2010125268A (en) |
| WO (1) | WO2009065664A1 (en) |
| ZA (1) | ZA201002993B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103306139A (en) * | 2013-07-10 | 2013-09-18 | 苏州市相城区开来化工有限公司 | Environment-friendly fluorinated polysiloxane waterproof agent |
| CN103502317A (en) * | 2011-05-04 | 2014-01-08 | 庄臣及庄臣视力保护公司 | Macroinitiator containing hydrophobic segment |
| CN106832294A (en) * | 2017-01-21 | 2017-06-13 | 苏州逸微光电科技有限公司 | A kind of new silicon-fluorine polymer thing and surface conditioning agent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703261B (en) * | 2012-06-12 | 2014-04-02 | 大连工业大学 | Cleaning agent for processing of precision part |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3422268C1 (en) * | 1984-06-15 | 1985-07-25 | Goldschmidt Ag Th | Siloxanes containing betaine groups, their production and use in hair care products |
| GB8704002D0 (en) * | 1987-02-20 | 1987-03-25 | Unilever Plc | Conditioning fabrics & compositions |
| US5153294A (en) * | 1991-03-25 | 1992-10-06 | Siltech Inc. | Silicone ester quaternary compounds |
| DE19739991A1 (en) * | 1997-09-11 | 1999-03-18 | Wacker Chemie Gmbh | Aminosiloxane polyether polymers |
| WO1999055953A1 (en) * | 1998-04-27 | 1999-11-04 | The Procter & Gamble Company | Fabric wrinkle control composition and method |
| US6307000B1 (en) * | 1999-06-18 | 2001-10-23 | Gobal Wealth (Bvi) Ltd | Multifunctional nonionic siloxane copolymer for modification of synthetic materials |
| ATE270685T1 (en) * | 2000-07-27 | 2004-07-15 | Ge Bayer Silicones Gmbh & Co | POLYAMMONIUM-POLYSILOXANE COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US6313256B1 (en) * | 2000-12-06 | 2001-11-06 | Siltech Llc | Dimethicone copolyol amido quats |
| DE10214982A1 (en) * | 2002-04-04 | 2003-12-18 | Cht R Beitlich Gmbh | Polysiloxane and textile auxiliaries containing a polysiloxane |
| GB0209134D0 (en) * | 2002-04-22 | 2002-05-29 | Procter & Gamble | Silicones |
| DE102007015372A1 (en) * | 2007-03-28 | 2008-10-02 | Cht R. Beitlich Gmbh | Polysiloxane and textile auxiliaries containing a polysiloxane |
-
2008
- 2008-10-08 RU RU2010125268/04A patent/RU2010125268A/en unknown
- 2008-10-08 WO PCT/EP2008/063442 patent/WO2009065664A1/en active Application Filing
- 2008-10-08 EP EP08805132A patent/EP2212374A1/en not_active Withdrawn
- 2008-10-08 CN CN200880117329A patent/CN101868493A/en active Pending
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502317A (en) * | 2011-05-04 | 2014-01-08 | 庄臣及庄臣视力保护公司 | Macroinitiator containing hydrophobic segment |
| CN103502317B (en) * | 2011-05-04 | 2017-02-08 | 庄臣及庄臣视力保护公司 | Macroinitiator containing hydrophobic segment |
| CN103306139A (en) * | 2013-07-10 | 2013-09-18 | 苏州市相城区开来化工有限公司 | Environment-friendly fluorinated polysiloxane waterproof agent |
| CN106832294A (en) * | 2017-01-21 | 2017-06-13 | 苏州逸微光电科技有限公司 | A kind of new silicon-fluorine polymer thing and surface conditioning agent |
| CN106832294B (en) * | 2017-01-21 | 2019-10-29 | 苏州逸微光电科技有限公司 | A kind of novel silicon-fluorine polymer object and surface treating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201002993B (en) | 2011-07-27 |
| EP2212374A1 (en) | 2010-08-04 |
| MX2010005404A (en) | 2010-06-01 |
| RU2010125268A (en) | 2011-12-27 |
| WO2009065664A1 (en) | 2009-05-28 |
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