CN100540590C - Hydrophilic copolysiloxanes and manufacture method thereof - Google Patents

Hydrophilic copolysiloxanes and manufacture method thereof Download PDF

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CN100540590C
CN100540590C CNB2003801069324A CN200380106932A CN100540590C CN 100540590 C CN100540590 C CN 100540590C CN B2003801069324 A CNB2003801069324 A CN B2003801069324A CN 200380106932 A CN200380106932 A CN 200380106932A CN 100540590 C CN100540590 C CN 100540590C
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group
compound
general formula
copolysiloxanes
carbon atom
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CN1729232A (en
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克里斯蒂安·赫尔齐希
齐格弗里德·多尔迈尔
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Wacker Polymer Systems GmbH and Co KG
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Abstract

The invention discloses a kind of novel hydrophilic silicone copolymers, it is to be made by following steps: in the first step, make each molecule have at least one silicon bond hydrogen atom, the organopolysiloxane (1) that is preferably at least two silicon bond hydrogen atoms with have general formula (I), the oligomeric or high polymeric compound (2) of type reaction R linearly basically 1-(A-C nH 2n) m-A 1-H (I); In second step, make gained have H-A 1The intermediate product of-Ji (4) reacts with the organic compound (5) that each molecule has two isocyanate group at least; Its condition is: in order to the compound (1) of making hydrophilic copolysiloxanes and the water-content of (2), based on the gross weight of compound (1) and (2) for being lower than 2000 ppm by weight.

Description

Hydrophilic copolysiloxanes and manufacture method thereof
Technical field
The present invention relates to hydrophilic copolysiloxanes and manufacture method thereof.
Background technology
US A5 has described a kind of method of making polyurethane(s) in 001,210, wherein with the cyclic carbonate reaction after, with vulcabond or polymeric polyisocyanate amino-functional silicone end of the chain functional group is changed into the purpose product.Used polyethers is the form that is the diamino polyethers, and these diamino polyethers are than polyether Glycols and polyethers monohydroxy-alcohol costliness.
Described by alkenyl polyether and di-isocyanate reaction among the EP-A 1 178 069 and add have the hydrolysis sensitive group silane to make polyethers carbamate intermediate product.Can't make the siloxane chain polymkeric substance with this method.
Chemical Abstracts 136:38808 discloses the branching type polyether silicone.Hydrogen siloxane reacts with divinylsiloxanes and allyl polyether simultaneously.Polyethers excessive in product mixtures still keeps not-connected status.These products are as textile softener, and not amido-containing acid ester base and urea groups.
US 2003/0032726 and the WO 02/088209 (A.Andrew Shores) suitable with it have described the reaction product of following material: (A) polymeric polyisocyanate, (B) contain the silicone resin of a dimethyl polysiloxane fragment and one or more isocyanate-reactive groups, (C) has the reactant of one or more isocyanate-reactive groups and one or more ionogens, and (D) optionally contain one or more isocyanate-reactive groups but do not have the organic substance of ionogen, and (E) provide the compound of counter ion for described ionogen, wherein this silicone resin (B) or this reactant (C) or both are all contained an isocyanate-reactive group.
The reaction product of following material has been described: (A) polymeric polyisocyanate among the US 2003/0032751 (A.Andrew Shores), (B) contain the silicone resin of a dimethyl polysiloxane fragment and one or more isocyanate-reactive groups, (C) has the reactant of one or more isocyanate-reactive groups and one or more ionogens, and (D) optionally contain one or more isocyanate-reactive groups but do not have the organic substance of ionogen, and (E) provide different in nature ionic compound for described ionogen, wherein the molecular-weight average of this reaction product is 600 to 20,000.
Summary of the invention
So the purpose of this invention is to provide hydrophilic copolysiloxanes, wherein said hydrophilic segment or block are that these organic groups work as donor or acceptor when forming hydrogen bond by organic group institute at interval.Another object of the present invention provides hydrophilic copolysiloxanes, and described multipolymer can and can easily disperse in water with simple method manufacturing, especially can promptly form a kind of emulsion, particularly microemulsion, and need not to use emulsifying agent from disperseing.This purpose is realized by the present invention.
The present invention relates to hydrophilic copolysiloxanes, it can be made by following all steps:
In the first step
Make each molecule have at least one silicon bond hydrogen atom, be preferably the linearly oligomeric or high polymeric compound (2) of the type reaction basically of organopolysiloxane (1) with the general formula (I) of at least two silicon bond hydrogen atoms
R 1-(A-C nH 2n) m-A 1-H (I)
Wherein
R 1But additive group Si-H, the univalence hydrocarbyl that randomly is substituted are preferably the alkyl with aliphatic carbons carbon multikey in the hydrogen silylation reactive,
A be selected from two valency polarity organic group :-O-in following group ,-C (O)-O-,-O-C (O)-,-O-C (O)-O-,-C (O)-NH-,-NH-C (O)-, carbamate groups and urea groups, be preferably Sauerstoffatom-O-,
A 1Be be selected from two valency polarity organic group :-O-in following group ,-NH-and-NR '-(wherein R ' is the univalence hydrocarbyl with 1 to 18 carbon atom), be preferably Sauerstoffatom-O-,
N is 1 to 20 integer, is preferably 1 to 4, more preferably 2 or 3, and
M is 0 or positive integer, is preferably 5 to 50;
In second step
Make gained have H-A 1The intermediate product of-Ji (4) reacts with the organic compound (5) that each molecule has two isocyanate group at least;
Its condition is: based on the gross weight of compound (1) and (2), be lower than 2000 ppm by weight in order to the compound (1) of making hydrophilic copolysiloxanes and the water-content of (2), be preferably and be lower than 1500 ppm by weight, more preferably be lower than 1000 ppm by weight.
This water-content is to be benchmark with room temperature (20 ℃) and ambient atmosphere pressure (1,020 hundred pascal).
The viscosity of silicone copolymers of the present invention under 25 ℃ is preferably 1,000 to 100,000,000 milli pascal second, more preferably 10,000 to 10,000,000 milli pascal second.
The invention still further relates to a kind of method in order to the manufacturing hydrophilic copolysiloxanes, it comprises:
In the first step
Make each molecule have at least one silicon bond hydrogen atom, be preferably the linearly oligomeric or high polymeric compound (2) of the type reaction basically of organopolysiloxane (1) with the general formula (I) of at least two silicon bond hydrogen atoms
R 1-(A-C nH 2n) m-A 1-H (I)
Wherein
R 1But additive group Si-H, the univalence hydrocarbyl that randomly is substituted are preferably the alkyl with aliphatic carbons carbon multikey in the hydrogen silylation reactive,
A be selected from two valency polarity organic group :-O-in following group ,-C (O)-O-,-O-C (O)-,-O-C (O)-O-,-C (O)-NH-,-NH-C (O)-, carbamate groups and urea groups, be preferably Sauerstoffatom-O-,
A 1Be be selected from two valency polarity organic group :-O-in following group ,-NH-and-NR 2-(R wherein 2Be univalence hydrocarbyl with 1 to 18 carbon atom), be preferably Sauerstoffatom-O-,
N is 1 to 20 integer, is preferably 1 to 4, more preferably 2 or 3, and
M is 0 or positive integer, is preferably 5 to 50;
In second step
Make gained have H-A 1The intermediate product of-Ji (4) reacts with the organic compound (5) that each molecule has two isocyanate group at least
Its condition is: based on the gross weight of compound (1) and (2), in order to the compound (1) of making hydrophilic copolysiloxanes and the water-content of (2), be lower than 2000 ppm by weight, be preferably and be lower than 1500 ppm by weight, more preferably be lower than 1000 ppm by weight.
Preferably in the first step use linear pattern, ring-like or branching type, have the unitary organopolysiloxane of general formula (II) as organopolysiloxane (1):
R e H f SiO 4 - e - f 2 - - - ( II )
Wherein
R can be identical or different, and the univalence hydrocarbyl that has 1 to 18 carbon atom, randomly is substituted for each group,
E is 0,1,2 or 3,
F is 0,1 or 2,
And e+f and be 0,1,2 or 3,
Its condition is: each molecule has at least one silicon bond hydrogen atom, is preferably at least two silicon bond hydrogen atoms.
Have following general formula person as preferred use of organopolysiloxane (1):
H gR 3-gSiO(SiR 2O) o(SiRHO) pSiR 3-gH g (III)
Wherein
The definition of R is same as described above,
G is 0,1 or 2,
O is 0 or 1 to 1500 integer, and
P is 0 or 1 to 200 integer,
Its condition is: each molecule has at least one silicon bond hydrogen atom, is preferably at least two silicon bond hydrogen atoms.
Within the scope of the present invention, general formula (III) is interpreted as, o unit-(SiR 2O)-and p unit-(SiRHO)-can distribute in any way at this organopolysiloxane intramolecularly.
Be preferably g in the general formula (III) especially and be 1 and general formula (III) in p be 0, and use α, ω-dihydro gather diorganosiloxane, especially preferred α, ω-dihydro polydimethylsiloxane is as organopolysiloxane (1).
The average viscosity of organopolysiloxane (1) preferably is 10 to 1,000 milli pascal seconds under 25 ℃, more preferably is 50 to 1000 milli pascal seconds under 25 ℃, is 60 to 600 milli pascal seconds under 25 ℃.
The example of radicals R is: alkyl, as methyl, ethyl, n-propyl, sec.-propyl, 1-normal-butyl, 2-normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl; Hexyl is as n-hexyl; Heptyl is as n-heptyl; Octyl group, as n-octyl and iso-octyl, as 2,2, the 4-tri-methyl-amyl; Nonyl is as n-nonyl; Decyl is as positive decyl; Dodecyl is as dodecyl; Octadecyl is as the Octadecane base; Cycloalkyl is as cyclopentyl, cyclohexyl, suberyl and methylcyclohexyl; Aryl is as phenyl, naphthyl, anthryl and phenanthryl; Alkaryl, as adjacent-,-, right-tolyl, xylyl and ethylphenyl; And aralkyl, as phenmethyl, α-styroyl and β-styroyl.
The example of the radicals R that is substituted is: haloalkyl, as 3,3,3-three fluoro-n-propyls, 2,2,2,2 ', 2 ', 2 '-hexafluoro sec.-propyl, seven fluorine sec.-propyls, and halogenated aryl, as adjacent-,-and right-chloro-phenyl-.
Radicals R is preferably the univalence hydrocarbyl with 1 to 6 carbon atom, more preferably methyl.
The example of radicals R be applicable to fully radicals R '.
R 1Be preferably univalence hydrocarbyl with aliphatic carbons carbon multikey.
Radicals R 1Example be: thiazolinyl, as vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl group, 3-butenyl and 4-pentenyl, and alkynyl, as ethynyl, propargyl and 1-proyl.
Radicals R 1Be preferably thiazolinyl, more preferably ω-thiazolinyl is preferably allyl group especially.
Used oligomeric or high polymeric compound (2) is preferably the polyethers of general formula (IV):
H 2C＝CH-R 2-(OC nH 2n) m-OH (IV)
Wherein
R 2Be two valency alkyl, be preferably the group of following general formula :-CH with 1 to 20 carbon atom 2-,-CH (CH 3)-or-C (CH 3) 2-, and
The definition of n and m is same as described above.
Polyethers (2) preferred examples is general formula (IV ') person:
H 2C＝CH-R 2-(OCH 2CH 2) a[OCH 2CH(CH 3)] b-OH (IV′)
R wherein 2Definition same as described above, and
A and b are 0 or 1 to 200 integers,
Its condition is: a+b and be at least 1, be preferably 5 to 50.
Other examples oligomeric or high polymeric compound (2) are: unsaturated polyester, and as H 2C=CH-R 2-[O (O) CC nH 2n] m-OH, the unsaturated polyester carbonic ether is as H 2C=CH-R 2-[OC (O) OC nH 2n] m-OH, and unsaturated polyester acid amides are as H 2C=CH-R 2-[NHC (O) C nH 2n] m-NH 2, R wherein 2, n and m definition same as described above.
In the first step, compound (2) usage quantity of every grammeatom silicon bond hydrogen is preferably 1.0 to 4.0 in the organopolysiloxane (1), more preferably 1.3 to 2.5 moles of radicals R 1, this radicals R 1Be preferably group, more preferably ω-thiazolinyl with aliphatic carbons carbon multikey.
The preferred catalyzer (3) that uses is to impel silicon bond hydrogen and aliphatic multikey addition in the first step.The used catalyzer (3) of the inventive method also can be with identical in order to the catalyzer that impels silicon bond hydrogen and aliphatic multikey addition at present.These catalyzer are preferably the metal that belongs to platinum family or belong to the compound or the complex compound of platinum family.The example of these catalyzer is: can place the compound or the complex compound of metal platinum finely divided on the carrier such as silicon-dioxide, aluminum oxide or gac, platinum, halogenation platinum for example is as PtCl 4, H 2PtCl 66H 2O, Na 2PtCl 44H 2O, platinum-alkene complex compound, platinum-alcohol complex, platinum-alcoholate complex compound, platinum-ether complexes, platinum-aldehyde complex compound, platinum-ketone complex compound, comprise H 2PtCl 66H 2The reaction product of O and pimelinketone, platinum-vinylsiloxane complex compound, as contain or do not contain the platinum-1 of detectable inorganic bond halogen, 3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound, molybdenyl dichloride (γ-picolyl) platinum, dichloride trimethylene bipyridyl platinum, dichloride dicyclopentadienyl platinum, dichloride dimethyl sulphide oxygen base ethylidene platinum (II), dichloride cyclooctadiene base platinum, dichloride norbornadiene base platinum, dichloride γ-picolyl platinum, dichloride cyclopentadienyl platinum, and Tetrachloroplatinum is with the reaction product of alkene and primary amine or secondary amine or primary amine and secondary amine, as is dissolved in the reaction product of Tetrachloroplatinum and the sec-butylamine or the ammonium-platinum complex of 1-octene.
The usage quantity of catalyzer in the first step (3) is calculated with elements platinum and based on the gross weight of organopolysiloxane (1) and compound (2), is preferably 1 to 50 ppm by weight, more preferably 2 to 20 ppm by weight.
Preferably under environment atmospheric pressure, promptly about 1,020 hundred pascals (definitely) implement down the first step, but also can implement under higher or lower pressure.In addition, the first step is preferably implemented under 60 ℃ to 140 ℃ temperature, more preferably 80 ℃ to 120 ℃.
Preferably in second step use logical formula V person that each molecule has at least two isocyanate group as organic compound (5):
O＝C＝N-R 3-N＝C＝O (V)
R wherein 3Be the two valency alkyl that each group has 4 to 40 carbon atoms.
The example of organic compound (5) is: 1, hexamethylene-diisocyanate, isophorone diisocyanate, methylene phenyl-2,4-vulcabond, methylene phenyl-2,6-vulcabond, phenylene-1,3-vulcabond, 4,4 '-methylene-bis (cyclohexyl isocyanate), 4,4 '-methylene-bis (phenyl isocyanate) and dimethyl benzene group diisocyanate.
The usage quantity of organic compound (5) is preferably in second step: with respect to contained every mole of H-A in the intermediate product (4) 1-Ji has 0.5 to 1.0 mole of isocyanate group, more preferably 0.8 to 1.0 mole.
Opposite with method of the present invention, when beginning, among described US 2003/0032726 and the US2003/0032751, all use with isocyanate-reactive group to be the obvious excessive polymeric polyisocyanate of benchmark.Use less amount during beginning in the described United States Patent (USP), this is because less amount increases the viscosity of product, thereby makes it be difficult to handle and need solvent.Therefore it has at the amount of the used polymeric polyisocyanate of the present invention (5) the obvious prejudice less than 0.5 to 1.0 mole.
Condensation catalyst (6) is preferably used in reaction in second step of the inventive method, as di-n-butyltin dilaurate, stannous octoate (II), dibutyltin diacetate, potassium octanoate or tertiary amine, as dimethylcyclohexylam,ne, dimethylaminopropyl dipropanolamine, pentamethyl-dipropylenetriamine, N-Methylimidazole or N-ethylmorpholine.
Preferred silicone copolymers can be made by following all steps: in the first step, excessive α, ω-dihydro gather polyethers (2) reaction of diorganosiloxane (1) and general formula (IV); And in second step, make vulcabond (5) reaction of intermediate product (4) HO-polyether-polysiloxane-polyethers-OH and logical formula V, wherein carbamate groups is introduced in the silicone copolymers.Free polyethers from the first step also passes through to form carbamate and bond:
CH 2＝CH-R 2-(OC nH 2n) m-OC(O)NH-R 3-NHC(O)O[(C nH 2nO) m-R 2-CH 2CH 2-R 2SiO(R 2SiO) o-R 2SiO-CH 2CH 2-R 2-(OC nH 2n) m-OC(O)NH-R 3-NHC(O)O] x(C nH 2nO) m-R 2-CH＝CH 2?(VI)，
Wherein R, R 2, R 3, n, m and o definition same as described above, and
X is 0 or 1 to 20 integer, is preferably 0 or 1 to 4 integer.
Carbamate groups in the hydrophilic copolysiloxanes of the present invention can be used as donor when forming hydrogen bridge band and acceptor works.
In second step of the inventive method, except that organic compound (5), also can use isocyanate group is had reactive other compounds (7).The example of other compounds (7) is for being selected from following general formula person:
R 4-(A-C nH 2n) m-A 1-H (VII)，
HO-R 5-NR 4-R 5-OH (VIII)，
HO-R 5-NR 4 2 (IX)，
HO-R 6(NR 4 2) 2 (X)，
HO-R 7(NR 4 2) 3 (XI)，
(HO) 2R 6-NR 4 2 (XII)，
HNR 4 2 (XIII)，
R wherein 4Be hydrogen atom or the optional radicals R that contains one or more nitrogen-atoms,
R 5For each group has two valency alkyl of 1 to 10 carbon atom,
R 6For each group has 1 to 100 carbon atom, contains the trivalent organic group of one or more Sauerstoffatoms, be preferably trivalent hydrocarbon radical with 1 to 100 carbon atom,
R 7For each group has 1 to 100 carbon atom, contains the quadrivalent organic radical group of one or more Sauerstoffatoms, be preferably tetravalence alkyl with 1 to 100 carbon atom,
A 1, n and m definition same as described above.
General formula (VII) examples for compounds is: methyl polyethylene oxide, butyl polyethylene oxide, methyl polyethylene/polypropylene oxides and methyl poly(propylene oxide).
General formula (VIII) examples for compounds is: N methyldiethanol amine, N-methyl dipropanolamine, dimethylaminopropyl dipropanolamine, N-dodecyl diethanolamine and N-stearyl dipropanolamine.
General formula (IX) examples for compounds is: N, N-dimethylethanolamine, N, N-diethylpropanolamine, N, N-dimethylaminopropyl Mono Methyl Ethanol Amine and dimethyl-2-(2-amino ethoxy) ethanol.
General formula (X) examples for compounds is: 1, and two (the dimethylamino)-pentanes of 5--3-alcohol, 1, two (the methylamino)-pentanes of 5--3-alcohol, 1, the two pure and mild N of (dimethylamino)-heptane-4-of 7-, two (3-the dimethylaminopropyl)-N-Yi Bingchunans of N-.
General formula (XI) examples for compounds is: 2,4, and 6-three (dimethylaminomethyl) phenol, 1,1,1-three (dimethylaminomethyl) methyl alcohol and 2,4,6-three (dimethylaminomethyl) hexalin.
General formula (XII) examples for compounds is:
N, two (the dimethylaminopropyl)-3-aminopropanes-1 of N-, the 2-glycol,
N, two (the dimethylaminopropyl)-2-aminopropane-1 of N-, the 3-glycol,
N, two (3-the dimethylaminopropyl)-carboxylamine direactive glycerides of N-.
General formula (XIII) examples for compounds is: dibutylamine, octylame, benzylamine, 3-(cyclohexyl amino) propylamine, 2-(diethylamino) ethamine, dipropylenetriamine, isophorone diamine, dimethylaminopropyl methylamine, aminopropyl morpholine, N, two (dimethylaminopropyl) amine of N-, dimethylamino propylamine.
The compound of general formula (VIII) to (XIII) is used in the nitrogen that introducing can be protonated in the silicone copolymers.
The usage quantity of second step formula of (VII) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of H-A 1-Ji, more preferably 0 to 1 mole.
The usage quantity of second step formula of (VIII) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of HO-base, more preferably 0 to 1 mole.
The usage quantity of second step formula of (IX) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of HO-base, more preferably 0 to 1 mole.
The usage quantity of second step formula of (X) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of HO-base, more preferably 0 to 1 mole.
The usage quantity of second step formula of (XI) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of HO-base, more preferably 0 to 1 mole.
The usage quantity of second step formula of (XII) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of HO-base, more preferably 0 to 1 mole.
The usage quantity of second step formula of (XIII) compound is preferably: with respect to contained every mole of H-A in the compound (2) 1-Ji has 0 to 2 mole of HN-base, more preferably 0 to 1 mole.
For the isocyanate group of guaranteeing insalubrity complete reaction safely, even under the situation of using compound (7), when in shortage, preferably use polymeric polyisocyanate (5).Therefore the usage quantity of organic compound (5) is preferably in second step: with respect to contained every mole of isocyanate-reactive group in intermediate product (4) and the compound (7), have 0.5 to 1.0 mole of isocyanate group altogether, more preferably 0.8 to 1.0 mole.
Second step, promptly about 1,020 hundred pascals (definitely) implemented down, but also can implement under higher or lower pressure preferably at environment atmospheric pressure.In addition, second step was preferably implemented more preferably 60 ℃ to 100 ℃ under 40 ℃ to 140 ℃ temperature.
For part reduces the very high viscosity of product, can choose wantonly and add low-molecular-weight material, as alcohol or ether.The example is: ethanol, Virahol, propyl carbinol, butoxy ethanol, diethylene glycol monobutyl ether, tetrahydrofuran (THF), diethylene glycol diethyl ether and glycol dimethyl ether, wherein diethylene glycol monobutyl ether is a preferred examples.Under the very high situation of the viscosity of product, preferred addition is the highest 50 weight %, more preferably the highest 30 weight % based on hydrophilic copolysiloxanes of the present invention.Other advantages of this additive are: products made thereby disperses in water than pure siloxane multipolymer is easier.
Need not other auxiliarys such as emulsifying agent, silicone copolymers of the present invention can easily disperse in water, therefore can disperse certainly, and make emulsion, especially microemulsion.
So the emulsion of the present invention relates to is preferably microemulsion, it comprises:
(A) hydrophilic copolysiloxanes of the present invention, and
(B) water.
The content of hydrophilic copolysiloxanes of the present invention (A) is preferably 20 to 60 weight % in this emulsion, more preferably 30 to 50 weight %.
The invention still further relates to and a kind ofly be preferably the method for microemulsion in order to make emulsion, it is by mixing:
(A) hydrophilic copolysiloxanes of the present invention, and
(B) water.
The technology that is used to make organic silicon emulsion is known.Usually with silicone copolymers of the present invention and water simple agitation in addition, randomly use rotor-stator homogenizer, colloidal mill or high-pressure homogenizer homogenizing in addition subsequently.
Embodiment
Embodiment 1:
With 491 grams, have 0.055 weight % silicon bond hydrogen, water-content is the α of 50 ppm by weight, ω-dihydro polydimethylsiloxane restrained, has following general formula with 1001 allyl alcohol b-oxide/propoxide mixes:
H 2C＝CH-CH 2-(OCH 2CH 2) a[OCH 2CH(CH 3)] b-OH，
The ratio of a: b=1.0 wherein, water-content is that 978 ppm by weight and iodine number are 13.7 (iodine number is represented in per 100 grams material to be detected gram number with aliphatic multikey iodine that addition consumes), with this mixture heating up to 100 ℃, and by measuring with 0.28 gram, concentration is 2.7 weight % (are benchmark with the elements platinum), 25 ℃ of following viscosity is 1000 milli pascal seconds, platinum-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound is at α, solution in ω-divinyl dimethyl polysiloxane, the solution (its manufacture method is referring to US 3,775, described in 452) that is so-called Karstedt catalyzer adds in this mixture.Make the temperature of reaction mixture raise about 6 ℃, under this temperature, add the catalyzer of equivalent again by metering.Make this reaction mixture homogenizing then.After reaction under 100 to 110 ℃ 1 hour, make the sample cooling of polyether-polysiloxane intermediate product, its viscosity under 25 ℃ is 2,220 square millimeters/second.
Under 100 ℃, restrain hexamethylene diisocyanates (contained every mole of HO-base has 1.0 moles of isocyanate group in respect to intermediate product), and react with the formation of 100 milligrams of di-n-butyltin dilaurate catalytic amino manthanoate by being metered into 45.5.After two hours, under 100 ℃, make clarifying reaction product cooling.Its viscosity under 25 ℃ is about 100,000 milli pascal seconds.
Heavy oil with 40 grams under 50 ℃ mixes with the water of 60 grams.This product is easy to emulsification, and the formation urethane content is the oyster white microemulsion of 0.14 milliequivalent/gram.
Comparative example:
Spirit according to embodiment 1 repeats, and wherein for relatively, uses the polyethers of other batchings, and its working condition is for containing 3, the water of 620ppm.With regard to total batching, water-content is 2 now, 350ppm, but not 636ppm.
When reacting, produce a large amount of foams with hexamethylene diisocyanate.Behind the reaction terminating, the oil that acquisition almost can't be stirred after the water of 1.5 times of amounts of adding (oil-contg is 40%), does not form emulsion automatically.Apply high shearing for a long time with the Turrax device, form muddy and uneven mixture.
Embodiment 2:
With 960 grams, water-content be 50 ppm by weight, from the α of embodiment 1, the polyethers that ω-dihydro polydimethylsiloxane restrains with 536, water-content is 686 ppm by weight, have a following general formula mixes:
H 2C＝CH-CH 2-(OCH 2CH 2) 10.2-OH，
And be heated to 100 ℃.Add the Karstedt catalyst solution described in the 0.28 gram embodiment 1 then, the temperature of reaction mixture rises to 19 ℃ thus, and forms clarifying product.Under 100 to 110 ℃, silicon bond hydrogen all transforms after 1 hour.The viscosity of this polyether-polysiloxane intermediate product under 25 ℃ is 760 square millimeters/second.
Successively by being metered into 63 N methyldiethanol amines that restrain (with respect to contained every mole of HO-base in the polyethers, have 1.02 moles of HO-yls) and 178 grams 1, hexamethylene-diisocyanate (, having 0.99 mole of isocyanate group altogether) with respect to contained every mole of HO-base in intermediate product and the N methyldiethanol amine.Formation reaction with 100 milligrams di-n-butyltin dilaurate catalytic amino manthanoate.At 100 ℃ of following 2 hours postcooling, and at 70 ℃ of acetate that add 64 grams down.The viscosity of clarifying brown product under 25 ℃ is 120,000 milli pascal seconds.
Under 50 ℃, the heavy oil of 40 grams and the water of 60 grams are mixed.Under gentle agitation, form urethane content and be 0.39 milliequivalent/gram and amine number and be 0.12 (this amine number corresponding in and milliliter number of the required 1N hydrochloric acid of 1 gram material).
Embodiment 3:
With 1411 grams from allyl alcohol b-oxide/propoxide of embodiment 1 and 813 grams, have the α of 0.052 weight % silicon bond hydrogen, ω-dihydro polydimethylsiloxane mixes, and is heated to 100 ℃ of thoroughly stirrings.Catalysis was in an identical manner reacted after 1 hour, and the viscosity of polyether-polysiloxane intermediate product under 25 ℃ of acquisition is 2,490 square millimeters/second.
Under 100 ℃, be stirred into the N of 83 grams, two (3-the dimethylaminopropyl)-N-Yi Bingchunans of N-, and by the hexamethylene diisocyanate that is metered into 92 grams.The NCO-base is 0.995 with ratio with the organic group total amount of its reaction, if consider wherein contained water, then only is 0.87.Weak thermopositive reaction post-heating to 120 ℃, adds 50 milligrams dibutyl tin laurate after, continue reaction 3 hours and in IR, can not detect viscosity increase simultaneously again until isocyanic ester.Very heavy-gravity oil contains the basic nitrogen of 0.42 milliequivalent/gram under 25 ℃.
Embodiment 4:
With the α of 635 grams from embodiment 3, ω-dihydro polydimethylsiloxane and the polyether reactant that restrains, has following general formula as 205 among the embodiment 2:
H 2C＝CH-CH 2-(OCH 2CH 2) 9.5-OH
The OH concentration of this polyether-polysiloxane intermediate product is 0.512 milliequivalent/gram, and contains the water of 177ppm.
200 these intermediate products of gram are mixed with two (dimethylaminopropyl) amine of 10.3 grams, and be heated to 84 ℃; By being metered into 13.2 gram hexamethylene diisocyanates.
The NCO-base is 0.998 with ratio with the organo-functional group total amount of its reaction, then is 0.97 if count water.
Under the situation of not having other katalysis, under about 90 ℃, in 1 hour, in weak thermopositive reaction, realize the conversion fully of isocyanate group.This polymeric blends contains the basic nitrogen of 0.49 milliequivalent/gram.
With restraining these polymkeric substance with 32 in the solution of 1.04 gram acetate in 8 gram diethylene glycol monobutyl ethers.After stirring with spatula with the water of 60 grams, form flaxen microemulsion automatically.
Embodiment 5:
Made 200 gram polyether-polysiloxane intermediate products (0.512 millinormal OH/g) among the embodiment 4 and extra 26.2 grams are used for its synthetic polyethers and two (dimethylaminopropyl) amine reactions of 14.8 grams, and are heated to 80 ℃.Add 19.8 gram hexamethylene diisocyanates, begin the demulcent thermopositive reaction immediately, and after under 90 ℃ about 2 hours, stop, can not detect isocyanic ester again.NCO has been 0.995 when not including entry with ratio with group (OH, the NH) total amount of its reaction, if consider that contained water then only is 0.97.The concentration of the basic nitrogen of this high-viscosity polymer mixture is 0.60 milliequivalent/gram.
Be the preparation microemulsion,, stir with 60 water that restrain then with in the solution of 1.29 gram acetate in 8 gram diethylene glycol monobutyl ethers and these products of 32 grams.
Embodiment 6:
200 made among the embodiment 4 gram polyether-polysiloxane intermediate products (0.512 millinormal OH/g) only are heated to 88 ℃ with two (dimethylaminopropyl) amine of 4.5 grams, and do not add polyethers.Add 10.6 gram hexamethylene diisocyanates, the weak thermopositive reaction of beginning.The NCO-base is 0.998 with ratio with the organo-functional group total amount of its reaction, if consider that the water that exists in the reaction mixture then is 0.97.
At 100 ℃ after following 1 hour, promptly detect less than isocyanic ester.The basic n content of this high-viscosity polymer is 0.22 milliequivalent/gram.
With restraining alkaline product with 32 in the solution of 0.46 gram acetate in 8 gram diethylene glycol monobutyl ethers, be stirred into 60 gram water, promptly make stable microemulsion liquid.

Claims (11)

1. hydrophilic copolysiloxanes, it is to be made by following steps:
In the first step
Make linear oligomeric or high polymeric compound (2) reaction of organopolysiloxane (1) that each molecule has at least one silicon bond hydrogen atom and general formula (I),
R 1-(A-C nH 2n) m-A 1-H (I)
R wherein 1But be the univalence hydrocarbyl of additive group Si-H in the hydrogen silylation reactive,
A be selected from two valency polarity organic group :-O-in following group ,-C (O)-O-,-O-C (O)-,-O-C (O)-O-,-C (O)-NH-,-NH-C (O)-, carbamate groups and urea groups,
A 1Be be selected from two valency polarity organic group :-O-in following group ,-NH-and-NR '-, wherein R ' is the univalence hydrocarbyl with 1 to 18 carbon atom,
N is 1 to 20 integer, and
M is 0 or positive integer;
In second step
Make gained have H-A 1The intermediate product of-Ji (4) reacts with the organic compound (5) that each molecule has two isocyanate group at least;
Its condition is: based on the gross weight of compound (1) and (2), be lower than 1500 ppm by weight in order to the compound (1) of making hydrophilic copolysiloxanes and the water-content of (2), and each molecule has the usage quantity of the organic compound (5) of at least two isocyanate group and is: with respect to contained every mole of H-A in the intermediate product (4) 1-Ji has 0.5 to 1.0 mole of isocyanate group.
2, hydrophilic copolysiloxanes as claimed in claim 1 is characterized in that, used organopolysiloxane (1) is following general formula person:
H gR 3-gSiO(SiR 2O) o(SiRHO) pSiR 3-gH g (III)
Wherein
R is identical or different, and for each group has the univalence hydrocarbyl of 1 to 18 carbon atom,
G is 0,1 or 2,
O is 0 or 1 to 1500 integer, and
P is 0 or 1 to 200 integer,
Its condition is: each molecule has at least one silicon bond hydrogen atom.
3, hydrophilic copolysiloxanes as claimed in claim 2 is characterized in that, organopolysiloxane (1) is α, ω-dihydro diorganopolysiloxaneand.
4, as the hydrophilic copolysiloxanes of one of claim 1 to 3, it is characterized in that A and A in the general formula (I) 1Be Sauerstoffatom-O-.
As the hydrophilic copolysiloxanes of one of claim 1 to 3, it is characterized in that 5, compound (2) is the polyethers with following general formula:
H 2C＝CH-R 2-(OC nH 2n) m-OH (IV)
R wherein 2Be two valency alkyl with 1 to 10 carbon atom, and
The definition of n and m is identical with claim 1.
As the hydrophilic copolysiloxanes of one of claim 1 to 3, it is characterized in that 6, compound (5) is the vulcabond with following general formula:
O＝C＝N-R 3-N＝C＝O (V)
R wherein 3Be the two valency alkyl that each group has 4 to 40 carbon atoms.
7, as the hydrophilic copolysiloxanes of one of claim 1 to 3, it is characterized in that, use the compound be selected from following general formula as other compounds (7) in second step:
R 4-(A-C nH 2n) m-A 1-H (VII)，
HO-R 5-NR 4-R 5-OH (VIII)，
HO-R 5-NR 4 2 (IX)，
HO-R 6(NR 4 2) 2 (X)，
HO-R 7(NR 4 2) 3 (XI)，
(HO) 2R 6-NR 4 2 (XII)，
HNR 4 2 (XIII)，
Wherein
R 4Be hydrogen atom or the optional radicals R that contains nitrogen-atoms,
R 5For each group has two valency alkyl of 1 to 10 carbon atom,
R 6For each group has 1 to 100 carbon atom and contains the trivalent organic group of one or more Sauerstoffatoms,
R 7For each group has 1 to 100 carbon atom and contains the quadrivalent organic radical group of one or more Sauerstoffatoms,
A 1, n and m definition identical with claim 1.
As the hydrophilic copolysiloxanes of one of claim 1 to 3, it is characterized in that 8, it is following general formula person:
CH 2＝CH-R 3-(OC nH 2n) m-OC(O)NH-R 2-NHC(O)O[(C nH 2nO) m-R 3-CH 2CH 2-R 2SiO(R 2SiO) o-R 2SiO-CH 2CH 2-R 3-(OC nH 2n) m-OC(O)NH-R 2-NHC(O)O] x(C nH 2nO) m-R 3-CH＝CH 2 (VI)，
Wherein
R is identical or different, and for each group has the univalence hydrocarbyl of 1 to 18 carbon atom,
R 2For having two valency alkyl of 1 to 10 carbon atom,
R 3For each group has two valency alkyl of 4 to 40 carbon atoms,
N is 1 to 20 integer,
M is a positive integer,
O is 0 or 1 to 1500 integer, and
X is 0 or 1 to 20 integer.
9, a kind of in order to make the method as the hydrophilic copolysiloxanes of one of claim 1 to 8, this method comprises following all steps:
In the first step
Make linear oligomeric or high polymeric compound (2) reaction of organopolysiloxane (1) that each molecule has at least one silicon bond hydrogen atom and general formula (I),
R 1-(A-C nH 2n) m-A 1-H (I)
Wherein
R 1But be the univalence hydrocarbyl of additive group Si-H in the hydrogen silylation reactive,
A be selected from two valency polarity organic group :-O-in following group ,-C (O)-O-,-O-C (O)-,-O-C (O)-O-,-C (O)-NH-,-NH-C (O)-, carbamate groups and urea groups,
A 1Be be selected from two valency polarity organic group :-O-in following group ,-NH-and-NR '-, wherein R ' is the univalence hydrocarbyl with 1 to 18 carbon atom,
N is 1 to 20 integer, and
M is 0 or positive integer;
In second step
Make gained have H-A 1The intermediate product of-Ji (4) reacts with the organic compound (5) that each molecule has two isocyanate group at least;
Its condition is: based on the gross weight of compound (1) and (2), be lower than 1500 ppm by weight in order to the compound (1) of making hydrophilic copolysiloxanes and the water-content of (2), and each molecule has the usage quantity of the organic compound (5) of at least two isocyanate group and is: with respect to contained every mole of H-A in the intermediate product (4) 1-Ji has 0.5 to 1.0 mole of isocyanate group.
10, emulsion, it comprises:
(A) as the hydrophilic copolysiloxanes of one of claim 1 to 8, and
(B) water.
11, in order to make the method as the emulsion of claim 10, it obtains by mixing following material:
(A) as the hydrophilic copolysiloxanes of one of claim 1 to 8, and
(B) water.
CNB2003801069324A 2002-12-19 2003-12-18 Hydrophilic copolysiloxanes and manufacture method thereof Expired - Fee Related CN100540590C (en)

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