CN112513148A - Modified resin aqueous dispersion liquid - Google Patents
Modified resin aqueous dispersion liquid Download PDFInfo
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- CN112513148A CN112513148A CN201880095940.XA CN201880095940A CN112513148A CN 112513148 A CN112513148 A CN 112513148A CN 201880095940 A CN201880095940 A CN 201880095940A CN 112513148 A CN112513148 A CN 112513148A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Abstract
The present invention relates to an aqueous modified resin dispersion containing a nonionic emulsifier having an HLB value of 12 or more and a silicone-modified polyester resin. It can be widely applied to the field of coatings.
Description
Technical Field
The present invention relates to an aqueous modified resin dispersion. It can be widely applied to the field of coatings.
Background
The polysiloxane modified resin has wide application value, especially in the coating industry. It can be used for producing high temperature resistant coating, powder coating, weather-proof protective coating, H-grade insulating paint, sealing coating for electric appliance components, glass cloth impregnation coating, glass tube coating, wire enamel, metal plate coil coating and the like.
The modification method of the polysiloxane modified resin comprises a physical blending method and a chemical method. The physical blending method can easily cause microphase separation of products, thereby reducing the mechanical hardness. The chemical modification can be carried out by connecting other organic resins on the tail end or a side chain of a polysiloxane main chain through condensation polymerization, free radical polymerization and addition reaction to form a block, graft or interpenetrating network copolymer; or condensation reaction of hydroxyl or alkoxy silane or siloxane and hydroxyl or alkoxy low molecular weight polyester resin or its intermediate in the presence of catalyst.
The reaction of the polysiloxane with the resin may be carried out in solution beforehand or at the time of film formation. In the coatings industry, when other organic resins are modified with silicone intermediates, the proportion of silicone intermediate in the final product is generally between 5 and 80% by weight. When the proportion is less than 10 wt%, the modification effect is not obvious; ratios higher than 50 wt% are too costly. The polysiloxane modified resin mainly comprises polysiloxane modified alkyd resin, polyester resin, polyacrylate, epoxy resin, polyurethane and the like. However, the current products of polysiloxane modified polyester resin are mainly solvent-based, and the content of the solvent can reach 35 wt% or more, and the production and application processes thereof have negative effects on the environment and the health of production line personnel.
Disclosure of Invention
The invention unexpectedly discovers a polysiloxane modified polyester resin aqueous system which has the advantages of good stability and good yellowing resistance. When a suitable emulsifier is selected, the aqueous system can also be used to prepare food-contact appliances.
The technical scheme for achieving the purpose of the invention can be summarized as follows:
an aqueous system of polysiloxane modified polyester resin, which contains a nonionic emulsifier with HLB value more than or equal to 12, wherein the nonionic emulsifier contains ethylene oxide repeating units;
the polysiloxane modified polyester resin is in discontinuous oil phase; the polysiloxane modified polyester resin is prepared by co-condensation reaction of polyester or polyester intermediate product containing alkoxy and/or hydroxyl and polysiloxane intermediate a containing alkoxy and/or hydroxyl under the condition of using catalyst or not using catalyst; the polysiloxane intermediate a is a silicon resin containing silanol and/or siloxy;
further, it comprises 1-50 wt%, preferably 1-30 wt%, more preferably 1-20 wt%, more preferably 1-10 wt%, more preferably 3-8 wt% in the discontinuous oil phase; more preferably 5 to 7% by weight of silicone intermediate b, based on 100% by weight of the aqueous system.
The aqueous system as described above wherein there is no chemical linkage between the silicone intermediate b and the silicone modified polyester resin, polyester or polyester intermediate.
The aqueous system as described above, wherein the aqueous system has a chemical bond between a part of reactive functional groups on the silicone intermediate b, which is less than or equal to 50%, preferably less than or equal to 30%, preferably less than or equal to 10%, calculated as 100 mol% of all reactive functional groups in the silicone intermediate b, and the silicone modified polyester resin, polyester or polyester intermediate after 12 months of storage at 23 ℃.
The aqueous system as described above, wherein the silicone intermediate a is present in an amount of between 5 and 80 wt% of the silicone-modified polyester resin; preferably between 15 and 60 wt%; more preferably between 15 and 50 wt%, based on 100 wt% polysiloxane modified polyester resin.
The aqueous system as described above, wherein the silicone intermediate b is present in an amount of between 5 and 25 wt% of the silicone-modified polyester resin; preferably between 8 and 20 wt%; more preferably between 10 and 18 wt%, based on 100 wt% of the polysiloxane modified polyester resin.
The aqueous system as described above wherein the amount of polysiloxane modified polyester resin is between 10 and 50 wt%, preferably between 30 and 45 wt%, based on 100 wt% aqueous system.
An aqueous system as described above wherein under one atmosphere of conditions, the melting point of silicone intermediate a and/or silicone intermediate b is 85 ℃ or less; preferably 23 ℃ or lower; more preferably 5 ℃ or lower.
The aqueous system as described above, wherein the content of alkoxy and/or hydroxyl groups of the silicone intermediate a is 3 wt% or more; preferably 10 wt% or more and 30 wt% or less; more preferably 12 wt% or more and 20 wt% or less; calculated on 100 wt% of silicone intermediate a.
The aqueous system as described above, wherein the content of alkoxy and/or hydroxyl groups of the silicone intermediate b is 3 wt% or more; preferably 10 wt% or more and 30 wt% or less; more preferably 12 wt% or more and 20 wt% or less; calculated on 100 wt% of silicone intermediate b.
Higher alkoxy and/or hydroxyl content means that the polysiloxane intermediate a is more reactive with the polyester or polyester intermediate.
The aqueous system as described above, wherein the hydroxyl group content of the silicone intermediate b is 10% by weight or less; preferably less than or equal to 5 wt%; more preferably 3% by weight or less, based on 100% by weight of silicone intermediate b.
An aqueous system as described above wherein the silicone intermediate a and/or the silicone intermediate b have methyl and/or phenyl substituents thereon.
The aqueous system as described above, wherein the weight average molecular weight Mw of the silicone intermediate a and/or the silicone intermediate b is between 500 and 3000 g/mol; preferably between 900-2000 g/mol.
An aqueous system as described above wherein silicone intermediate b is the same or different from silicone intermediate a.
The aqueous system as described above, wherein the oil phase comprises the silicone-modified polyester resin, the solvent and the silicone intermediate b.
An aqueous system as described above wherein the oil phase does not contain an emulsifier.
The aqueous system as described above, wherein the calculated HLB value of the single nonionic emulsifier or the combination of all nonionic emulsifiers is ≥ 17; preferably the calculated HLB value is greater than or equal to 18; more preferably the calculated HLB value is greater than or equal to 18.5; more preferably 22. gtoreq. HLB calculated value ≥ 18.5; more preferably 20. gtoreq. HLB calculated value.gtoreq.18.5.
The aqueous system as described above, wherein the nonionic emulsifier is a combination of one or more of the formulas (Ia) to (IV),
R1[CH2CH2O]nH (Ia)
HO[CH2CH2O]mR*1[CH2CH2O]nH (Ib)
HO[CH2CH2O]p[CH2CH(CH3)O]r[CH2CH2O]qH (II)
HO[CH2CH(CH3)O]d[CH2CH2O]e[CH2CH(CH3)O]fH (III)
wherein R is1Is of the general formula R (C ═ O)kA monovalent radical of O-, wherein R is a monovalent C5-C20 hydrocarbon radical, k is 0 or 1,
preferably R1Is a monovalent C6-C20 alkoxy group or phenol group or alkoxycarbonyl group, more preferably an undecyloxy group, a dodecyloxy group, a hexadecyloxy group, an octadecyloxy group, an octadecyloxycarbonyl group, a nonylphenol group, an octylphenol group, a dodecylphenol group,
R*1is represented by the general formula-R (C ═ O)lDivalent radicals of O-, wherein R is a divalent C5-C20 hydrocarbon radical, l is 0 or 1,
and p is 0 or a positive integer, m, n, q, r, d, e, f are positive integers, and p + q > r, d + f < e,
the number-average molecular weight Mn of the formulae (Ia), (Ib), (II), (III) ranges between 1000 and 30000 g/mol; preferably between 3000 and 20000 g/mol;
wherein R is5Is a divalent C4-C24 alkylene radical, preferably C6-C20 alkylene, C6-C20 monooleene, C6-C20 diolefine, C6-C20 tetraolefin,
R6is a monovalent C4-C24 hydrocarbon group, preferably C6-C20 alkyl, C6-C20 monoolefin, C6-C20 diolefin, C6-C20 tetraolefin,
R7is an alkyl group from H, C1 to C3, preferably H,
R8is a hydrocarbon radical of C6-C20, or
R9Is a hydrocarbon radical of C6-C20, or
x, y and z are 0 or positive integers, and x, y and z are not 0 at the same time; preferably x + y + z is equal to or greater than 36;
-EO-is an ethylene oxide unit.
The aqueous system as described above, wherein the non-ionic emulsifier is selected from one or more of the following group: ethylene oxide propylene oxide copolymer, stearic acid polyoxyethylene ester, stearyl alcohol polyoxyethylene ether, C16-C18 alcohol polyoxyethylene ether, C12-C14 alcohol polyoxyethylene ether, C16-C18 fatty acid polyoxyethylene ester, C12-C14 fatty acid polyoxyethylene ester, ethylene oxide modified castor oil, ethylene oxide modified hydrogenated castor oil and nonylphenol polyoxyethylene ether; and the calculated HLB value of the nonionic emulsifiers in the set is greater than or equal to 17.
An aqueous system as described above, wherein the non-ionic emulsifier is a linear or branched C16-C18 alcohol ethoxylate and/or a linear or branched C12-C14 alcohol ethoxylate; preferably, when the hydrophobic segment is a linear or branched C12-14 alcohol, the EO number is between 100-160, and when the hydrophobic segment is a linear or branched C16-18 alcohol, the EO number is between 120-180; more preferred are linear or branched C12-14-EO120, linear or branched C12-14-EO100, linear or branched C16-18-EO 120.
The aqueous system as described above, wherein the non-ionic emulsifier is used in an amount of between 0.16 and 3 wt% based on the mass of the whole aqueous system; preferably between 0.5 and 2.5 wt.%, more preferably between 1 and 2 wt.%, calculated on 100 wt.% of the aqueous system.
An aqueous system as described above, wherein the weight ratio of all oil phases to emulsifier is between 30 and 50, preferably between 35 and 50; more preferably between 40 and 50, more preferably between 45 and 50.
The aqueous system as described above, wherein water is the continuous phase, and the mass percent of water in the entire aqueous system is between 15 and 90 wt%; preferably between 25 and 40 wt.%, more preferably between 35 and 40 wt.%, calculated on the basis of 100 wt.% of the aqueous system.
An aqueous system as described above having a solids content in the range of from 10 to 65% by weight; preferably between 20 and 60 wt%; more preferably between 40 and 55 wt%, based on 100 wt% aqueous system.
An aqueous system as described above, the system comprising an emulsion, an emulsion and a suspension; the system is preferably emulsion, wherein the particle size of the emulsion is 100nm-2000 nm; more preferred are oil-in-water emulsions having an emulsion particle size in the range of 200-500 nm.
The aqueous system as described above, wherein the acid value of the polysiloxane-modified polyester resin is from 0.2 to 50mgKOH/g, more preferably from 0.5 to 25 mgKOH/g; more preferably between 0.5 and 10 mgKOH/g; more preferably between 2.5 and 10 mgKOH/g.
Aqueous systems as described above, wherein the oil phase is a discontinuous phase, which may contain, but is not limited to, alcohols, ethers, esters, ketones, hydrocarbons, alcohol ethers and/or alcohol ether esters and/or dibasic ester mixtures; comprises ethyl acetate, butyl acetate and a dibasic ester mixture containing dimethyl succinate, dimethyl glutarate and dimethyl adipate; acetone, butanone, cyclohexanone; aromatic hydrocarbons, butyl cellosolve, n-butanol; glycol ether esters, propylene glycol ether esters; preferably comprises one or a mixture of more of butanol, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate and diethylene glycol butyl ether acetate.
The silicone modified polyester resin product may be solid or liquid. The solid silicone-modified polyester resin should be pre-dissolved in a solvent to form a homogeneous solution. In general, it is preferable to prepare a highly concentrated solution having a small amount of solvent. The solvent is the above alcohols, ethers, esters, ketones, hydrocarbons, alcohol ethers and/or alcohol ether esters and/or dibasic ester mixture.
Adding the polysiloxane modified polyester resin solution, the polysiloxane intermediate b and a proper amount of nonionic emulsifier into a reaction kettle, stirring uniformly at room temperature, adding water into the reaction kettle under stirring, and adding a proper amount of preservative to obtain the aqueous system. In some cases, in order to achieve better mixing of the silicone-modified polyester resin solution and the nonionic emulsifier, it is necessary to add an appropriate amount of water simultaneously when mixing the two.
The solid content of the aqueous system is the ratio of the mass of the obtained solid matter to the mass of the initial aqueous system, wherein 2 plus or minus 0.2g of a sample is placed in a culture dish with the diameter of 75mm and dried for 60 minutes at the temperature of (150 plus or minus 2) DEG C.
The polysiloxane modified polyester resin is prepared by reacting polyester or polyester intermediate product containing alkoxy and/or hydroxyl with polysiloxane intermediate a containing alkoxy and/or hydroxyl under the condition of using catalyst or not using catalyst. This reaction is a co-condensation process well known to those skilled in the art. For a typical preparation method, reference is made to "synthetic process and application of silicone product" from bridge, happy people, chemical industry press, second edition of 5 months 2010, section 8.4.2 about the content of the polyester modified silicone resin part.
Preferred silicone intermediates a OR silicone intermediates b are silicone resins containing silanol (containing Si-OH functional groups) and/OR siloxy (containing Si-OR functional groups) (silicone resins see definition in the first edition 2010, chapter 4, section 4.1 and section 4.2 of "silane coupling agents and silicone resins" huang wen ru, sichuan scientific technical press), containing one OR more of M units, D units, T units, Q units:
R3 aR4 bSiO1/2m unit
R3 aR4 bSiO2/2D unit
R3 aR4 bSiO3/2T unit
SiO4/2Q unit
R3、R4Independently of one another, represents a C1-C20 hydrocarbon group, optionally incorporating a heteroatom linking group, such as, but not limited to:
-O-，-S-，-NH-，
a is an integer of 0, 1,2 or 3, preferably 0, 1 or 2;
b is an integer of 0, 1,2 or 3, preferably 0, 1 or 2; and
in the M units, a + b is 3,
in the D unit, a + b is 2, and
in the T unit, a + b is 1.
R3、R4Independently of one another, C1-C18 alkyl groups, C6-C20 aryl groups, C7-C18 arylalkyl groups, C5-C12 cycloalkyl groups, C2-C18 alkenyl groups, diol groups, epoxy groups (the oxygen atom is not directly bonded to the silicon atom), C1-C18 alkoxy groups, C2-C20 unsaturated hydrocarbon groups (such as vinyl, allyl, propenyl, isopropenyl groups) and terminal C4-C18 alkenyl groups, alkynyl groups, vinyl ether groups and allyl ether groups are preferred. R3、R4More preferred are, independently of one another, methyl, ethyl, vinyl, allyl, methoxy, ethoxy and phenyl.
The molecules may contain or form silsesquioxanes and polyphenylsilsesquioxanes and/or polymethylsilsesquioxanes built up from T units.
The silicone intermediate may be terminated with conventional end groups such as one or more of trialkylsilyl, dialkylsilanol, dialkylalkoxysilyl, alkyldialkoxysilyl, trialkoxysilyl, dialkylvinylsilyl, triarylsilyl, diarylsilanol, diarylalkoxysilyl, aryldialkoxysilyl, diarylvinylsilyl.
Preferred silicone intermediates a or b are methoxyphenyl/methylsilicone resins, wherein the molar ratio of phenyl groups to methoxy groups (and/or alkyl groups) is (0.5-2):1, preferably (0.5-1.5):1, more preferably (0.8-1.2): 1. The content of phenyl in the resin is between 20 and 50 weight percent.
Commercial silicone intermediates suitable for use in the present invention include:
SY 231、
601、
SY300、
IC 232、
IC 368、
IC 678、
IC 836, KR211, KR212, KR214, KR216, Dow Corning Z6018, Dow Corning 3037, Dow Corning 233, Dow Corning 249, or Dow Corning 3074 from shin-Etsu corporation.
The polyesters to which the invention relates are heterochain macromolecular compounds having a plurality of carboxylate groups as part of their backbone structure, which are distinguished from other ester-containing polymers whose carboxylate groups form pendant from the backbone structure, such as cellulose esters, polyacrylates and polyvinyl acetates. The polyester resin according to the present invention is more preferably a polyester resin having ester groups in both main side chain structures.
Preferred polyesters of the invention are those obtained by the polycondensation of di-or polycarboxylic acids or functional derivatives thereof with di-or polyhydric alcohols/phenols.
Suitable polyesters are synthesized in a conventional manner from carboxylic acids (or anhydrides thereof) having 2 or more acid functional groups and polyols having 2 or more hydroxyl functional groups. Examples of suitable polyfunctional carboxylic acids (anhydrides) include: succinic acid (anhydride), glutaric acid (anhydride), benzene-1, 2, 4-tricarboxylic acid, phthalic acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), endo-bicyclo-2, 2, 1-5-heptyne-2, 3-dicarboxylic acid, tetrachlorophthalic acid (anhydride), cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, azelaic acid, maleic acid (anhydride), 1,3, 5-benzenetricarboxylic acid, 3, 6-dichlorophthalic acid, tetrachlorophthalic acid, adipic acid, sebacic acid, and the like. Examples of suitable polyfunctional alcohols include: glycerin, trimethylolpropane, pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, heptanediol, hexanediol, octanediol, 2-ethyl-2-butyl-1, 3-propanediol, neopentyl glycol, trimethylpentanediol, 1, 4-cyclohexanedimethanol, and the like.
Whether the polyester is predominantly carboxylic acid functional with-COOH moieties or hydroxyl functional with-OH groups depends on the molar ratio of-COOH/-OH in the monomer mixture. The vast majority of polyesters useful in the present invention may be essentially linear with 2 or more hydroxyl or carboxylic acid functional groups, or may be branched with more than 2.5 hydroxyl or carboxylic acid functional groups. More often, polyesters having a variety of structural units are suitable.
Examples
In the following examples, the parts are parts by mass unless otherwise specified.
SILRES IC 232 belongs to the group of silicone intermediates b, substituted by methylphenyl, having a molecular weight Mw of about 1200g/mol, containing from about 13 to about 15% by weight of methoxy and/or hydroxy groups; supplied by wacker chemical company;
SILRES IC 678 belongs to polysiloxane intermediate b; substituted by phenyl, having a molecular weight Mw of about 900g/mol, containing from about 13 to about 15% by weight of methoxy and/or hydroxy groups; supplied by wacker chemical company;
SILRES 601 belongs to polysiloxane intermediate b; substituted with phenyl, containing about 5 wt% hydroxyl; supplied by wacker chemical company;
pluronic F127, ethylene oxide propylene oxide copolymer; according to the product manual, its HLB value is 22; supplied by BASF corporation; preparing a 15 wt% aqueous solution before use;
lutensol AT 80, linear C16-C18 alcohol polyoxyethylene ether, containing 80 ethylene oxide units per molecule; calculated HLB of 18.2; supplied by BASF corporation; preparing 10 wt% aqueous solution before use;
ETOCAS 200-SO- (MV), ethylene oxide modified castor oil containing 200 ethylene oxide units per molecule; according to the product manual, its HLB value is 18.1; supplied by Croda corporation; preparing 50% water solution before use;
C12-14-EO100, C12-C14 secondary alcohol polyoxyethylene ether containing 100 ethylene oxide units per molecule; calculated HLB of 18.8; supplied by the Tech technologies of Huangma, Zhejiang; preparing 10 wt% aqueous solution before use;
C12-14-EO120, C12-C14 secondary alcohol polyoxyethylene ether, wherein each molecule contains 120 ethylene oxide units; calculated HLB is 19; supplied by the Tech technologies of Huangma, Zhejiang; preparing 10 wt% aqueous solution before use;
polysiloxane-modified polyester resin solution 1 (abbreviated to SMP1 solution) in which the methoxy-functional methyl/phenyl polysiloxane comprises 30% by weight of the mass of the polysiloxane-modified polyester resin. The solution has a solids content of 60% by weight and the solvents are 34% by weight of propylene glycol monomethyl ether acetate (abbreviated to PMA), 3% by weight of n-butanol and 3% by weight of ethylene glycol butyl ether; wherein the polyester resin portion is a polycondensation product of a polyhydric diol, a polybasic acid anhydride; the acid value of SMP1 is less than 10mg KOH/g; offered by Changxing chemical industry corporation, under the designation 50734-S-60;
polysiloxane-modified polyester resin solution 2 (abbreviated as SMP 2 solution), the methoxy-functional methyl/phenyl polysiloxane accounted for 25 wt.% of the mass of the polysiloxane-modified polyester resin. The solid content of the solution is 64.5 wt%, and the solvent is PMA; wherein the polyester resin part is a polycondensation product of a polyhydric diol and a polybasic acid anhydride; hydroxyl value is 0-200 mgKOH/g; supplied by Kestro corporation under the designation SPE 2388;
polysiloxane-modified polyester resin solution 3 (abbreviated as SMP 3 solution), in which the methoxy-functional methyl/phenyl polysiloxane comprises 30% by weight of the mass of the polysiloxane-modified polyester resin. The solution has a solids content of 70 wt% and the solvent is PMA. Wherein the polyester resin portion is: neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol and phthalic acid dimethyl esterPolycondensation products of acid anhydride, isophthalic acid and terephthalic acid. The acid value of the SMP 3 is 3.2mg KOH/g, and the hydroxyl value of the SMP 3 is between 25 and 500mg KOH/g; molecular weight MWBetween 15000 and 17000g/mol, Mw/Mn is 6, and the molecular weight is measured by GPC with polystyrene as a standard sample and tetrahydrofuran as a solvent; offered by the Changxing chemical industries, Inc.
MBS is an isothiazolinone preservative provided by the company THOR, UK.
The HLB value, i.e., the hydrophilic-lipophilic balance, is used in the present invention to denote the hydrophilicity of the surfactant. For some manufacturers who cannot provide emulsifiers with HLB values, the calculated HLB value is calculated by referring to the following empirical formula of fatty alcohol-polyoxyethylene ether emulsifiers:
nonionic surfactant HLB calculated value (hydrophilic group moiety molar mass/surfactant molar mass) x (100/5)
TABLE 1
TABLE 2
| Ex.2 | Ex.4 | Ex.5 | Ex.7 | Ex.8 | Ex.9 | |
| SMP1 solution | 58.07 | 58.07 | 56.85 | 57.09 | 57.09 | 57.09 |
| SILRES IC 232 | 5.12 | 5.04 | 5.04 | 5.04 | ||
| SILRES 601 | 5.28 | |||||
| SILRES IC 678 | 5.12 | |||||
| Lutensol AT 80 | 1.08 | 1.08 | 1.51 | |||
| ETOCAS 200-SO | 0.43 | 0.43 | ||||
| C12-14-EO100 | 1.26 | 1.26 | ||||
| C12-14-EO120 | 1.26 | |||||
| MBS | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| Water (W) | 35.22 | 35.22 | 36.53 | 36.28 | 36.53 | 36.53 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Oil phase/emulsifier wt/wt | 41.85 | 41.85 | 49.31 | 41.15 | 49.31 | 49.31 |
| Stable storage cycle number at 50 ℃ | 2.5 | 2.5 | 3 | 3 | 4 | 5 |
| Particle size (Z-average) | 308 | 310 | 714 | 386 | 326 | 326 |
As can be seen from the examples and comparative examples in Table 1, the stability of the aqueous system is significantly improved after the polysiloxane intermediate b is added to the same aqueous system. It is clear from comparative examples c.ex.2.2 and c.ex.3.2 that it is difficult to emulsify the silicone intermediate b to obtain a stable emulsion under the same conditions, and that the samples of comparative examples c.ex.2.2 and c.ex.3.2, after the preparation is completed and the stirring is stopped, the system is broken and the particle size cannot be measured with the instrument.
And the samples prepared in example ex.1 can also be used to prepare cookware for food contact.
Examples ex.8 and ex.9 used emulsifiers with higher calculated HLB and gave better sample stability.
The product of each example was uniformly coated on an experimental aluminum plate supplied from Q-Lab corporation (A-36) with an 80 μm wire bar under normal temperature conditions. The coating thickness was about 12-18 microns (dry film after cure, cure conditions were 280 ℃ for 10 minutes).
The degree of yellowing of the coating was measured and the data obtained was as follows:
TABLE 3
| Ex.6 | C.Ex.6 | |
| SMP1 solution | 57.6 | 60.7 |
| SILRES IC 232 | 5.1 | / |
| Pluronic F127 | 1.78 | 1.87 |
| MBS | 0.10 | 0.11 |
| Water (W) | 35.42 | 37.32 |
| Total up to | 100 | 100 |
| Oil phase/emulsifier wt/wt | 35.22 | 32.45 |
| Thickness of coating layer | 14 | 12 |
| dE yellowing at 280 ℃ for 1h | 5.59 | 6.29 |
| dE yellowing at 280 ℃ for 3h | 7.76 | 11.21 |
| dE yellowing at 280 ℃ for 5h | 10.89 | 12.56 |
A smaller value of the yellowing dE indicates a lower degree of yellowing of the sample. As can be seen from the above test data, example ex.6 of the present invention is superior in yellowing resistance to comparative example c.ex.6 which does not contain silicone intermediate b.
The particle sizes tested in the present invention were Mastersizer 2000 and Zetasizer Nano ZS 90.
For the present invention, the particle size of the emulsion is measured based on the laser diffraction-light scattering principle. The volume average particle size of the emulsion is the weighted average of the emulsion particle size to the emulsion particle volume based on the following formula (p-4, q-3):
the present invention defines the emulsion particle size distribution span (span) as: (D90-D10)/D50.
Where D50 is the particle size value at 50% cumulative distribution. For example, if D50 is 0.68 μm, it means that 50% of the sample particles are larger than 0.68 μm and 50% of the sample particles are smaller than 0.68 μm. D10 or D90 represent particle size values at 10% or 90% cumulative distribution, respectively. For example, if D10 ═ 0.1 μm, it means that 10% of the sample particles are smaller than 0.1 μm; d90 ═ 1 μm, meaning that 90% of the sample particles were smaller than 1 μm.
The gloss tester used in the present invention was "Spectro-Guide 45/0" manufactured by BYK corporation, and the test was conducted according to ISO 2813 standard, and the data in the table shows the result of the test under the condition of 60 °. The color difference meter used in the invention is 'Spectro-Guide 45/0' produced by BYK company and is tested according to GB/T11186.1-89 standard.
Claims (14)
1. An aqueous system of polysiloxane modified polyester resin, which contains a nonionic emulsifier with HLB value more than or equal to 12, wherein the nonionic emulsifier contains ethylene oxide repeating units;
the polysiloxane modified polyester resin is in discontinuous oil phase; the polysiloxane modified polyester resin is prepared by co-condensation reaction of polyester or polyester intermediate product containing alkoxy and/or hydroxyl and polysiloxane intermediate a containing alkoxy and/or hydroxyl under the condition of using catalyst or not using catalyst; the polysiloxane intermediate a is a silicon resin containing silanol and/or siloxy;
further, it comprises 1-50 wt%, preferably 1-30 wt%, more preferably 1-20 wt%, more preferably 1-10 wt%, more preferably 3-8 wt% in the discontinuous oil phase; more preferably 5 to 7% by weight of silicone intermediate b, based on 100% by weight of the aqueous system.
2. The aqueous system of claim 1 wherein the silicone intermediate a is present in an amount of between 5 and 80 weight percent of the silicone-modified polyester resin; preferably between 15 and 60 wt%; more preferably between 15 and 50 wt%, based on 100 wt% polysiloxane modified polyester resin.
3. The aqueous system of claim 1 or 2 wherein the silicone intermediate b is present in an amount of between 5 and 25 wt% of the silicone modified polyester resin; preferably between 8 and 20 wt%; more preferably between 10 and 18 wt%, based on 100 wt% of the polysiloxane modified polyester resin.
4. Aqueous system according to any of claims 1 to 3, wherein the alkoxy and/or hydroxy content of the silicone intermediate b is 3 wt.% or more; preferably 10 wt% or more and 30 wt% or less; more preferably 12 wt% or more and 20 wt% or less; calculated on 100 wt% of silicone intermediate b.
5. The aqueous system of any of claims 1-4 wherein the hydroxyl content of silicone intermediate b is less than or equal to 10 wt%; preferably less than or equal to 5 wt%; more preferably 3% by weight or less, based on 100% by weight of silicone intermediate b.
6. The aqueous system of any of claims 1-5 wherein silicone intermediate a and/or silicone intermediate b have methyl and/or phenyl substituents.
7. The aqueous system of any of claims 1-6 wherein the calculated HLB value of a single nonionic emulsifier or a combination of all nonionic emulsifiers is ≥ 17; preferably the calculated HLB value is greater than or equal to 18; more preferably the calculated HLB value is greater than or equal to 18.5; more preferably 22. gtoreq. HLB calculated value ≥ 18.5; more preferably 20. gtoreq. HLB calculated value.gtoreq.18.5.
8. The aqueous system of any of claims 1-7 wherein the nonionic emulsifier is a combination of one or more of formulas (Ia) to (IV),
R1[CH2CH2O]nH (Ia)
HO[CH2CH2O]mR*1[CH2CH2O]nH (Ib)
HO[CH2CH2O]p[CH2CH(CH3)O]r[CH2CH2O]qH (II)
HO[CH2CH(CH3)O]d[CH2CH2O]e[CH2CH(CH3)O]fH (III)
wherein R is1Is of the general formula R (C ═ O)kA monovalent radical of O-, wherein R is a monovalent C5-C20 hydrocarbon radical, k is 0 or 1,
preferably R1Is a monovalent C6-C20 alkoxy group or phenol group or alkoxycarbonyl group, more preferably an undecyloxy group, a dodecyloxy group, a hexadecyloxy group, an octadecyloxy group, an octadecyloxycarbonyl group, a nonylphenol group, an octylphenol group, a dodecylphenol group,
R*1is represented by the general formula-R (C ═ O)lDivalent radicals of O-, wherein R is a divalent C5-C20 hydrocarbon radical, l is 0 or 1,
and p is 0 or a positive integer, m, n, q, r, d, e, f are positive integers, and p + q > r, d + f < e,
the number-average molecular weight Mn of the formulae (Ia), (Ib), (II), (III) ranges between 1000 and 30000 g/mol; preferably between 3000 and 20000 g/mol;
wherein R is5Is a divalent C4-C24 alkylene radical, preferably C6-C20 alkylene, C6-C20 monooleene, C6-C20 diolefine, C6-C20 tetraolefin,
R6is a monovalent C4-C24 hydrocarbon group, preferably C6-C20 alkyl, C6-C20 monoolefin, C6-C20 diolefin, C6-C20 tetraolefin,
R7is an alkyl group from H, C1 to C3, preferably H,
R8is a hydrocarbon radical of C6-C20, or
R9Is a hydrocarbon radical of C6-C20, or
x, y and z are 0 or positive integers, and x, y and z are not 0 at the same time; preferably x + y + z is equal to or greater than 36;
-EO-is an ethylene oxide unit.
9. The aqueous system of any one of claims 1-8, wherein the non-ionic emulsifier is selected from one or more of the group consisting of: ethylene oxide propylene oxide copolymer, stearic acid polyoxyethylene ester, stearyl alcohol polyoxyethylene ether, C16-C18 alcohol polyoxyethylene ether, C12-C14 alcohol polyoxyethylene ether, C16-C18 fatty acid polyoxyethylene ester, C12-C14 fatty acid polyoxyethylene ester, ethylene oxide modified castor oil, ethylene oxide modified hydrogenated castor oil and nonylphenol polyoxyethylene ether; and the calculated HLB value of the nonionic emulsifiers in the set is greater than or equal to 17.
10. The aqueous system of any of claims 1 to 9, wherein the non-ionic emulsifier is a linear or branched C16-C18 alcohol ethoxylate and/or a linear or branched C12-C14 alcohol ethoxylate; preferably, when the hydrophobic segment is a linear or branched C12-14 alcohol, the EO number is between 100-160, and when the hydrophobic segment is a linear or branched C16-18 alcohol, the EO number is between 120-180; more preferably, the emulsifier is a linear or branched C12-14 alcohol containing 120 EO units, a linear or branched C12-14 alcohol containing 100 EO units, a linear or branched C16-18 alcohol containing 120 EO units.
11. The aqueous system of any of claims 1-10 wherein the amount of non-ionic emulsifier is between 0.16 and 3 wt% of the total aqueous system mass; preferably between 1 and 2 wt.%, calculated on the basis of 100 wt.% of the aqueous system.
12. The aqueous system of any of claims 1-11, wherein the weight ratio of all oil phases to emulsifier is between 30-50, preferably between 35-50; more preferably between 40 and 50, more preferably between 45 and 50.
13. The aqueous system of any of claims 1-12 having a solids content in the range of from 10 to 65 wt%; preferably between 20 and 60 wt%; more preferably between 40 and 55 wt%, based on 100 wt% aqueous system.
14. The aqueous system of any of claims 1-13, wherein the acid value of the polysiloxane-modified polyester resin is between 0.2 and 50mgKOH/g, more preferably between 0.5 and 25 mgKOH/g; more preferably between 0.5 and 10 mgKOH/g; more preferably between 2.5 and 10 mgKOH/g.
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| PCT/CN2018/097152 WO2020019225A1 (en) | 2018-07-26 | 2018-07-26 | Aqueous dispersion of modified resins |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613893A (en) * | 2004-07-16 | 2005-05-11 | 南京大学 | Preparation of carboxy silicon oil emulsion |
| CN103732730A (en) * | 2010-09-20 | 2014-04-16 | 宝洁公司 | Fabric care formulations and methods |
| CN104583349A (en) * | 2012-08-23 | 2015-04-29 | 瓦克化学股份公司 | Aqueous epoxy and organo-substituted branched organopolysiloxane emulsions |
| CN104861175A (en) * | 2014-02-20 | 2015-08-26 | 瓦克化学（中国）有限公司 | Modified resin aqueous dispersion liquid |
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2018
- 2018-07-26 CN CN201880095940.XA patent/CN112513148A/en active Pending
- 2018-07-26 WO PCT/CN2018/097152 patent/WO2020019225A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613893A (en) * | 2004-07-16 | 2005-05-11 | 南京大学 | Preparation of carboxy silicon oil emulsion |
| CN103732730A (en) * | 2010-09-20 | 2014-04-16 | 宝洁公司 | Fabric care formulations and methods |
| CN104583349A (en) * | 2012-08-23 | 2015-04-29 | 瓦克化学股份公司 | Aqueous epoxy and organo-substituted branched organopolysiloxane emulsions |
| CN104861175A (en) * | 2014-02-20 | 2015-08-26 | 瓦克化学（中国）有限公司 | Modified resin aqueous dispersion liquid |
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