CN1227576A - Water-based sulfonated polymer compositions - Google Patents
Water-based sulfonated polymer compositions Download PDFInfo
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- CN1227576A CN1227576A CN97197245A CN97197245A CN1227576A CN 1227576 A CN1227576 A CN 1227576A CN 97197245 A CN97197245 A CN 97197245A CN 97197245 A CN97197245 A CN 97197245A CN 1227576 A CN1227576 A CN 1227576A
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- water
- sulfonated
- polyvinyls
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- polyurethane
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G2270/00—Compositions for creating interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
Abstract
A method for the preparation of sulfonated polymer compositions wherein water dispersible isocyanate-terminated polyurethane prepolymers are reacted in the presence of aqueous polyvinyl dispersions which may contain active hydrogen atoms. The invention is further directed to a water-based sulfonated polyurethane polyvinyl hybrid latex wherein a sulfonated polyurethane is used as a seed for the polymerization of ethylenically unsaturated monomers and a method for preparing the same. The inventive compositions develop interpenetrating polymer networks or may form core-shell type structures, and are characterized as having enhanced mechanical and adhesion properties.
Description
Invention field
The present invention relates to aqueous-based polymers, be specifically related to the method for the water-based sulfonated polymer compositions that processing machinery performance and adhesive property increase.
Background of invention
The patent documentation that relates to the water-based sulfonated polymer compositions preparation method has some pieces of writing:
U.S. Patent No. 5,334,690 (Hoechst companies) disclose a kind of can the mixing with other aqueous polymer dispersion, and water-based sulfonated polyurethane-urea that usually can be compatible with it.
U.S. Patent No. 4,888,383 (E.I.Du Pont Company) disclose a kind of by amine and/or hydrazides official can polyacrylic polymer and isocyanate-terminated polyurethane prepolymer react the method for the acrylic polymers for preparing the modification of waterbased urethane urea.
U.S. Patent No. 4,491,646 (Ashland) disclose a kind of by hydroxyl-functional polyvinyl polymkeric substance and the dispersible polyfunctional isocyanate's blend of water and the tackiness agent that makes.
Other relevant patent comprises United States Patent (USP) 5,371,133 (National Starch), 5,200,463 (Huels), 5,204,404 (Du Ponts), 5,173,526 (air products and chemical company) and 5,071,904 (PPG).
Summary of the invention
The invention discloses water-based sulfonated polymer compositions, wherein comprise:
A) at least a water-based sulfonated polyurethaneurea polymer comprises:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein sulfonic acid group is with the form of an alkali metal salt
Exist;
B) at least a polyvinyls water dispersion comprises:
1) at least a ethylene linkage unsaturated monomer; With
2) randomly, at least a free radical reaction protection glue that contains reactive hydrogen atom
Body, and randomly,
C) at least a sulfonated polyurethane-vinyl polymer compositions, said composition are following group
The reaction product of dividing:
1) at least a isocyanate-terminated polyurethane prepolymer comprises:
A) at least a polyisocyanates; With
B) at least a sulfonated polyester polyol, wherein sulfonic acid group is with the shape of an alkali metal salt
Formula exists; With
2) a kind of polyvinyls water dispersion comprises:
A) at least a ethylene linkage unsaturated monomer; Preferably,
B) at least a free radical reaction protective colloid that contains reactive hydrogen atom.
Surprisingly, this sulfonated polymer compositions has enhanced mechanical property and bond properties, and in the pH value greater than showing stability at about 2 o'clock.By inference, some performance in these special performances can give the credit to the formation of interpenetrating polymer networks and be arranged in sulfonate characteristic on the polyether polyols with reduced unsaturation polyvalent alcohol segment.
Composition of the present invention can be used as tackiness agent, tackiness agent, coating and priming paint, can be applied on any matrix thing, comprise paper, timber, metal, cement, glass, cloth and synthetic polymer, and can be used for comprising the purposes of aspects such as glass fibre starching, wood working, automobile, film laminating and shoemaking.
On the other hand, the invention discloses a kind of method for preparing sulfonated polymer compositions, wherein isocyanate-terminated polyurethane prepolymer is dispersed in the polyvinyls water dispersion, this dispersion can contain primary amine, secondary amine, primary hydroxyl, secondary hydroxyl and carbonylamino group.This method comprises:
A) it is pre-to make following component reaction form the dispersible isocyanate-terminated urethane of a kind of water
Polymers:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein sulfo group is with the form of an alkali metal salt
Exist;
B) make following component carry out the water-dispersion that radical polymerization forms a kind of polyvinyls
Body:
1) at least a ethylene linkage unsaturated monomer and randomly,
2) at least a free radical reaction protective colloid that contains reactive hydrogen atom; And it is right
After
C) with A) product be dispersed in B) in.
Another aspect the invention discloses a kind of water-based sulfonated polymer compositions and the method by inoculation emulsion polymerization prepared said composition.Said composition comprises the reaction product of following component:
A) at least a sulfonated polyurethane dispersion;
B) at least a moisture ethylene linkage unsaturated monomer pre-emulsion wherein comprises at least a ethylene linkage
Unsaturated monomer; With
C) a kind of initiator.
The method for preparing said composition comprises the following steps:
A) form a kind of moisture pre-emulsion, wherein comprise at least a ethylene linkage unsaturated monomer pre-emulsion, comprise at least a ethylene linkage unsaturated monomer and randomly at least a tensio-active agent; With
B) described moisture pre-emulsion and at least a sulfonated polyurethane dispersion are randomly reacted in the presence of initiator solution and randomly in the presence of reductant solution.
Another aspect the invention discloses a kind of urethane/polyvinyls hybrid latex and the method by inoculation emulsion polymerization prepared this hybrid latex.This hybrid latex comprises the inoculation emulsion polymerization product of following component:
A) at least a sulfonated polyurethane dispersion, this urethane is as seed;
B) at least a moisture ethylene linkage unsaturated monomer pre-emulsion wherein comprises at least a ethylene linkage unsaturated monomer; With
C) at least a radical initiator.
The accompanying drawing summary
Fig. 1 illustrates for latex prepared among the embodiment 6 (water-based sulfonated polymer compositions), the funtcional relationship of seed urethane size-grade distribution (dotted line) and final hybrid latex size-grade distribution (solid line).
Fig. 2 illustrates for latex prepared among the embodiment 7 (water-based sulfonated polymer compositions), the funtcional relationship of seed urethane size-grade distribution (dotted line) and final hybrid latex size-grade distribution (solid line).
Detailed description of the invention
Its corresponding water-based sulfonated polyurethaneurea polymer of sulfonated polymer compositions, polyvinyls aqueous dispersion and simple blend thereof are compared, and have mechanical performance and the bond properties of enhancing. For the application, the polyvinyls dispersion comprises the dispersion of the polyaddition products of ethylene linkage unsaturated monomer, and the ethylene linkage unsaturated monomer includes, but are not limited to (methyl) acrylate monomer. Also have, in this application, polyurethane refers to contain the polymer that surpasses 1 urethano, and in order to comprise the polyurethane (polyurethane-urea) that also contains urea groups. By inference, some performance in these special performances can give the credit to the formation of interpenetrating polymer networks. " interpenetrating polymer networks " word is defined as and contains the crosslinked of at least 2 kinds of dissimilar or not identical polymer and/or half cross-linking system. Irving Skeist " adhesive handbook (" Handbook of Adhesives "), the 3rd edition, the 1st chapter has further description to IPN (interpenetrating polymer networks) in the 18th page (Van Nostrand, NY, 1990).
Concerning the application, " hybrid " refers to the polymer that is made of two or more dissimilar polymer. This dissimilar polymer can be that covalent bond connects, and also can not be that covalent bond connects.
In the present invention, when isocyanate-terminated polyurethane prepolymer dispersion can contain active hydrogen atom for example in the aqueous dispersion of the polyvinyls of primary amine, secondary amine, primary hydroxyl and secondary hydroxy group the time, isocyanate-terminated polyurethane prepolymer dispersion will interact with this polyvinyls water prose style free from parallelism, forms IPN and cross-linked network. This interactional frequency is present in isocyanates in each polymeric dispersions and the impact of active hydrogen atom quantity. The structure polyvinyls aqueous dispersion that uses a kind of wherein reactive hydrogen atom to be distributed on the particle table can increase crosslink density. At the end add the ethylene linkage unsaturated monomer that contains reactive hydrogen atom in the free-radical emulsion polymerization process, just can produce structured particles. Can think that so a kind of particle shape has improved the collision frequency of isocyanates/reactive hydrogen atom reaction, thereby increase the crosslink density of said composition.
The particle that disperses can contain the cooperation mixture of the polymer that is comprised of sulfonated polyurethane urea polymers, polyvinyls and sulfonated polyurethane-polyvinyl. When dissimilar or not identical polymer diffusion and occur to interact with contiguous particle or just can form this particles mixture that cooperates when crosslinked basically basically. This diffusion process may produce the particle that contains the polymer different from the polymer on this particle surface in the particle. Its example is included in to contain on the polyurethane-urea advantage basal granule sub-surface mainly based on the particle of polyvinyls or in polyvinyls advantage basal granule sub-surface and contains mainly particle based on polyurethaneurea polymer. Such superficial layer can be continuous or discrete, and thickness can be different. If the particle surface layer has sizable thickness, and be continuous, so this particle is just near a kind of core-shell-type structure.
Isocyanate-terminated polyurethane prepolymer of the present invention can form with monoisocyanates and polyisocyanates. Isocyanates can be linear aliphatic, cyclic aliphatic, aromatics or its mixture. The example of commodity polyisocyanates comprises VestanatIPDI namely derives from the IPDI of HULS u s company (Piscataway, New Jersey); TMXDT, namely derive from the tetramethylene diisocyanate of Cyanamid company (Wayne, New Jersey); LuxateHM namely derives from Olin company (Stamford, hexamethylene diisocyanate CN); Derive from the '-diphenylmethane diisocyanate of UPjohn polymer chemistry product companies (Kalamazoo, MI); DesmodurW, namely derive from the dicyclohexyl methyl hydride-4,4 of Bayer AG (Pennsylvania, Pittsburgh) '-vulcabond and toluene di-isocyanate(TDI) (TDI). Preferred vulcabond is hexamethylene diisocyanate, different Buddhist diketone vulcabond and composition thereof.
If desired, can use isocyanate content greater than 2.1 polyisocyanates. In addition, also can use from the modified polyisocyanate of hexamethylene diisocyanate, IPDI and toluene di-isocyanate(TDI) preparation. Described polyisocyanates can contain functional groups such as comprising ammonia ester, uretdiones, isocyanuric acid ester, biuret and composition thereof.
Hydroxyl value for the preparation of the sulfonated polyester polyol component of isocyanate-terminated polyurethane prepolymer is measured according to ASTM standard E-222-67 (method B), can be in about scope of 20～about 140, and preferred about 40～about 110. Polyalcohol can be used such as binary acid, dihydroxylic alcohols, sulfonation dihydroxylic alcohols and sulfonation binary acid and form. This polyalcohol and preparation method thereof is at United States Patent (USP) 5,334, further narration arranged in 690, and this patent is incorporated this paper into as a reference. Preferred sulfonated polyester polyol is based on those polyalcohols of the single sodium salt of 5-sulfoisophthalic acid, adipic acid and 1,6-hexylene glycol and/or diethylene glycol. Can think that polymer was dispersed and stable when the characteristic that is present in the sulfonate in this polyalcohol segment had strengthened low pH.
Randomly, non-sulfonated polymer polyalcohol can be used in combination with this sulfonated polyester polyol. The hydroxyl value of this polyalcohol can be in about scope of 20～about 140, and preferred about 40～about 110. Non-sulfonated polymer polyalcohol can comprise the mixture of PEPA, PPG, polycarbonate polyol, polyurethane polyol, polyacetals polyalcohol, polyacrylate polyol, polycaprolactone polyol, polyester amide polyol, polythiaether polyalcohol and these polyalcohols.
Also can prepare isocyanate-terminated prepolymer with aklylene glycol. Can the have an appointment hydroxyl value of 130～about 1250 scopes of this aklylene glycol, preferred about 950～about 1250. Preferred aklylene glycol comprises BDO, 1,6-hexylene glycol and 2-methyl isophthalic acid, ammediol. Take 100 parts of total prepolymer solids as benchmark, the content of aklylene glycol in isocyanate-terminated prepolymer is about 0.1% weight～about 10.0% weight, is preferably about 0.5% weight～5.0% weight.
Can prepare polyurethaneurea polymer with the polyalcohol of higher functionality. Applicable example comprises glycerine, trimethylolpropane, BT, 1,2,6-hexanetriol and composition thereof. Preferred high functionality polyalcohol is trimethylolpropane. Take 100 parts of total isocyanate-terminated polyurethane prepolymer solids as benchmark, the content of described polyalcohol can be about 0.1% weight～about 1.0 % weight, preferred about 0.3% weight～about 0.7% weight.
Preferably, when preparing isocyanate-terminated polyurethane prepolymer, can use dihydroxy carboxylic acids. Preferred dihydroxy carboxylic acids is dihydromethyl propionic acid. Take 100 parts of total polyurethane prepolymer solids as benchmark, the content of dihydroxy carboxylic acids component can be about 0.05% weight～about 1.0% weight, is preferably about 0.2% weight～about 0.5% weight.
Can use in the compounds such as alkali metal hydroxide, organic tert-butylamine, ammonia and composition thereof and the dihydroxy carboxylic acids group. Preferred nertralizer is NaOH and triethylamine. Before can being dispersed at isocyanate-terminated polyurethane prepolymer in the polyvinyls dispersion mixture, or simultaneously, acid groups is changed into ionic group (salt).
Isocyanate-terminated polyurethane prepolymer is by making the excessive polyisocyanates of stoichiometry and described polyol component react to prepare. The ratio of reactant is such, so that take 100 parts of total isocyanate-terminated polyurethane prepolymer solids as benchmark, the content of isocyanates is about 1.0% weight～about 10.0% weight in the gained prepolymer, preferably about 2.O%～about 5.0% weight. This prepolymer can at about 30 ℃～about 110 ℃, preferably be processed about 65 ℃～about 85 ℃ temperature range.
In addition, can accelerate with a small amount of catalyst the reaction of hydroxyl/isocyanate. Take 100 parts of total isocyanate-terminated polyurethane prepolymer solids as benchmark, the consumption of catalyst can be about 0.05% weight～about 2.0% weight, preferred about 0.13% weight～about 0.15% weight. An example of catalyst is MetacureTMT-12 namely derives from a kind of organo-tin compound of air products and chemical company (Allentown, Pennsylvania).
The ethylene linkage unsaturated monomer can comprise cholesterol monomer, many unsaturated monomers and composition thereof. Its example comprises methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid n-propyl, propylene isopropyl ester, methyl methacrylate, butyl methacrylate, vinyl acetate, propionate, vinyl ethers, the unsaturated fumarate of ethylene linkage, the unsaturated maleate of ethylene linkage, styrene, acrylonitrile, acrylamide, butanediol diacrylate, hexanediyl ester, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
Can use the ethylene linkage unsaturated monomer that contains anion and/or ionic group. The example of this monomer comprises acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid. Mesaconic acid, maleic acid, citraconic acid and/or their corresponding ionic group. Take 100 parts of total composition solids as benchmark, the content of described monomer can be about 0.1% weight～about 2.5% weight, preferred about 0.1% weight～about 10.0% weight.
Also can use the ethylene linkage unsaturated monomer that contains reactive hydrogen atom. " reactive hydrogen atom " word refers to by Kohlerin, J.Am.Chem.Soc., and (JACS) 49,3181 (1927) described Zerewitinoff tests can demonstrate active hydrogen. Its example comprises the amino crotonates of mono acrylic ester, itaconic acid and the methyl of hydroxy-ethyl acrylate, allyl alcohol, allylamine, N hydroxymethyl acrylamide, dihydroxylic alcohols-3-.
Can prepare polyvinyls aqueous dispersion of the present invention with the colloid of amine and hydroxyl-functional protection. Applicable example comprises the dispersible polyvinyl alcohol-copolymerization of water (vinylamine) polymer described in the EP 0599245 that transfers air products and chemical company (Allentown, Pennsylvania). The amine content of this shielded colloid can be about 0.5 milliequivalent amine/gram～about 3.5 milliequivalents amine/gram, preferred 1.0 milliequivalents amine/gram～about 3.0 milliequivalents amine/gram. Number-average molecular weight can be about 10,000 g/mols-Yue 350,000 g/mols, preferred about 30,000 g/mols～about 250,000 g/mols. Take 100 parts of total polyacrylic acid solids as benchmark, described colloidal content can be about 0.1% weight～about 20% weight, preferred about 0.5% weight～about 5.0% weight. Suppose that graft reaction occurs in emulsion polymerization process. C.A.Finch has further described graft copolymerization in " the Polyvinyl Alcohol Developments " of volume (John Wiley ﹠ Sons, New York, 1992, the 449-453 pages or leaves) literary composition.
Also can in the vinyl aqueous dispersion, add particular monomers, this class monomer comprises United States Patent (USP) 4,745,028 (PPG) and United States Patent (USP) 5,236, amino-organosilanes coupling agent, United States Patent (USP) 5 described in 982 (Ovens Corning Incorporateds), 496,907 (H.B.Fuller companies, St.Paul, the Minnesota) imidazolidinone official described in can wet adhesive bonding monomer and Vinamer EF, namely derives from the N-vinyl formyl of air products and chemical company (Allentown, Pennsylvania).
When Vinamer EF monomer joins in the polyvinyls aqueous dispersion, the available alkali that comprises NaOH, hydrochloric acid and sulfuric acid or acid catalyst in connection with formamido be hydrolyzed into primary amine. The polyvinyls of gained amine official energy can be used as the reactive component of technique of the present invention.
Moisture polyvinyls can form with known material and free radical polymerization process in the present technique. For example, adding radical initiator used in the polymerizing technology can be water miscible, oil-soluble or its mixture. Its example comprises hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, 2,2-azo two (2, the 4-methyl pentane nitrile), 2,2-azo two (2-methyl propionitrile) and mixture are such as tert-butyl hydroperoxide, FeEDTA and arabo-ascorbic acid. Take 100 parts of total solids as benchmark, described initiator content can be about 0.05% weight～about 1.5% weight, preferred about 0.1% weight～about 0.5% weight. In addition, oxidation catalyst can use separately, or is used in combination with reducing agent such as sodium formaldehyde sulphoxylate, ferrous salt, sodium dithionate, sodium dithionite, sodium sulfite and sodium thiosulfate. Take 100 parts of total solids as benchmark, the content of oxidation reduction catalyst can be about 0.05% weight～about 1.5% weight, preferred about 0.1% weight～about 0.5% weight.
The ethylene linkage unsaturated monomer carries out polymerization with known radical polymerization technique in the present technique. Radical initiator can once all add, and slowly adds in time, and perhaps a part adds then in time slowly adding of remainder as initial charge.
Raolical polymerizable can be at about 5 ℃～about 85 ℃, carry out in the preferred about 25 ℃～about 80 ℃ temperature range.
Water-based sulfonated polymer compositions of the present invention adopts such method to form, and wherein isocyanate-terminated polyurethane prepolymer is dispersed in the polyvinyls aqueous dispersion of groups such as can containing primary amine, secondary amine, primary hydroxyl, secondary hydroxyl and formamide. Also can be first the polyurethane prepolymer that this is isocyanate-terminated be dispersed in water, then immediately with the blend of polyvinyls aqueous dispersion. Randomly, this polyvinyls aqueous dispersion can join in the isocyanate-terminated polyurethane prepolymer pure or aqueous dispersion. More about 25 ℃～about 95 ℃ in dissimilar polymer, preferred about 45 ℃～about 75 ℃ interior mixing of temperature range.
If use amine functional ethylene base polymer aqueous dispersion, then this polymers compositions can be about 1: 10～about 10: 5 by the equivalent proportion of amine active hydrogen and isocyanates, preferably carries out blending in about 1: 5～about 5: 1.
If wish, can allow the water soluble compound and the polymeric blends of the present invention that contain uncle and/or secondary amine react. The example that is fit to comprises MEA, ethylenediamine, diethylenetriamines and ammonia.
The viscosity of water-based sulfonated polymer compositions can be about 10mPa.s～about 1,000mPa.s, preferably about 10mPa.s～about 500mPa.s. Size distribution can be single mode or multi-modal, and its average diameter is generally about 0.01 micron～about 2.0 microns.
The solids content of water-based sulfonated polymer compositions can be about 20%～about 70%, preferred about 35%～about 55% of total composition weight.
Dry sulfonated polymer compositions can have one or more glass transition temperatures (Tg) ,-100 ℃ approximately～+ 200 ℃ approximately of its scopes.
The present invention also relates to a kind of water-based sulfonated polymer compositions that particularly can be used for the glass fibre starching and preparation method thereof. Water-based sulfonated polyurethane polyvinyls hybrid latex of the present invention comprises at least a sulfonated polyurethane dispersion and the product that contains at least a moisture ethylene linkage unsaturated monomer pre-emulsion of at least a ethylene linkage unsaturated monomer and at least a for example above-mentioned those disclosed radical initiator.
The present invention also relates to a kind of water-based sulfonated polymer compositions that contains particle, described particle comprises sandwich layer and surface layer, its center core layer comprises basically different polymer from surface layer, sandwich layer comprises at least a polymer that is selected from this group that is comprised of sulfonated polyurethane polymer and sulfonated polyurethane urea polymers and composition thereof, and surface layer then mainly comprises polyvinyls. This combination can by at least a ethylene linkage unsaturated monomer in the presence of sulfonated polyurethane or polyurethane-urea dispersion, be carried out free radical inoculation emulsion polymerisation with polyurethane as the polymerization seed and form.
Be applicable to sulfonated polyurethane dispersion of the present invention those disclosed dispersion in the United States Patent (USP) 5,608,000 people such as () Duan, United States Patent (USP) 5,610,232 people such as () Duan is for example arranged. Two kinds of sulfonated polyurethane dispersions as the specific embodiments of above-mentioned two inventions, be NP-4062-M or NP-4073, the two is produced by H.B.Fuller company, these two kinds of dispersions are specially adapted to the present invention, but other sulfonated polyurethane dispersion, and comprise that the sulfonated polyurethane ureas dispersion also is operable.
Moisture ethylene linkage unsaturated monomer is preferably selected from following monomer: (methyl) acrylate monomer, (methyl) acrylic monomers, vinyl monomer, allyl monomer, acrylamide monomer and their mixture. Its example comprises methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid n-propyl, isopropyl acrylate, butyl methacrylate, hexanediyl ester, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate and their mixture. Preferably, the emulsion that contains monomer will comprise methyl methacrylate, n-butyl acrylate, hydroxyethyl methacrylate and composition thereof. But above-mentioned any ethylene linkage unsaturated monomer for example contains the ethylene linkage unsaturated monomer of anion and/or ionic group, or the ethylene linkage unsaturated monomer that contains reactive hydrogen atom also can use. When the preparation pre-emulsion, can use suitable surfactant, for example combination of Pluronic L64 (BASF AG's manufacturing) or various surfactants.
In a specific embodiments, the ratio of sulfonated polyurethane solid and polyvinyls solid is about 9: 1～about 1: 9. Preferably, this ratio is about 4: 1～about 1: 4, and most preferably, this ratio is about 4: 1～about 2: 1.
The present invention also relates to contain the water-based sulfonated polyurethane polyvinyls hybrid latex that average grain diameter is at least the polyurethane polyvinyls particle of 200 nanometers.
The feature of the water-based sulfonated polymer compositions that forms by the inoculation emulsion polymerisation be have at least about 350psi (pounds/square inch) high lap shear strength.
The present invention also relates to prepare the method for above-mentioned polyurethane polyvinyls latex hybrid. The method comprises the following steps: to form a kind of moisture pre-emulsion that contains at least a ethylene linkage unsaturated monomer, described pre-emulsion contains at least a acrylate and randomly, a kind of surfactant, and this moisture pre-emulsion and at least a sulfonated polyurethane dispersion are reacted in the presence of at least a radical initiator.
This moisture polyvinyls pre-emulsion can lead to ethylene linkage unsaturated monomer dispersion in water, and simultaneously this mixture is stirred to form with a kind of surfactant.
Then in dispersions of polyurethanes, add initiator solution such as tert-butyl hydroperoxide, reducing agent such as bisulfites and above-mentioned pre-emulsion, form polyurethane polyvinyls latex dispersion. Another kind method is, initator is Already in the pre-emulsion or in the dispersions of polyurethanes. Allow this mixture at 50 ℃～100 ℃, preferably under 65 ℃ temperature, react a period of time.
The feature of this water-based sulfonated polymer compositions is to carry out modification by adding following compounds: surfactant, defoamer, coalescing aid, fungicide, bactericide, multifunctional crosslinking agent, plasticizer, thickener, filler, pigment, reactive pigment, pigment dispersing agent, colouring agent, class fragrance material, UV light stabilizing agent, sequestering agent, wax, oil, fire retardant chemical and organic solvent. These materials can be introduced in any stage in process of production.
Following example further specifies the present invention
Example
Adopt following test method in the example.
Tensile strength and elongation:
It is dry female film of about 20 mils～about 40 mils that this polymeric dispersions curtain coating is become thickness.Tailor V-type Eight characters sample with Dewes Gumbs punch die, then balance at least 24 hours in the environment of 50% relative humidity and 23 ℃.These samples are tested with the pinblock speed of 5.0 cm per minute according to ASTM D-638.
Shearing resistance:
Polymeric dispersions is coated on steel, acrylonitrile butadiene-vinylbenzene (ABS) material and on glass, dry 24 hours then.Method with hand mates up similar base material, carries out thermal activation 30 minutes at 70 ℃ then.According to ASTM-D-1002, be that 0.5 * 1.0 inch sample is tested to bonding area with the pinblock speed of 1.27 cm per minute.
Stripping strength:
Stripping strength is measured as follows.With Virahol the transparent compacting polishing PVC of one 10 mil thick is tailored thin slice (10.5 * 12.75 inches) wash clean in advance, place it in then on the sheet glass or aluminium sheet that contains a small amount of Virahol.Remove excessive Virahol to obtain good sealing effectiveness.With and propyl alcohol the PVC surface that exposes is cleaned.Method curtain coating one deck on this PVC thin slice according to ASTM standard D-323-87 distributes the adhesive films of coming from being set in the thin machine of being coated with of 5 mils.Make this tackiness agent dry at ambient temperature.Second PVC thin slice is placed on first PVC thin slice that was coated with after the method for cleaning first thin slice is cleaned with being similar to.This PVC adhesive clip layer material is cut into 1 inch strip, allows its dry 2 hours then.
This strip is put into heat sealing machine uncoated PVC is contacted with top board, this top board has been preheating to 190 °F in advance, and the pressure of heat sealing machine is set in 50psi.After 30 second residence time, the temperature of bonding coat is 160 °F.Each strip seals 6 adhesive spots at least, and total bond area is 1 inch * 7 inches, and 1.5 inches at two ends are not bonding.
Allow adhesive spots aging at ambient temperature 1-2 hour and 1 week, and then test.Test is carried out on a Thwing Albert Intellect500 type instrument, and pinblock speed is 12 inch per minute clocks, 1 inch of prestripping, and record is peeled off 3 inches.
Lap shear strength:
Sample is coated on glass, allows its dry night then, bond area is 0.5 * 1.0 square inch.This lap shear sample was kept 30 minutes at 160 °F.Then according to the pinblock velocity determination lap shear strength of ASTMD-1002 standard method with 0.5 inch per minute clock.Measurement is to finish in the environment of 50% relative humidity and 23 ℃ of temperature.
Example 1:
This example illustrates water-based sulfonated polyurethaneurea polymer preparation of compositions method.Its corresponding polymeric constituent of said composition and performance thereof compares.
Compound 1A
Compound 1A is a kind of moisture polyvinyls dispersion with a kind of reactive emulsifier preparation, described reactive emulsifier is the polyvinyl alcohol polyethylene base amine copolymer thing (PVOH-PVAM) that derives from air products and chemical company (Allentown, Pennsylvania).
(1) the reinforced gram of reactor
PVOH/PVAM (6% vinyl amine, intermediate molecular weight) 1.50
Deionized water acetate 350.00
Acetate 0.30
(2) pre-emulsion
Methyl methacrylate 155.00
N-butyl acrylate 145.00
Methacrylic acid 3.90
Thiol-acetic acid 0.10
(3) postpone the tensio-active agent charging
T-Det 0-407 (deriving from Harcros) 7.50
Deionized water 30.00
(4) initiator feed
Tertbutyl peroxide 1.28
Deionized water 20.00
(5) reductive agent charging
Sodium formaldehyde sulfoxylate 0.92
Deionized water 20.00
In the reactor that is equipped with agitator, thermometer, condenser and nitrogen wash device, add reactor reinforced (1).With mixture heating up to 65 ℃ and stirred 30 minutes.Times adding pre-emulsion (2) and tensio-active agent charging (3) with 3 hours make temperature of reaction maintain 65 ℃ simultaneously.Times adding initiator feed (4) and reductive agent charging (5) with 3.5 hours.After in case all materials add, just with dispersion reheat 30 minutes.The solid content of polymkeric substance is 33.2%, and pH is 2.65.
Compound 1B
Compound 1B is a kind of water-based sulfonated polyurethaneurea polymer.
In reactor, add 4.5 gram (0.099 hydroxyl equivalent) 2-methyl isophthalic acids, ammediol and 95.4 gram (0.093 hydroxyl equivalent) fusion Rucoflex
XS-5570-55, a kind of sulfonation polyvalent alcohol that promptly derives from Ruco Polymer Company based on the single sodium salt (4% weight) of 5-sulfoisophthalic acid, hexanodioic acid and Diethylene Glycol.In this mixture, add the 39.96 different Buddhist diketone vulcabond of gram and 1 dibutyl tin laurate, be heated to 80 ℃ then and kept 2 hours, to generate a kind of isocyanate-terminated polyurethane prepolymer.
The polyurethane prepolymer that gained is isocyanate-terminated is dispersed in 70 ℃ the deionized water of 247.0 grams, carries out middling speed and stirs, 65 ℃ of reheat 2 hours.
Compound 1C
Compound 1C is a kind of water-based sulfonated poly-propylhomoserin urea polymers.
With temperature is that 80 ℃ the isocyanate-terminated polyurethane prepolymer (making by the method that prepare compound 1B) of 139.86 grams is dispersed in 139.86 and restrains in the deionized waters, and stirs 5 minutes.In this dispersive prepolymer, add 341.5 donaxines and hydroxyl functional ethylene polymer dispersion (compound 1A).This mixture was 65 ℃ of stirring heating 2 hours.The solid content of the water-based sulfonated polyurethaneurea polymer of gained is 40.2%, and pH is 6.4.
Test tensile strength, elongation and the shearing resistance of above-mentioned each compound on glass, steel plate and acrylonitrile-butadiene styrol copolymer (ABS).The results are shown in the following table 1.
Table 1. tensile strength, elongation and shearing resistance
| Compound | Tensile strength (kg/cm 3) | Elongation rate (%) | Shearing resistance (kg/cm 3) | ||
| Steel/steel | Glass/glass | ABS/ABS | |||
| Compound 1A | ?117.40 | ?1,020 | ?20.38 | ?18.98 | ?40.07 |
| Compound 1B | ?60.45 | ?3,810 | ?18.98 | ?21.79 | ?26.71 |
| Compound 1C | ?75.92 | ?1,680 | ?33.04 | ?40.07 | ?39.36 |
| Compound 1A and 1B (50/50 blend) | ?44.29 | ?1,130 | ?21.79 | ?26.71 | ?37.26 |
Data declaration sulfonated polyurethane-vinyl polymer in the table (compound 1C) is compared with the blend of compound 1A and 1B, has the enhanced mechanical property.These data also show with compound 1A, compound 1B and their 50/50 blend to be compared, and compound 1C has the enhanced bond properties, therefore illustrates that the present invention has practicality.
Example 2:
This example explanation method of the water-based sulfonated polyurethane-vinyl polymer of vinyl acetate preparation.Its corresponding polymeric constituent of polymer performance of the present invention compares.
Compound 2A
Compound 2A is that described emulsifying agent is the polyvinyl alcohol-polyvinylamine multipolymer (PVOH-PVAM) that derives from air products and chemical company (Allentown, Pennsylvania) with a kind of a kind of aqueous polyvinyl acetate dispersions of reactive emulsifier preparation.
This polymkeric substance is by the preparation of method described in the example 1 (compound 1A), and different is that pre-emulsion comprises 265.0 gram vinyl acetate between to for plastics, 35.0 gram butyl acrylates, 3.9 gram methacrylic acids and 0.10 gram thiol-acetic acid.The solid content of resulting polymers dispersion is 33.6%, and pH is 2.5.
Compound 2B
Compound 2B is a kind of sulfonated polyurethane prepolymer.
This polymkeric substance is to prepare according to method described in the example 1 (compound 1B) fully.
Compound 2C
Compound 2C is a kind of water-based sulfonated urethane-vinyl acetate polymkeric substance.
With temperature is 80 ℃ of preparation methods according to compound 1B, but before disperseing, the isocyanate-terminated polyurethane prepolymer of 139.86 grams of preparation is dispersed in the 247 gram deionized waters (70 ℃), and stir about 10 minutes.Add 341.5 in the prepolymer after this dispersion and digest amine described in the compound 2A and hydroxyl-functional polyvinyls dispersion.Mixture is heated to 65 ℃ and kept 2 hours under middling speed stirs.The solid content of the water-based sulfonated urethane-vinyl acetate polymer compositions of gained is 35.5%, and pH is 6.5.
Test tensile strength, elongation and the shearing resistance of above-mentioned each compound on glass, steel plate and acrylonitrile-butadiene-styrene copolymer (ABS).The results are shown in Table 2.
Table 2 tensile strength, elongation and shearing resistance
| Compound | Tensile strength (kg/cm 3) | Elongation rate (%) | Shearing resistance (kg/cm 3) | ||
| Steel/steel | Glass/glass | ABS/ABS | |||
| Compound 2A | ?131.46 | ?330 | ?9.14 | ?3.51 | ?16.17 |
| Compound 2B | ?60.45 | ?3810 | ?21.79 | ?21.79 | ?26.71 |
| Compound 2C | ?120.91 | ?1,190 | ?26.71 | ?32.33 | ?34.45 |
| Compound 2A and 2B (50/50 blend) | 71.00 | ?920 | ?18.28 | ?33.74 | ?47.10 |
Data declaration sulfonated polyurethane-vinyl acetate polymer in the table (compound 2C) is compared with the blend of compound 2A and 2B has the enhanced mechanical property.These data also show with compound 2A to be compared with compound 2B, and compound 2C has the enhanced bond properties, therefore illustrates that the present invention has practicality.
Example 3:
This example illustrates the preparation method of water-based sulfonated polyurethane-vinyl polymer, wherein amine functional ethylene polymer dispersion is with Vinamer EF monomer, derive from promptly that the N-vinyl formamide of air products and chemical company (Allentown, Pennsylvania) forms.
Compound 3A
Compound 3A is a kind of amine functional ethylene polymer dispersion with the preparation of N-vinyl formamide.
(1) the reinforced gram of reactor
Deionized water 295.0
Potassium Persulphate 0.42
Deionized water 20.0
(2) pre-emulsion gram
Deionized water 80.0
T-Det?0-407(Hacros)????????????????????8.86
Foamaster?111??????????????????????????0.325
Potassium Persulphate 0.55
Methyl methacrylate 155.0
N-butyl acrylate 155.0
Methacrylic acid 0.5
(3) initiator feed gram
Deionized water 20.0
Potassium Persulphate 0.42
(4) monomer feed gram
Vinamer?EF?????????????????????????????3.1
Pre-emulsion (2) is to prepare with following step.Water, tensio-active agent, defoamer and initiator are combined, stirred 15 minutes.Under agitation monomer is joined in this mixture, form a kind of white pre-emulsion of milk shape with time of 30 minutes.
Reactor reinforced (1) is joined in the reactor that is equipped with agitator, thermometer, condenser and nitrogen purging device.Material is heated to about 80 ℃, adds 2% total pre-emulsion (2) then, restir 15 minutes.In 3 hours, add pre-emulsion (2), keep 80 ℃ of temperature of reaction simultaneously.Begin charging at pre-emulsion and add monomer feed (4) after about 1.5 hours.After in case all materials add, just with reaction mixture reheat 30 minutes.In this dispersion, add 3.1 gram Igepal CO-710, promptly derive from a kind of tensio-active agent of Rhone-Poulenc company, with reaction mixture heating 1 hour, make described monomeric Raolical polymerizable complete again.Make the Vinamer EF monomer of adding be hydrolyzed into primary amine then.This is to restrain 5% sodium hydroxide solution by adding 17.5, and finishes in 2 hours at 80 ℃ of reheat.
Compound 3B
Compound 3B is a kind of water-based sulfonated poly-ammonia pattern-vinyl polymer.
In reaction flask, add A95.4 gram (0.093 hydroxyl equivalent) Rucoflex
XS-5570-55 and 4.5 gram 2-methyl isophthalic acids, ammediol.Material is heated to 50 ℃, adds the 39.96 different Buddhist diketone vulcabond of gram and 1 dibutyl tin laurate then.Mixture was 80 ℃ of reheat 2 hours.The isocyanate-terminated polyurethane prepolymer of gained is dispersed in the solution that contains 315 donaxine functional ethylene base polymers (compound 3A) and 244 gram deionized waters.Again this dispersion was stirred 2 hours at 60 ℃.
The mechanical property and the bond properties of above-claimed cpd are listed in the table 3.
Table 3. tensile strength, elongation and shearing resistance
| Compound | Tensile strength (kg/cm 3) | Elongation rate (%) | Shearing resistance (kg/cm 3) | ||
| Steel/steel | Glass/glass | ABS/ABS | |||
| Compound 3A | ?55.46 | ?1,987 | ?10.89 | ?14.34 | ?23.90 |
| Compound 3B | ?48.36 | ?2,118 | ?19.47 | ?17.78 | ?27.27 |
Example 4:
The preparation method of example 4 explanation water-based polymer compositions, wherein isocyanate-terminated sulfonated polyurethane prepolymer is dispersed in the water base polyacrylic dispersion of hydroxyl-functional.
Compound 4A
Compound 4A is a kind of hydroxyl-functional polyacrylic dispersion, and wherein said oh group is in latex particle.
(1) the reinforced gram of reactor
Deionized water 275.0
Methacrylic acid 1.0
(2) pre-emulsion gram
Deionized water 80.0
T-Det?0-407(Hacros)????????????????????????8.86
Methyl methacrylate 155.0
N-butyl acrylate 155.0
Hydroxyethyl acrylate 10.85
N-dodecane mercaptan 0.31
(3) initiator feed gram
Deionized water 20.0
Tertbutyl peroxide 1.37
(4) reductive agent charging gram
Deionized water 20.0
Sodium formaldehyde sulfoxylate 0.97
In the reactor that is equipped with agitator, thermometer, condenser and nitrogen purging device, add reactor reinforced (1).Water is heated to about 65 ℃, adds 3% total pre-emulsion (2) then.When keeping 65 ℃ of temperature of reaction, in 3 hours, add pre-emulsion (2), in 4 hours, add initiator feed (3) and reductive agent charging (4) simultaneously.After adding about 75% pre-emulsion, in this reaction mixture, add 10.85 gram Hydroxyethyl acrylates.In case all materials add and finish, just with reaction mixture reheat 1 hour.Dispersions obtained solid content is 45.2%, and pH is 2.65, and number average bead diameter is 443 nanometers.
Compound 4B
Compound 4B is a kind of hydroxyl-functional polyacrylic dispersion, and wherein a part of oh group is distributed on the particle surface.
(1) the reinforced gram of reductive agent
Deionized water 275.0
Methacrylic acid 1.0
(2) pre-emulsion gram
Deionized water 80.0
T-Det?0-407(Hacros)????????????????????????8.86
Methyl methacrylate 155.0
N-butyl acrylate 155.0
N-dodecane mercaptan 0.31
(3) initiator feed gram
Deionized water 20.0
Tertbutyl peroxide 1.37
(4) reductive agent charging gram
Deionized water 20.0
Sodium formaldehyde sulfoxylate 0.97
In the reactor that is equipped with agitator, thermometer, condenser and nitrogen purging device, add reactor reinforced (1).Water is heated to about 65 ℃, adds 3% total pre-emulsion (2) then.When keeping 65 ℃ of temperature of reaction, in 3 hours, add pre-emulsion (2), in 4 hours, add initiator feed (3) and reductive agent charging (4) simultaneously.After adding about 75% pre-emulsion, in this reaction mixture, add 10.85 gram Hydroxyethyl acrylates.In case all materials add and finish, just with reaction mixture reheat 1 hour.Dispersions obtained solid content is 45.2%, and pH is 2.65, and number average bead diameter is 443 nanometers.
Compound 4C
Compound 4C is a kind of sulfonated polyurethane prepolymer.
In reactor, add 4.5 gram (0.099 hydroxyl equivalent) 2-methyl isophthalic acids, ammediol and 95.4 gram (0.093 hydroxyl equivalent) fusion Rucoflex
XS-5570-55, a kind of sulfonation polyvalent alcohol that promptly derives from Ruco Polymer Company based on the single sodium salt (4% weight) of 5-sulfoisophthalic acid, adipic acid and Diethylene Glycol.In this mixture, add the 39.96 different Buddhist diketone vulcabond of gram and 1 dibutyl tin laurate, be heated to 80 ℃ then and kept 2 hours.
Compound 4D
Compound 4D is a kind of water-based sulfonated polyurethaneurea polymer.
Restrain adding 629.3 gram deionized waters (65 ℃) in the prepolymer (80 ℃) that is described as compound 4C 139.86, stirred 2 hours, maintain the temperature at below 65 ℃.
Compound 4E
Compound 4E is a kind of water-based sulfonated polyurethane-acrylate polymer compositions.
139.86 the prepolymer (80 ℃) that gram is described as compound 4C is dispersed in 309.4 grams and is described as in the hydroxyl-functional polyacrylic dispersion (65 ℃) of compound 4A.This dispersion mixture was stirred 5 minutes, then toward wherein adding 250.0 gram deionized waters (65 ℃).This material is 65 ℃ of reheat 2 hours, is 40.2% to generate a kind of solid content, pH is 6.5 polymer composition.
Compound 4F
Compound 4F is by being similar to the preparation of method described in the compound 4E, and different is to use 312.2 to digest the hydroxyl-functional polyacrylic dispersion described in the compound 4B.The solid content of this polymer composition is 40%, and pH is 6.5.
The mechanical property of above-mentioned each compound is listed in the table below 4:
Table 4. tensile strength and elongation
| Compound | Tensile strength (kg/cm 3) | Elongation rate (5) |
| Compound 4A | ????71.8 | ????1,484 |
| Compound 4B | ????94.3 | ????1,648 |
| Compound 4C | ????60.7 | ????3,807 |
| Compound 4D | ????120.8 | ????2,205 |
| Compound 4E | ????117.0 | ????2,437 |
| Compound 4A and 4C (50/50 blend) | ????61.0 | ????2,620 |
| Compound 4B and 4C (50/50 blend) | ????68.3 | ????2,537 |
Data declaration polymer composition of the present invention (compound 4E and 4F) is compared with 50/50 blend of compound 4B and 4D with 50/50 blend of compound 4A, compound 4B, compound 4D, compound 4A and 4D in the table, has the enhanced tensile strength.
Example 5
This example illustrates the water-based sulfonated polyurethane-urea/preparation method of poly-ethyl polymkeric substance and the comparison of performance polymeric constituent corresponding with it thereof.
Compound 5A
Compound 5A explanation does not contain the preparation method of the polyvinyls dispersion of reactive hydrogen atom.
(1) the reinforced gram of reactor
Deionized water 290.0
(2) pre-emulsion gram
Deionized water 90.0
T-Det?0-407(Hacros)?????????????????????15.0
Methyl methacrylate 170.0
N-butyl acrylate 180.0
Methacrylic acid 7.0
N-dodecane mercaptan 7.0
(3) initiator feed gram
Deionized water 30.0
Tertbutyl peroxide 2.15
(4) reductive agent charging gram
Deionized water 30.0
Sodium formaldehyde sulfoxylate 2.10
In the reactor that is equipped with agitator, thermometer, condenser and nitrogen purging device, add reactor reinforced (1).Water is heated to about 65 ℃, adds total pre-emulsion (2) of 3% weight then.When keeping 65 ℃ of temperature of reaction, in 3 hours, add pre-emulsion (2), initiator feed (3) and reductive agent charging (4).In case all materials add and finish, just with dispersion reheat 1 hour.
Compound 5B
Compound 5B is a kind of water-based sulfonated polyurethaneurea polymer.
In reactor, add 95.4 gram (0.093 hydroxyl equivalent) Rucoflex
XS-5570-55 and 4.5 gram 2-methyl isophthalic acids, ammediol.Mixture heating up to 50 ℃ is then toward wherein adding 39.96 gram isophorone diisocyanate and 1 dibutyl tin laurate.Under stirring, middling speed, kept about 2 hours mixture heating up to 80 ℃.Then this isocyanate-terminated polyurethane prepolymer is dispersed in the 339.4 gram deionized waters, and in wherein adding the solution that contains 2.88 gram quadrols, 1.09 gram diethylenetriamine and 20 gram deionized waters.
Compound 5C
Compound 5C is a kind of water-based sulfonated polyurethane-urea/polyvinyls dispersion.
In reactor, add 95.4 gram (0.093 hydroxyl equivalent) Rucoflex
XS-5570-55 and 4.5 gram 2-methyl isophthalic acids, ammediol.Mixture heating up to 50 ℃ is then toward wherein adding 39.96 gram isophorone diisocyanate and 1 dibutyl tin laurate.Under middling speed stirs,, kept about 2 hours, obtain a kind of isocyanate-terminated polyurethane prepolymer mixture heating up to 80 ℃.Then will this isocyanate-terminated polyurethane prepolymer be dispersed in and contain 339.4 gram deionized waters and 969.3 gram polyacrylic dispersions, be in the mixture of compound 5A, this mixture was adjusted to pH=9.3 with 10% aqueous sodium hydroxide solution before dispersion process.Add in the isocyanate-terminated polyurethane prepolymer/polyvinyls dispersion that is generated and contain 2.88 gram quadrols.1.09 in the solution of gram diethylenetriamine and 20 gram deionized waters.The solid content of resulting water-based sulfonated polyurethane-urea/polyvinyls dispersion is 35%, and pH is 9.0.
Test above-mentioned each compound at glass, the shearing resistance on steel plate and the acrylonitrile-butadiene-styrene copolymer (ABS).The results are shown in the following table 5.
Table 5: shearing resistance
| Shearing resistance (kg/cm 3) | Shearing resistance (kg/cm 3) | ||
| Glass/glass | Steel/steel | ABS/ABS | |
| Compound 5A | ?41.6 | ?55.95 | ?19.19 |
| Compound 5B | ?20.87 | ?11.17 | ?25.94 |
| Compound 5C | ?75.71 | ?59.82 | ?31.21 |
| Compound 5A and 5B (50/50 blend) | ?23.48 | ?23.97 | ?23.12 |
Data declaration polymkeric substance of the present invention (compound 5C) is compared with 50/50 blend of compound 5A and 5B with compound 5A, compound 5B in the table, has the enhanced shearing resistance, thereby explanation the present invention has practicality.
Embodiment 6 and 7 relates to the method that forms water-based sulfonated polymer compositions, wherein uses polyurethane dispersions to make (methyl) polymerizable acrylic monomer as cenospecies.Formed water-based sulfonated polymer compositions can be used for the glass fibre starching.Here used acrylic acid or the like is meant acrylate, methacrylic acid and acrylamide.
Synthesizing of example 6. polyurethane dispersions acrylic acid or the like hybrid latex
Example 6 explanations prepare the method for water-based sulfonated polymer compositions and the comparison of performance polymeric constituent blend corresponding with it thereof with the inoculation emulsion polymerization.
Compound 6A
Compound 6A is a kind of polyacrylic ester pre-emulsion.
(1) the reinforced gram of reactor
Deionized water 90.8
Pluronic L64 (a kind of tensio-active agent of BASF) 9.08
(2) monomer mixture
Methyl methacrylate (ICI) 159.6
N-butyl acrylate (Hoechst Celanese) 163.5
Hydroxyethyl methylacrylate (Rohm ﹠amp; Haas) 6.49
Under agitation reactor reinforced (1) is joined in the reactor, and under 25 ℃ of temperature, mixed 10 minutes.Under agitation in 30 minutes, monomer mixture (2) is joined in this reactor then.At 25 ℃ with mixture remix 10 minutes.The pre-emulsion that is generated is transferred in the charging stock tank.
Compound 6B
Compound 6B is a kind of polyurethane dispersions, is used to prepare composition of the present invention.
(1) the reinforced gram of reactor
Deionized water 181.7
Thiolactic acid (Evans) 0.065
Hydrosulphite AWC (Henkel) 0.065
Hamp-O14.5% iron (Hampshire) 0.039
Reactor reinforced (1) is joined in the reactor that cleans up of the strap clamp cover that is equipped with agitator, thermometer, condenser and nitrogen purging device, and thorough mixing.Then 332.3 gram NP-4062-M (a kind of polyurethane dispersions, H.B.Fuller company makes) are joined in this mixture.Reactor stirs under nitrogen protection, and makes temperature rise to 65 ℃.
Compound 6C
Compound 6C is a kind of water-based sulfonated polymer compositions with the preparation of inoculation emulsion polymerization.
In 4.5 hours, with polyacrylic ester pre-emulsion (compound 6A), contain the initiator solution of 1.95 gram tertbutyl peroxides (Akzo) and 19.5 gram deionized waters and contain 0.91 gram hydrosulphite AWC (Henkel) and 19.5 reductant solutions that restrain deionized waters join in the clean reactor that fills polyurethane dispersions mixture (compound 6B) that the strap clamp that is equipped with agitator, thermometer, condenser and nitrogen purging device overlaps.Behind reinforced the finishing, mixture kept constant temperature 1 hour again, and monomer is transformed fully.Make reactor cooling to room temperature then, formed latex is filtered by 200 order strainers.Obtain a kind of solid content and be 45%, pH is 7.35, viscosity is the stabilized latex of 316 centipoises.
Also preparation is similar to other compounds of compound 6C, changes the consumption of compound 6B, the water-based sulfonated polymer compositions that obtains having different polyurethane/polyacrylates (PU/PA) ratio.Compound 6C and the compound for preparing have similarly been tested with different urethane/polyacrylic polymer ratio, and the tensile strength and the elongation of the blend of compound 6A and 6B (not having initiator and reductant solution), stripping strength (making the matrix thing) and lap shear strength with white and transparent PVC sheet material.The results are shown among the table 6-9, the ratio that note that urethane and polyacrylic ester is that the solids content with urethane and polyacrylic ester is benchmark calculating.For example, 75/25PU/PA needs 3 fens urethane solids than every part of polyacrylic acid solid of expression.Note that also " hybrid " mentioned in the table 9 is to prepare by the method among the compound 6C, the ratio of its PU/PA is 25/75.The ratio of the PU/PA of the blend in the table 9 is 25/75.
Table 6. tensile strength and elongation
| Tensile strength (PSI) | Tensile elongation (%) | ||||
| The PU/PA ratio | Blend | | Blend | Hybrid | |
| 100/0 | ?6505 | ??- | ?3383 | ??- | |
| ?75/25 | ?3285 | ?3386 | ?3383 | ?3636 | |
| ?50/50 | ?1793 | ?1860 | ?3011 | ?3166 | |
| ?25/75 | ?1190 | ?1317 | ?2356 | ?2386 | |
| ?0/100 | ?908 | ??- | ?1780 | ??- |
Table 7. stripping strength, the transparent PVC film
| Green strength (PSI) | Intensity after 7 days (PSI) | ||||
| The PU/PA ratio | Blend | | Blend | Hybrid | |
| 100/0 | ?5.6 | ??- | ?3.2 | ??- | |
| ?75/25 | ?5.4 | ?6.1 | ?5.1 | ?6.8 | |
| ?50/50 | ?4.3 | ?5.9 | ?1.7 | ?6.8 | |
| ?25/75 | ?2.0 | ?6.3 | ?0.6 | ?5.4 | |
| ?0/100 | ??2.5 ?2.5 | ??- | ?0.8 ?0.8 | ??- |
Table 8. stripping strength, white PVC film: (with the hybrid of example 6 preparations)
| Green strength (PSI) | Intensity after 7 days (PSI) | ||||
| The PU/PA ratio | Blend | | Blend | Hybrid | |
| 100/0 | ?2.6 | ??- | ?2.0 | ??- | |
| ?75/25 | ?4.6 | ?4.4 | ?4.2 | ?3.7 | |
| ?50/50 | ?5.4 | ?5.3 | ?4.6 | ?5.1 | |
| ?25/75 | ?4.6 | ?5.4 | ?1.1 | ?4.4 | |
| ?0/100 | ?4.3 | ??- | ?2.2 | ??- |
Table 9. lap shear strength (glass is to glass)
| Material | Lap shear strength (PSI) |
| NP-4062 | 54 |
| Hybrid | 393 |
| Blend | 210 |
| | 60 |
Synthesizing of example 7. water-chainpropagation water-based sulfonated polymer compositions
Sample technology with example 6, method according to example 6C has prepared another kind of water-based sulfonated polymer compositions, different is to replace being used to prepare the polyurethane dispersions NP-4062 of compound 6B with NP-4073 (a kind of sulfonated polyurethane dispersion of H.B.Fuller company).
Growing state with the latex particle in capillary hydrodynamics fractionating process (Capillary HydrodynamicFractionation) the monitoring example 6 and 7.Fig. 1 and Fig. 2 represent the inoculation urethane size-grade distribution (dotted line) of the latex (water-based sulfonated polymer compositions) of preparation in example 6 and 7 and the funtcional relationship of final hybrid latex size-grade distribution (solid line) respectively.Two width of cloth figure illustrate all and do not produce new acrylic polymers particle sub-group that this just means the hybrid structure that has formed urethane-core-polyacrylic polymer-shell.The hydridization form of this uniqueness of the water-based sulfonated polymer compositions in the disclosure has caused the physicals than corresponding blend or common alloy excellence.
Claims (10)
1. water-based sulfonated polymer compositions wherein comprises the sulfonated polyurethane polyvinyls of the reaction product that contains following component:
A) at least a polymkeric substance that contains the reaction product of following component:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein this sulfo group is deposited with alkali metal salt
; With
B) at least a polyvinyls that contains the radical polymerization product of following component disperses
Body:
1) at least a ethylene linkage unsaturated monomer; With
2) randomly, at least a protectiveness colloidality that contains reactive hydrogen atom.
2. water-based sulfonated polymer compositions wherein comprises:
A) at least a polymkeric substance that contains the reaction product of following component:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein this sulfo group is deposited with alkali metal salt
;
B) at least a polyvinyls that contains the radical polymerization product of following component disperses
Body:
1) at least a ethylene linkage unsaturated monomer; With
2) randomly, at least a protectiveness colloidality that contains reactive hydrogen atom; With
C) a kind of urethane-polyvinyls that contains the reaction product of following component:
1) the end capped sulfonated polyurethane prepolymer of at least a isocyanic acid wherein comprises following group
The reaction product of dividing:
A) at least a polyisocyanates; With
B) at least a sulfonated polyester polyol, wherein sulfo group is deposited with alkali metal salt
; With
2) at least a polyvinyls dispersion, the reaction that wherein comprises following component is produced
Thing:
A) at least a ethylenically unsaturated monomers; With
B) randomly, at least a protective colloid that contains reactive hydrogen atom.
3. a method for preparing water-based sulfonated polymer compositions comprises the following steps:
A) make following component reaction form the dispersible isocyanate-terminated prepolymer of a kind of water:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein sulfo group exists with alkali metal salt;
B) provide a kind of polyvinyls dispersion, wherein
The radical polymerization product that comprises following component:
1) at least a ethylenically unsaturated monomers; With
2) randomly, at least a protective colloid that contains reactive hydrogen atom; Then
C) with A) and B) merging.
4. one kind prepares the method for water-based sulfonated polymer compositions by the inoculation emulsion polymerisation process, comprises the following steps:
A) provide at least a radical initiator;
B) form at least a pre-emulsion, wherein comprise;
1) at least a ethylene linkage unsaturated monomer;
2) water; With
3) randomly, at least a tensio-active agent;
C) provide a kind of waterbased urethane, wherein comprise the reaction product of following component:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein sulfo group exists with alkali metal salt;
Then
D) with A) and B) join C) in, use the thermal initiation Raolical polymerizable then, with poly-ammonia
Ester is as cenospecies.
5. water-based sulfonated polymer compositions wherein comprises the reaction product of following component:
A) at least a radical initiator;
B) at least a pre-emulsion wherein comprises:
1) at least a ethylene linkage unsaturated monomer;
2) water; With
3) randomly, at least a tensio-active agent; With
C) at least a water-based polyurethane dispersion wherein comprises the reaction product of following component:
1) at least a polyisocyanates; With
2) at least a sulfonated polyester polyol, wherein sulfo group exists with alkali metal salt;
Wherein said dispersion is used as the polymerization seed in the radical polymerization process of described emulsion.
6. any one described composition in the claim as described above, said composition contains particle, and described particle contains and is selected from following one group polymkeric substance: sulfonated polyurethane polymkeric substance, polyvinyls, sulfonated polyurethane-polyvinyls and composition thereof.
7. any one described composition in the claim as described above, said composition contains particle, described particle contains sandwich layer and surface layer, and wherein this sandwich layer and surface layer comprise and be selected from following one group polymkeric substance: sulfonated polyurethane polymkeric substance, polyvinyls and sulfonated polyurethane-polyvinyls.
8. goods that comprise the matrix thing, described matrix thing contains the dry polymeric layer on its at least a portion, and wherein this polymkeric substance comprises as described above any one described composition in the claim.
9. a tackiness agent, coating, tackiness agent and priming paint wherein comprise as described above any one described composition in the claim.
10. the glass fibre paste compound that contains any one described composition in the aforementioned claim.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/689,752 US5807919A (en) | 1996-08-13 | 1996-08-13 | Water-based sulfonated polymer compositions |
| US08/909,578 US6031045A (en) | 1996-08-13 | 1997-08-12 | Water-based sulfonated polymer compositions |
| US08/689,752 | 1997-08-12 | ||
| US08/909,578 | 1997-08-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1227576A true CN1227576A (en) | 1999-09-01 |
Family
ID=27104479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97197245A Pending CN1227576A (en) | 1996-08-13 | 1997-08-13 | Water-based sulfonated polymer compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0918807A1 (en) |
| JP (1) | JP2002514233A (en) |
| CN (1) | CN1227576A (en) |
| BR (1) | BR9711064A (en) |
| CA (1) | CA2259364A1 (en) |
| WO (1) | WO1998006768A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882637B (en) * | 2003-08-13 | 2010-07-14 | 瓦尔斯帕供应公司 | Water-based polyurethane-polyethylene compositions |
| CN101638559B (en) * | 2008-07-29 | 2013-02-13 | 上海奇想青晨新材料科技股份有限公司 | Improved water-based laminating adhesive and method for preparing same |
| CN103387344A (en) * | 2012-05-09 | 2013-11-13 | 第一工业制药株式会社 | Sizing agent for glass fibers |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005113128A (en) * | 2003-09-16 | 2005-04-28 | Jsr Corp | Pressure-sensitive adhesive composition, method for producing the same, and pressure-sensitive adhesive product |
| US20090088846A1 (en) | 2007-04-17 | 2009-04-02 | David Myung | Hydrogel arthroplasty device |
| US20080075685A1 (en) * | 2006-09-22 | 2008-03-27 | Steven Michael Baxter | Polymer compositions containing polyurethanes |
| US20120209396A1 (en) | 2008-07-07 | 2012-08-16 | David Myung | Orthopedic implants having gradient polymer alloys |
| CA2727777A1 (en) * | 2008-07-07 | 2010-01-14 | Biomimedica, Inc. | Hydrophilic interpenetrating polymer networks derived from hydrophobic polymers |
| KR20110040969A (en) | 2008-08-05 | 2011-04-20 | 바이오미메디카, 인코포레이티드 | Polyurethane-grafted hydrogels |
| CA2808528A1 (en) | 2010-08-27 | 2012-03-01 | Biomimedica, Inc. | Hydrophobic and hydrophilic interpenetrating polymer networks derived from hydrophobic polymers and methods of preparing the same |
| CA2885996A1 (en) | 2011-10-03 | 2013-04-11 | Biomimedica, Inc. | Polymeric adhesive for anchoring compliant materials to another surface |
| US9114024B2 (en) | 2011-11-21 | 2015-08-25 | Biomimedica, Inc. | Systems, devices, and methods for anchoring orthopaedic implants to bone |
| JP5830444B2 (en) | 2012-07-02 | 2015-12-09 | 信越ポリマー株式会社 | A conductive polymer composition, a coated article provided with an antistatic film obtained from the composition, and a pattern forming method using the composition. |
| US11077228B2 (en) | 2015-08-10 | 2021-08-03 | Hyalex Orthopaedics, Inc. | Interpenetrating polymer networks |
| US10869950B2 (en) | 2018-07-17 | 2020-12-22 | Hyalex Orthopaedics, Inc. | Ionic polymer compositions |
| FR3109583B1 (en) * | 2020-04-28 | 2022-07-29 | Arkema France | Aqueous dispersion of poly(ester-urethane) or poly(ester-urea-urethane) |
| US11801143B2 (en) | 2021-07-01 | 2023-10-31 | Hyalex Orthopaedics, Inc. | Multi-layered biomimetic osteochondral implants and methods of using thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56157476A (en) * | 1980-05-09 | 1981-12-04 | Toyobo Co Ltd | Aqueous treating agent |
| US4318833A (en) * | 1980-05-16 | 1982-03-09 | Inmont Corporation | Water reducible coating compositions of acrylic-urethane polymers |
| US5134035A (en) * | 1990-06-25 | 1992-07-28 | Minnesota Mining And Manufacturing Company | Magnetic recording medium containing a polyurethane copolymer with a free radically polymerized polymer segment grafted to the polyurethane through a sulfur atom |
| DE4137429A1 (en) * | 1991-11-14 | 1993-05-19 | Bayer Ag | WAFEREN BINDER COMBINATION, A METHOD OF MANUFACTURING THEM AND THEIR USE |
| US5834554A (en) * | 1996-03-05 | 1998-11-10 | H. B. Fuller Licensing & Financing, Inc. | Laminating adhesives for flexible packaging |
-
1997
- 1997-08-13 JP JP51005598A patent/JP2002514233A/en active Pending
- 1997-08-13 BR BR9711064A patent/BR9711064A/en not_active Application Discontinuation
- 1997-08-13 WO PCT/US1997/014386 patent/WO1998006768A1/en not_active Application Discontinuation
- 1997-08-13 EP EP97938336A patent/EP0918807A1/en not_active Withdrawn
- 1997-08-13 CA CA002259364A patent/CA2259364A1/en not_active Abandoned
- 1997-08-13 CN CN97197245A patent/CN1227576A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882637B (en) * | 2003-08-13 | 2010-07-14 | 瓦尔斯帕供应公司 | Water-based polyurethane-polyethylene compositions |
| CN101638559B (en) * | 2008-07-29 | 2013-02-13 | 上海奇想青晨新材料科技股份有限公司 | Improved water-based laminating adhesive and method for preparing same |
| CN103387344A (en) * | 2012-05-09 | 2013-11-13 | 第一工业制药株式会社 | Sizing agent for glass fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2259364A1 (en) | 1998-02-19 |
| EP0918807A1 (en) | 1999-06-02 |
| BR9711064A (en) | 1999-08-17 |
| WO1998006768A1 (en) | 1998-02-19 |
| JP2002514233A (en) | 2002-05-14 |
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