WO2021087769A1 - 一种聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用 - Google Patents

一种聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用 Download PDF

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WO2021087769A1
WO2021087769A1 PCT/CN2019/115783 CN2019115783W WO2021087769A1 WO 2021087769 A1 WO2021087769 A1 WO 2021087769A1 CN 2019115783 W CN2019115783 W CN 2019115783W WO 2021087769 A1 WO2021087769 A1 WO 2021087769A1
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Prior art keywords
polyurethane
component
diisocyanate
aqueous dispersion
reactive functional
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PCT/CN2019/115783
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English (en)
French (fr)
Inventor
宋泽峰
孙永建
纪学顺
黎会亮
张延成
王远勇
Original Assignee
万华化学集团股份有限公司
万华化学（宁波）有限公司
万华化学（广东）有限公司
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Application filed by 万华化学集团股份有限公司, 万华化学（宁波）有限公司, 万华化学（广东）有限公司 filed Critical 万华化学集团股份有限公司
Priority to EP19951694.9A priority Critical patent/EP4026864A4/en
Priority to US17/772,055 priority patent/US20220363804A1/en
Priority to PCT/CN2019/115783 priority patent/WO2021087769A1/zh
Publication of WO2021087769A1 publication Critical patent/WO2021087769A1/zh

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    • C08G18/2805—Compounds having only one group containing active hydrogen
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/3271—Hydroxyamines
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    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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Definitions

  • the invention belongs to the technical field of polyurethane water dispersions, and in particular relates to a polyurethane or polyurethane-urea water dispersion and a preparation method and application thereof.
  • polyurethane or polyurethane urea water dispersions have excellent paintability, excellent initial adhesion and peel strength, and outstanding resistance, they have been widely used in coatings, adhesives and textile coatings.
  • polyester polymer polyol is mainly used for synthesis.
  • the ester polymer is in the process of processing, use and storage. The effect of water vapor and acidic substances in the environment will cause irreversible hydrolysis.
  • Patent documents DE19954500, DE4410557 or EP792908 propose to introduce carboxylates into the water dispersion of polyurethane or polyurethane urea, and then compound with carbodiimide to improve the adhesion performance.
  • This is mainly based on the use of carboxylic acid and carbon two
  • the reaction of imines increases the cross-linking density and improves the strength of the adhesive.
  • the carboxylate is obtained by adding dimethylolpropionic acid to the polyurethane or polyurethane urea and then neutralizing it with a tertiary amine.
  • the reactivity of the carboxyl group and the carbodiimide in the compounding scheme of this type of binder is low, and the final performance is usually insufficient to meet the requirements of the binder for hydrolysis resistance at room temperature.
  • Patent document EP1272588 describes a kind of containing at least one crystalline polyester-polyurethane dispersion, polyacrylate copolymer, polychloroprene dispersion, heat curable resin and stabilizer (amino alcohol, carbodiimide and Magnesium oxide) adhesive compound, wherein the stabilizer used has the function of inhibiting the hydrolysis of the polyester in the system and maintaining the stability of the system.
  • stabilizer amino alcohol, carbodiimide and Magnesium oxide
  • Patent document CN102216359 describes that by adding monoamino and/or monohydroxy carboxylic acid in the synthesis process, an aqueous dispersion of polyurethane or polyurethane urea containing carboxyl groups at the end is obtained, and then compounded with carbodiimide to form an adhesive ; Due to the high activity of the terminal carboxyl group, it can have a rapid cross-linking reaction with carbodiimide, thereby significantly improving the performance of the coating film.
  • this carboxylic acid will affect the stability of the polyurethane or polyurethane urea aqueous dispersion, and the carbodiimide itself is not stable, which is not conducive to the storage of this system.
  • Patent document CN103980461 describes a method for synthesizing an aqueous dispersion containing epoxy resin crosslinking agent and 1-aminopropyl-2-methylimidazole, through the combination of 1-aminopropyl-2-methylimidazole and prepolymer -NCO group reaction can generate a covalent bond hybrid network structure, thereby forming a hybrid network structure.
  • epoxy resin is introduced to form a cross-linked structure, which improves the water resistance of the product.
  • the use of cross-linking agent and the formation of the network structure will affect the activation of the product, which in turn affects the initial viscosity and strength of the product.
  • Patent document CN106634785 describes the preparation of a strong water-resistant waterborne polyurethane adhesive, which uses stearic acid, lipase and hydrogen peroxide to epoxy modification of cottonseed oil and castor oil, and then mixes it with KH-550 after modification.
  • the modified oil can be obtained; the water-based polyurethane emulsion is modified by the modified oil to improve the water resistance of the product, and finally the modified water-based polyurethane emulsion is mixed with water-reducing agent, cross-linking agent and other substances to obtain water-resistant The water-based polyurethane adhesive.
  • This method has complicated process steps, uses many raw materials, and does not use industrialized production and control.
  • this patent uses more cross-linking agents, leading to deviations in other properties of the adhesive.
  • Activation refers to: when the water dispersion is coated on the substrate, the water is removed by heating. At the same time, the mobility of the polyurethane segment increases at this temperature, and the polyurethane or polyurethane urea transforms into a viscoelastic state, and then Perform operations such as fitting. In polyurethane or polyurethane urea aqueous dispersions, the cross-linked structure reduces the mobility of the polyurethane segments, makes it insufficiently activated, and affects the initial adhesion, strength, and heat resistance.
  • the purpose of the present invention is to provide a hydrolysis-resistant polyurethane or polyurethane-urea water solution in view of the problems in the prior art in the preparation of polyurethane or polyurethane-urea water dispersions using polyester polyols as raw materials to improve hydrolysis resistance. Dispersion and its preparation method and application.
  • the side chain or main chain of the polyurethane or polyurethane-urea contained in the water dispersion contains tertiary amine groups (tertiary amine groups), which makes the water dispersion due to tertiary amine groups during storage.
  • the amine group has strong basicity, which can eliminate acidic substances in the system, thereby eliminating the catalysis of acidic substances on ester polymers, greatly reducing the hydrolysis rate of ester polymers, and making the water dispersion stable in storage and storage time Long, it can greatly improve the hydrolysis resistance of the adhesive obtained from the dispersion, while maintaining the adhesive's good bonding strength and heat resistance.
  • a hydrolysis-resistant polyurethane or polyurethane-urea aqueous dispersion is prepared by reacting raw materials containing the following components:
  • polyurethane or polyurethane-urea aqueous dispersion provided by the present invention, in some examples, based on the total weight amount of each component (for example, 100% by weight),
  • the amount of component a) is 0.02 ⁇ 5wt% (0.04wt%, 0.08wt%, 0.1wt%, 0.5wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.5wt%, 3.5wt%, 4wt%, 4.5wt%), preferably 0.05 to 3wt%;
  • the amount of component b) is 5-94wt% (8wt%, 15wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 65wt%, 74wt%, 76wt%, 80wt%, 85wt%), preferably 70 ⁇ 90wt%;
  • the amount of component c) is 5-40wt% (6wt%, 10wt%, 13wt%, 15wt%, 18wt%, 25wt%, 30wt%, 35wt%), preferably 8-20wt%;
  • the amount of component d) is 0.2-50wt% (0.4wt%, 0.8wt%, 1.5wt%, 2wt%, 4wt%, 8wt%, 15wt%, 20wt%, 30wt%, 40wt%), preferably 1 to 5wt%;
  • the amount of component e) is 0.01-20wt% (0.04wt%, 0.08wt%, 0.1wt%, 0.5wt%, 0.8wt%, 1wt%, 1.5wt%, 2wt%, 3.5wt%, 5wt%, 10wt% %, 15wt%), preferably 0.5-3wt%;
  • the amount of component f) is 0-10wt% (0.01wt%, 0.1wt%, 0.4wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3.5wt%, 5wt%, 8wt%), preferably 0.5 ⁇ 3wt%;
  • the amount of component g) is 0-15wt% (0.01wt%, 0.1wt%, 1wt%, 2wt%, 5wt%, 7wt%, 10wt%, 12wt%), preferably 0-8wt%.
  • the polyurethane or polyurethane-urea contains a structural unit represented by formula (I):
  • R is selected from component a) the residue after removing the NCO reactive functional group.
  • R can be N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldiethylenetriamine, N-methyldiethanolamine, N-ethyldiethanolamine, 1,4 -Bis(aminopropyl)piperazine, N-methylpiperazine, N-ethylpiperazine or N,N-dimethylethanolamine and other compounds are the residues after the NCO reactive functional group is removed. That is, these residues contain tertiary amine groups.
  • the NCO reactive functional group is selected from one or more of primary amino group (-NH 2 ), secondary amino group (-NH-) and hydroxyl group (-OH).
  • the component a) is selected from N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldipropylenetriamine, N-methyldiethanolamine, N-ethyl One or more of diethanolamine, 1,4-bis(aminopropyl)piperazine, N-methylpiperazine, N-ethylpiperazine and N,N-dimethylethanolamine, more preferably selected from N-aminoethylpiperazine, N-hydroxyethylpiperazine, N,N-dimethyldipropylenetriamine, N-methyldiethanolamine, N-ethyldiethanolamine and 1,4-bis(aminopropyl One or more of piperazine.
  • suitable polyester polyols can be linear polyester diols or micro-branched polyester diols (containing a small amount of polyester polyols with a functionality greater than 3), for example,
  • the known means consist of carboxylic acid or acid anhydride (such as aliphatic dicarboxylic acid or polycarboxylic acid, alicyclic dicarboxylic acid or polycarboxylic acid, aromatic dicarboxylic acid or polycarboxylic acid, or its corresponding anhydride, etc.) and Polyol is obtained through dehydration and condensation.
  • carboxylic acids or anhydrides described herein include, but are not limited to, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid Acid, decane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acid, maleic acid, fumar Acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride, or mixtures thereof.
  • polyols described herein include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3- Propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl- 1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-twelve Alkanediol or their mixture.
  • a higher functional polyol for example, trimethylolpropane, glycerol, or penta
  • the polyester polyols can also be homopolymers or copolymers of lactones, which can be obtained by ring-opening reaction of lactones or mixtures of lactones with suitable diols and/or higher-functional low-molecular-weight polyols.
  • suitable examples of the lactones described here include but are not limited to butyrolactone, ⁇ -caprolactone, methyl- ⁇ -caprolactone and their mixtures; the polyols described here preferably use 1,4- Butylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol and mixtures thereof.
  • the component b) is selected from linear polyester diols with a number average molecular weight of 400 to 5000 and/or micro-branched polyester diols with a number average molecular weight of 400 to 5000.
  • the component c) is selected from diisocyanates and/or polyisocyanates, preferably diisocyanates (its structural formula is Y(NCO) 2 ).
  • Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms, a divalent aromatic hydrocarbon group containing 6-15 carbon atoms, or a divalent aromatic hydrocarbon group containing 6-15 carbon atoms.
  • polyisocyanates having a functionality of more than 2 isocyanate groups per molecule are also suitable.
  • polyisocyanates prepared by simple modification of aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates or aromatic diisocyanates e.g., carbodiimide groups, allophanate groups, Polyisocyanate modified by isocyanurate group, urethane group or biuret group), or polyisocyanate synthesized from at least two diisocyanates (synthetic polyisocyanate has uretdione, isocyanuric acid Ester, carbamate, allophanate, biuret, carbodiimide, iminooxadiazinedione or oxadiazinetrione structure).
  • the diisocyanate in component c) may be aliphatic diisocyanate and alicyclic diisocyanate, for example, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate and mixtures thereof.
  • the diisocyanate is selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate , Isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-benzene diisocyanate, 2,4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate And one or more of p-xylylene diisocyanate; more preferably selected from 1,4-
  • the component c) is a mixture of hexamethylene diisocyanate and isophorone diisocyanate, or hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate A mixture of acids.
  • the mass ratio of hexamethylene diisocyanate and isophorone diisocyanate is 1-50:1, preferably 3-10:1; hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate
  • the mass ratio of isocyanate is 1-50:1, preferably 3-10:1.
  • the latent ion group contained refers to a functional group having a covalent bond.
  • a neutralizing agent By adding a neutralizing agent to the reaction system, as the pH of the solution changes, the potential ion group is easily converted into a corresponding salt.
  • the preferred potentially ionic group is an acid group selected from the group consisting of carboxyl -COOH and/or sulfonic acid -SO 3 H.
  • the ionic groups contained include carboxylate -COO- and/or sulfonate -SO 3 -.
  • the NCO reactive group contained is selected from hydroxyl (-COOH) and/or amino (for example, -NH 2 , -NH-).
  • a neutralizer can be added before, during or after the dispersion of the NCO-terminated polyurethane prepolymer obtained after the prepolymerization is completed, so that the potential ionic group can be eliminated.
  • the regiment is neutralized.
  • the amount of the neutralizing agent added is an amount that can partly or all of the potential ionic groups become ionic groups.
  • Suitable neutralizing agents are, for example, one or more of primary amines, secondary amines, tertiary amines, alkali metal compounds and alkaline earth metal compounds; examples of suitable neutralizing agents include but are not limited to ammonia, ethanolamine, diethanolamine, Triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N-methylmorpholine, dimethylisopropylamine, N-methyldiethanolamine, triethylamine , One or more of dimethylcyclohexylamine, ethyldiisopropylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide.
  • sufficient neutralizing agent is added so that the degree of neutralization is at least 50%, preferably at least 75%, and not more than 150% based on the acid groups introduced.
  • the degree of neutralization exceeds 100%, in addition to 100% of the ionic salt groups, there are also free neutralizing amines.
  • the degree of neutralization is 95 to 110%.
  • hydrophilic compound containing a nonionic group examples include, but are not limited to, polyether diols, such as homopolymers of styrene oxide, oxides Styrene copolymer or styrene oxide graft product, ethylene oxide homopolymer, ethylene oxide copolymer or ethylene oxide graft product, propylene oxide homopolymer, propylene oxide copolymer or propylene oxide Grafted product, homopolymer of tetrahydrofuran, copolymer of tetrahydrofuran or grafted product of tetrahydrofuran, homopolymer of butylene oxide, copolymer of butylene oxide or grafted product of butylene oxide, homopolymer of epichlorohydrin Polyols, copolymers of epichlorohydrin or grafted products of epichlorohydrin, dehydr
  • the non-ionic group-containing hydrophilic compound can also be a multifunctional polyethoxy ether, such as pentaerythritol and sugar as the initiator, and the polymerization unit is one or two of propylene oxide and ethylene oxide.
  • the polymerization unit is one or two of propylene oxide and ethylene oxide.
  • One is preferably ethylene oxide.
  • the number of ethylene oxide per molecule is 4 to 200, preferably 12 to 75.
  • the component d) is selected from hydrophilic compounds containing ionic groups and containing 2-3 NCO reactive functional groups, and hydrophilic compounds containing potential ionic groups and containing 2-3 NCO reactive functional groups And one or more of hydrophilic compounds containing non-ionic groups and containing 2-3 NCO reactive functional groups.
  • the hydrophilic compound containing an ionic group and containing 2-3 NCO reactive functional groups and/or the hydrophilic compound containing a potential ionic group containing 2-3 NCO reactive functional groups is selected from dihydroxy groups Carboxylic acid and its salt, trihydroxy carboxylic acid and its salt, dihydroxy sulfonic acid and its salt, trihydroxy sulfonic acid and its salt, diamino sulfonic acid and its salt, triamino sulfonic acid and its salt, diamino carboxylic acid One or more of its salts and triamino carboxylic acids and their salts; more preferably selected from dimethylol acetic acid and its alkali metal and/or ammonium salts, dimethylol propionic acid and its alkali metal salts And/or ammonium salt, dimethylolbutyric acid and its alkali metal salt and/or ammonium salt, dihydroxysuccinic acid and its alkali metal salt and/or ammonium salt,
  • the hydrophilic compound containing nonionic groups and containing 2-3 NCO reactive functional groups is a polyether glycol, more preferably a number average molecular weight of 200-8000 and the number of ethylene oxide It is a polyether diol of 4 to 200.
  • the component d) is more preferably selected from the group consisting of N-(2-aminoethyl)-2-aminoethanesulfonic acid alkali metal salt, ammonium dimethylolpropionate and Ymer TM of Perstop (Perstop) One or more of N-120.
  • component d) is sodium N-(2-aminoethyl)-2-aminoethanesulfonate.
  • the component e) of the present invention is a polyethoxy ether containing one hydroxyl group or one amino group (for example, -NH 2 , -NH-).
  • the initiator of the polyethoxy ether include, but are not limited to, saturated monohydric alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomer
  • saturated monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomer
  • saturated monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomer
  • the component e) is selected from monofunctional polyethoxy ethers having a number average molecular weight of 200 to 8000 and the number of ethylene oxides of 4 to 200, preferably selected from a number average molecular weight of 500 to 3000 and Polyethylene glycol monomethyl ether with 12 to 75 ethylene oxide.
  • n 12 ⁇ 75.
  • the NCO reactive functional group is selected from one or more of hydroxyl, primary amino (-NH 2 ) and secondary amino (-NH-).
  • component f) is a compound containing 2 to 3 NCO reactive functional groups, at least one of the NCO reactive functional groups is a primary amino group or a secondary amino group.
  • Component f can be selected from aliphatic primary or secondary monoamines, alicyclic primary or secondary monoamines (e.g., ethylamine, diethylamine, isopropylamine, butylamine, cyclohexamine ); It can also be an amino alcohol, that is, a compound containing an amino group and a hydroxyl group in the molecule (for example, ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino-2-propanol, N -(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine or 2-propanolamine); it can also be diamine and triamine, for example, 1,2-Ethylenediamine, 1,6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), Piperazine, 1,
  • the component f) is selected from aliphatic primary monoamine, aliphatic secondary monoamine, alicyclic primary monoamine, alicyclic secondary monoamine, amino alcohol, aliphatic diamine, alicyclic One or more of aliphatic diamine, aliphatic triamine, alicyclic triamine and hydrazine, preferably selected from isophorone diamine, N-(2-hydroxyethyl) ethylene diamine and 1 , One or more of 6-hexamethylene diamine.
  • Component f) can act as a chain extender to achieve higher molecular weight, or as a monofunctional compound to limit molecular weight; or optionally also introduce other reactive groups, such as free hydroxyl groups, as other crosslinking points.
  • Component g) can be a blocking agent commonly used in the field of isocyanates (which can be removed at higher temperatures), for example, butanone oxime, dimethylpyrazole, caprolactam, malonate, triazole, dimethyl triazole Azole, tert-butylbenzylamine, cyclopentanone carboxyethyl ester; and unsaturated compounds containing polymerization reactive groups, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, methacrylic acid Hydroxybutyl ester, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate.
  • the blocking agent in the field of isocyanate refers to a substance used to block the monofunctional active hydrogen in the active isocyanate.
  • the component g) is selected from butanone oxime, dimethylpyrazole, caprolactam, malonate, triazole, dimethyltriazole, tert-butylbenzylamine, cyclopentanone carboxylate
  • ethyl ester hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate
  • ethyl ester hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate
  • pentaerythritol triacrylate pentaerythritol triacrylate
  • the polyurethane or polyurethane-urea aqueous dispersion has a solid content of 15 to 70 wt%, preferably a solid content of 30 to 60 wt%.
  • the average particle size of the polyurethane or polyurethane-urea aqueous dispersion is 20-750 nm, preferably 50-450 nm.
  • the pH of the polyurethane or polyurethane-urea aqueous dispersion is 7.5-11, more preferably 7.5-10, and still more preferably 7.5-8.5.
  • the pH level is positively correlated with the content of tertiary amine groups in the water dispersion.
  • Component b), component c), component e) and optional component g) are mixed in proportion, and then polymerized to form an isocyanate-terminated polyurethane prepolymer; the resulting polyurethane prepolymer is combined with component d ).
  • Optional component f) undergoes a chain extension reaction, and then is dispersed in water or added to the mixture obtained after the chain extension reaction for dispersion to obtain an aqueous dispersion of polyurethane or polyurethane-urea; wherein, the group Component d) is a hydrophilic compound containing ionic or non-ionic groups and containing 2-3 NCO reactive functional groups; during the reaction, component a) can be added to the reaction system at any stage for reaction;
  • component b), component c), component d), component e) and optional component g) are mixed in proportion, and then polymerized to form an isocyanate-terminated polyurethane prepolymer; make the resulting polyurethane
  • the prepolymer is neutralized with the neutralizer, and then dispersed in water or added to the mixture obtained after the neutralization reaction for dispersion.
  • the component a) is added for further reaction before, during or after the dispersion, An aqueous dispersion of polyurethane or polyurethane-urea is obtained; wherein the component d) is a hydrophilic compound containing a latent ion group and containing 2-3 NCO reactive functional groups.
  • component a) is added to the system, no neutralization reaction is performed to ensure that the prepared polyurethane or polyurethane-urea contains tertiary amine groups.
  • the system can be diluted by adding a solvent, and the solvent can be partially or completely removed by distillation during or after the dispersion.
  • a water-miscible solvent that is inert to isocyanate groups may optionally be added for dilution during the reaction.
  • Suitable solvents can be one or more of acetone, methyl isobutyl ketone, methyl ethyl ketone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether and 1-methyl-2-pyrrolidone; they can not only It is added at the beginning of the preparation and can also be added during or after the polymerization reaction. It can also be added in batches.
  • the solvent is preferably acetone and methyl ethyl ketone, more preferably acetone.
  • Optionally used solvents, such as acetone are distilled off during and/or after dispersion.
  • the preparation method can be carried out in a homogeneous phase in one or more stages, or partly in a dispersed phase in the case of a multistage reaction.
  • the complete or partial polymerization reaction is followed by a dispersing, emulsifying or dissolving step.
  • addition polymerization or modification can be further carried out in the dispersed phase later.
  • the component b), component c), component e) and optional component g) are mixed in one or more steps and then polymerized to form an isocyanate-terminated polyurethane prepolymer;
  • the one-stage or two-stage reaction allows the obtained prepolymer to react with component a), component d) and optional component f), and then disperse the resultant product with water to obtain a polyurethane or polyurethane-urea aqueous dispersion .
  • the polymerization reaction process is to pre-place all or part of the components b), d), e) and optional g) in the reactor, and optionally add water miscibility that is inert to isocyanate groups
  • the solvent is diluted, and then the component c) is metered in between room temperature and 120° C. for prepolymerization to obtain an isocyanate-terminated polyurethane prepolymer.
  • This reaction can be carried out in a single stage or in multiple stages.
  • a multi-stage reaction for example, can be: pre-place component b), component c), component e) in the reactor and add component g) after reacting with a part of component c), which can then still exist with Another part of the component c) reaction, component a) can be added at any stage.
  • the conversion degree is usually monitored by tracking the NCO content of the reaction mixture.
  • spectroscopic measurement for example, infrared or near-infrared spectroscopy, determination of refractive index
  • chemical potentiometric titration for example, chemical titration by taking samples
  • a catalyst can optionally be added.
  • the conventional catalyst may be a catalyst known to those of ordinary skill in the art for accelerating the reaction of -NCO and -OH.
  • tin acid bismuth neodecanoate and bismuth 2-ethylhexanoate. It is preferably bismuth neodecanoate or bismuth 2-ethylhexanoate, and more preferably bismuth neodecanoate.
  • the temperature in the chain extension reaction stage is usually 10-100°C, preferably 25-60°C.
  • the preparation method of polyurethane or polyurethane-urea aqueous dispersion is as follows: pre-add component b), component c), component e) and optional solvent in proportion to mix and heat to 50-100 °C while stirring. Using an exothermic reaction, the reaction mixture is stirred at 40-150°C until the theoretical isocyanate content has been reached or slightly lowered, optional component g) is added, and the reaction is continued to reach or slightly lower than the theoretical isocyanate content.
  • component a) and component d) diluted with solvent are added respectively
  • component f) undergoes chain extension.
  • dispersion is carried out by adding distilled water or by transferring the mixture to distilled water placed in advance, and during or after the dispersion step, all or part of the solvent used is distilled off and some auxiliary agents are added afterwards.
  • Agent for example, emulsifier Tween 20
  • the polymerization reaction may optionally add a catalyst (for example, bismuth neodecanoate).
  • an application of the polyurethane or polyurethane-urea aqueous dispersion as described above or the polyurethane or polyurethane-urea aqueous dispersion obtained by the preparation method as described above in an adhesive is provided.
  • the polyurethane or polyurethane-urea aqueous dispersion prepared by the present invention can be used alone or together with known auxiliary substances and additives (in coating and adhesive technology).
  • auxiliary substances and additives such as emulsifiers, light stabilizers (for example, UV absorbers and sterically hindered amines (HALS)), antioxidants, fillers, anti-settling agents, defoamers, wetting agents, flow regulators, Reactive diluents, plasticizers, neutralizers, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents, tackifiers, etc.
  • auxiliary substances and additives can be added before or after polymerization.
  • auxiliary substances and additives can also be added after dispersion.
  • oligomers or polymers are, for example, polyvinyl ester, polyvinyl ether, polyvinyl alcohol, polyethylene, polystyrene, polybutadiene, polyvinyl chloride, polyurethane, polyurethane-polyurea, polyurethane-poly Acrylate, polyester, polyacrylate. Simple preliminary tests need to be used in each case to test the compatibility of such mixtures.
  • the prepared polyurethane or polyurethane-urea aqueous dispersion and the adhesive or adhesive composition based thereon are suitable for bonding any substrate.
  • These substrates for example, all types of metals, alloys, wood, wood-based materials, particle board, MDF boards, ceramics, stones, concrete, asphalt, hard fibers, glass, glass fibers, carbon fibers, carbon nanotubes, porcelain, leather, Textiles and inorganic materials, etc.
  • They are also suitable for bonding rubber materials (for example, natural rubber and synthetic rubber), various plastics (for example, polyurethane, polyvinyl acetate, polyvinyl chloride, especially polyvinyl chloride containing plasticizers).
  • thermoplastics such as ABS (acrylic butadiene styrene), PC (polycarbonate), polyolefin plastics and their mixtures.
  • the prepared polyurethane or polyurethane-urea aqueous dispersion adhesive is also suitable for use in articles made therefrom.
  • these products include, but are not limited to, shoe soles, such as soles based on polyvinyl chloride (especially polyvinyl chloride containing plasticizers), soles based on polyethylene vinyl acetate or polyurethane elastomer foam, and made of leather or artificial leather Adhesion of the finished shoe upper. It is also particularly suitable for bonding films based on polyvinyl chloride or polyvinyl chloride containing plasticizers with wood.
  • the side chain or main chain of the polyurethane or polyurethane-urea has a segment (ie, a tertiary amine group) contained in component a).
  • a segment ie, a tertiary amine group contained in component a.
  • the tertiary amine group can eliminate the acidic substance in the system, greatly reduce the hydrolysis rate of the ester polymer, and can significantly improve the hydrolysis resistance of the adhesive obtained from the dispersion, while maintaining The adhesive has good bonding strength and heat resistance.
  • the water dispersion of the present invention is used as a binder, and it has excellent hydrolysis resistance.
  • the existing waterborne polyurethane-polyurea water dispersion is less than 6 Within -10 days (storage at 70°C), the hydrolysis resistance of the water dispersion of the present invention can reach 15-20 days (storage at 70°C).
  • the existing waterborne polyurethane-polyurea dispersions need to be added with crosslinking agents such as isocyanate or carbodiimide before use, and need to be mixed according to the ratio before construction.
  • the operation is complicated, and the formulated adhesive must be used within the specified time.
  • the open time is short, and the addition of the crosslinking agent also has a significant reduction effect on the initial viscosity of the adhesive; and the water dispersion of the present invention does not need to add additional crosslinking agents such as isocyanate or carbodiimide to meet performance requirements. It can be used as a one-component adhesive product with simple operation and long open time, which greatly increases construction efficiency.
  • Isocyanate I Hexamethylene diisocyanate ( HDI, Wanhua Chemical),
  • Isocyanate II isophorone diisocyanate ( IPDI, Wanhua Chemical);
  • Polyether I monofunctional polyethoxy ether with an average molecular weight of 1200g/mol (MPEG1200, LOTTE CHEM),
  • Polyether II monofunctional polyethoxy ether with an average molecular weight of 520g/mol (MPEG520, LOTTE CHEM);
  • Emulsifier Tween 20 (Shanghai Bangjing Industrial).
  • Measurement of average particle size of water dispersion use Malvern particle size analyzer Nano S90 for testing.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.0.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 55 wt% and an average particle diameter of 220 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.2.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 45% by weight and an average particle diameter of 150 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.8.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.7.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 30% by weight and an average particle diameter of 164 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.7.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.3.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50 wt% and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 40% by weight and an average particle diameter of 195 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.9.
  • a 35 g aqueous solution in which 4.63 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate and 1 g of hydroxyethyl ethylenediamine are dissolved is added to the prepolymer-dissolved acetone solution while vigorously stirred. Stir for 20 min, and then disperse the mixture by adding 300 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 40% by weight and an average particle diameter of 195 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 165 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.5.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 178 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.3.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 185 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.2.
  • a 35 g aqueous solution in which 1 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate and 6.9 g of N-aminoethylpiperazine are dissolved is added to the prepolymer-dissolved acetone solution while stirring vigorously. After stirring for 20 min, the mixture was dispersed by adding 241 g of water. After separating the acetone by distillation, 4 g of emulsifier Tween 20 was added.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 8.9.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 180 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.0.
  • a solvent-free polyurethane-polyurea aqueous dispersion was obtained, which had a solid content of 50% by weight and an average particle diameter of 176 nm measured by laser correlation in the dispersed phase, and its pH was determined to be 7.0.
  • the particle size and pH data of the polyurethane or polyurethane-urea aqueous dispersion prepared through each example show that we have successfully synthesized the PUD dispersion. Because in polyurethane or polyurethane-urea water dispersion containing tertiary amine group-introduced segment, the obvious change is the increase in pH value, and the pH value of the dispersion containing tertiary amine group is between 7.5-8.9, and The pH value of the dispersion without or with trace tertiary amine groups is basically 7.0.
  • tertiary amine groups The content of tertiary amine groups is very low compared to the entire polyurethane system and cannot be characterized by conventional spectroscopy. Because the tertiary amine group-containing component a) contains a group capable of reacting with NCO, and the NCO group is in excess, we believe that the tertiary amine group can be connected to the polyurethane or polyurethane urea molecular chain.
  • the substrate 1 (rubber) and the substrate 2 (rubber) are polished. Then use a brush to thinly apply the prepared adhesive to a 2.5cm wide and 15cm long substrate strip and dry it in an oven at 65°C for 3 minutes, then take it out, and pass it through a hot press at 30kg/cm 2 Under the conditions of pressing for 10 seconds, a composite material A was prepared.
  • the peel strength was measured with a GOTECH tensile machine at a peel rate of 200 mm/min. Among them, the initial strength: directly go to the tensile machine to test the peel strength after pressing. Later strength: After placing the specimen at room temperature for 24 hours, test its peel strength. The test results are shown in Table 2.
  • the one-component adhesive (Comparative Examples 1 and 2) obtained from the polyurethane water dispersion without or containing a trace (less than 0.02%) tertiary amine groups
  • the one-component adhesives (Comparative Examples 1 and 2) are prepared based on the present invention.
  • Polyurethane or polyurethane-urea water dispersion one-component adhesive, its initial peel strength and later peel strength are equivalent, meet performance requirements, and do not affect normal use.
  • the molecular weight of the polyurethane or polyurethane urea segment will decrease, which in turn will cause the initial heat resistance of the substrate bonded with the water-based polyurethane or polyurethane urea as the adhesive to deteriorate. Therefore, the initial heat resistance value under high temperature/normal temperature conditions is used to characterize its hydrolysis resistance. The lower the initial heat resistance value, the better the hydrolysis resistance.
  • High temperature (70°C) hydrolysis resistance Store the aqueous dispersions prepared in each example and comparative example at 70°C, respectively after 0 days, 3 days, 6 days, 9 days, 12 days, 15 days, 18 days and 21 days Take a sample and test the initial heat resistance level of the sample (using it as an adhesive) coated on the rubber substrate. The results of the high temperature hydrolysis resistance test are shown in Table 4.
  • Normal temperature (30°C) resistance to hydrolysis Store the water dispersions prepared in the examples and comparative examples at 30°C for 0 days, 30 days, 60 days, 90 days, 120 days, 150 days, 180 days, and 210 days. A sample was taken after days to test the initial heat resistance level of the sample (using it as an adhesive) coated on the rubber substrate. The results of the hydrolysis resistance test at room temperature are shown in Table 5.
  • the side chain or main chain has the segment (ie, the segment containing the tertiary amine group) introduced by component a), which can react with the carboxylic acid present in the dispersion system, reduce the acid concentration in the system, and eliminate The catalyzed effect of carboxylic acid on the hydrolysis of ester groups, thereby reducing the hydrolysis of ester bonds in polyurethane or polyurethane urea polymers; the effect of hydrolysis resistance is reflected in the initial heat resistance test: as time goes by, the initial heat resistance drops extremely slow.
  • the segment ie, the segment containing the tertiary amine group introduced by component a
  • the polyurethane dispersion prepared in Comparative Example 1 does not contain acid-eliminating structures or groups, and the irreversible ester group hydrolysis reaction will be accelerated due to the effect of acidic substances present in the system. Hydrolysis will cause cracks and breaks of macromolecules.
  • the effect of hydrolysis resistance is reflected in the initial heat resistance test: as time goes by, the initial heat resistance drops rapidly. This shows that the water dispersion of polyurethane or polyurethane urea with tertiary amine group-containing segments in the side chain or main chain has excellent hydrolysis resistance.
  • the content of the segment containing tertiary amine groups on the side chain or the main chain will also affect the hydrolysis resistance.
  • the adhesive obtained from the polyurethane dispersion of Example 10 has the best hydrolysis resistance; and Comparative Example 2
  • the hydrolysis resistance of the adhesive obtained by the polyurethane dispersion system is not as good as that of the examples.

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Abstract

一种聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用，所述聚氨酯或聚氨酯-脲是通过包含如下组分的原料反应制得：a)含有叔胺基团和至少一个NCO反应性官能团的化合物，b)数均分子量为400～5000且官能度为2～3的聚酯多元醇，c)具有至少两个异氰酸酯基团的有机化合物，d)含有离子基团、潜离子基团和非离子基团中的一种或多种且含有2-3个NCO反应性官能团的亲水化合物，e)含有至少一个NCO反应性官能团的单官能度非离子亲水化合物。该水分散体存储稳定、存储时间长，提高了由该分散体制得的粘合剂的耐水解性能，同时可保持其较好的粘结强度和耐热性。

Description

一种聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用 技术领域
本发明属于聚氨酯水分散体的技术领域，尤其涉及一种聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用。
背景技术
由于聚氨酯或聚氨酯脲的水分散体具有优良的涂刷性、优异的初粘和剥离强度以及突出的耐性，已经广泛地应用在涂料、粘合剂和纺织涂层等领域。聚氨酯或聚氨酯脲的水分散体在粘合剂中使用时，为提高粘合剂的性能，主要采用聚酯型聚合物多元醇进行合成，酯类聚合物在加工、使用及储存过程中，由于环境中存在的水汽和酸性物质的作用，会发生不可逆的水解反应。水解引起的大分子的开裂、断裂，直接导致材料的拉伸强度、模量、硬度的减低以及断裂伸长率的增加，进而使粘接强度降低，导致粘接失败。因此，如何高效、简便的提高水性聚氨酯或聚氨酯脲的耐水性成为本领域技术人员亟待解决的问题。
专利文件DE19954500、DE4410557或EP792908中提出在聚氨酯或聚氨酯脲的水分散体中引入羧酸盐，然后再与碳二亚胺复配来提高粘合性能，这主要是利用其中的羧酸与碳二亚胺的反应来增加交联密度，提高粘合剂的强度。其中的羧酸盐是通过在聚氨酯或聚氨酯脲加入二羟甲基丙酸然后再用叔胺中和得到的。但是，此类粘结剂的复配方案中羧基与碳二亚胺的反应活性较低，最终获得的性能通常不足以满足粘合剂对于常温耐水解的要求。
专利文件EP1272588记载了一种含有至少一种结晶性聚酯-聚氨酯分散体、聚丙烯酸酯共聚物、聚氯丁二烯分散体、可热固化树脂和稳定剂(氨基醇、碳二亚胺和氧化镁)的粘合剂复合物，其中所使用的稳定剂具有抑制体系中聚酯的水解和保持体系稳定的功能。但是，这样的多组分体系价格昂贵、失效快，严重限制了其在实际生活中的使用。
专利文件CN102216359记载了通过在合成过程中加入单氨基和/或单羟基的羧酸得到了一种末端含有羧基的聚氨酯或聚氨酯脲的水分散体，再 与碳二亚胺复配成粘合剂；由于末端羧基的高活性，可以与碳二亚胺发生快速的交联反应，从而明显提高涂膜性能。但是，这种羧酸会影响聚氨酯或聚氨酯脲水分散体的稳定性，同时碳二亚胺本身稳定性不好，这些都不利于这种体系的存储。
专利文件CN103980461记载了含有环氧树脂交联剂和1-氨丙基-2-甲基咪唑的水性分散体的合成方法，通过1-氨丙基-2-甲基咪唑与预聚物中的-NCO基团反应可生成共价键混合网络结构，从而形成杂化网络结构，同时引入环氧树脂而形成交联结构，提高产品耐水性能。但是，交联剂的使用及网状结构的形成将影响产品的活化，进而影响产品的初粘性及强度等。
专利文件CN106634785记载了一种强耐水性水性聚氨酯胶黏剂的制备，其利用硬脂酸、脂肪酶和双氧水对棉籽油和蓖麻油进行环氧改性，改性后再和KH-550混合，即可得到改性油；利用改性油对水性聚氨酯乳液进行改性提高其产品的耐水性，最后将改性后的水性聚氨酯乳液和减水剂、交联剂等物质混合后得到具有耐水性的水性聚氨酯胶黏剂。此方法工艺步骤复杂、使用原料较多，不利用工业化生产及控制。另外，本专利使用交联剂较多，导致胶黏剂的其它性能偏差。
上述专利文件虽然在一定程度上能够提升耐水解性能，但都使用了交联剂使聚合物分子性能交联的网状结构，这一类方法都不适用于活化性产品的使用。活化是指：当水分散体被涂覆在基材上以后，通过加热的方法除去水分，同时在该温度下，聚氨酯链段的活动性增加，聚氨酯或聚氨酯脲转变成粘弹态，然后再进行贴合等操作。聚氨酯或聚氨酯脲水分散体中，交联结构降低了聚氨酯链段的移动性，使其活化不充分，影响了初粘性、强度和耐热等性能。
因此，探索不会影响活化处理时产品的初粘性、强度和耐热等性能的耐水解性聚氨酯或聚氨酯脲水分散体，就显得尤为重要。
发明内容
本发明的目的在于，针对现有技术在以聚酯多元醇为原料制备聚氨酯或聚氨酯-脲的水分散体提升耐水解性能方面存在的问题，提供一种耐水解 的聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用，该水分散体含有的聚氨酯或聚氨酯-脲的侧链或主链中含有叔胺基团(三级胺基团)，使水分散体在存储过程中由于叔胺基团的碱性较强，能够消除体系中的酸性物质，进而消除酸性物质对酯类聚合物的催化作用，大幅度降低酯类聚合物的水解速率，使得水分散体存储稳定、存储时间长，进而可极大地提高由该分散体制得的粘合剂的耐水解性能，同时可保持粘合剂较好的粘结强度和耐热性。
为了实现上述目的，本发明的技术方案如下：
在本发明的一个方面，提供一种耐水解的聚氨酯或聚氨酯-脲的水分散体，该水分散体中含有的聚氨酯或聚氨酯-脲是通过包含如下组分的原料反应制得：
a)含有叔胺基团和至少一个NCO反应性官能团的化合物，
b)数均分子量为400～5000且官能度为2～3的聚酯多元醇，
c)具有至少两个异氰酸酯基团的有机化合物，
d)含有离子基团、潜离子基团和非离子基团中的一种或多种且含有2-3个NCO反应性官能团的亲水化合物，
e)含有至少一个NCO反应性官能团的单官能度非离子亲水化合物，
f)任选地，含有1～3个NCO反应性官能团的化合物，
g)任选地，异氰酸酯领域的封闭剂或含有聚合反应活性基团的不饱和化合物。
根据本发明提供的聚氨酯或聚氨酯-脲的水分散体，一些示例中，以各组分的总重量用量(例如，100wt％)计，
组分a)的用量为0.02～5wt％(0.04wt％、0.08wt％、0.1wt％、0.5wt％、1wt％、1.2wt％、1.5wt％、1.8wt％、2wt％、2.5wt％、3.5wt％、4wt％、4.5wt％)，优选为0.05～3wt％；
组分b)的用量为5～94wt％(8wt％、15wt％、20wt％、30wt％、40wt％、50wt％、60wt％、65wt％、74wt％、76wt％、80wt％、85wt％)，优选为70～90wt％；
组分c)的用量为5～40wt％(6wt％、10wt％、13wt％、15wt％、18wt％、25wt％、30wt％、35wt％)，优选为8～20wt％；
组分d)的用量为0.2～50wt％(0.4wt％、0.8wt％、1.5wt％、2wt％、4wt％、8wt％、15wt％、20wt％、30wt％、40wt％)，优选为1～5wt％；
组分e)的用量为0.01～20wt％(0.04wt％、0.08wt％、0.1wt％、0.5wt％、0.8wt％、1wt％、1.5wt％、2wt％、3.5wt％、5wt％、10wt％、15wt％)，优选为0.5～3wt％；
组分f)的用量为0～10wt％(0.01wt％、0.1wt％、0.4wt％、1wt％、1.5wt％、2wt％、2.5wt％、3.5wt％、5wt％、8wt％)，优选为0.5～3wt％；
组分g)的用量为0～15wt％(0.01wt％、0.1wt％、1wt％、2wt％、5wt％、7wt％、10wt％、12wt％)，优选为0～8wt％。
优选地，所述聚氨酯或聚氨酯-脲中，包含如式(I)所示的结构单元：
Figure PCTCN2019115783-appb-000001
其中，R选自组分a)脱去NCO反应性官能团后的残基。例如，R可以为N-氨乙基哌嗪、N-羟乙基哌嗪、N,N-二甲基二乙烯三胺、N-甲基二乙醇胺、N-乙基二乙醇胺、1,4-双(氨基丙基)哌嗪、N-甲基哌嗪、N-乙基哌嗪或N,N-二甲基乙醇胺等这些化合物脱去NCO反应性官能团后的残基。即，这些残基中含有叔胺基团。
优选地，所述NCO反应性官能团选自伯氨基(-NH 2)、仲氨基(-NH-)和羟基(-OH)中的一种或多种。
优选地，所述组分a)选自N-氨乙基哌嗪、N-羟乙基哌嗪、N,N-二甲基二丙烯三胺、N-甲基二乙醇胺、N-乙基二乙醇胺、1,4-双(氨基丙基)哌嗪、N-甲基哌嗪、N-乙基哌嗪和N,N-二甲基乙醇胺中的一种或多种，更优选选自N-氨乙基哌嗪、N-羟乙基哌嗪、N,N-二甲基二丙烯三胺、N-甲基二乙醇胺、N-乙基二乙醇胺和1,4-双(氨基丙基)哌嗪中的一种或多种。
所述组分b)中，合适的聚酯多元醇可以是直链聚酯二元醇或微支链聚酯二元醇(含有少量大于3官能度的聚酯多元醇)，例如，可以通过已知的手段由羧酸或酸酐(如脂肪族二羧酸或多元羧酸、脂环族二羧酸或多元羧酸、芳香族二羧酸或多元羧酸，或其相应的酸酐等)与多元醇经过脱水缩和得到。这里所述的羧酸或酸酐的例子包括但不限于琥珀酸、甲基琥珀 酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、壬烷二羧酸、癸烷二羧酸、对苯二甲酸、间苯二甲酸、邻苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸、环己烷二羧酸、马来酸、富马酸、丙二酸、偏苯三酸、邻苯二甲酸酐、偏苯三酸酐、琥珀酸酐或它们的混合物。这里所述的多元醇的例子包括但不限于乙二醇、二乙二醇、三乙二醇、四乙二醇、1,2-丙二醇、二丙二醇、三丙二醇、四丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、2,3-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,4-二羟基环己烷、1,4-二羟甲基环己烷、1,8-辛二醇、1,10-癸二醇、1,12-十二烷二醇或它们的混合物。任选地，制备所述聚酯多元醇的过程中可以加入具有更高官能的多元醇，例如，三羟甲基丙烷、甘油或季戊四醇。
所述聚酯多元醇也可以是内酯的均聚物或共聚物，它们可以通过内酯或内酯的混合物与适合的二元醇和/或更高官能的低分子量多元醇开环反应获得。这里所述的内酯，合适的例子包括但不限于丁内酯、ε-己内酯、甲基-ε-己内酯以及他们的混合物；这里所述的多元醇，优选使用1,4-丁二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇以及它们的混合物。
一些示例中，所述组分b)选自数均分子量为400～5000的直链聚酯二元醇和/或数均分子量为400～5000的微支链聚酯二元醇。
一些示例中，所述组分c)选自二异氰酸酯和/或多异氰酸酯，优选为二异氰酸酯(其结构式为Y(NCO) 2)。该结构式中，Y代表含4-12个碳原子的二价脂族烃基、含6-15个碳原子的二价脂环族烃基、含6-15个碳原子的二价芳族烃基或含7-15个碳原子的二价芳脂族烃基。
除了这些简单的二异氰酸酯之外，每分子中具有多于2个异氰酸酯基的官能度的多异氰酸酯也是合适的。例如，通过简单的脂肪族二异氰酸酯、脂环族二异氰酸酯、芳脂族二异氰酸酯或芳族二异氰酸酯的改性制备得到的多异氰酸酯(例如，碳二亚胺基、脲基甲酸酯基、异氰脲酸酯基、氨基甲酸酯基或缩二脲基改性得到的多异氰酸酯)，或者由至少两种二异氰酸酯合成的多异氰酸酯(合成的多异氰酸酯具有脲二酮、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、缩二脲、碳二亚胺、亚氨基噁二嗪二酮或噁二嗪三酮结构)。
组分c)中的二异氰酸酯可以为脂肪族二异氰酸酯和脂环族二异氰酸 酯，例如，六亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸、4,4'-二环己基丙烷二异氰酸及其混合物。在优选实施方式中，所述二异氰酸酯选自四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基丙烷二异氰酸酯、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、四甲基二甲苯基二异氰酸酯和对苯二甲基二异氰酸酯中的一种或多种；更优选选自1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯和4,4'-二环己基甲烷二异氰酸酯中的一种或多种。
在一些优选实施方式中，所述组分c)为六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯的混合物，或者六亚甲基二异氰酸酯和4,4'-二环己基甲烷二异氰酸的混合物。其中，六亚甲基二异氰酸酯与异佛尔酮二异氰酸酯的质量比为1～50:1，优选为3～10:1；六亚甲基二异氰酸酯与4,4'-二环己基甲烷二异氰酸酯的质量比为1～50:1，优选为3～10:1。
本发明的组分d)中，含有的潜离子基团是指具有共价键的官能团。通过在反应体系中添加中和剂，随着其溶液的pH的改变，该潜离子基团容易转换为相应的盐。优选的潜离子基团为酸基，所述酸基选自羧基-COOH和/或磺酸基-SO 3H。
含有的离子基团包括羧酸根-COO-和/或磺酸根-SO 3-。
含有的NCO反应性基团选自羟基(-COOH)和/或氨基(例如，-NH 2、-NH-)。
如果使用含有潜离子基团的化合物作为组分d)，可在预聚结束后得到的NCO封端的聚氨酯预聚体进行分散之前、之中或之后加入中和剂，以便可以对潜在的离子基团进行中和。加入的中和剂的量为可使潜离子基团部分或者全部成为离子基团的用量。合适的中和剂，例如为伯胺、仲胺、叔胺、碱金属化合物和碱土金属化合物中的一种或多种；合适的中和剂的例子包括但不限于氨、乙醇胺、二乙醇胺、三乙醇胺、二甲基乙醇胺、2-氨基-2-甲基-1-丙醇、吗啉、N-甲基吗啉、二甲基异丙基胺、N-甲基二乙醇胺、三乙胺、二甲基环己胺、乙基二异丙胺、氢氧化钠、氢氧化钾、氢氧 化锂和氢氧化钙中的一种或多种。总体而言，加入足够的中和剂，使得基于引入的酸基，中和度至少为50％，优选至少为75％，并且不超过150％。当中和度超过100％时，除了100％的离子盐基团外，还存在游离的中和胺。特别优选中和度为95～110％。
含有非离子基团的亲水化合物作为所述组分d)时，该含有非离子基团的亲水化合物的例子包括但不限于聚醚二元醇，如氧化苯乙烯的均聚物、氧化苯乙烯的共聚物或氧化苯乙烯的接枝产物，氧化乙烯的均聚物、氧化乙烯的共聚物或氧化乙烯的接枝产物，氧化丙烯的均聚物、氧化丙烯的共聚物或氧化丙烯的接枝产物，四氢呋喃的均聚物、四氢呋喃的共聚物或四氢呋喃的接枝产物，氧化丁烯的均聚物、氧化丁烯的共聚物或氧化丁烯的接枝产物，表氯醇的均聚物、表氯醇的共聚物或表氯醇的接枝产物，多元醇或其混合物的脱水缩合产物，以及通过二元醇、二元胺和单氨基醇的烷氧基化反应获得的聚醚二元醇。其中，含有非离子基团的亲水化合物的每个分子中，环氧乙烷个数为4～200，优选为12～75。
该含有非离子基团的亲水化合物也可以是多官能度的聚乙氧基醚，如以季戊四醇、糖为起始剂，聚合单元为环氧丙烷和环氧乙烷中的一种或两种，优选为环氧乙烷。其中，每个分子中环氧乙烷个数为4～200，优选为12～75。
一些示例中，所述组分d)选自含有离子基团且含有2-3个NCO反应性官能团的亲水化合物、含有潜离子基团且含有2-3个NCO反应性官能团的亲水化合物和含有非离子基团且含有2-3个NCO反应性官能团的亲水化合物中的一种或多种。
在优选实施方式中，含有离子基团且含有2-3个NCO反应性官能团的亲水化合物和/或含有潜离子基团且含有2-3个NCO反应性官能团的亲水化合物选自二羟基羧酸及其盐、三羟基羧酸及其盐、二羟基磺酸及其盐、三羟基磺酸及其盐、二氨基磺酸及其盐、三氨基磺酸及其盐、二氨基羧酸及其盐和三氨基羧酸及其盐中的一种或多种；更优选选自二羟甲基乙酸及其碱金属盐和/或铵盐、二羟甲基丙酸及其碱金属盐和/或铵盐、二羟甲基丁酸及其碱金属盐和/或铵盐、二羟基琥珀酸及其碱金属盐和/或铵盐、N-(2-氨乙基)-2-氨基乙烷磺酸及其碱金属盐和/或铵盐、N-(3-氨基丙基)-2-氨基 乙磺酸及其碱金属盐和/或铵盐、N-(3-氨基丙基)-3-氨基丙磺酸及其碱金属盐和/或铵盐和N-(2-氨乙基)-3-氨基丙磺酸及其碱金属盐和/或铵盐中的一种或多种。
在优选实施方式中，所述含有非离子基团且含有2-3个NCO反应性官能团的亲水化合物为聚醚二元醇，更优选为数均分子量为200～8000且环氧乙烷个数为4～200的聚醚二元醇。
所述组分d)更优选选自N-(2-氨乙基)-2-氨基乙烷磺酸碱金属盐、二羟甲基丙酸铵盐和柏斯托(Perstop)公司的Ymer TM N-120中的一种或多种。例如，组分d)为N-(2-氨乙基)-2-氨基乙磺酸钠。
本发明的组分e)为包含一个羟基或一个氨基(例如，-NH 2、-NH-)的聚乙氧基醚。所述聚乙氧基醚的起始剂的实例，包括但不限于饱和一元醇(比如，甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、异构的戊醇、己醇、辛醇、壬醇、正癸醇、正十二醇、正十四醇、正十六醇、环己醇、羟甲基环己烷以及3-乙基-3-羟甲基氧杂环)，不饱和醇(比如，烯丙醇、1,1-二甲基-烯丙醇或油醇；芳香醇如酚、异构的甲酚或者羟甲基苯酚；芳脂族醇如苄醇、茴香醇或者肉桂醇)，一元仲胺(例如，二甲胺、二乙胺、二丙胺、二异丙胺、二正丁胺、二异丁胺、双(2-乙基己基)-胺、N-甲基-和N-乙基环己基胺或者二环己基胺)，杂环的仲胺(比如，吗啉、吡咯烷、哌啶乙基吡唑)等；优选的起始剂是具有最多4个碳原子的饱和一元醇，尤其优选甲醇作为起始剂。所述聚乙氧基醚的聚合单元为环氧丙烷和/或环氧乙烷，优选为环氧乙烷。其中，每个聚乙氧基醚分子中的环氧乙烷个数为4～200，优选为12～75。
一些示例中，所述组分e)选自数均分子量为200～8000且环氧乙烷个数为4～200的单官能度聚乙氧基醚，优选选自数均分子量500～3000且环氧乙烷个数为12～75的聚乙二醇单甲醚。
均分子量500～3000且环氧乙烷个数为12～75的聚乙二醇单甲醚的结构式如式(II)所示：
Figure PCTCN2019115783-appb-000002
式中，n＝12～75。
组分f)中，所述NCO反应性官能团选自羟基、伯氨基(-NH 2)和仲氨基(-NH-)中的一种或多种。一些示例中，当组分f)为含有2～3个NCO反应性官能团的化合物时，其中至少有一个NCO反应性官能团为伯氨基或仲氨基。组分f)，例如可选自脂肪族的伯单胺或仲单胺、脂环族的伯单胺或仲单胺(如，乙胺、二乙胺、异丙胺、丁胺、环已胺)；也可以为氨基醇，即分子中含氨基和羟基的化合物(例如，乙醇胺、N-甲基乙醇胺、二乙醇胺、二异丙醇胺、1,3-二氨基-2-丙醇、N-(2-羟乙基)亚乙基二胺、N,N-双(2-羟乙基)亚乙基二胺或2-丙醇胺)；还可以是二胺和三胺，例如，1,2-乙二胺、1,6-六亚甲基二胺、1-氨基-3,3,5-三甲基-5-氨甲基环己烷(异佛尔酮二胺)、哌嗪、1,4-二氨基环己烷、双-(4-氨基环己基)甲烷或二亚乙基三胺。还可以是特殊的胺，例如，己二酸二酰肼、肼。也可以使用上述化合物的混合物。在优选实施方式中，所述组分f)选自脂肪族伯单胺、脂肪族仲单胺、脂环族伯单胺、脂环族仲单胺、氨基醇、脂肪族二胺、脂环族二胺、脂肪族三胺、脂环族三胺以及肼中的一种或多种，优选选自异佛尔酮二胺、N-(2-羟乙基)亚乙基二胺和1,6-六亚甲基二胺中的一种或多种。
组分f)可以充当扩链剂以达到更高分子量，或充当单官能化合物以限制分子量；或任选地还引入其它反应性基团，例如游离羟基，作为其它交联点。
组分g)可以是常用于异氰酸酯领域的封闭剂(可在较高温度下脱去)，例如，丁酮肟、二甲基吡唑、己内酰胺、丙二酸酯、三唑、二甲基三唑、叔丁基苄胺、环戊酮羧乙基酯；以及含有聚合反应活性基团的不饱和化合物，例如，丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯。这里的异氰酸酯领域的封闭剂是指用于封闭活性异氰酸酯中含单官能活性氢的物质。
在优选实施方式中，所述组分g)选自丁酮肟、二甲基吡唑、己内酰胺、丙二酸酯、三唑、二甲基三唑、叔丁基苄胺、环戊酮羧乙基酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯和季戊四醇三丙烯酸酯中的一种或多种。
根据本发明提供的聚氨酯或聚氨酯-脲的水分散体，一些示例中，所述聚氨酯或聚氨酯-脲的水分散体具有15～70wt％的固含量，优选为30～60wt％的固含量。
一些示例中，所述聚氨酯或聚氨酯-脲的水分散体的平均粒径为20～750nm，优选为50～450nm。
优选地，所述聚氨酯或聚氨酯-脲的水分散体的pH值为7.5～11，更优选为7.5～10，进一步优选为7.5～8.5。pH的高低与水分散体中叔胺基团的含量呈正相关。
在本发明的另一方面，提供一种如上所述的聚氨酯或聚氨酯-脲的水分散体的制备方法，包括如下步骤：
按比例将组分b)、组分c)、组分e)和任选的组分g)混合，然后进行聚合反应形成端异氰酸酯的聚氨酯预聚体；使所得聚氨酯预聚体与组分d)、任选的组分f)进行扩链反应，然后分散在水中或将水加入到扩链反应后得到的混合物中进行分散，得到聚氨酯或聚氨酯-脲的水分散体；其中，所述组分d)为含有离子基团或非离子基团且含有2-3个NCO反应性官能团的亲水化合物；反应过程中，组分a)可以在任何阶段加入反应体系进行反应；
或者，按比例将组分b)、组分c)、组分d)、组分e)和任选的组分g)混合，然后进行聚合反应形成端异氰酸酯的聚氨酯预聚体；使所得聚氨酯预聚体与中和剂进行中和反应，然后分散在水中或将水加入到中和反应后得到的混合物中进行分散，在分散前、分散中或分散后加入组分a)进行进一步反应，得到聚氨酯或聚氨酯-脲的水分散体；其中，所述组分d)为含有潜离子基团且含有2-3个NCO反应性官能团的亲水化合物。
本发明的制备方法中，在体系加入组分a)后，不进行中和反应，以保证所制得的聚氨酯或聚氨酯-脲中含有叔胺基团。
根据本发明提供的聚氨酯或聚氨酯-脲的水分散体的制备方法，一些示例中，可以通过加入溶剂对体系进行稀释，在分散期间或分散之后通过蒸馏操作部分或完全地除去溶剂。例如，反应期间可任选地加入对异氰酸酯基呈惰性的可与水混容性溶剂稀释。适合的溶剂可以是丙酮、甲基异丁基 酮、丁酮、四氢呋喃、二噁烷、乙腈、二丙二醇二甲醚和1-甲基-2-吡咯烷酮中的一种或多种；它们不但可以在制备的开始时添加而且也可以在聚合反应过程中或者结束以后添加。还可以分批添加。溶剂优选为丙酮和丁酮，更优选为丙酮。任选使用的溶剂，例如丙酮在分散期间和/或分散之后馏出。
所述制备方法可以按一个或多个阶段在均相中进行，或者在多阶段反应的情况下部分地在分散相中进行。完全或部分聚合反应之后是分散、乳化或溶解步骤。任选地，后面可以进一步在分散相中进行加聚或改性。
一些示例中，以一步或多步反应使组分b)、组分c)、组分e)与任选的组分g)混合后进行聚合反应，以形成端异氰酸酯的聚氨酯预聚物；以一阶段或二阶段反应使所得预聚物与组分a)、组分d)和任选的组分f)进行反应，然后将所得产物用水分散，即得到聚氨酯或聚氨酯-脲的水分散体。
一些示例中，聚合反应过程是将所有或部分组分b)、d)、e)和任选的g)预先置入反应器，任选地加入对异氰酸酯基呈惰性的可与水混容性溶剂稀释，然后在室温到120℃之间计量添加组分c)进行预聚反应以得到端异氰酸酯的聚氨酯预聚体。这种反应可以单阶段或以多阶段进行。
多阶段反应，例如可以是：将组分b)、组分c)、组分e)预先置入反应器并在与一部分组分c)反应之后添加组分g)，其然后可以与仍然存在的另一部分组分c)反应，组分a)可以在任何阶段加入。
反应过程中，通常通过跟踪反应混合物的NCO含量以监测转化度。为此可以选用分光测量(例如红外或近红外谱、折射指数的测定)和化学电位滴定(例如经取出样品的化学滴定)实现，优选化学电位滴定。
反应过程中，任选地还可以加入催化剂。常规催化剂可以是本领域普通技术人员已知用于加速-NCO与-OH反应的催化剂。例如，三乙胺、1,4-二氮杂双环-[2,2,2]-辛烷、氧化二丁锡、二辛酸锡、二月桂酸二丁锡、双-(2-乙基己酸)锡、新癸酸铋和2-乙基己酸铋中的一种或多种。优选为新癸酸铋或2-乙基己酸铋，更优选为新癸酸铋。
反应过程中，扩链反应阶段的温度通常为10～100℃，优选为25～60℃下进行。
一些优选实施方式中，聚氨酯或聚氨酯-脲的水分散体的制备方法为： 按比例预先加入组分b)、组分c)、组分e)和任选的溶剂混合并加热到50～100℃，同时搅拌。利用放热反应，在40～150℃下搅拌该反应混合物直至已经达到或略微低于理论异氰酸酯含量，加入任选的组分g)，继续反应达到或略微低于理论异氰酸酯含量。然后通过添加溶剂稀释到25～95wt％，优选40～80wt％的固体含量，然后在10～100℃，优选25～60℃下，分别添加用溶剂稀释后的组分a)、组分d)和任选地组分f)进行扩链。在2～60分钟的反应时间之后，通过添加蒸馏水或通过将混合物转移到预先置入的蒸馏水中进行分散，并在分散步骤期间或之后，全部或部分蒸馏出所使用的溶剂以及之后再加入一些助剂(例如，乳化剂Tween 20)。聚合反应可以任选地添加催化剂(例如，新癸酸铋)。
从现有技术获知的所有方法，例如乳化剂剪切力、丙酮、预聚物混合、熔体乳化、酮亚胺和固体自发分散方法或它们的衍生方法，均可以用于本发明所述的聚氨酯或聚氨酯-脲的水分散体的制备。这些方法的综述可以参见Methoden der organischen Chemie(Houben-Weyl,Erweiterungs-und
Figure PCTCN2019115783-appb-000003
zur 4.Auflage,卷E20,H.Bartl和J.Falbe,Stuttgart,New York,Thieme 1987,第1671-1682页)。优选使用熔体乳化法、预聚物混合法和丙酮法。尤其优选使用丙酮法。
在本发明的另一方面，提供一种如上所述的聚氨酯或聚氨酯-脲的水分散体或如上所述的制备方法所得聚氨酯或聚氨酯-脲的水分散体在粘合剂中的应用。
本发明制备的聚氨酯或聚氨酯-脲的水分散体可以单独使用或与(涂料与粘合剂技术中)已知的辅助物质和添加剂一起使用。常用的辅助物质和添加剂，例如，乳化剂、光稳定剂(例如，UV吸收剂和空间位阻胺(HALS))、抗氧化剂、填料、抗沉降剂、消泡、湿润剂、流动调节剂、反应性稀释剂、增塑剂、中和剂、催化剂、辅助溶剂、增稠剂、颜料、染料、消光剂、增粘剂(Tackifier)等。
可以在聚合之前或聚合之后加入辅助物质和添加剂。当然，还可以在分散之后加入辅助物质和添加剂。
也可以将制备的聚氨酯或聚氨酯-脲的水分散体与其它含水或含溶剂 的低聚物或聚合物混合使用，以提高共混乳液的存储性能。这些低聚物或聚合物，例如为聚乙烯基酯、聚乙烯基醚、聚乙烯醇、聚乙烯、聚苯乙烯、聚丁二烯、聚氯乙烯、聚氨酯、聚氨酯-聚脲、聚氨酯-聚丙烯酸酯、聚酯、聚丙烯酸酯。需要在每种情况下利用简单的初步试验测试此类混合物的相容性。
制备的聚氨酯或聚氨酯-脲的水分散体及基于其的粘合剂或粘结剂组合物适合于粘结任何基材。这些基材，例如，所有类型的金属、合金、木材、木材基材料、刨花板、MDF板、陶瓷、石料、混凝土、沥青、硬纤维、玻璃、玻璃纤维、碳纤维、碳纳米管、瓷器、皮革、纺织品和无机材料等。它们同样适合于粘结橡胶材料(例如，天然橡胶和合成橡胶)，各种塑料(例如聚氨酯、聚乙酸乙烯酯、聚氯乙烯，尤其是含增塑剂的聚氯乙烯)。它们同样适合于粘结热塑性塑料，例如，ABS(丙烯酸类-丁二烯-苯乙烯)、PC(聚碳酸酯)、聚烯烃塑料和它们的混合物。
制备的聚氨酯或聚氨酯-脲的水分散体的粘合剂同样适合用于由其制成的制品。这些制品的实例，包括但不限于鞋底，例如基于聚氯乙烯(尤其是含增塑剂的聚氯乙烯)的鞋底、基于聚乙烯乙酸乙烯酯或聚氨酯弹性体泡沫的鞋底，以及由皮革或人造革制成的鞋帮的粘结。还尤其适合于将基于聚氯乙烯或含增塑剂的聚氯乙烯的膜与木材的粘结。
相对于现有技术，本发明技术方案的有益效果在于以下几个方面：
本发明所得水分散体中，聚氨酯或聚氨酯-脲的侧链或主链具有组分a)含有的链段(即，叔胺基团)。水分散体在存储过程中，由于该叔胺基团的碱性较强，能够消除体系中的酸性物质，进而消除酸性物质对酯类聚合物的催化作用，能够使得该水分散体可以稳定储存。在存储过程中，该叔胺基团因能够消除体系中的酸性物质，大幅度降低酯类聚合物的水解速率，可明显提高由该分散体制得的粘合剂的耐水解性能，同时可保持粘合剂较好的粘结强度和耐热性。
与现有的水性聚氨酯-聚脲水分散体相比，本发明的水分散体作为粘合剂使用，其具有优异的耐水解性能，现有的水性聚氨酯-聚脲水分散体耐水解在6-10天(70℃存储)以内，而本发明所述的水分散体耐水解性能可以 达到15-20d(70℃存储)。
现有的水性聚氨酯-聚脲分散体在使用前需要加入异氰酸酯或者碳二亚胺等交联剂，施工前需要按配比混合，操作复杂，并且配制的粘合剂必须在规定的时间内使用，开放时间短，且交联剂的加入对胶黏剂的初粘性也有明显的降低效果；而本发明的水分散体不需要额外添加异氰酸酯或者碳二亚胺等交联剂即可满足性能需求，可作为单组份粘合剂产品使用，操作简单、开放时间长，大大增加施工效率。
具体实施方式
为了能够详细地理解本发明的技术特征和内容，下面将更详细地描述本发明的优选实施方式。虽然实施例中描述了本发明的优选实施方式，然而应该理解，可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。
<原料来源>
聚酯I：聚己二酸-1,4-丁二醇酯二醇，OH值＝56mg KOH/g(
Figure PCTCN2019115783-appb-000004
WHP-204，万华化学)，
聚酯II：由1,6-己二醇、新戊二醇和己二酸构成的聚酯二醇，OH值＝74mg KOH/g(
Figure PCTCN2019115783-appb-000005
WHP-1556，万华化学)，
聚酯III：聚己二酸-1,4-丁二醇酯二醇，OH值＝112mg KOH/g(
Figure PCTCN2019115783-appb-000006
WHP-104，万华化学)，
聚酯IV：聚邻苯二甲酸-1,6-己二醇酯二醇，OH值＝56mg KOH/g(PH-56，斯泰潘)，
聚酯V：聚碳酸酯二醇，OH值＝56mg KOH/g(PCDL T5652，旭化成公司)；
异氰酸酯I：六亚甲基二异氰酸酯(
Figure PCTCN2019115783-appb-000007
HDI，万华化学)，
异氰酸酯II：异佛尔酮二异氰酸酯(
Figure PCTCN2019115783-appb-000008
IPDI，万华化学)；
聚醚I：单官能度的聚乙氧基醚，具有平均分子量1200g/mol(MPEG1200，LOTTE CHEM)，
聚醚II：单官能度的聚乙氧基醚，具有平均分子量520g/mol (MPEG520，LOTTE CHEM)；
新癸酸铋(
Figure PCTCN2019115783-appb-000009
Shepferd)；
N-(2-氨乙基)-2-氨基乙磺酸钠(Vestamin A95，赢创)；
N-氨乙基哌嗪(金锦乐华学)，
N,N-二甲基二丙烯三胺(恒景瑞化工)，
N-乙基二乙醇胺(恒景瑞化工)；
羟乙基乙二胺，即N-(2-羟乙基)亚乙基二胺(扬子巴斯夫)，
异佛尔酮二胺(万华化学)；
丁酮肟(金锦乐华学)；
乳化剂Tween 20(上海邦景实业)。
<检测方法>
水分散体的平均粒径测定：采用马尔文粒径仪Nano S90进行测试。
实施例1
将210g经过脱水处理的聚酯I、29g异氰酸酯I、2g经过脱水处理的聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80～90℃下搅拌该混合物直到NCO达到2.09％。将所得预聚体溶解在400g丙酮中并冷却到50℃。将溶解有4.63g N-(2-氨乙基)-2-氨基乙磺酸钠、2.47g N-氨乙基哌嗪、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加250g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的180nm的平均粒径，测定其pH值是8.0。
实施例2
将150g经过脱水处理的聚酯I、53g经过脱水处理的聚酯II、29g异氰酸酯I、24g丙酮、0.04g新癸酸铋、2g经过脱水处理聚醚II加入到装有氮气进出口的1L四口圆底烧瓶中，在80～90℃搅拌该混合物直到NCO达 到1.94％。将所得预聚体溶解在380g丙酮中并冷却到50℃。将溶解有2g N-(2-氨乙基)-2-氨基乙磺酸钠、4g N,N-二甲基二丙烯三胺、1g羟乙基乙二胺的30g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加210g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有55wt％的固体含量和在分散相中通过激光相关测定的220nm的平均粒径，测定其pH值是8.2。
实施例3
将80g经过脱水处理的聚酯I、33g经过脱水处理的聚酯III、23g经过脱水处理的聚酯IV、2g经过脱水处理的聚醚I、22g异氰酸酯I、18g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.13％。将所得预聚体溶解在309g丙酮中并冷却到50℃。将溶解有4.6g N-(2-氨乙基)-2-氨基乙磺酸钠、1.5g N,N-二甲基二丙烯三胺、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加224g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有45wt％的固体含量和在分散相中通过激光相关测定的150nm的平均粒径，测定其pH值是7.8。
实施例4
将60g经过脱水处理的聚酯I、77g经过脱水处理的聚酯II、35g经过脱水处理的聚酯III、29g异氰酸酯I、2g经过脱水处理聚醚I、25g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.05％。将所得预聚体溶解在405g丙酮中并冷却到50℃。将溶解有4g N-(2-氨乙基)-2-氨基乙磺酸钠、1g异佛尔酮二胺、1.5g N-氨乙基哌嗪、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加238g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和 在分散相中通过激光相关测定的180nm的平均粒径，测定其pH值是7.7。
实施例5
将120g经过脱水处理的聚酯I、72g经过脱水处理的聚酯II、29g异氰酸酯I、2g经过脱水处理聚醚I加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.15％。将所得预聚体溶解在424g丙酮中并冷却到50℃。将溶解有5g N-(2-氨乙基)-2-氨基乙磺酸钠、2g异佛尔酮二胺、1.2g N,N-二甲基二丙烯三胺、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加558g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有30wt％的固体含量和在分散相中通过激光相关测定的164nm的平均粒径，测定其pH值是7.7。
实施例6
将210g经过脱水处理的聚酯I、43g异氰酸酯I、2g经过脱水处理聚醚I加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到4.98％，然后加入在50℃加入15.2g丁酮肟，待NCO降低至2.20％。将所得预聚体溶解在450g丙酮中并冷却到50℃。将溶解有5g N-(2-氨乙基)-2-氨基乙磺酸钠、4.5g N-氨乙基哌嗪、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加253g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的180nm的平均粒径，测定其pH值是8.3。
实施例7
将210g经过脱水处理的聚酯I、20g异氰酸酯I、11.1g异氰酸酯II、2g经过脱水处理聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到1.98％。 将所得预聚体溶解在405g丙酮中并冷却到50℃。将溶解有4.8g N-(2-氨乙基)-2-氨基乙磺酸钠、3g N-氨乙基哌嗪、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加241g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的176nm的平均粒径，测定其pH值是8。
实施例8
将170g经过脱水处理的聚酯I、29g异氰酸酯I、4g N-羟乙基哌嗪、2g经过脱水处理聚醚I、24g丙酮、0.02g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.05％。将所得预聚体溶解在419g丙酮中并冷却到50℃。将溶解有4.5g N-(2-氨乙基)-2-氨基乙磺酸钠、2.5g异佛尔酮二胺、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加300g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有40wt％的固体含量和在分散相中通过激光相关测定的195nm的平均粒径，测定其pH值是7.9。
实施例9
将210g经过脱水处理的聚酯I、32g异氰酸酯I、3g N-乙基二乙醇胺、2g经过脱水处理聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到1.92％。将所得预聚体溶解在413g丙酮中并冷却到50℃。将溶解有4.63g N-(2-氨乙基)-2-氨基乙磺酸钠、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加300g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有40wt％的固体含量和在分散相中通过激光相关测定的195nm的平均粒径，测定其pH值是8。
实施例10
将190g经过脱水处理的聚酯I、12g经过脱水处理的聚酯V、20g异氰酸酯I、11g异氰酸酯II、2g经过脱水处理聚醚I、23g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.15％。将所得预聚体溶解在400g丙酮中并冷却到50℃。将溶解有4.63g N-(2-氨乙基)-2-氨基乙磺酸钠、3.2g N-氨乙基哌嗪、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加238g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的165nm的平均粒径，测定其pH值是8.5。
实施例11
将190g经过脱水处理的聚酯I、20g经过脱水处理的聚酯V、20g异氰酸酯I、13g异氰酸酯II、2g经过脱水处理聚醚I、23g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.05％。将所得预聚体溶解在400g丙酮中并冷却到50℃。将溶解有4.63g N-(2-氨乙基)-2-氨基乙磺酸钠、3.2g N-氨乙基哌嗪、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加238g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的178nm的平均粒径，测定其pH值是8.3。
实施例12
将80g经过脱水处理的聚酯I、120g经过脱水处理的聚酯II、30g经过脱水处理的聚酯III、28.35g异氰酸酯I、2g经过脱水处理聚醚I、25g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到1.92％。将所得预聚体溶解在395g丙 酮中并冷却到50℃。将溶解有5g N-(2-氨乙基)-2-氨基乙磺酸钠、3g N,N-二甲基二丙烯三胺、1g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加238g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的185nm的平均粒径，测定其pH值是8。
实施例13
将210g经过脱水处理的聚酯I、20g异氰酸酯I、11.1g异氰酸酯II、2g经过脱水处理聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到1.98％。将所得预聚体溶解在405g丙酮中并冷却到50℃。将溶解有4.8g N-(2-氨乙基)-2-氨基乙磺酸钠、0.12g N-氨乙基哌嗪、2.5g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加241g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的176nm的平均粒径，测定其pH值是7.2。
实施例14
将180g经过脱水处理的聚酯I、20g异氰酸酯I、11.1g异氰酸酯II、7g经过脱水处理聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到2.5％。将所得预聚体溶解在405g丙酮中并冷却到50℃。将溶解有1g N-(2-氨乙基)-2-氨基乙磺酸钠、6.9g N-氨乙基哌嗪的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加241g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的176nm的平均粒径，测定其pH值是8.9。
对比例1
将210g经过脱水处理的聚酯I、28.35g异氰酸酯I、2g经过脱水处理的聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃下搅拌该混合物直到NCO达到1.72％。将所得预聚体溶解在405g丙酮中并冷却到50℃。将溶解有5.1g N-(2-氨乙基)-2-氨基乙磺酸钠、3.51g异佛尔酮二胺、0.86g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加300g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的180nm的平均粒径，测定其pH值是7.0。
对比例2
将210g经过脱水处理的聚酯I、20g异氰酸酯I、11.1g异氰酸酯II、2g经过脱水处理聚醚I、24g丙酮、0.04g新癸酸铋加入到装有氮气进出口的1L四口圆底烧瓶中，在80-90℃搅拌该混合物直到NCO达到1.98％。将所得预聚体溶解在405g丙酮中并冷却到50℃。将溶解有4.8g N-(2-氨乙基)-2-氨基乙磺酸钠、0.02g N-氨乙基哌嗪、2.6g羟乙基乙二胺的35g水溶液，添加到溶解有预聚体的丙酮溶液中同时剧烈搅拌。搅拌20min，然后通过添加241g水将该混合物分散。在通过蒸馏分离出丙酮之后，添加4g乳化剂Tween 20。即，获得了无溶剂的聚氨酯-聚脲的水分散体，其具有50wt％的固体含量和在分散相中通过激光相关测定的176nm的平均粒径，测定其pH值是7.0。
通过各实施例制得的聚氨酯或聚氨酯-脲水分散体的粒径和pH值数据，表明我们成功合成了PUD分散体。因为在聚氨酯或聚氨酯-脲水分散体中含引入叔胺基团的链段后明显的变化是pH值升高，其中含有叔胺基团的分散体的pH值在7.5-8.9之间，而不含或含微量叔胺基团的分散体的pH值基本为7.0。
叔胺基团的含量较整个聚氨酯体系来说含量很低，无法通过常规的波谱法表征。因为含叔胺基团的组分a)上含有能够与NCO反应的基团，而 NCO基团是过量的，因此，我们认为叔胺基团能够连接到聚氨酯或聚氨酯脲分子链上。
粘合剂的制备
将100g各实施例和对比例所得水分散体与0.05g BYK024(毕克化学)混合，在500rpm条件下搅拌5min，再加入0.2g Tego245(迪高)，搅拌5min，再加入0.15g Vesmody U604(万华化学)，然后在600rpm搅拌10min，即得到对应于各个实施例和对比例的各个粘合剂。
测试所用试样的制备和测试
(1)用表1中的复合材料制备测试所用试样：
复合材料 基材1 基材2
A 橡胶 橡胶
B 帆布 帆布
C PVC PVC
首先对基材1(橡胶)、基材2(橡胶)进行打磨处理。然后使用刷子将所制得的粘合剂细薄地施涂到2.5cm宽且15cm长的基材条形物上并在65℃烘箱中干燥3分钟后取出，通过热压机在30kg/cm 2条件下压合10秒，制得复合材料A。
同上，使用同样的方法制备复合材料B、复合材料C。
(2)测试所得复合材料的剥离强度
用GOTECH拉力机在200mm/min的剥离速率下测定剥离强度。其中，初期强度：压合完后直接到拉力机测试其剥离强度。后期强度：将试件在室温放置24小时后，测试其剥离强度。测试结果见表2。
表2 不同基材上的各个粘合剂的剥离强度
Figure PCTCN2019115783-appb-000010
Figure PCTCN2019115783-appb-000011
由表2中看出，相对于不含有或含有微量(小于0.02％)叔胺基团的聚氨酯水分散体所得单组份粘合剂(对比例1和2)来说，基于本发明制得的聚氨酯或聚氨酯-脲水分散体的单组份粘合剂，其初期剥离强度和后期剥离强度相当，满足性能要求，不影响正常使用。
(3)测试所得复合材料的耐热性
初期耐热：将做好的试样挂一个重500克的砝码，放在80℃烘箱中，测试其在30分钟内该试样拉开的长度。
后期耐热：将做好的试样在室温放置3天后，挂一个重1千克的砝码，放在70℃烘箱中，测试其在24小时内该试样拉开的长度。
测试结果见表3。
表3 不同基材上的各个粘合剂的耐热性
Figure PCTCN2019115783-appb-000012
Figure PCTCN2019115783-appb-000013
由表3可以看出，相对于不含有或含有微量(小于0.02％)叔胺基团的聚氨酯分散体所得单组份粘合剂(对比例1和2)来说，基于本发明制得的聚氨酯或聚氨酯-脲水分散体的单组份粘合剂，其初期耐热和后期耐热都有了明显的提高。
(4)测试聚氨酯分散体的耐水解性能
若体系中存在水解反应，将导致聚氨酯或聚氨酯脲链段分子量降低，进而导致以该水性聚氨酯或聚氨酯脲作为胶黏剂粘结的基材的初期耐热变差。因此，通过高温/常温条件下初期耐热数值表征其耐水解能力。初期耐热数值越低，说明耐水解性能越优异。
高温(70℃)耐水解：将各实施例和对比例制备的水分散体在70℃存放，分别在0天、3天、6天、9天、12天、15天、18天和21天后取样，测试样品(将其作为粘合剂)涂覆于橡胶基材上的初期耐热水平。高温耐水解测试结果如表4所示。
常温(30℃)耐水解：将本各实施例和对比例制备的水分散体在30℃存放，分别在0天、30天、60天、90天、120天、150天、180天和210 天后取样，测试样品(将其作为粘合剂)涂覆于橡胶基材上的初期耐热水平。常温耐水解测试结果如表5所示。
表4 高温存储后，橡胶基材上的各个粘合剂的初期耐热
Figure PCTCN2019115783-appb-000014
表5 常温存储后，橡胶基材上的各个粘合剂的初期耐热
Figure PCTCN2019115783-appb-000015
Figure PCTCN2019115783-appb-000016
从表4和表5可以明显的看出，相对于不含有或含有微量(小于0.02％)叔胺基团的聚氨酯分散体所得单组份粘合剂(对比例1和2)来说，基于本发明制得的聚氨酯或聚氨酯-脲水分散体的单组份粘合剂，其高温(70℃)耐水解和常温(例如，25℃)耐水解能力都明显高于对比例1和2。这是因为侧链或主链具有组分a)引入的链段(即，含叔胺基团的链段)，能够与分散体系中存在的羧酸反应，降低体系中的酸的浓度，消除了羧酸对酯基水解的催化作用，进而降低了聚氨酯或聚氨酯脲聚合物中的酯键的水解；耐水解效果体现在初期耐热测试上为：随着时间的推移，初期耐热下降极其缓慢。而对比例1所制得的聚氨酯分散体中不含有可消除酸的结构或基团，由于体系中存在的酸性物质的作用，会加速不可逆的酯基水解反应。而水解会导致大分子的开裂、断裂，耐水解效果体现在初期耐热测试上为：随着时间的推移，初期耐热迅速下降。这说明侧链或主链具有含叔胺基团链段的聚氨酯或聚氨酯脲水分散体具有优异的耐水解性能。另外，侧链或主链上含叔胺基团的链段含量也会对耐水解性能产生影响，如，实 施例10的聚氨酯分散体制得的粘合剂耐水解性能最优；而对比例2的聚氨酯分散体制得的粘合剂耐水解性能不如各实施例。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。

Claims (10)

  1. 一种耐水解的聚氨酯或聚氨酯-脲的水分散体，其特征在于，该水分散体中含有的聚氨酯或聚氨酯-脲是通过包含如下组分的原料反应制得：
    a)含有叔胺基团和至少一个NCO反应性官能团的化合物，
    b)数均分子量为400～5000且官能度为2～3的聚酯多元醇，
    c)具有至少两个异氰酸酯基团的有机化合物，
    d)含有离子基团、潜离子基团和非离子基团中的一种或多种且含有2-3个NCO反应性官能团的亲水化合物，
    e)含有至少一个NCO反应性官能团的单官能度非离子亲水化合物，
    f)任选地，含有1～3个NCO反应性官能团的化合物，
    g)任选地，异氰酸酯领域的封闭剂或含有聚合反应活性基团的不饱和化合物。
  2. 根据权利要求1所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，以各组分的总重量用量计，
    组分a)的用量为0.02～5wt％，优选为0.05～3wt％；
    组分b)的用量为5～94wt％，优选为70～90wt％；
    组分c)的用量为5～40wt％，优选为8～20wt％；
    组分d)的用量为0.2～50wt％，优选为1～5wt％；
    组分e)的用量为0.01～20wt％，优选为0.5～3wt％；
    组分f)的用量为0～10wt％，优选为0.5～3wt％；
    组分g)的用量为0～15wt％，优选为0～8wt％。
  3. 根据权利要求1或2所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，所述聚氨酯或聚氨酯-脲中，包含如式(I)所示的结构单元：
    Figure PCTCN2019115783-appb-100001
    其中，R选自组分a)脱去NCO反应性官能团后的残基。
  4. 根据权利要求1-3中任一项所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，所述NCO反应性官能团选自伯氨基、仲氨基和羟基中的一种或多种。
  5. 根据权利要求1-4中任一项所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，
    所述组分a)选自N-氨乙基哌嗪、N-羟乙基哌嗪、N,N-二甲基二丙烯三胺、N-甲基二乙醇胺、N-乙基二乙醇胺、1,4-双(氨基丙基)哌嗪、N-甲基哌嗪、N-乙基哌嗪和N,N-二甲基乙醇胺中的一种或多种，优选选自N-氨乙基哌嗪、N-羟乙基哌嗪、N,N-二甲基二丙烯三胺、N-甲基二乙醇胺、N-乙基二乙醇胺和1,4-双(氨基丙基)哌嗪中的一种或多种。
  6. 根据权利要求1-5中任一项所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，所述组分b)选自数均分子量为400～5000的直链聚酯二元醇和/或数均分子量为400～5000的微支链聚酯二元醇；和/或
    所述组分c)选自二异氰酸酯和/或多异氰酸酯，优选为二异氰酸酯；
    所述二异氰酸酯优选选自四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基丙烷二异氰酸酯、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、四甲基二甲苯基二异氰酸酯和对苯二甲基二异氰酸酯中的一种或多种；更优选选自1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯和4,4'-二环己基甲烷二异氰酸酯中的一种或多种；
    所述组分c)更优选为六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯的混合物，或者六亚甲基二异氰酸酯和4,4'-二环己基甲烷二异氰酸的混合物。
  7. 根据权利要求1-6中任一项所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，
    所述组分d)选自含有离子基团且含有2-3个NCO反应性官能团的亲水化合物、含有潜离子基团且含有2-3个NCO反应性官能团的亲水化合物和含有非离子基团且含有2-3个NCO反应性官能团的亲水化合物中的一种或多种；
    含有离子基团且含有2-3个NCO反应性官能团的亲水化合物和/或含有潜离子基团且含有2-3个NCO反应性官能团的亲水化合物优选选自二羟基羧酸及其盐、三羟基羧酸及其盐、二羟基磺酸及其盐、三羟基磺酸及其盐、二氨基磺酸及其盐、三氨基磺酸及其盐、二氨基羧酸及其盐和三氨基羧酸及其盐中的一种或多种，更优选选自二羟甲基乙酸及其碱金属盐和/或铵盐、二羟甲基丙酸及其碱金属盐和/或铵盐、二羟甲基丁酸及其碱金属盐和/或铵盐、二羟基琥珀酸及其碱金属盐和/或铵盐、N-(2-氨乙基)-2-氨基乙烷磺酸及其碱金属盐和/或铵盐、N-(3-氨基丙基)-2-氨基乙磺酸及其碱金属盐和/或铵盐、N-(3-氨基丙基)-3-氨基丙磺酸及其碱金属盐和/或铵盐和N-(2-氨乙基)-3-氨基丙磺酸及其碱金属盐和/或铵盐中的一种或多种；
    所述含有非离子基团且含有2-3个NCO反应性官能团的亲水化合物优选为聚醚二元醇，更优选为数均分子量为200～8000且环氧乙烷个数为4～200的聚醚二元醇；
    所述组分d)更优选选自N-(2-氨乙基)-2-氨基乙烷磺酸碱金属盐、二羟甲基丙酸铵盐和柏斯托公司的Ymer TM N-120中的一种或多种；和/或
    所述组分e)选自数均分子量为200～8000且环氧乙烷个数为4～200的单官能度聚乙氧基醚，优选选自数均分子量500～3000且环氧乙烷个数为12～75的聚乙二醇单甲醚；和/或
    所述组分f)选自脂肪族伯单胺、脂肪族仲单胺、脂环族伯单胺、脂环族仲单胺、氨基醇、脂肪族二胺、脂环族二胺、脂肪族三胺、脂环族三胺以及肼中的一种或多种，优选选自异佛尔酮二胺、N-(2-羟乙基)亚乙基二胺和1,6-六亚甲基二胺中的一种或多种；和/或
    所述组分g)选自丁酮肟、二甲基吡唑、己内酰胺、丙二酸酯、三唑、二甲基三唑、叔丁基苄胺、环戊酮羧乙基酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯和季戊四醇三丙烯酸酯中的一种或多种。
  8. 根据权利要求1-7中任一项所述的聚氨酯或聚氨酯-脲的水分散体，其特征在于，所述聚氨酯或聚氨酯-脲的水分散体具有15～70wt％的固含量，优选为30～60wt％的固含量；
    所述聚氨酯或聚氨酯-脲的水分散体的pH值为7.5～11，优选为7.5～10，更优选为7.5～8.5；
    所述聚氨酯或聚氨酯-脲的水分散体的平均粒径为20～750nm，优选为50～450nm。
  9. 一种如权利要求1-8中任一项所述的聚氨酯或聚氨酯-脲的水分散体的制备方法，其特征在于，包括如下步骤：
    按比例将组分b)、组分c)、组分e)和任选的组分g)混合，然后进行聚合反应形成端异氰酸酯的聚氨酯预聚体；使所得聚氨酯预聚体与组分d)、任选的组分f)进行扩链反应，然后分散在水中或将水加入到扩链反应后得到的混合物中进行分散，得到聚氨酯或聚氨酯-脲的水分散体；其中，所述组分d)为含有离子基团或非离子基团且含有2-3个NCO反应性官能团的亲水化合物；反应过程中，组分a)可以在任何阶段加入反应体系进行反应；
    或者，按比例将组分b)、组分c)、组分d)、组分e)和任选的组分g)混合，然后进行聚合反应形成端异氰酸酯的聚氨酯预聚体；使所得聚氨酯预聚体与中和剂进行中和反应，然后分散在水中或将水加入到中和反应后得到的混合物中进行分散，在分散前、分散中或分散后加入组分a)进行进一步反应，得到聚氨酯或聚氨酯-脲的水分散体；其中，所述组分d)为含有潜离子基团且含有2-3个NCO反应性官能团的亲水化合物。
  10. 如权利要求1-8中任一项所述的聚氨酯或聚氨酯-脲的水分散体或如权利要求9所述的制备方法所得聚氨酯或聚氨酯-脲的水分散体在粘合剂中的应用。
PCT/CN2019/115783 2019-11-05 2019-11-05 一种聚氨酯或聚氨酯-脲的水分散体及其制备方法和应用 WO2021087769A1 (zh)

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