TWI558767B - One kind of waterborne polyurethane dispersion and its preparation methods - Google Patents

Description

Aqueous polyurethane dispersion and preparation method thereof

The invention relates to an aqueous polyurethane dispersion liquid and a preparation method thereof, and is a novel environmental protection material for waterborne polyurethane (WPU) containing a bisphenol fluorene structure, the film can be decomposed, has no VOC pollution, has simple process and has excellent heat resistance property. The invention prepares an aqueous polyurethane dispersion with different bisphenolphthalein content by a prepolymer mixing method, and the aqueous polyurethane dispersion can be further dried to form a water-based polyurethane film containing a bisphenol fluorene structure.

The development of water-based PU has been more than 30 years, and the commercialization has a history of nearly 20 years. The process technology is quite mature. However, the application of the product is still not very extensive. The main reasons are as follows:

(1) Slow drying : Since the entropy of water is higher than that of organic solvents, the energy required for drying of aqueous PU is more than three times that of solvent-based PU at the same solid content, resulting in the application manufacturer not modifying existing drying equipment. In this case, only by reducing the production rate can the product be dried.

(2) Poor wettability : Due to the large surface tension of aqueous PU, the wettability of substrates with lower polarity such as release paper and PP film is not good, and rheological modifiers and other interface modifiers are required. To achieve the desired wetting and coating effect.

(3) Poor water resistance : Since a hydrophilic functional group is introduced into the aqueous PU main chain, it has relatively high hydrophilicity, and thus has poor water resistance.

The comparison of waterborne and solvent-based PU properties is shown in Table 1.

(4) Poor flame resistance : When the conventional water-based PU is used as a coating, it is difficult to be used as a fire-retardant material due to insufficient flame resistance.

(5) Higher price : the high reactivity of aromatic diisocyanate to water, so the commercial product is still based on the higher unit price of aliphatic or cycloaliphatic diisocyanate, making the raw material cost of aqueous PU more solvent-based PU. The raw material costs of high, water-based PU and solvent-based PU are shown in Table 2.

The shortcomings of these products have gradually improved under the continuous advancement of technology and have been applied Leather surface protective coating, followed by waterproof and moisture permeable treatment of fabrics, glass fiber sizing agents and other products. Especially in the obstacles of higher prices, there has been considerable progress. Technically, in addition to the use of TDI to synthesize an excellent water-based PU, it is also possible to introduce a lower-priced acrylic in the process, so that the product can achieve the purpose of reducing the cost of raw materials without losing physical properties.

The aqueous PU dispersion is a function of introducing a hydrophilic functional group into a PU molecular chain to have an emulsifier-like function, and can be emulsified (dispersed) in water without adding an emulsifier. Due to the different nature of the ionic groups introduced, the PU ionization can be divided into:

1. Cationomer: a functional group having nitrogen is introduced into the PU main chain, and is subjected to quaternization to make the PU hydrophilic.

2. Anionomer: a functional group having a Carboxylic Acid or a Sulfonic Acid is introduced into the PU main chain, and neutralized with a tertiary amine to produce Carboxylate and Sulfonante, so that the PU has Hydrophilic.

3. Zwitterionomer: It has the above two ionicities on the PU main chain. The method comprises the steps of: synthesizing a prepolymer having an NCO terminal group and reacting with N-methyl-diethanolamine and 1,3-propane sultone, respectively.

4. Nonionic: The long chain polyols of hydrophilic Ethylene oxide or Propylene oxide repeating unit are introduced into the PU main chain or side chain to make the PU water-dispersible.

The anionic hydrophilic monomer used in water-based PU, the most commonly used commercially is Dimethylol Propionic Acid (DMPA), in addition to the hydrophilic hydrophilic sodium sulfonate-type hydrophilic group, both Compare as shown in Table 3. In general, non-ionic PU is less toxic, less prone to hydrolysis, and has better electrolyte stability and low-temperature shear resistance than ionic polymers, but has high temperature instability. Ionic PU is highly prone to coulomb force due to its intermolecular interaction force, The film has better mechanical properties and higher stability to temperature, but its electrolyte stability is poor due to dissociation into ions in water.

It is necessary to use an aliphatic or cycloaliphatic diisocyanate which is less reactive with water, such as Isophorone diisocyanate (IPDI), hexamethylene diisocyanate. (Hexamethylene diisocyanate, HDI) or 4,4'-Dicyclohexylmethane diisocyanate (H ₁₂ MDI), etc., these diisocyanates are expensive, making the raw material cost of aqueous PU more Other materials are much higher. In addition, after the traditional water-based PU is impregnated and coated, the fusion between the water-based PU particles is not good, and the crucible is easily cracked when it is formed into a film, so that the film material after film formation cannot exhibit PU. Original high-performance features. Therefore, how to prepare a water-based PU with low cost and suitable for impregnation and coating processes and maintaining high toughness and high functional properties after film formation is a joint goal of the glove industry and the thin-walled elastic products industry. .

The invention develops an aqueous polyurethane dispersion liquid and a preparation method thereof, and is a water-based polyurethane (WPU) dispersion liquid containing a ruthenium structure (Cardo), which is a novel environmental protection material, and the formed film is biodegradable and volatile organic-free ( VOC) can achieve the above objectives by pollution, simple process and excellent heat resistance.

The invention relates to an aqueous polyurethane dispersion and a preparation method thereof. The dispersion is prepared by a prepolymer mixing method, and a polyisocyanate and a polyol mixture are first reacted into a prepolymer, and then the appropriate base is added to neutralize the prepolymer. Then, it is dispersed in water, and then a chain extender containing a hydroxyl group or an amine group is reacted with the prepolymer, and finally another chain extender containing no alkane and a remaining NCO group of the prepolymer are added. The aqueous polyurethane dispersion of the present invention is obtained by reacting, wherein the polyol comprises: (A) a polyol compound having a bisphenol oxime structure, and (B) having a hydrophilic group (carboxylic acid group and/or sulfonic acid group and/or phosphoric acid) a polyol compound of a group, and/or a phosphonic acid group, and (C) a polyol having a molecular weight of 500 to 8,000 different from (A) and (B), and by regulating (A), (B), (C) The content ratio is to obtain the properties of different water-based polyurethanes, and further to make various applications.

The aqueous polyurethane dispersion of the present invention has different contents of the polyol compound (A) having a bisphenol fluorene structure, for example, 9,9-bisphenol 4-(2-hydroxyethoxy) ruthenium (9,9). -Aqueous polyurethane (BHEOPF/WPU) dispersion prepared by -Bis[4-(2-hydroxyethoxy)phenyl]fluorene, BHEOPF), and found that the aqueous polyurethane is bisphenol quinone polyol When the content of the compound increased, the viscosity and Zeta potential of the BHEOPF/WPU dispersion remained unchanged. The particle size of the emulsion of the aqueous polyurethane dispersion increased with the increase of the content of bisphenol quinone. The aqueous polyurethane dispersion was dried and dried to form a BHEOPF/WPU film. Then, the aqueous polyurethane film increases with the content of bisphenol quinone, and the contact angle becomes larger, indicating that the film is more hydrophobic and the thermal stability of the film increases. The surface morphology of the film is extremely flat and does not change with increasing bisphenol quinone content. The prepared BHEOPF/WPU dispersion was applied to the cloth to measure the increase of flame resistance, and it was found that the water-based polyurethane containing bisphenol oxime was superior to the simple water-based polyurethane, and at room temperature, the mixture of water and organic solvent The osmotic separation effect is good.

The present invention prepares a water-based polyurethane (WPU) dispersion having a cockroach structure by a prepolymer mixing process, and (A) a polyol compound having a bisphenol fluorene structure as a partial polyol, for example, 9 9,9-bis(4-hydroxyphenyl)fluorene, which is reacted with a polyisocyanate to obtain a prepolymer containing a bisphenolphthalein unit in the main segment. The bisphenol oxime unit has a good heat resistance and high refractive enthalpy (Cardo) skeleton, imparting high heat resistance, high refraction, high weather resistance and high mechanical properties to the polymer, and the prepolymer further uses an alkoxy group containing a hydroxyl group or an amine group. As a chain extender, for example, 3-amino-propyl-triethoxysilane, the amino group and the NCO of the prepolymer The base reaction, and the triethoxysilane functional group can carry out the sol-gel reaction at room temperature during the drying process of the coating film to produce a crosslinked structure to enhance the mechanical properties of the aqueous polyurethane.

The aqueous polyurethane dispersion according to the present invention, wherein the polyol comprises: (A) a polyol compound having a bisphenol oxime structure, (B) having a hydrophilic group (selected from a carboxylic acid group and/or a sulfonic acid group and/or a phosphoric acid group) a polyol compound of the group, and/or a phosphonic acid group, and (C) different from (A) and (B) and having a molecular weight a polyol of 500 to 8,000, (A) a polyol compound having a bisphenol fluorene structure, such as 9,9-bisphenol 4-(2-hydroxyethoxy) fluorene (9,9-bis(4-hydroxyphenyl)) Fluorene), (B) a polyol containing a hydrophilic group (selected from a carboxylic acid group, and/or a sulfonic acid and/or a phosphate group, and/or a phosphonic acid group), such as dimethylol propionic acid, DMPA), the (C) polyol, for example, polytetramethylene ether glycol (PTMEG) having a molecular weight of 500-8000, reacted with a polyisocyanate at about 75 ° C, and polymerized to an end. The base is an NCO prepolymer, followed by the addition of a suitable amount of a base such as triethylamine to neutralize the carboxylic acid group, and/or the sulfonic acid group, and/or the phosphate group, and/or the phosphonic acid group on the prepolymer. The polymer ion body is then dispersed in water, and finally a chain extender such as ethylene-diamine or other diamines, or other diol or amine alcohol compound, preferably a diamine. a compound in which an amine group reacts excess NCO functional groups of the prepolymer and extends the molecular weight of the aqueous polyurethane to obtain an aqueous polyurethane emulsion, When reacting with the NCO functional group of the prepolymer, the amine group is nearly 1000 times faster than the OH group of water, so the diamine compound can carry out the chain extension reaction more efficiently. The aqueous polyurethane dispersion of the present invention can be further formed into a film, for example, by a cast film method, in which an appropriate amount of an aqueous polyurethane dispersion liquid is placed in a Teflon tank, and the temperature is gradually dried to reduce the probability of generating bubbles. An aqueous polyurethane (BHEOPF/WPU) film having a bisphenol fluorene structure is formed after molding.

(A) a polyol compound having a bisphenol fluorene structure according to the present invention, having the structure of the following chemical formula (1) Wherein each R is independently a substituent such as hydrogen, halogen, nitro, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, haloalkyl, hydroxy, amidino or amine; It is an integer from 1 to 6. The bisphenolphthalein is preferably 9,9-bisphenol 4-(2-hydroxyethoxy)anthracene.

(B) a hydrophilic group-containing polyol according to the present invention, a hydrophilic group such as a carboxylic acid group, a sulfonic acid group (-SO ₃ H) and/or a phosphate group (-OPO ₃ H ₂ ), and/or a phosphonic acid group (-PO ₃ H ₂ ), the (B) hydrophilic group-containing polyol, for example, a polyol compound having the following formula (2) or (3) or (4) Wherein R, R', and ⁴ R are: C ₁ to C ₅ alkylene groups, and ² R is hydrogen, a C ₁ to C ₅ alkyl group, and a hydrophilic polyether polyol structure. Preferably, R, R', ⁴ R is methylene, ethyl, propyl or butyl, ² R is selected from the group consisting of hydrogen, methyl, hydroxy, polyethylene glycol monomethyl ether (Methoxypolyethylene glycol MPEG) ); more preferably, the R, R ', ⁴ R is selected from methylene, ethyl stretch. The (B) hydrophilic group-containing polyol is preferably a carboxylic acid group-containing polyol having a fatty acid diol having an arithmetic mean molecular weight of generally from 100 to 1,000, and a specific example thereof is dimethylolpropionic acid (DMPA). And dimethylolbutanoic acid (DMBA) is preferred to impart a hard touch to the aqueous PU resin, preferably dimethylolpropionic acid (DMPA).

The polyol of the present invention has, in addition to (A) a polyol compound having a bisphenol oxime structure, (B) having a hydrophilic group (selected from a carboxylic acid group, and/or a sulfonic acid group, and/or a phosphate group, and/or The polyhydric alcohol compound of the phosphonic acid group further comprises (C) a polyol different from (A) and (B) and having a molecular weight of 500 to 8000, the polyol of (C) selected from the group consisting of polyether polyols, crystals Polyester polyol, amorphous polyester polyol, polycarbonate polyol, polyethylene glycol, polytetramethylene glycol, polypropylene glycol, poly (four methylene Alkyl ether), or a mixture of the foregoing. Preferably, the polyol of (C) is a polyether polyol of poly(tetramethylene ether) glycol.

The polyol of (C) according to the present invention, wherein the source of the polyester diol is synthesized from the following two types of monomers selected: (1) the first monomer is a diacid such as adipic acid. (adipic acid); and (2) the second type of monomer is a diol selected from the group consisting of ethylene glycol, 1.2-propylene glycol, and 1,4-butanediol (1, 4-butanediol), 1,5-diethylene glycol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol (1, One or more of the group consisting of 4-dimethylol cyclohexane. Wherein, the molecular weight of the polyester diol used in the embodiment is 500 to 8000, and the polyester diol used is a combination of one to five polyester diols obtained as described above. a mixture.

The polyol of (C) according to the present invention, wherein the polyether diol is selected from the group consisting of polytetramethylene ether glycol (PTMEG, molecular weight 500 to 8000) and polypropylene glycol (PPG, molecular weight 500 to 8000). And one or five of the group consisting of polyethylene glycol (PEG, molecular weight 500 to 8000) of the main chain and the side chain. Preferably, the ethoxy group-containing diol is polyethylene glycol, and the molecular weight of the polyethylene glycol used in this case is between 500 and 8,000.

The polyol of (C) according to the present invention, wherein the polyol of the polycarbonate polyol raw material may, for example, be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane. Glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecane Glycol or the like or 1,3-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,6-diol, 2-methyl-1,3-pentane An aliphatic diol such as an alkanediol, neopentyl glycol or 2-methyl-1,8-octanediol; 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2, 2'-bis(4-hydroxycyclohexyl)propane, alicyclic diol such as 1,4-cyclohexanedimethanol; aromatic diol such as 1,4-benzenedimethanol; trimethylolpropane, pentaerythritol, etc. Polyfunctional polyol Wait. The above polyol may be used as the polycarbonate polyol alone or in combination of plural kinds to form a polycarbonate polyol. The polycarbonate polyol is preferably a polycarbonate polyol containing the above aliphatic diol or alicyclic diol unit, more preferably a polycarbonate polyol containing the alicyclic diol unit, particularly A polycarbonate polyol containing a 1,4-cyclohexanedimethanol unit is preferred.

The polyisocyanate of the present invention may be an aliphatic, cyclic aliphatic or aromatic polyisocyanate, preferably a diisocyanate, such as Isophorone diisocyanate (IPDI). Since the PU resin is produced by an aromatic diisocyanate (such as toluene diisocyanate, TDI, 4,4-diphenyl methane diisocyanate, MDI), there is a yellowing phenomenon, and therefore, the polyisocyanate of the present invention is used as In the case of coating, aliphatic or cyclic aliphatic diisocyanate is used, and the synthesized PU resin has no yellowing phenomenon, so it is synthesized by using aliphatic or cyclic aliphatic in general light paint or coating. PU resin.

The aromatic diisocyanate of the present invention has at least one aromatic ring, such as phenyl, biphenyl or naphthalene, wherein the aromatic ring may further include halogen, nitro, cyano, C ₁ -C ₆ alkyl, C. _a substituent such as a ₁ to C ₆ alkoxy group, a haloalkyl group, a hydroxyl group, a carboxyl group, a decylamino group or an amine group.

The aromatic diisocyanate of the present invention is, for example, Toluene diisocyanate (TDI), p-Phenylene diisocyanate (PPDI), diisocyanate 4,4' -4,4'-Diphenylmethane diisocyanate (MDI) or p,-diphenyl cyanide (p,p'-Bisphenyl diisocyanate, BPDI), 1,3-phenylene Diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolyl diisocyanate (TDI), 2,6-tolyl diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4 '-Diisocyanate biphenyl, 3,3'- Dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-anaphthyl diisocyanate An aromatic polyisocyanate compound such as m-isocyanatophenylsulfonyl isocyanate or p-isocyanatophenylsulfonyl isocyanate.

The aliphatic or cyclic aliphatic diisocyanate of the present invention is, for example, Hexamethylene diisocyanate (HDI), Aliphatic diisocyanate (ADI), Trimethylhexamethylene diisocyanate (Trimethyl). -hexamethylene diisocyanate, TMDI) and ethyl diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethyl six Methylene diisocyanate, diazonium diisocyanate, 2,6-diisocyanatomethyl hexanoate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanate) Aliphatic polyisocyanate compounds such as ethyl ethyl carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate; Isophorone diisocyanate (IPDI), 1, 3-bis(isocyanatomethyl)cyclohexane (H ₆ XDI), 4,4'-dicyclohexylmethane diisocyanate (I,4,4'-Methylene dicyclohexyl diisocyanate , H ₁₂ MDI)), 1,4-cyclohexane diisocyanate (CHDI), cyclohexyl diisocyanate Ester, methylcyclohexyl diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate An alicyclic polyisocyanate compound such as 2,6-norbornane diisocyanate may be used alone or in combination of plural kinds. Preferably, the isocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI).

The polyol of the present invention comprises: (A) a polyol compound having a bisphenol fluorene structure, and (B) having a hydrophilic group (carboxylic acid group, and/or sulfonic acid group, and/or phosphate group, and/or phosphonic acid group). a polyol compound, and (C) a polyol having a molecular weight of 500 to 8,000 different from (A) and (B), and controlled by The content ratios of (A), (B), and (C) are used to obtain the properties of different aqueous polyurethanes, and further various applications are made. The content of the polyol controls the moisture permeability, hydrophobicity and viscosity of the polyurethane. The more (B), the higher the content of the hydrophilic functional group, the higher the hydrophilicity, and the higher the moisture permeability of the polyurethane obtained after polymerization. High, but the content is too high, so that the viscosity of the synthesized polyurethane is increased, so that the processing viscosity at 100 ° C is too high, resulting in poor bonding effect; conversely, the lower the hydrophilic functional group content, the lower the hydrophilicity, that is, the polyurethane obtained after polymerization. The lower the moisture permeability, the higher the content of (A), the higher the content of bisphenol quinone structure, the greater the hydrophobicity, flame retardancy, mechanical properties, etc. of the polyurethane obtained after polymerization; therefore, the present invention utilizes the (C) The polyol, such as polyether polyol or polyester polyol or polycarbonate polyol, has a molecular weight controlled between 500 and 8000, and is coordinated with (A) a polyol having a bisphenolphthalein structure and (B) The content of the hydrophilic group-containing polyol can be used as an adhesive agent to have both good moisture permeability and washing resistance, so that it is excellent for use in fabrics.

The polyol of the present invention is preferably a ratio of 100% by mole of the total molar percentage of the polyol for polymerization, and the percentage of moles of the polyol having the bisphenol fluorene structure (A) is from 0.1 to 90 mole%. (B) The hydroxyl group-containing polyol has a molar percentage of 10 to 80 mole%; and the (C) polyol having a molecular weight of 500 to 8000 has a molar percentage of 1 to 60 mole%.

The alkoxy oxirane having a hydroxyl group or an amine group according to the present invention is preferably a metal alkoxy decane having a chemical formula of H ₂ NR ³ -Si(R) as a chain extender. ² ) _a (OR ¹ ) _3-a , wherein R ¹ , R ² are H or C ₁ -C ₄ alkyl, a is 0 or 1, and R ³ is a C ₁ -C ₁₀ alkyl group or R ⁵ -NH -R ⁴ , R ⁴ and R ⁵ are C ₁ -C ₁₀ alkyl groups. The amino alkoxydecane may comprise a primary amine group, a secondary amine group or a combination thereof. For example, the amino alkoxydecane can be N-[3-(trimethoxysilyl)propyl]ethylenediamine or 3-aminopropyltri 3-aminopropyltriethoxysilane.

In addition, the polyurethane may further comprise a non-oxyalkylene chain extender for increasing the molecular weight of the polymerization, and an antioxidant, and the chain extender may be a polyol compound, a polyamine compound, or a polyol amine compound. The diamine compound is preferred, and the amine compound chain extender is not particularly limited, and examples thereof include ethylenediamine ethylenediamine, 1,4-tetramethylenediamine, and 2-methyl group. -1,5-pentanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine , 1,3-bis(aminomethyl)cyclohexane, xylylenediamine, hexahydropyridyl (iperazine), 2,5-dimethylhexahydropyridyl , diethylenetriamine, triamethylenetetramine, hydrazine, ethylene triamine, hydrazine, diterpene succinate, diterpene terephthalate, piperazine, etc. Amines and the like; among them, preferred are, for example, a primary diamine compound. These may be used alone or in combination of plural kinds. Wherein the polyol compound is preferably an aliphatic polyol, which may include, but is not limited to, an aliphatic diol, an aliphatic triol, etc., and is selected from the group consisting of ethylene glycol, 1,3-dihydroxypropane, and 1,4. 1,4-dihydroxy-butane, 1,6-dihydroxyhexane, 2-methyl-1,3-propanediol, 1,3 butanediol (1,3- Butanediol; 1,3BG), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol. Specific examples of the aliphatic triol may include, but are not limited to, glycerol, trimethylol methane, trimethylolethane, trimethylolpropane (TMP) hydroquinone bis (2-hydroxyethoxy)benzene, HQEE) is preferably trimethylolpropane (TMP) or glycerol. A polyalkylene glycol represented by polyethylene glycol. The polyol amine compound is selected from the group consisting of Diethanol amine, 3-((hydroxyethyl)amino)propanol (3-[(2-hydroxyethyl)amino)propan-1-ol or 4-((2-hydroxyl) Ethyl)amino)butanol (4-[(3-hydroxypropyl)amino]butan-1-ol).

Since the use of the chain extender and the antioxidant is a commonly used reagent in the polyurethane synthesis process, and is not the focus of the present invention, the related amounts and characteristics thereof will not be further described.

The present invention provides an aqueous polyurethane using (B) a polyol having a hydrophilic group (a carboxylic acid group, a sulfonic acid group and/or a phosphoric acid group, and/or a phosphonic acid group), the hydrophilic group anionic group, The anionic group is neutralized with a neutralizing agent; the neutralizing agent is a base. Containing an organic neutralizing agent and/or an inorganic neutralizing agent. Suitable organic neutralizing agents may include, but are not limited to, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, N-methylmorphorine, and amine groups. An organic amine such as methyl propanol, aminomethylpropanediol, aminoethylpropanediol, trishydroxymethylaminomethane or monoethanolamine. These may be used alone or in combination of plural kinds. Suitable inorganic neutralizing agents may include, but are not limited to, potassium hydroxide, sodium hydroxide, lithium hydroxide or any combination of the foregoing. The aforementioned neutralizing agents may be used singly or in combination of two or more kinds.

The organic solvent is generally used in an amount of from 3 to 15% by weight based on 100% by weight based on the total weight of the aqueous polyurethane dispersion.

Further, in one aspect of the invention, the aqueous polyurethane dispersion contains a polyurethane resin, and the polyurethane resin has a large amount of hydrophilic groups, and since the hydrophilic groups have polarity, the intermolecular attraction of the polyurethane resin Therefore, the heat dissipating composition containing the aqueous polyurethane dispersion has good film forming properties, and a lubricating layer having good mechanical strength and high adhesion can be formed on the substrate. The use of the above neutralizing agent further enhances the stability function of the aqueous polyurethane dispersion. Moreover, since the lubricating layer formed by the aqueous polyurethane dispersion has excellent water solubility, when the lubricating sheet of the present invention is used for cleaning the surface of the lubricated sheet and the processed surface of the cutter by water after cutting, drilling, or the like, It is easy to dissolve and remove the residual glue and debris that have been attached to the cutter and need to be removed, and the debris is removed, thereby shortening the time for subsequent cleaning operations.

On the other hand, in another aspect of the present invention, the aqueous polyurethane dispersion contains a polyurethane resin, and the polyurethane resin further has a large amount of hydrophilic groups and an appropriate amount of a bisphenol hydrazine hydrophobic group, so that when the textile coating is processed, Improve the moisture permeability and waterproof function of the fabric.

The above-mentioned water-based polyurethane resin should be added with an appropriate amount of bridging agent in the textile coating application to improve the adhesion and water washing resistance of the polyurethane resin to the fiber.

The (C) polyol of the present invention may be a polyester polyol, a polycarbonate polyol or a polyether polyol, or may be a composition comprising a polyester polyol, a polycarbonate polyol, and a polyether polyol. The nonionic groups thereof are located on the main chain and side chains of the polyurethane resin, for example, from an ethoxy group-containing glycol, such as polyethylene glycol. It should be noted that the nonionic group is used to increase the hydrophilicity of the polyurethane resin, and therefore, the nonionic group of the present invention means a non-ionic compound and a hydrophilic polyol, and when the above polypolyol is One can also provide a nonionic group of the present invention when it provides good hydrophilic properties.

The (B) polyol having a hydrophilic group, wherein the anionic group is used as an internal emulsifier of the polyurethane resin, that is, directly modifying the polymer molecule of the polyurethane resin to have a high polarity and having a carboxyl group and a sulfonic acid. A compound of a benzyl group, a phosphoric acid group or a phosphonic acid group, such that the urethane resin can be dispersed in an aqueous phase solvent without the need for an additional emulsifier. Further, the structure of the anionic group has a large steric barrier, thereby suppressing re-aggregation between the dispersed polyurethane resins, thereby achieving a state of uniform dispersion. For example, the source of the anionic group can be 2,2-dimethylolpropionic acid (DMPA). It is to be understood that any compound having a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group which satisfies the above properties can also be used as a source of the anionic group of the present invention.

The neutralizing agent is a base, and the base may be an alkylamine or a hydrogen atom of a different carbon number. A tertiary amine such as triethylamine (TEA), tripropylamine (TPA, tripropylamine) or tributylamine (TBA, tributylamine). In the present invention, the neutralizing agent is used to neutralize the carboxyl group, the sulfonic acid group, the phosphoric acid group, and the phosphonic acid group of the anionic group to generate an ion center, and when the neutralizing agent and the aqueous phase solvent are volatilized, the ion The central neutralizer portion is removed to leave a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a phosphonic acid group of the anionic group. At this time, the aqueous polyurethane resin forms a crosslinked carboxyl group, a sulfonic acid group, or a phosphoric acid group. , a phosphonic acid-based film with good adhesion.

The organic solvent of the present invention may be, for example, N-methyl-2-pyrrolidone (NMP), isopropyl alcohol, sec-butyl alcohol, acetone ( Acetone), methyl ethyl ketone, toluene, N,N-dimethylformamide (DMF, Dimethyl Formamide) or N,N-dimethylacetamide (DMAc, Dimethyl Acetamide). The organic solvent used in the present invention is preferably N-methylpyrrolidone, acetone, methyl ethyl ketone or any combination thereof.

Optionally add catalyst and/or antioxidants as needed. The foregoing catalyst may include, but is not limited to, tin octylate, monobutyltin triacetate, monobutyltin monooctanate, monobutyltin monoacetate, monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, distearate. Organotin compounds such as butyltin, dibutyltin dilaurate, dibutyltin maleate; organotitanium compounds such as tetraisopropyl titanate and tetra-n-butyl titanate; triethylamine, N,N-diethylcyclohexane Tertiary amines such as hexylamine, N,N,N',N'-tetramethylethylethylamine, and triethylethylenediamine. The aforementioned antioxidant may include, but is not limited to, an organic phosphite compound, which is specifically, for example, tetraphenyl dipropyleneglycol diphosphite (TDD), diphenyl pentaerythritol diphosphite, diphenylisoindole. Phosphite trimethyl isodecyl phosphite, diphenyl phosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, di(2,4-di Tert-butylphenyl)pentaerythritol diphosphite, di(octadecyl)pentaerythritol diphosphite, triphenylphosphite, tris(nonylphenol) phosphite, tetra (2,4-di-tert Butylphenol)-4,4'-biphenyldiphosphite, phenyldiisodecylphosphite, poly-4,4'-isopropylidenediphenol tetraphenol phosphite, poly(two Propylene glycol) phenyl phosphite (PDP), an esterification catalyst for organometallic compounds, etc., among which is an environmentally friendly esterification catalyst of organometallic compounds (ES CAT-100E, Seho Tech Inc., Korea ) is better.

In addition, it should be noted that the ions (ie, an anionic group and a neutralizing agent) contained in the above aqueous polyurethane resin form an appropriate number of ion centers in the aqueous polyurethane resin to further enhance the polyurethane resin and the aqueous solvent. The interaction between the polyurethane resin increases the stability of the dispersion and promotes the stability of the dispersion. At the same time, the excessively high ion content is avoided, and the hardness of the subsequently produced film is too high. When the film is used in the IC process, the film is reduced. The needle break rate of the drill when drilling.

First Figure The particle size distribution of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.

Second Figure Average particle size diagram of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.

Third Fig. Viscosity diagram of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.

Fig. 4 is a graph showing the change of zeta potential with BHEOPF content of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.

Fig. 5 is a graph showing the swelling degree of the aqueous polyurethane (BHEOPF/WPU) film of the present invention.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

Preparation of aqueous polyurethane dispersion

EXAMPLES In the formulation table 4 (BHEOPF/WPU 3) as an example

1, join

9,9-bisphenol 4-(2-hydroxyethoxy)fluorene (9,9-bis(4-hydroxyphenyl)fluorene, BHEOPF) 2.1925g

N-methyl-2-pyrrolidone (NMP) 12.5682g

Dimethylol propionic acid (DMPA) 2.4203g

Polytetramethylene ether glycol (PTMEG; molecular weight 1000g/mole) 26.9354g

Isophorone diisocyanate (IPDI) 20g

After stirring at 300 rpm, a few drops of the catalyst dibutyltin dilaurate (T12) was added, and the temperature was raised to 75 ° C for 2 hours, and then the temperature was lowered to 51 ° C.

2. The above reactant was neutralized by adding 1.8391 g of triethylamine (TEA) and stirred at 500 rpm for 10 minutes.

3. Increase the rotation speed to 1000 rpm and add 128.2504 g of deionized water. Stir to a small bubble.

4. A mixture of 1.6611 g of 3-aminopropyltriethoxysilane (APTES) and 5 g of acetone was added and stirred for 5 minutes.

5. A mixture of 2.4035 g of ethylenediamine (EDA) and 10 g of deionized water was added and stirred for 1 hour to complete the aqueous polyurethane dispersion of the present invention.

Preparation of waterborne polyurethane film

After the above aqueous polyurethane dispersion was allowed to stand on a Teflon plate for one day, the temperature was set to 30 ° C every other day, and then the temperature was raised by 5 ° C at the same time every day until the film was taken out at 75 ° C.

One specific waterborne polyurethane synthesis example reaction equation of the present invention

Waterborne polyurethane dispersion formula table, Table 4

Physical properties and stability test of the polyurethane (BHEOPF/WPU) dispersion of the present invention

Particle size analysis

In the formulation conditions used in the experiment, the BHEOPF/WPU dispersion has no precipitate, and its particle size distribution does not widen with the increase of BHEOPF content. Referring to the first figure, the volume average particle size will increase with the increase of BHEOPF content, as shown in the table. 5. The average particle size diagram of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention is as shown in the second figure.

Viscosity analysis

When the viscosity of the waterborne polyurethane (BHEOPF/WPU) dispersion of the present invention is measured, the viscosity of the dispersion increases with the rotation speed of the rotor, and as the rotation speed increases, the viscosity of the dispersion increases, and the shear variability on the X axis changes with time, Y The shear stress of the shaft is tangent to the force surface, and the shear variability is proportional to the shear stress is Newtonian fluid. The third graph is a plot of viscosity at 250 rpm versus different BHEOPF levels. The results show that the viscosity of the aqueous polyurethane (BHEOPF/WPU) dispersion is maintained at 5-7 cps.

Interface potential analysis

The stability of the dispersion can be analyzed by the interface potential. Generally, the electric double layer is a fixed layer (called the Stern layer) adsorbed on the surface of the colloidal particles. When the colloidal particles move relative to the outside, the fixed layer will be brought together. Movement, so the potential difference between the surface of the fixed layer and the external diffusion layer is called the zeta potential. When a colloidal particle having a surface charge moves in an environment where an electric field is applied, relative to a stationary liquid, it is called electrophoresis, and the potential of the surface of the particle can be obtained by the electrophoretic behavior of the colloidal particle, that is, the interface. Potential. Generally, the larger the absolute value of the zeta potential, the larger the repulsive force between the particles and the particles, the better the particle dispersion effect, the less prone to agglomeration, and the better the stability of the solution.

The fourth figure is a graph showing the change of zeta potential with BHEOPF content of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention. The absolute value of the zeta potential of the WPU dispersion without BHEOPF is -19.97±2 mV, and the WPU dispersion containing BHEOPF. The zeta potential is between -18 and -20 mV. The zeta potential value of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention does not change with the increase of the BHEOPF content, and the display potential is stable.

Contact angle measurement

Since the surface of the film may have a hydrophilic group, or the surface itself is hydrophobic, in order to investigate this property, it is necessary to measure the hydrophilicity of the film by a contact angle meter. This property is important because the film can exhibit hydrophobicity. Sexually broad, and more hydrophilic, it is low in endurance and easy to decompose. The invention dries the aqueous polyurethane (BHEOPF/WPU) dispersion into a film, and the film is analyzed by a contact angle measuring instrument. The test results are listed in Table 5. The general aqueous polyurethane contact angle is about 67°, and the bisphenol quinone is used. The more the content, the greater the tendency of the measured angle, indicating the more hydrophobic nature.

Swelling analysis

The swelling test was carried out, and the film was immersed in water and allowed to stand for every 15 minutes after 1, 2, 4, 8, 12, and 15 minutes, and the film was taken out and weighed with each time. The fifth figure is BHEOPF/WPU film swelling degree curve, in which the water content (the formula is obtained) is the Y axis and the time is the X axis. The results show that the water absorption rate of the film changes slowly with time, and the water absorption of the film after about 100 minutes. After reaching saturation, the curve afterwards is horizontal. The WPU curve shows the most water absorption, and then the BHEOPF/WPU1 curve to BHEOPF/WPU5. It is known that the more the bisphenol bismuth content, the less water absorbing, the contact angle test can be The more the bisphenol bismuth content is obtained, the larger the angle is, the more hydrophobic it is, and this characteristic is also corresponding to the swelling test. The more bisphenol quinone content, the lower the water absorbing property and the hydrophilicity of the film.

Physical properties of polyurethane (BHEOPF/WPU) dispersions, Table 5

Industrial availability

The aqueous polyurethane dispersion prepared by the invention is prepared into a water-based polyurethane film containing bisphenol quinone, which is used for osmosis evaporation to recover the waste solution of the waste plant, filter the water, improve the purity of the solution, and develop the flame retardant material. Polyurethane (PU) resins are used in coatings, adhesives, inks, and fiber treatment agents.

The aqueous polyurethane dispersion of the invention has good chemical resistance and is resistant to dissolution Formulation, abrasion resistance, excellent elasticity and heat deformation resistance, can be widely used in coatings, adhesives, furniture, bed cushions, linings, building insulation, cable, refrigerator insulation, synthetic leather, waterproof material, Vehicle paint, wear-resistant tire, waterproof building materials, wear-resistant furniture, sealant, fill-in agent, waterproofing agent, elastic fiber, fiber fabric treatment agent, foam, IC process, printed circuit board, leather surface treatment agent and various additives The use of the above, applied to various electronic IC factories and chemical plants, has improved the quality of life of people.

While the present invention has been described above in terms of several preferred embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. The scope of the present invention is defined by the scope of the appended claims.

Claims (10)

A method for preparing an aqueous polyurethane dispersion, comprising: a polyurethane resin having a bisphenol fluorene structure in a main chain, (A) a polyol compound having a bisphenol fluorene structure, and (B) a polyol compound having a hydrophilic group, And/or (C) a prepolymer formed by reacting a polyol having a molecular weight of 500 to 8,000 and a polyisocyanate differently from (A) and (B), neutralized with a suitable alkali agent, and then added with water to form a prepolymer aqueous solution. The dispersion, which is then reacted with a chain extender and a NCO group of the prepolymer to increase the molecular weight to form an aqueous polyurethane dispersion; wherein the hydrophilic group of (B) is selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphine group. Acid group, or two or four of the above. The method for preparing an aqueous polyurethane dispersion according to claim 1, wherein the polyol of (A), (B), and (C) and the polyisocyanate are dissolved in an organic solvent to carry out a prepolymerization reaction, and the neutralization is carried out. The agent is selected from the group consisting of organic bases and/or inorganic bases. The method for preparing an aqueous polyurethane dispersion according to claim 1, wherein the polyol of (C) is selected from the group consisting of polyether polyols, crystalline polyester polyols, amorphous polyester polyols, and polycarbonates. Polyol, polyethylene glycol, polytetramethylene glycol, polypropylene glycol, poly(tetramethylene ether) glycol, or a mixture of the foregoing. The method for producing an aqueous polyurethane dispersion according to the first aspect of the invention, wherein (A) the polyol compound polyol having a bisphenol fluorene structure has the following chemical formula (1) Wherein each R is independently a substituent such as hydrogen, halogen, nitro, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, haloalkyl, hydroxy, amidino or amine; It is an integer from 1 to 6. The method for preparing an aqueous polyurethane dispersion according to claim 1, wherein the aqueous prepolymer dispersion is first reacted with a chain extender containing a hydroxyl group or an amine group, and a prepolymer thereof. Finally, other rhodium-free chain extenders are added to react with the remaining NCO groups in the prepolymer. The method for producing an aqueous polyurethane dispersion according to the first aspect of the invention, wherein the (B) polyol compound having a hydrophilic group is selected from the group consisting of the following formula (2), and/or (3), and/or Or (4) a polyol compound Wherein R, R', ⁴ R are: C ₁ -C ₅ alkylene, ² R is: hydrogen, C ₁ -C ₅ alkyl, hydrophilic polyether polyol structure, ² R is selected from hydrogen , methyl, hydroxyl, polyethylene glycol monomethyl ether. The method for producing an aqueous polyurethane dispersion according to claim 1, wherein the polyisocyanate is selected from the group consisting of aliphatic, and/or cyclic aliphatic, and/or aromatic polyisocyanate. The method for producing an aqueous polyurethane dispersion according to claim 5, wherein the chain extender containing no alkane is selected from the group consisting of a polyol compound and/or a polyamine compound, and/or a polyol amine compound. An aqueous polyurethane dispersion obtained by the method for producing an aqueous polyurethane dispersion according to any one of claims 1 to 8 of the present invention. Preparation of aqueous polyurethane dispersion according to any one of claims 1 to 8 The aqueous polyurethane dispersion obtained by the method or the aqueous polyurethane dispersion of the ninth item can be applied to coatings, adhesives, furniture, bed cushions, linings, building insulation, cable, refrigerator insulation layer, synthesis Leather, waterproof material, vehicle paint, wear-resistant tire, sealant, fill-in agent, waterproofing agent, elastic fiber product, fabric treatment agent, foam, IC process, printed circuit board, leather surface treatment agent and various additives .