WO2024020779A1 - 一种聚氨酯-聚脲水分散体及其制备方法和应用 - Google Patents

一种聚氨酯-聚脲水分散体及其制备方法和应用 Download PDF

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Publication number
WO2024020779A1
WO2024020779A1 PCT/CN2022/107894 CN2022107894W WO2024020779A1 WO 2024020779 A1 WO2024020779 A1 WO 2024020779A1 CN 2022107894 W CN2022107894 W CN 2022107894W WO 2024020779 A1 WO2024020779 A1 WO 2024020779A1
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Prior art keywords
component
polyurethane
aqueous dispersion
polyol
acid
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PCT/CN2022/107894
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English (en)
French (fr)
Inventor
王震
晋云全
纪学顺
曹玉阳
张续
李卫飞
王海梅
邓俊英
孙家宽
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万华化学集团股份有限公司
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Priority to PCT/CN2022/107894 priority Critical patent/WO2024020779A1/zh
Publication of WO2024020779A1 publication Critical patent/WO2024020779A1/zh

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/015—Protective gloves
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
    • A61F6/02—Contraceptive devices; Pessaries; Applicators therefor for use by males
    • A61F6/04—Condoms, sheaths or the like, e.g. combined with devices protecting against contagion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B63/00—Auxiliary devices, not otherwise provided for, for operating on articles or materials to be packaged
    • B65B63/04—Auxiliary devices, not otherwise provided for, for operating on articles or materials to be packaged for folding or winding articles, e.g. gloves or stockings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to the technical field of preparation of soft elastic products (such as gloves, condoms, etc.), and in particular to a polyurethane-polyurea aqueous dispersion that is beneficial to obtaining high-performance soft elastic products and its preparation method and application.
  • Soft elastic products such as disposable gloves are widely used in medical gloves, examination gloves, household and industrial fields.
  • the materials used to prepare soft elastic products (such as disposable gloves, condoms, etc.) on the market mainly include natural latex, chloroprene, etc. Rubber, nitrile rubber, PVC, etc.
  • Natural latex contains protein, which can easily cause allergies in some people; products such as chloroprene rubber and nitrile rubber have problems such as strong odor and high production pollution.
  • polyurethane dispersions are superior to the resins of the above materials in terms of mechanical strength, extensibility, breathability and environmental protection during the glove preparation process. At present, there have been some research reports on the use of polyurethane to produce soft elastic products.
  • Patent document CN104725590B discloses a low-modulus polyurethane dispersion for disposable gloves.
  • the polyurethane dispersion uses polytetrahydrofuran diol, polypropylene glycol and toluene diisocyanate as raw materials.
  • the prepared gloves have properties similar to rubber products.
  • products prepared using polypropylene glycol have poor water resistance. If they are exposed to water during use, their strength will drop significantly and they have no practical value.
  • Patent document CN108864394A discloses a glove for medical use prepared by compounding sulfonate polyester and polypropylene glycol. It claims to have excellent alcohol resistance. In fact, no system using polypropylene glycol can achieve good alcohol resistance. , and the overall strength of the gloves is low and the applicability is not strong.
  • the invention provides a polyurethane-polyurea aqueous dispersion suitable for preparing soft elastic products.
  • Soft elastic products are prepared based on the polyurethane-polyurea aqueous dispersion, which can take into account good elasticity, strength, water resistance and wearing feel. performance.
  • the present invention provides a polyurethane-polyurea aqueous dispersion, which contains units derived from component a, which component a contains at least one polyol with a functionality of 2 or more, and component a contains at least 40wt%
  • the above semi-crystalline polyester polyol obtained by reacting a diol with component I, wherein the component I includes an aliphatic dicarboxylic acid and component II in a molar ratio of 2.1-10:1, so The component II is aromatic dicarboxylic acid and/or aromatic dicarboxylic anhydride.
  • the diol used to prepare the semi-crystalline polyester polyol includes at least one or more of 1,4-butanediol and 1,6-hexanediol, and optionally includes other glycols with a relative molecular weight lower than 150, and the other glycols include ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diacetate One or more of ethylene glycol and dipropylene glycol; among the glycols used to prepare the semi-crystalline polyester polyol, the proportion of the other glycols is less than 50wt%;
  • the component II used to prepare the semi-crystalline polyester polyol is selected from one or more of phthalic acid and phthalic anhydride; preferably, the phthalic acid is selected from Isophthalic acid and/or phthalic acid; more preferably, the component II is isophthalic acid;
  • the aliphatic dicarboxylic acid used to prepare the semi-crystalline polyester polyol is adipic acid.
  • the semi-crystalline polyester polyol is an opaque waxy solid at room temperature.
  • the polyurethane-polyurea aqueous dispersion is prepared by reacting raw materials containing the following components:
  • Component a includes at least one polyol with a functionality of 2 or more, and the proportion of the semi-crystalline polyester polyol in the component a is more than 40wt%, preferably the semi-crystalline polyester The proportion of polyol in component a is 70-100wt%;
  • Component b polyisocyanate
  • Component c hydrophilic compound.
  • the hydrophilic compound contains 2-3 groups that are reactive with NCO.
  • the hydrophilic group of the hydrophilic compound includes one or more of an ionic group and a potential ionic group. variety;
  • Optional component d alcohol chain extender different from component a;
  • Component f polyamine with a number average molecular weight not exceeding 500 g/mol.
  • the raw material when the hydrophilic group of component c does not include the ionic group, the raw material further includes component e, and the component e is capable of ionizing component c. compound;
  • the dosage ratio of the following components is used to prepare the polyurethane-polyurea aqueous dispersion.
  • these are: component a, 56 ⁇ 85wt%; component b, 10 ⁇ 30wt%; component c, 0.8 ⁇ 4wt%; component d, 0 ⁇ 3wt%; component f, 0.5 ⁇ 4wt%; component e ,0.6 ⁇ 4wt%;
  • the dosage ratio of the following components used to prepare the polyurethane-polyurea dispersion is: Component a, 56 ⁇ 85wt%; component b, 10 ⁇ 30wt%; component c, 0.8 ⁇ 4wt%; component d, 0 ⁇ 3wt%; component f, 0.5 ⁇ 4wt%.
  • the polyol in the component a, has a number average molecular weight of 500-15000 g/mol, preferably the polyol has a number-average molecular weight of 800-10000 g/mol and a functionality of 2-4 Polyol, more preferably the polyol is a polyol with a number average molecular weight of 1000-5000 g/mol and a functionality of 2-3;
  • the polyisocyanate is selected from one or more aromatic, aliphatic and alicyclic polyisocyanates, preferably the polyisocyanate has at least two isocyanate groups;
  • the group reactive with NCO contained in the hydrophilic compound is a hydroxyl group and/or an amino group
  • the ionic group is preferably a carboxylate ion and/or a sulfonate ion, and the potential ionic group is preferably a carboxyl group;
  • the alcohol chain extender different from the component a is a small molecular alcohol compound with a relative molecular weight of less than 150;
  • the component e is triethylamine
  • the component f is a polyamine with a relative molecular weight of 60 to 500, preferably ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, One or more of 2-methylpentane-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine and diethylenetriamine.
  • the hydrophilic compound as the component c is selected from dimethylol propionic acid, dimethylol butyric acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2- One or more of aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid and their salts, including the corresponding alkali metal salts, alkaline earth metal salts or ammonium salts One or more, preferably the component c is dimethylol propionic acid;
  • the alcohol chain extender as the component d is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dihydroxycyclohexane, 1,4-dihydroxymethylcyclohexane , 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and one or more of 2-ethyl-1.3-hexanediol; preferably 1,2-propanediol, 1,3-propane
  • the component a optionally includes other polyols different from the semi-crystalline polyester polyol, and the other polyols are selected from polyester polyols, polycaprolactone polyols, One or more polycarbonate polyols and polyether polyols, the proportion of the other polyols in the component a is 0-60wt%.
  • the present invention also provides the above-mentioned method for preparing the polyurethane-polyurea aqueous dispersion, which is prepared by reacting the raw materials containing component a to obtain the polyurethane-polyurea aqueous dispersion;
  • the raw materials also include component b, component c, optional component d and component f;
  • the component b is a polyisocyanate;
  • the component c is a hydrophilic compound, and the hydrophilic compound contains 2-3 groups reactive with NCO;
  • the component d is different from the component alcohol chain extender a;
  • the component f is a polyamine with a number average molecular weight not exceeding 500 g/mol; when the component c does not contain an ionic group, the raw material also includes component e, so The component e is a compound that can ionize component c;
  • the preparation method includes the step of reacting at 60 to 90°C to obtain an isocyanate-terminated prepolymer.
  • the present invention also provides a soft elastic product, which is made based on the polyurethane-polyurea aqueous dispersion described above.
  • the soft elastic product includes gloves and/or condoms.
  • the present invention also provides a method for preparing soft elastic products, which includes the step of applying a liquid containing polyurethane-polyurea aqueous dispersion to a mold required for preparing soft elastic products; preferably, the soft elastic products include gloves. and/or condoms; the polyurethane-polyurea aqueous dispersion adopts the polyurethane-polyurea aqueous dispersion described above.
  • the polyurethane-polyurea dispersion provided by the present invention is obtained based on a polyol component (ie, component a) containing at least 40 wt% of a semi-crystalline polyester polyol containing a benzene ring structure.
  • Alcohol is obtained by reacting a specific molar ratio of aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and/or aromatic dicarboxylic acid anhydride) with glycol.
  • Soft elastic products are prepared using such polyurethane-polyurea dispersion. For example, gloves, condoms, etc.
  • the polyurethane-polyurea dispersion of the present invention can be used to prepare soft elastic products suitable for medical, household and industrial use, such as gloves; it is also particularly suitable for the production of condoms.
  • One aspect of the present invention provides a polyurethane-polyurea aqueous dispersion, which contains units derived from component a, component a contains at least one polyol with a functionality of 2 or more, and component a contains at least 40wt%
  • the above semi-crystalline polyester polyol obtained by reacting a glycol with component I, wherein component I includes a molar ratio of 2.1-10:1 (for example, a molar ratio of 2.1:1, 2.5:1, 3: 1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.) aliphatic dicarboxylic acid and component II, component II is an aromatic dicarboxylic acid Acids and/or aromatic dianhydrides.
  • the polyol (component a) used contains at least 40wt% or more (for example, 40wt%, 42wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 90wt%, 100%, etc.) of semi-crystalline polyester polyol, and the semi-crystalline polyester polyol is an aliphatic dicarboxylic acid with a molar ratio of 2.1-10:1
  • the acid and component II aromatic dicarboxylic acid and/or aromatic dicarboxylic anhydride
  • the polyurethane-polyurea dispersion prepared based on the scheme of the present invention can reduce the crystallization of polyester. properties, while improving elasticity and obtaining good strength and other characteristics; the polyurethane-polyurea aqueous dispersion is used for the preparation of soft elastic products, and the obtained polyurethane-polyurea aqueous dispersion is particularly suitable for soft elastic products such as gloves and/or Preparation of condoms; the polyurethane-polyurea aqueous dispersion is used for the preparation of soft elastic products.
  • the obtained soft elastic products have significantly improved comprehensive properties and can take into account good tensile strength, elongation, resilience, etc., and the material is soft and Highly elastic for improved wear feel.
  • semi-crystalline polyester polyol is not used or the proportion of semi-crystalline polyester polyol in the polyol (component a) is less than 40wt%, or the basis of semi-crystalline polyester polyol does not meet the molar ratio of 2.1 -10:1 aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and/or aromatic dicarboxylic acid anhydride) are obtained, and the performance of the resulting soft elastic product is significantly deteriorated, and good comprehensive properties cannot be taken into account.
  • component a the proportion of semi-crystalline polyester polyol obtained by reacting glycol with component I reaches 70-100 wt%, which is beneficial to obtaining soft elastic products with better performance. .
  • the glycols used to prepare semi-crystalline polyester polyols include at least one or more of 1,4-butanediol and 1,6-hexanediol, and optionally include Other glycols with a relative molecular weight below 150, including ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diethylene glycol, One or more of dipropylene glycol, etc.; among the diols used to prepare semi-crystalline polyester polyol, the proportion of other diols is less than 50wt%, that is, the amount is less than 1,4 -Butanediol and/or 1,6-hexanediol.
  • the diol used is preferably 1,4-butanediol and/or 1,6-hexanediol, or preferably more than 50wt% (based on the total amount of diol) 1 , 4-butanediol and/or 1,6-hexanediol, can improve the properties of the final soft elastic product.
  • component II used to prepare semi-crystalline polyester polyol is selected from one or more of phthalic acid and phthalic anhydride; preferably, phthalic acid is selected from isophthalic acid. Formic acid and/or phthalic acid; more preferably, component II is isophthalic acid. It is preferred to use isophthalic acid, which is beneficial to obtaining soft elastic products with better performance.
  • the aliphatic dicarboxylic acid used to prepare the semi-crystalline polyester polyol is adipic acid.
  • the glycols used to prepare semi-crystalline polyester polyols include at least one or more of 1,4-butanediol and 1,6-hexanediol, and the component II used is One or more selected from isophthalic acid, phthalic acid, and phthalic anhydride, preferably isophthalic acid, the aliphatic dicarboxylic acid used is adipic acid, and adipic acid and the component
  • the molar ratio of II is 2.1-10:1; the polyurethane-polyurea aqueous dispersion based on the preferred semi-crystalline polyester polyol can obtain better product properties, and the resulting product has significantly improved tensile strength, Elongation, resilience, wear feel and water resistance.
  • the semi-crystalline polyester polyol obtained by this preferred method is an opaque waxy solid at room temperature, and the semi-crystalline polyester polyol has a certain regularity; where room temperature refers to 25°C.
  • the semi-crystalline polyester polyol used can be prepared by conventional polyester polyol preparation processes in this field, or commercial products that meet the above requirements can be directly used.
  • the semi-crystalline polyester polyol can be prepared by a melt polycondensation method well known to those skilled in the art, and can be carried out directly with reference to existing processes.
  • the preparation method of polyester polyol in patent CN110724249B can be referred to.
  • Preparation specifically, refer to the examples of this document; for example, the formulation amount of aliphatic dicarboxylic acid, component II (aromatic dicarboxylic acid and/or aromatic dicarboxylic acid) required to prepare semi-crystalline polyester polyol dicarboxylic anhydride) and glycol into the reaction kettle, heat the system to 130-180°C to react until the system becomes transparent, then heat the system to 200-230°C to react (for example, react for about 2-3 hours) until the amount of water is produced Close to the theoretical water output, then add the catalyst and raise the temperature to 235-250°C and turn on the vacuum device (for example, under a vacuum pressure of -0.095Mpa) to continue the reaction until the acid value of the system reaches below 0.3 mgKOH/g, and then lower the temperature (for example, under a vacuum pressure of -0.095Mpa) Cool to about 120°C), discharge and package to obtain the target semi-crystalline polyester polyol; during the reaction process, a catalyst can also be added to the
  • the amount of catalyst can be 50-300ppm of the total mass of the reactants; during the preparation process, dibasic acids and diols The dosage ratio between them can be determined according to the molecular weight of the target polyester polyol. Generally, the dosage of glycol can be 105-120% of the theoretical input amount.
  • component a optionally includes polyols other than semi-crystalline polyester polyols.
  • the number average molecular weight of the polyol i.e., semi-crystalline polyester polyol and optional other polyols
  • the polyol has a functionality of 2 to 4 at 10,000 g/mol, and more preferably the polyol has a number average molecular weight of 1,000 to 5,000 g/mol and a polyol with a functionality of 2 to 3.
  • component a other polyols involved in component a can be selected from one or more of polyester polyols, polycaprolactone polyols, polycarbonate polyols and polyether polyols, and other polyols are included in component a.
  • the proportion in is 0-60wt%.
  • polyols conventionally allowed to be added in polyurethane-polyurea aqueous dispersions can be used.
  • the polyester polyol among the other polyols can be obtained by reacting carboxylic acids and/or acid anhydrides with polyols through known preparation processes, for example, from aliphatic, alicyclic, aromatic dicarboxylic acids or Polycarboxylic acids or their corresponding anhydrides are obtained by dehydration and condensation with polyhydric alcohols.
  • carboxylic acids or anhydrides include but are not limited to succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid Dicarboxylic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride or mixtures thereof.
  • polyols examples include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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-dihydroxymethylcyclohexane alkanes, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or mixtures thereof; optionally, polyols with higher functionality, such as trihydroxyl Methylpropane.
  • Polyester polyols may also include fatty acid-containing polyesters having an average OH functionality of about 2 and may include transesterification products of castor oil with oils other than castor oil.
  • the other polyols in component a are dibasic acids containing one or more of isophthalic acid, terephthalic acid, and adipic acid, and dibasic acids containing neopentyl glycol, ethylene glycol, Polyester polyols with one or more diols selected from butylene glycol and hexylene glycol as structural components.
  • Polyester polyols among other polyols can also be homopolymers or copolymers of lactones, which can be obtained by ring-opening of lactones or mixtures of lactones with suitable di- and/or higher functional polyols .
  • Polycarbonates having hydroxyl groups prepared by using diols and carbonates are also suitable as further polyols mentioned in component a.
  • the diol used in the polycarbonate is preferably 1,4-butanediol and/or 1,6-hexanediol
  • the carbonate can be diaryl carbonate and/or dialkyl carbonate.
  • the base ester is, for example, diphenyl carbonate
  • the dialkyl carbonate is, for example, dimethyl carbonate.
  • Polyether polyols are also suitable as the other polyols mentioned in component a, and a preferred polyether polyol is polytetrahydrofuran polyol.
  • a preferred polyether polyol is polytetrahydrofuran polyol.
  • the other polyols are polytetrahydrofuran polyols to obtain better elasticity.
  • the polyurethane-polyurea aqueous dispersion is prepared by reacting raw materials containing the following components:
  • Component a includes at least one polyol with a functionality of 2 or more, and the proportion of semi-crystalline polyester polyol in component a is more than 40wt%;
  • Component b polyisocyanate
  • Component c hydrophilic compound.
  • the hydrophilic compound contains 2-3 groups that are reactive with NCO;
  • Optional component d alcohol chain extender different from component a;
  • Component f polyamine with a number average molecular weight not exceeding 500 g/mol.
  • the raw material further includes component e, which is a compound that can ionize component c that does not contain ionic groups. .
  • component e does not need to be added.
  • the raw material when the raw material includes component e, the following amounts of each component are used to prepare the polyurethane-polyurea dispersion based on the total weight of components a, b, c, d, e, and f.
  • the proportions are: component a, 56 ⁇ 85wt%; component b, 10 ⁇ 30wt%; component c, 0.8 ⁇ 4wt%; component d, 0 ⁇ 3wt%; component f, 0.5 ⁇ 4wt%; component e, 0.6 ⁇ 4wt%;
  • the dosage ratio of the following components used to prepare the polyurethane-polyurea dispersion is: component a , 56 ⁇ 85wt%; component b, 10 ⁇ 30wt%; component c, 0.8 ⁇ 4wt%; component d, 0 ⁇ 3wt%; component f, 0.5 ⁇ 4wt%.
  • the specific selection of polyisocyanate is not particularly limited, and those polyisocyanates commonly used in this field can be used.
  • the polyisocyanate may be selected from one or more of aromatic, aliphatic and cycloaliphatic polyisocyanates, preferably the polyisocyanate has at least two isocyanate groups.
  • the molecular formula of the polyisocyanate is Y(NCO) 2 , where Y represents a divalent aliphatic hydrocarbon group containing 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6 to 15 carbon atoms, and a divalent aliphatic hydrocarbon group containing 6 to 15 carbon atoms.
  • the polyisocyanate may be tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodedecane diisocyanate, 1,4-cyclohexane diisocyanate, Isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2, 6-Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate,
  • Component b may also include small amounts of polyisocyanates of higher functionality known in polyurethane chemistry, or containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and/or biuret-based modified polyisocyanates.
  • component b is preferably one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate.
  • the group contained in the hydrophilic compound that is reactive with NCO is hydroxyl and/or amino.
  • the hydrophilic group of the hydrophilic compound includes one or more of an ionic group and a potential ionic group.
  • the ionic group is preferably a carboxylate ion and/or a sulfonate ion, and a potential ionic group.
  • the group is preferably carboxyl.
  • the hydrophilic compound as component c is selected from dimethylol propionic acid, dimethylol butyric acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethyl One or more of alkane sulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid and their salts, the salts including one of the corresponding alkali metal salts, alkaline earth metal salts or ammonium salts One or more, preferably component c is dimethylol propionic acid.
  • the alcohol chain extender different from component a is a small molecular alcohol compound with a relative molecular weight of less than 150.
  • the alcohol chain extender as component d is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2 ,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dihydroxycyclohexane, 1,4-dihydroxymethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane
  • component e is a volatile tertiary amine compound, preferably triethylamine.
  • component f is a polyamine with a relative molecular weight of 60 to 500, preferably ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2 - one or more of methylpentane-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine and diethylenetriamine; preferably ethylenediamine and one or both of isophorone diamine.
  • the polyurethane-polyurea aqueous dispersion of the present invention can be prepared by referring to the existing polyurethane-polyurea aqueous dispersion preparation process in the field, and there are no special requirements for this.
  • the polyurethane-polyurea aqueous dispersion is prepared by reacting the raw materials containing component a; further specifically, the raw materials further include component b, component c, optional component d and component f; wherein, the component b is a polyisocyanate; the component c is a hydrophilic compound, and the hydrophilic compound contains 2-3 groups reactive with NCO; the component d is different from The alcohol chain extender of component a; the component f is a polyamine with a number average molecular weight not exceeding 500 g/mol; when the component c does not contain ionic groups, the raw material also includes component e , the component e is a compound that can ionize component c.
  • the preparation method includes the step of reacting at 60 to 90°C to obtain an isocyanate-terminated prepolymer.
  • the specific preparation steps include: combining component a, component b, component c, and optional component d in the presence of a solvent (such as acetone) at 60 to React at 90°C to obtain an isocyanate-terminated prepolymer, dilute it with a solvent (such as acetone), add component e for neutralization, disperse (for example, add water under high-speed stirring at 800-1000r/min for dispersion), and add component f for expansion.
  • a solvent such as acetone
  • the solvent (acetone) is removed after the reaction is completed, and a polyurethane-polyurea aqueous dispersion is obtained.
  • component c contains ionic groups
  • the specific preparation steps include: reacting component a, component b, and optional component d in the presence of a solvent (such as acetone) at 60 to 90° C. to obtain a preparative preparation of terminal isocyanate. After diluting the polymer with a solvent (such as acetone), add component c and component f to continue the reaction, then add water for dispersion; remove the solvent (acetone) to obtain a polyurethane-polyurea aqueous dispersion.
  • a solvent such as acetone
  • the solid content of the polyurethane-polyurea aqueous dispersion prepared by the present invention is not less than 35wt%, for example, 35-40wt%, the pH value is preferably 6-10, and the average particle size is, for example, 80-300nm. .
  • the present invention also provides a soft elastic product, which is made based on the polyurethane-polyurea aqueous dispersion described above.
  • the soft elastic product can be a variety of products with soft and elastic properties, such as but not Limited to gloves and/or condoms.
  • the present invention also provides a method for preparing soft elastic products, including the step of applying a liquid containing the polyurethane-polyurea aqueous dispersion of the present invention described above to a mold required for preparing soft elastic products; preferably , soft elastic products include gloves and/or condoms.
  • a liquid containing the polyurethane-polyurea aqueous dispersion of the present invention described above to a mold required for preparing soft elastic products; preferably , soft elastic products include gloves and/or condoms.
  • the specific steps of the preparation method of soft elastic products can be carried out with reference to the existing corresponding conventional processes, but the key point is that the polyurethane-polyurea aqueous dispersion provided by the present invention is used in the material liquid.
  • those skilled in the art can refer to the conventional processes in the art for preparing corresponding soft elastic products.
  • an exemplary preparation step for reference includes: formulating the polyurethane-polyurea aqueous dispersion provided by the present invention and other auxiliary materials into a feed liquid, other auxiliary materials such as water required to dilute the dispersion, and according to Color paste, titanium dioxide, etc.
  • immerse the glove mold in the coagulation liquid such as an aqueous solution containing 10wt% calcium chloride, 5wt% release agent (such as calcium stearate)
  • the coagulation liquid such as an aqueous solution containing 10wt% calcium chloride, 5wt% release agent (such as calcium stearate)
  • the glove coating agent as needed, take it out to dry, and demold it to obtain the finished glove.
  • polyols 1-3 and 7-8 are prepared according to the following synthesis method:
  • the molar ratio is 1.17:1
  • the catalyst is tetraisopropyl titanate
  • the dosage is 150ppm
  • the molar ratio of 1,4-butanediol and neopentyl glycol is 7:3.
  • DMPA Dimethylolpropionic acid
  • aqueous solution and 13g of isophorone diamine were reacted for about 15 minutes, and 800g of deionized water was added under stirring to disperse. After separation of the acetone by distillation, a solvent-free dispersion was obtained with a solids content of 40 wt%, an average particle size of 218 nm, and a pH of 7.5.
  • Polyol 2 in Example 5 was changed to polycarbonate, and the rest remained unchanged. Has a solids content of 40 wt%, an average particle size of 161 nm, and a pH of 7.90.
  • Polyol 1 in Example 2 was replaced with polycaprolactone diol, and the rest remained unchanged, with a solid content of 40 wt%, an average particle size of 140 nm, and a pH value of 8.4.
  • Polyol 1 in Example 2 was replaced with polytetrahydrofuran diol, and the rest remained unchanged, with a solid content of 40 wt%, an average particle size of 130 nm, and a pH value of 8.1.
  • Polyol 1 in Example 2 was replaced with polyol 7, and the rest remained unchanged. It had a solid content of 40 wt%, an average particle size of 144 nm, and a pH value of 8.2.
  • Polyol 1 in Example 2 was replaced with polyol 8, and the rest remained unchanged. It had a solid content of 40 wt%, an average particle size of 151 nm, and a pH value of 8.4.
  • Preparation of matrix resin (liquid) for gloves Dilute the dispersion prepared above with deionized water to a solid content of 15wt%, then add 0.5wt% color paste and 5wt% titanium dioxide at low speed (rotation speed is 200-300r/ min) stir for half an hour and set aside.
  • Preparation of the coagulation liquid Use deionized water to prepare an aqueous solution containing 10wt% CaCl 2 and 5wt% release agent (calcium stearate), stir continuously for 1 hour, and set aside.
  • Tensile strength and elongation test Cut the palm part of the glove into a dumbbell shape with a width of 6mm and a length of 115mm, test the tensile strength on a tensile machine, and obtain the elongation at the same time.
  • Water resistance test Fill the glove with 800g of water and turn it upside down to observe the deformation and appearance of the glove.
  • Oxygen resistance Fill the gloves with 30wt% hydrogen peroxide and leave it for 10 minutes to observe whether there is any leakage or seepage.
  • Resistant to polar solvents Pour a 75wt% alcohol solution into the gloves and leave it for 10 minutes to observe whether there is any leakage or seepage.

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  • Polymers & Plastics (AREA)
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  • Biomedical Technology (AREA)
  • Reproductive Health (AREA)
  • Heart & Thoracic Surgery (AREA)
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Abstract

本发明提供一种聚氨酯-聚脲水分散体及其制备方法和应用，所述聚氨酯-聚脲水分散体，其中包含衍生自组分a的单元，所述组分a包含至少一种官能度为2以上的多元醇，且组分a中至少包含40wt％以上的通过使二元醇与组分I反应而获得的半结晶态聚酯多元醇，其中所述组分I包括摩尔比为2.1-10:1的脂族二羧酸和组分II，所述组分II为芳族二羧酸和/或芳族二羧酸酐。基于本发明提供的聚氨酯-聚脲水分散体制备软弹制品，能兼顾良好的弹性、强度、耐水性和穿戴手感等综合性能。

Description

一种聚氨酯-聚脲水分散体及其制备方法和应用 技术领域
本发明涉及软弹制品(例如手套、安全套等)制备技术领域，特别涉及一种利于获得高性能软弹制品的聚氨酯-聚脲水分散体及其制备方法和应用。
背景技术
软弹制品例如一次性手套产品广泛应用于医用手套、检查手套、家用及工业等领域，目前市场上用于制备软弹制品(例如一次性手套、安全套等)的材料主要有天然乳胶、氯丁橡胶、丁腈橡胶、PVC等。天然乳胶具有中因为含有蛋白质，易造成部分人群出现过敏现象；而氯丁橡胶及丁腈橡胶等产品存在气味大，生产污染大的问题。相比较而言，聚氨酯分散体在力学强度、延伸性、透气性及手套制备过程中的环保性均优于以上几种材料的树脂。目前对于利用聚氨酯生产软弹制品已有一些研究报道。
专利文献CN104725590B公开了一种低模量的聚氨酯分散体用于一次性手套，该聚氨酯分散体采用聚四氢呋喃二醇、聚丙二醇和甲苯二异氰酸酯为原料，制备的手套具有与橡胶制品相似的性能。然而，使用聚丙二醇制备的产品存在耐水差的问题，在使用过程中如果沾水，强度会下降十分明显，不具备实际的使用价值。
专利文献CN108864394A公开了一种使用磺酸盐聚酯和聚丙二醇复配制备的用于医用领域的手套，声称具有优异的耐醇性能，实际上使用聚丙二醇的体系均无法实现良好的耐醇性能，且手套整体强度均偏低，应用性不强。
专利文献CN106188477B中则用聚醚与一种高分子量回弹剂合成出一款具有高弹性的聚氨酯水分散体，将其用于手套的制备，但是该聚氨酯分散体中的高交联结构对弹性是不利的，该文献仅仅评价了树脂的力学性能，对手套的制备及性能没有相关阐述。
发明内容
本发明提供一种能适用于制备软弹制品的聚氨酯-聚脲水分散体，基于该聚氨酯-聚脲水分散体制备软弹制品，能兼顾良好的弹性、强度、耐水性和穿戴手感等综合性能。
本发明为达到其目的，提供如下技术方案：
本发明提供一种聚氨酯-聚脲水分散体，其中包含衍生自组分a的单元，所述组分a包含至少一种官能度为2以上的多元醇，且组分a中至少包含40wt％以上的通过使二元醇与组分I反应而获得的半结晶态聚酯多元醇，其中所述组分I包括摩尔比为2.1-10:1的脂族二羧酸和组分II，所述组分II为芳族二羧酸和/或芳族二羧酸酐。
一些实施方式中，制备所述半结晶态聚酯多元醇所用的所述二元醇至少包括1,4-丁二醇、1,6-己二醇中的一种或多种，还任选的包括相对分子量低于150的其他二元醇，所述其他二元醇包括乙二醇、1,3-丁二醇、新戊二醇、1,5-戊二醇、丙二醇、一缩二乙二醇、一缩二丙二醇中的一种或多种；制备所述半结晶态聚酯多元醇所用的所述二元醇中，所述其他二元醇的占比低于50wt％；
和/或，制备所述半结晶态聚酯多元醇所用的所述组分II选自苯二甲酸、邻苯二甲酸酐中的一种或多种；优选的，所述苯二甲酸选自间苯二甲酸和/或邻苯二甲酸；更优选的，所述组分II为间苯二甲酸；
和/或，制备所述半结晶态聚酯多元醇所用的所述脂族二羧酸为己二酸。
一些实施方式中，所述半结晶态聚酯多元醇在室温下为不透明的蜡状固体。
一些实施方式中，所述聚氨酯-聚脲水分散体为通过包含如下组分的原料经反应制备得到：
组分a：包括至少一种官能度为2以上的多元醇，且所述半结晶态聚酯多元醇在所述组分a中的占比为40wt％以上，优选所述半结晶态聚酯多元醇在 所述组分a中的占比为70-100wt％；
组分b：多异氰酸酯；
组分c：亲水化合物，所述亲水化合物含有2-3个与NCO成反应活性的基团，所述亲水化合物的亲水基团包括离子基团和潜离子基团的一种或多种；
任选的组分d：不同于组分a的醇类扩链剂；
组分f：数均分子量不超过500克/摩尔的多元胺。
一些实施方式中，当所述组分c的亲水基团不包括所述离子基团时，所述原料还包括组分e，所述组分e为能使所述组分c离子化的化合物；
优选的，当所述原料包括组分e时，基于组分a、b、c、d、e和f的总重量，制备所述聚氨酯-聚脲水分散体所用的如下各组分的用量比例为：组分a，56～85wt％；组分b，10～30wt％；组分c，0.8～4wt％；组分d，0～3wt％；组分f，0.5～4wt％；组分e，0.6～4wt％；
优选的，当所述原料不包括组分e时，基于组分a、b、c、d和f的总重量，制备所述聚氨酯-聚脲分散体所用的如下各组分的用量比例为：组分a，56～85wt％；组分b，10～30wt％；组分c，0.8～4wt％；组分d，0～3wt％；组分f，0.5～4wt％。
一些实施方式中，所述组分a中，所述多元醇的数均分子量为500～15000克/摩尔，优选所述多元醇为数均分子量为800～10000克/摩尔的官能度为2～4的多元醇，更优选所述多元醇为数均分子量为1000～5000克/摩尔的官能度为2～3的多元醇；
和/或，所述组分b中，所述多异氰酸酯选自芳香族、脂肪族和脂环族多异氰酸酯中的一种或多种，优选所述多异氰酸酯具有至少两个异氰酸酯基团；
和/或，所述组分c中，所述亲水化合物中含有的所述与NCO成反应活性的基团为羟基和/或氨基；
和/或，所述组分c中，所述离子基团优选羧酸根离子和/或磺酸根离子，所述潜离子基团优选羧基；
和/或，所述组分d中，所述不同于组分a的醇类扩链剂为相对分子量小于150的小分子醇类化合物；
和/或，所述组分e为三乙胺；
和/或，所述组分f为相对分子量为60～500的多元胺，优选乙二胺、1,2-二氨基丙烷、1,4-二氨基丁烷、1,6-己二胺、2-甲基戊烷-1,5-二胺、异佛尔酮二胺、4,4-二氨基二环己基甲烷、哌嗪和二乙烯三胺中的一种或多种。
一些实施方式中，作为所述组分c的所述亲水化合物选自二羟甲基丙酸、二羟甲基丁酸、二羟基琥珀酸、N-(2-氨乙基)-2-氨基乙烷磺酸、N-(3-氨基丙基)-2-氨基乙磺酸及其盐中的一种或多种，所述盐包括相应的碱金属盐、碱土金属盐或铵盐中的一种或多种，优选所述组分c为二羟甲基丙酸；
和/或，作为所述组分d的醇类扩链剂选自乙二醇、1,2-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、新戊二醇、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、新戊二醇、1,4-环己二醇、1,4-环己烷二甲醇和2-乙基-1.3-己二醇的一种或多种；优选1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、新戊二醇和1,4-环己烷二甲醇、1,6-己二醇中的一种或多种。
一些实施方式中，所述组分a中任选的包括不同于所述半结晶态聚酯多元醇的其他多元醇，所述其他多元醇选自聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇和聚醚多元醇中的一种或多种，所述其他多元醇在所述组分a中的占比为0-60wt％。
本发明还提供上文所述的聚氨酯-聚脲水分散体的制备方法，将包含组分a的原料经反应制备得到所述聚氨酯-聚脲水分散体；
优选的，所述原料中还包括组分b、组分c、任选的组分d和组分f；
其中，所述组分b为多异氰酸酯；所述组分c为亲水化合物，所述亲水化合物含有2-3个与NCO成反应活性的基团；所述组分d为不同于组分a的醇类扩链剂；所述组分f为数均分子量不超过500克/摩尔的多元胺；当所述 组分c中不含有离子基团时，所述原料还包括组分e，所述组分e为能使组分c离子化的化合物；
优选的，所述制备方法包括在60～90℃下反应得到端异氰酸酯的预聚体的步骤。
本发明还提供一种软弹制品，所述软弹制品基于上文所述的聚氨酯-聚脲水分散体制得，优选的，所述软弹制品包括手套和/或安全套。
本发明还提供一种制备软弹制品的方法，包括将含有聚氨酯-聚脲水分散体的料液施加于制备软弹制品所需的模具中的步骤；优选的，所述软弹制品包括手套和/或安全套；所述聚氨酯-聚脲水分散体采用上文所述的聚氨酯-聚脲水分散体。
本发明提供的技术方案具有如下有益效果：
本发明提供的聚氨酯-聚脲分散体，基于至少包含40wt％以上的含有苯环结构的半结晶态聚酯多元醇的多元醇组分(即组分a)得到，该半结晶态聚酯多元醇采用特定摩尔比的脂族二羧酸和组分II(芳族二羧酸和/或芳族二酸酐)与二元醇反应获得，采用这样的聚氨酯-聚脲分散体制备软弹制品，例如手套、安全套等，具有优异的综合性能，能兼顾良好的抗张强度、延伸率、回弹性、穿戴手感和耐水性，具有优异的耐氧化物及耐极性溶剂的能力。基于本发明的聚氨酯-聚脲分散体能制备适用于医疗、家用、工业使用的软弹制品，例如手套；也特别适用于安全套的生产。
具体实施方式
为了便于理解本发明，下面将结合实施例对本发明作进一步的说明。应当理解，下述实施例仅是为了更好的理解本发明，并不意味着本发明仅局限于以下实施例。
除非另有定义，本文所使用的所有的技术和科学术语与本发明所属技术领域的技术人员通常理解的含义相同。本文可能使用的术语“和/或”包括一个 或多个相关的所列项目的任意的和所有的组合。
实施例中未注明具体实验步骤或条件之处，可按照本技术领域中相应的常规实验步骤的操作或条件进行即可。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
本发明一方面提供一种聚氨酯-聚脲水分散体，其中包含衍生自组分a的单元，组分a包含至少一种官能度为2以上的多元醇，且组分a中至少包含40wt％以上的通过使二元醇与组分I反应而获得的半结晶态聚酯多元醇，其中组分I包括摩尔比为2.1-10:1(例如摩尔比2.1:1、2.5:1、3:1、4.5:1、5:1、6:1、7:1、8:1、9:1、10:1等)的脂族二羧酸和组分II，组分II为芳族二羧酸和/或芳族二酸酐。
本发明人发现，在制备聚氨酯-聚脲水分散体时，使用的多元醇(组分a)至少包含40wt％以上(例如40wt％、42wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、90wt％、100％等)的半结晶态聚酯多元醇，且该半结晶态聚酯多元醇为摩尔比2.1-10:1的脂族二羧酸和组分II(芳族二羧酸和/或芳族二羧酸酐)与二元醇通过酯化反应得到，基于本发明方案制备获得的聚氨酯-聚脲分散体，能够降低聚酯的结晶性，同时提高弹性并且获得良好的强度等特性；将该聚氨酯-聚脲水分散体用于软弹制品的制备，得到的聚氨酯-聚脲水分散体特别适用于软弹制品例如手套和/或安全套的制备；将该聚氨酯-聚脲水分散体用于软弹制品的制备，所得软弹制品具有显著改善的综合性能，能兼顾良好的抗张强度、延伸率、回弹性等，材质柔软且富有弹性，带来改善的穿戴手感。而若不使用半结晶态聚酯多元醇或半结晶态聚酯多元醇在多元醇(组分a)中的占比低于40wt％，或者半结晶态聚酯多元醇基于不满足摩尔比2.1-10:1的脂族二羧酸和组分II(芳族二羧酸和/或芳族二酸酐)获得，所得软弹制品性能存在明显劣化，无法兼顾良好的综合性能。
较佳实施方式中，组分a中，通过使二元醇与组分I反应而获得的半结晶态聚酯多元醇的占比达到70-100wt％，有利于获得性能更佳的软弹制品。
一些较佳实施方式中，制备半结晶态聚酯多元醇所用的二元醇至少包括1,4-丁二醇、1,6-己二醇中的一种或多种，还任选的包括相对分子量低于150的其他二元醇，其他二元醇包括乙二醇、1,3-丁二醇、新戊二醇、1,5-戊二醇、丙二醇、一缩二乙二醇、一缩二丙二醇等中的一种或多种；制备半结晶态聚酯多元醇所用的所述二元醇中，其他二元醇的占比低于50wt％，即用量少于1,4-丁二醇和/或1,6-己二醇。在制备半结晶态聚酯多元醇时，本领域技术人员可以根据目标分子量容易地确定反应体系中二元醇的用量。制备半结晶态聚酯多元醇时，所用的二元醇优选为1,4-丁二醇和/或1,6-己二醇，或者优选采用50wt％(基于二元醇总量)以上的1,4-丁二醇和/或1,6-己二醇，可以改善最终所得软弹制品的性能。
一些较佳实施方式中，制备半结晶态聚酯多元醇所用的组分II选自苯二甲酸、邻苯二甲酸酐中的一种或多种；优选的，苯二甲酸选自间苯二甲酸和/或邻苯二甲酸；更优选的，组分II为间苯二甲酸。优选采用间苯二甲酸，有利于获得性能更优异的软弹制品。
一些较佳实施方式中，制备半结晶态聚酯多元醇所用的脂族二羧酸为己二酸。
一些更佳实施方式中，制备半结晶态聚酯多元醇所用的二元醇至少包括1,4-丁二醇、1,6-己二醇中的一种或多种，所用的组分II选自间苯二甲酸、邻苯二甲酸、邻苯二甲酸酐中的一种或多种，优选间苯二甲酸，所用的脂族二羧酸为己二酸，且己二酸与组分II的摩尔比为2.1-10:1；基于优选的半结晶态聚酯多元醇制得的聚氨酯-聚脲水分散体，可以获得更佳的产品性能，所得产品具有显著改善的抗张强度、延伸率、回弹性、穿戴手感和耐水性。采用该优选方式得到的半结晶态聚酯多元醇在室温下为不透明的蜡状固体，该半结晶态聚酯多元醇具有一定的规整性；其中，室温是指25℃。
本发明中的聚氨酯-聚脲水分散体中，所用的半结晶态聚酯多元醇可以通过本领域常规的聚酯多元醇制备工艺制得，也可以直接采用满足上述要求的商业化产品。具体的，所述半结晶态聚酯多元醇可以采用本领域技术人员熟 知的熔融缩聚法制备，可以直接参照现有工艺进行，示例的，例如可以参考专利CN110724249B中的聚酯多元醇的制备方法制备，具体如参见该文献的实施例；示例的，例如，将制备半结晶态聚酯多元醇所需配方量的脂肪族二羧酸、组分II(芳族二羧酸和/或芳族二羧酸酐)、二元醇加入反应釜中，将体系升温至130-180℃反应至体系呈透明状后，将体系升温到200-230℃进行反应(例如反应约2-3h)直至出水量接近理论出水量，然后加入催化剂并升温到235-250℃并开启真空装置，(例如在-0.095Mpa的真空压力下)继续反应至体系的酸值达到到0.3mgKOH/g以下，然后降温(例如降温到120℃左右)出料，包装即得到目标半结晶态聚酯多元醇；在反应过程中还可根据需要而在反应釜中加入催化剂，例如催化剂选自有机锡、有机铋、有机钛类(如钛酸四丁酯、钛酸四异丙酯等)等中的一种或多种，催化剂用量可以为反应物总质量的50-300ppm；在制备过程中，二元酸和二元醇之间的用量比例可以根据目标聚酯多元醇的分子量而确定，通常二元醇的用量可以为理论投料量的105-120％。
一些实施方式中，组分a中任选的包括不同于半结晶态聚酯多元醇的其他多元醇。一些实施方式中，组分a中，多元醇(即半结晶态聚酯多元醇和任选的其他多元醇)的数均分子量为500～15000克/摩尔，优选所多元醇为数均分子量为800～10000克/摩尔的官能度为2～4的多元醇，更优选多元醇为数均分子量为1000～5000克/摩尔的官能度为2～3的多元醇。
其中，组分a中涉及的其他多元醇可以选自聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇和聚醚多元醇中的一种或多种，其他多元醇在组分a中的占比为0-60wt％。对于上述其他多元醇的具体选择没有特别限制，可以采用聚氨酯-聚脲水分散体中常规允许添加的那些多元醇。
具体的，所述其他多元醇中的聚酯多元醇例如可以通过已知的制备工艺由羧酸和/或酸酐与多元醇反应得到，例如由脂肪族、脂环族、芳香族二羧酸或多元羧酸或其相应的酸酐等和多元醇经过脱水缩和得到，所述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。所述多元醇的例子包括但不限于乙二醇、1,2-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，可以加入具有更高官能度的多元醇，例如三羟甲基丙烷。聚酯多元醇还可包括含脂肪酸的聚酯，其具有约2的平均OH官能度，还可包括蓖麻油与除蓖麻油之外的其他油的酯交换反应产物。优选的，组分a中的其他多元醇为以含间苯二甲酸、对苯二甲酸、己二酸中的一种或多种的二元酸，和含新戊二醇、乙二醇、丁二醇、己二醇中的一种或多种的二元醇作为结构组分的聚酯多元醇。
作为其他多元醇中的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-和/或更高官能的多元醇开环获得。
通过使用二醇和碳酸酯制备的具有羟基的聚碳酸酯也适合作为组分a中所述的其他多元醇。其中，聚碳酸酯中所用的二醇优选为1,4-丁二醇和/或1,6-己二醇，碳酸酯可以是碳酸二芳基酯和/或碳酸二烷基酯，碳酸二芳基酯例如碳酸二苯酯，碳酸二烷基酯例如碳酸二甲基酯。
聚醚多元醇也适合作为组分a中所述的其他多元醇，较佳的聚醚多元醇为聚四氢呋喃多元醇。当在组分a中添加其他多元醇时，优选其他多元醇为聚四氢呋喃多元醇，可以获得较佳的弹性。
一些实施方式中，聚氨酯-聚脲水分散体为通过包含如下组分的原料经反应制备得到：
组分a：包括至少一种官能度为2以上的多元醇，且半结晶态聚酯多元醇在所述组分a中的占比为40wt％以上；
组分b：多异氰酸酯；
组分c：亲水化合物，亲水化合物含有2-3个与NCO成反应活性的基团；
任选的组分d：不同于组分a的醇类扩链剂；
组分f：数均分子量不超过500克/摩尔的多元胺。
当所述组分c的亲水基团不包括所述离子基团时，所述原料还包括组分e，所述组分e为能使不含离子基团的组分c离子化的化合物。当组分c中含有离子基团时则可不添加组分e。
一些实施方式中，当所述原料包括组分e时，基于组分a、b、c、d、e和f的总重量，制备所述聚氨酯-聚脲分散体所用的如下各组分的用量比例为：组分a，56～85wt％；组分b，10～30wt％；组分c，0.8～4wt％；组分d，0～3wt％；组分f，0.5～4wt％；组分e，0.6～4wt％；
当所述原料不包括组分e时，基于组分a、b、c、d和f的总重量，制备所述聚氨酯-聚脲分散体所用的如下各组分的用量比例为：组分a，56～85wt％；组分b，10～30wt％；组分c，0.8～4wt％；组分d，0～3wt％；组分f，0.5～4wt％。
所述组分b中，多异氰酸酯的具体选择没有特别限制，可以采用本领域常规使用那些多异氰酸酯。一些实施方式中，多异氰酸酯可以选自芳香族、脂肪族和脂环族多异氰酸酯中的一种或多种，优选多异氰酸酯具有至少两个异氰酸酯基团。优选的，多异氰酸酯的分子式为Y(NCO) 2，其中Y代表含4～12个碳原子的二价脂肪族烃基、含6～15个碳原子的二价脂环族烃基、含6～15个碳原子的二价芳香族烃基或含7～15个碳原子的二价芳脂族烃基。一些实施方式中，多异氰酸酯可以是四亚甲基二异氰酸酯、甲基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、对苯二甲基二异氰酸酯、对异丙叉基二 异氰酸酯中的一种或多种。组分b中还可以包括少量聚氨酯化学中已知的更高官能度的多异氰酸酯，或含有例如碳二亚胺基、脲基甲酸酯基、异氰脲酸酯基、氨基甲酸酯基和/或缩二脲基的改性多异氰酸酯。较佳的，组分b优选六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯中的一种或多种。
一些实施方式中，所述组分c中，亲水化合物中含有的与NCO成反应活性的基团为羟基和/或氨基。一些实施方式中，组分c中，亲水化合物的亲水基团包括离子基团和潜离子基团的一种或多种，离子基团优选羧酸根离子和/或磺酸根离子，潜离子基团优选羧基。一些实施方式中，作为组分c的所述亲水化合物选自二羟甲基丙酸、二羟甲基丁酸、二羟基琥珀酸、N-(2-氨乙基)-2-氨基乙烷磺酸、N-(3-氨基丙基)-2-氨基乙磺酸及其盐中的一种或多种，所述盐包括相应的碱金属盐、碱土金属盐或铵盐中的一种或多种，优选组分c为二羟甲基丙酸。
一些实施方式中，组分d中，不同于组分a的醇类扩链剂为相对分子量小于150的小分子醇类化合物。一些实施方式中，作为组分d的醇类扩链剂选自乙二醇、1,2-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、新戊二醇、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、新戊二醇、1,4-环己二醇、1,4-环己烷二甲醇和2-乙基-1.3-己二醇的一种或多种；优选1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、新戊二醇和1,4-环己烷二甲醇、1,6-己二醇中的一种或多种。
一些实施方式中，组分e为易挥发的叔胺化合物，优选三乙胺。
一些实施方式中，组分f为相对分子量为60～500的多元胺，优选乙二胺、1,2-二氨基丙烷、1,4-二氨基丁烷、1,6-己二胺、2-甲基戊烷-1,5-二胺、异佛尔酮二胺、4,4-二氨基二环己基甲烷、哌嗪和二乙烯三胺中的一种或多种；优选乙二胺和异佛尔酮二胺中的一种或两种。
本发明中，除非特别说明，涉及到的“多种”、“多元”中“多”的含 义均指二以上。
本发明的聚氨酯-聚脲水分散体可参照本领域现有的聚氨酯-聚脲水分散体制备工艺进行，对此没有特别要求。具体的，将包含组分a的原料经反应制备得到所述聚氨酯-聚脲水分散体；进一步具体的，其中的原料还包括组分b、组分c、任选的组分d和组分f；其中，所述组分b为多异氰酸酯；所述组分c为亲水化合物，所述亲水化合物含有2-3个与NCO成反应活性的基团；所述组分d为不同于组分a的醇类扩链剂；所述组分f为数均分子量不超过500克/摩尔的多元胺；当所述组分c中不含有离子基团时，所述原料还包括组分e，所述组分e为能使组分c离子化的化合物。优选的，所述制备方法包括在60～90℃下反应得到端异氰酸酯的预聚体的步骤。供参考的，组分c不含离子基团时，具体的制备步骤包括：将组分a、组分b、组分c、任选的组分d在溶剂(例如丙酮)存在下于60～90℃反应得到端异氰酸酯的预聚体，用溶剂(例如丙酮)稀释后加入组分e进行中和，分散(例如800-1000r/min高速搅拌下加入水进行分散)并加入组分f进行扩链反应，反应完毕脱除溶剂(丙酮)，得到聚氨酯-聚脲水分散体。当组分c含有离子基团时，具体的制备步骤包括：将组分a、组分b、任选的组分d在溶剂(例如丙酮)存在下于60～90℃反应得到端异氰酸酯的预聚体，用溶剂(例如丙酮)稀释后，加入组分c、组分f继续反应，然后加入水进行分散；脱除溶剂(丙酮)，得到聚氨酯-聚脲水分散体。
上述制备方法中关于聚氨酯-聚脲水分散体的制备所涉及的各组分或其他相关内容均可参照前文中关于聚氨酯-聚脲水分散体的描述，在此不再逐一赘述。
一些实施方式中，本发明制得的聚氨酯-聚脲水分散体的固体份含量不低于35wt％，例如为35-40wt％，pH值优选为6～10，平均粒径例如为80-300nm。
本发明还提供一种软弹制品，该软弹制品基于上文所述的聚氨酯-聚脲水分散体制得，优选的，软弹制品可以是各种具有柔软和弹性属性的制品，例如但不限于手套和/或安全套。
本发明还提供一种制备软弹制品的方法，包括将含有上文所述的本发明的聚氨酯-聚脲水分散体的料液施加于制备软弹制品所需的模具中的步骤；优选的，软弹制品包括手套和/或安全套。关于软弹制品制备方法的具体步骤可以参照现有的相应常规工艺进行，但关键在于料液中使用了本发明提供的聚氨酯-聚脲水分散体。对于软弹制品的制备方法未进行特别说明之处，本领域技术人员均可参照本领域制备相应软弹制品的常规工艺进行。以制备手套为例，一种供参考的示例性制备步骤包括：将本发明提供的聚氨酯-聚脲水分散体与其他辅料配制成料液，其他辅料例如稀释分散体所需的水，以及根据产品需要而添加的色浆、钛白粉等；将手套模具浸入凝固液(例如含有10wt％氯化钙、5wt％脱模剂(例如硬脂酸钙)的水溶液)中取出烘干后，浸入上述料液中，取出烘干后(可根据实际情况重复进行浸入料液和烘干的操作)，根据需要浸入手套涂饰剂中，取出晾干后，脱模，即可得到成品手套。
下面通过具体实施例对本发明进行示例性说明。
实施例或对比例中使用的部分原料说明如下：
其中以下多元醇1-3、7-8按照如下合成方法制备得到：
按配方量将对应所需的组分I、二元醇、催化剂加入反应釜中，将体系升温至140℃反应至体系中呈透明状后，将体系升温到210-220℃之间进行反应(约反应2-3h)直至出水量接近理论出水量，然后升温到235-240℃之间并开启真空装置，在-0.095Mpa的真空压力下将体系的酸值反应到0.3mgKOH/g以下，降温到120℃左右出料包装即得到聚酯多元醇。
多元醇1(半结晶态聚酯多元醇)：聚己二酸-间苯二甲酸-1,4-丁二醇酯(其中己二酸与间苯二甲酸的用量摩尔比为2.3:1)，官能度为2，Mn＝2000，在室温下为不透明的蜡状固体；制备该多元醇1时，1,4-丁二醇与组分I的摩尔比为1.21:1，催化剂为钛酸四丁酯，用量100ppm。
多元醇2(半结晶态聚酯多元醇)：聚己二酸-间苯二甲酸-1,6-己二醇酯(其中己二酸与间苯二甲酸的用量摩尔比为3.0:1)，官能度为2，Mn＝2000， 在室温下为不透明的蜡状固体；制备该多元醇2时，1,6-己二醇与组分I的摩尔比为1.27:1，催化剂为钛酸四丁酯，用量100ppm。
多元醇3(半结晶态聚酯多元醇)：聚己二酸-间苯二甲酸-1,4-丁二醇-新戊二醇酯(其中己二酸与间苯二甲酸的摩尔比为4.5:1)，官能度为2，Mn＝3000，在室温下为不透明的蜡状固体；制备该多元醇3时，1,4-丁二醇和新戊二醇的总量与组分I的摩尔比为1.17:1，催化剂为钛酸四异丙酯，用量150ppm，1,4-丁二醇与新戊二醇的摩尔比为7:3。
多元醇4：聚己二酸-1,4-丁二醇聚酯-新戊二醇酯，官能度为2，Mn＝3000，半结晶态，在室温下为不透明的蜡状固体；牌号为
Figure PCTCN2022107894-appb-000001
多元醇5：聚己二酸-新戊二醇酯，官能度为2，Mn＝2000，非晶态；牌号为
Figure PCTCN2022107894-appb-000002
多元醇6：聚己二酸-新戊二醇-1,6-己二醇酯，官能度为2，Mn＝1500，万华化学集团股份有限公司，半结晶态，在室温下为不透明的蜡状固体；牌号为
Figure PCTCN2022107894-appb-000003
多元醇7：聚己二酸-间苯二甲酸-1,4-丁二醇酯(其中己二酸与间苯二甲酸的摩尔比为1.7:1)，官能度为2，Mn＝2000，半结晶态，在室温下为不透明的蜡状固体；制备该多元醇7时，1,4-丁二醇与组分I的摩尔比为1.25:1，催化剂为钛酸四丁酯，用量100ppm。
多元醇8：聚己二酸-间苯二甲酸-1,4-丁二醇酯(其中己二酸与间苯二甲酸的摩尔比为0.8:1)，官能度为2，Mn＝2000，半结晶态，在室温下为不透明的蜡状固体；制备该多元醇8时，1,4-丁二醇与组分I的摩尔比为1.235:1，催化剂为钛酸四丁酯，用量130ppm。
异佛尔酮二胺、六亚甲基二异氰酸酯(HDI)、4,4’-二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)， 50％的N-(2-氨乙基)-2-氨基乙烷磺酸钠水溶液、新戊二醇，均来自万华化学集团股份有限公司；
聚碳酸酯：Mn＝2000，官能度为2，日本聚氨酯公司；
聚四氢呋喃二醇：Mn＝2000,官能度为2，日本三菱化学；
聚己内酯二醇：Mn＝2000，官能度为2，日本大赛璐公司；
二羟甲基丙酸(DMPA)：柏斯托公司；
1,4-丁二醇、乙二胺、三乙胺：国药化学试剂公司。
实施例1
将422.6g多元醇1、78g多元醇3、7.7gIPDI、78gHDI、7.16gDMPA、4.0g 1,4-丁二醇和110g丙酮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1.92wt％。降温到40-45℃加入500g丙酮稀释，然后加入4.8g三乙胺中和约5min，然后通过添加900g水将该混合物分散，搅拌中加入5g乙二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，148nm的平均粒径，pH值是8.3。
实施例2
将400多元醇1、48gIPDI、60gHDI、10gDMPA、8.0g1,4-丁二醇和120g丙酮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2.69wt％。降温到40-45℃加入500g丙酮稀释，然后加入7.0g三乙胺中和约5min，然后通过添加800g水将该混合物分散，搅拌中加入6.5g乙二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，140nm的平均粒径，pH值是8.3。
实施例3
将400g多元醇1、90g聚四氢呋喃二醇、60gTDI、30gHMDI、10gDMPA和120g丙酮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1.63wt％。降温到40-45℃加入500g丙酮稀释，然后加入6.8g 三乙胺中和约5min，然后通过添加895g水将该混合物分散，搅拌中加入11.8g异佛尔酮二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，170nm的平均粒径，pH值是7.80。
实施例4
将300g多元醇2、90g多元醇6、55gTDI、30gHMDI、12gDMPA和90g丙酮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2.3wt％。降温到40-45℃加入500g丙酮稀释，然后加入8.1g三乙胺中和约5min，然后通过添加895g水将该混合物分散，搅拌中加入11g异佛尔酮二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，170nm的平均粒径，pH值是8.0。
实施例5
将350g多元醇2、90g聚碳酸酯、55gHDI、30gHMDI、8gDMPA、3g新戊二醇和90g丙酮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1.75wt％。降温到40-45℃加入500g丙酮稀释，然后加入5.43g三乙胺中和约5min，然后通过添加825g水将该混合物分散，搅拌中加入11g异佛尔酮二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，170nm的平均粒径，pH值是7.90。
实施例6
将237.5g多元醇1、328g多元醇4、7.77gIPDI、76gHDI、8gDMPA、4.0g 1,4-丁二醇和110g丙酮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1.67wt％。降温到40-45℃加入500g丙酮稀释，然后加入5.4g三乙胺中和约5min，然后通过添加1000g水将该混合物分散，搅拌中加入4.6g乙二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，138nm的平均粒径，pH值是8.4。
实施例7
将240g多元醇2、135g多元醇6、60gTDI、29gHMDI、12gDMPA和90g丙酮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2.28wt％。降温到40-45℃加入500g丙酮稀释，然后加入8.1g三乙胺中和约5min，然后通过添加895g水将该混合物分散，搅拌中加入13g异佛尔酮二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，188nm的平均粒径，pH值是8.0。
实施例8
将220g多元醇2、220g聚碳酸酯、55gHDI、30gHMDI、8gDMPA、3g新戊二醇和90g丙酮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1.75wt％。降温到40-45℃加入500g丙酮稀释，然后加入5.43g三乙胺中和约5min，然后通过添加825g水将该混合物分散，搅拌中加入11g异佛尔酮二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，163nm的平均粒径，pH值是8.0。
实施例9
将450g多元醇1、52.1g HDI、30.2g IPDI、2.6g新戊二醇、67g丙酮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2.8％，降温加入740g丙酮稀释并降温到40～50℃，搅拌下加入5倍体积的水稀释的19g浓度为50wt％的N-(2-氨乙基)-2-氨基乙烷磺酸钠水溶液和13g异佛尔酮二胺，反应约15min，搅拌下加入800g去离子水分散。再通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，218nm的平均粒径，pH值是7.5。
实施例10
将350g多元醇1、250g聚四氢呋喃二醇、69g HDI、33g HMDI、87g丙酮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2.5wt％，降温加入740g丙酮稀释并降温到40～50℃，快速搅拌下加入5倍体积的水稀释的22g浓度为50wt％的N-(2-氨乙基)-2-氨基乙烷磺酸钠水溶液和10g异佛尔酮二胺，反应约15min，搅拌下加入900g去离子水分散。再通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，258nm的平均粒径，pH值是7.2。
对比例1
将实施例5中的多元醇2更改为聚碳酸酯，其余不变。具有40wt％的固体含量，161nm的平均粒径，pH值是7.90。
对比例2
将150g多元醇1、580g多元醇4、48gIPDI、60gHDI、10gDMPA、6.0g1,4-丁二醇和120g丙酮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1.39wt％。降温到40-45℃加入500g丙酮稀释，然后加入6.7g三乙胺中和约5min，然后通过添加1290g水将该混合物分散，搅拌中加入4.8g乙二胺进行后扩链，反应15min。然后通过蒸馏分离出丙酮之后获得了无溶剂的分散体，其具有40wt％的固体含量，178nm的平均粒径，pH值是8.3。
对比例3
将实施例2中的多元醇1换成聚己内酯二醇，其余不变，具有40wt％的固体含量，140nm的平均粒径，pH值是8.4。
对比例4
将实施例2中的多元醇1换成聚四氢呋喃二醇，其余不变，具有40wt％的固体含量，130nm的平均粒径，pH值是8.1。
对比例5
将实施例2中的多元醇1换成多元醇7，其余不变，具有40wt％的固体含量，144nm的平均粒径，pH值是8.2。
对比例6
将实施例2中的多元醇1换成多元醇8，其余不变，具有40wt％的固体含量，151nm的平均粒径，pH值是8.4。
手套用基体树脂(料液)的制备：将上述制备的分散体加去离子水稀释到固含量为15wt％，然后加入色浆0.5wt％、钛白粉5wt％，低速(转速在200-300r/min之间)搅拌半小时备用。
凝固液的配置：用去离子水配置含有10wt％CaCl 2，5wt％脱模剂(硬脂酸钙)的水溶液，持续搅拌1h，备用。
手套的制备：
1)将清洗干净的手套模具放入100℃的烘箱烘干。
2)取出手套模具降温至60℃，浸入凝固液中8s左右取出，放入120-140℃烘箱中烘干，
3)取出烘干后的手套模具，降温至60℃，浸入配置的基体树脂中8s左右，
取出后放入130℃烘箱烘烤4min左右，取出后再次浸入配置的基体树脂中8s左右，然后放入烘箱中继续烘烤20min左右。
4)将烘烤结束的手套模具取出后，浸入手套涂饰剂中，取出后自然晾干，脱模，即得到成品手套。
性能测试：
抗张强度和延伸率测试：选取手套的手掌部分裁成宽度为6mm、长度为115mm的哑铃状，在拉力机上测试抗张强度，同时获得延伸率。
耐水性测试：将手套灌入800g水倒置，观察手套形变和外观。
耐氧化物：手套灌入30wt％浓度的双氧水放置10min，观察有没有漏或渗 出。
耐极性溶剂：手套灌入75wt％浓度的酒精溶液放置10min观察有没有漏或渗出。
回弹性和穿戴手感：以表1中所列的“市售乳胶手套”为参照，评价各个实施例和对比例所得手套在穿戴时的回弹性和穿戴手感表现。
性能检测结果参见表1。
表1
Figure PCTCN2022107894-appb-000004
Figure PCTCN2022107894-appb-000005
从表中可以看出，基于本发明的聚氨酯-聚脲水分散体制备得到的手套在抗张强度、延伸率、回弹性、穿戴手感、耐水性等方面的综合性能明显优于对比例和市售丁腈手套，在抗张强度和耐水性方面明显优于市售乳胶手套。
容易理解的，上述实施例仅仅是为清楚地说明所作的举例，并不意味着本发明仅局限于此。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (11)

  1. 一种聚氨酯-聚脲水分散体，其特征在于，其中包含衍生自组分a的单元，所述组分a包含至少一种官能度为2以上的多元醇，且组分a中至少包含40wt％以上的通过使二元醇与组分I反应而获得的半结晶态聚酯多元醇，其中所述组分I包括摩尔比为2.1-10:1的脂族二羧酸和组分II，所述组分II为芳族二羧酸和/或芳族二羧酸酐。
  2. 根据权利要求1所述的聚氨酯-聚脲水分散体，其特征在于，制备所述半结晶态聚酯多元醇所用的所述二元醇至少包括1,4-丁二醇、1,6-己二醇中的一种或多种，还任选的包括相对分子量低于150的其他二元醇，所述其他二元醇包括乙二醇、1,3-丁二醇、新戊二醇、1,5-戊二醇、丙二醇、一缩二乙二醇、一缩二丙二醇中的一种或多种；制备所述半结晶态聚酯多元醇所用的所述二元醇中，所述其他二元醇的占比低于50wt％；
    和/或，制备所述半结晶态聚酯多元醇所用的所述组分II选自苯二甲酸、邻苯二甲酸酐中的一种或多种；优选的，所述苯二甲酸选自间苯二甲酸和/或邻苯二甲酸；更优选的，所述组分II为间苯二甲酸；
    和/或，制备所述半结晶态聚酯多元醇所用的所述脂族二羧酸为己二酸。
  3. 根据权利要求1或2所述的聚氨酯-聚脲水分散体，其特征在于，所述半结晶态聚酯多元醇在室温下为不透明的蜡状固体。
  4. 根据权利要求1-4任一项所述的聚氨酯-聚脲水分散体，其特征在于，所述聚氨酯-聚脲水分散体为通过包含如下组分的原料经反应制备得到：
    组分a：包括至少一种官能度为2以上的多元醇，且所述半结晶态聚酯多元醇在所述组分a中的占比为40wt％以上，优选所述半结晶态聚酯多元醇在所述组分a中的占比为70-100wt％；
    组分b：多异氰酸酯；
    组分c：亲水化合物，所述亲水化合物含有2-3个与NCO成反应活性的基团，所述亲水化合物的亲水基团包括离子基团和潜离子基团的一种或多种；
    任选的组分d：不同于组分a的醇类扩链剂；
    组分f：数均分子量不超过500克/摩尔的多元胺。
  5. 根据权利要求4所述的聚氨酯-聚脲水分散体，其特征在于，
    当所述组分c的亲水基团不包括所述离子基团时，所述原料还包括组分e，所述组分e为能使所述组分c离子化的化合物；
    优选的，当所述原料包括组分e时，基于组分a、b、c、d、e和f的总重量，制备所述聚氨酯-聚脲水分散体所用的如下各组分的用量比例为：组分a，56～85wt％；组分b，10～30wt％；组分c，0.8～4wt％；组分d，0～3wt％；组分f，0.5～4wt％；组分e，0.6～4wt％；
    优选的，当所述原料不包括组分e时，基于组分a、b、c、d和f的总重量，制备所述聚氨酯-聚脲分散体所用的如下各组分的用量比例为：组分a，56～85wt％；组分b，10～30wt％；组分c，0.8～4wt％；组分d，0～3wt％；组分f，0.5～4wt％。
  6. 根据权利要求5所述的聚氨酯-聚脲水分散体，其特征在于，所述组分a中，所述多元醇的数均分子量为500～15000克/摩尔，优选所述多元醇为数均分子量为800～10000克/摩尔的官能度为2～4的多元醇，更优选所述多元醇为数均分子量为1000～5000克/摩尔的官能度为2～3的多元醇；
    和/或，所述组分b中，所述多异氰酸酯选自芳香族、脂肪族和脂环族多异氰酸酯中的一种或多种，优选所述多异氰酸酯具有至少两个异氰酸酯基团；
    和/或，所述组分c中，所述亲水化合物中含有的所述与NCO成反应活性的基团为羟基和/或氨基；
    和/或，所述组分c中，所述离子基团优选羧酸根离子和/或磺酸根离子，所述潜离子基团优选羧基；
    和/或，所述组分d中，所述不同于组分a的醇类扩链剂为相对分子量小于150的小分子醇类化合物；
    和/或，所述组分e为三乙胺；
    和/或，所述组分f为相对分子量为60～500的多元胺，优选乙二胺、1,2-二氨基丙烷、1,4-二氨基丁烷、1,6-己二胺、2-甲基戊烷-1,5-二胺、异佛尔酮二胺、4,4-二氨基二环己基甲烷、哌嗪和二乙烯三胺中的一种或多种。
  7. 根据权利要求6所述的聚氨酯-聚脲水分散体，其特征在于，作为所述组分c的所述亲水化合物选自二羟甲基丙酸、二羟甲基丁酸、二羟基琥珀酸、N-(2-氨乙基)-2-氨基乙烷磺酸、N-(3-氨基丙基)-2-氨基乙磺酸及其盐中的一种或多种，所述盐包括相应的碱金属盐、碱土金属盐或铵盐中的一种或多种，优选所述组分c为二羟甲基丙酸；
    和/或，作为所述组分d的醇类扩链剂选自乙二醇、1,2-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、新戊二醇、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、新戊二醇、1,4-环己二醇、1,4-环己烷二甲醇和2-乙基-1.3-己二醇的一种或多种；优选1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、新戊二醇和1,4-环己烷二甲醇、1,6-己二醇中的一种或多种。
  8. 根据权利要求6所述的聚氨酯-聚脲水分散体，其特征在于，所述组分a中任选的包括不同于所述半结晶态聚酯多元醇的其他多元醇，所述其他多元醇选自聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇和聚醚多元醇中的一种或多种，所述其他多元醇在所述组分a中的占比为0-60wt％。
  9. 权利要求1-8任一项所述的聚氨酯-聚脲水分散体的制备方法，其特征在于，将包含组分a的原料经反应制备得到所述聚氨酯-聚脲水分散体；
    优选的，所述原料中还包括组分b、组分c、任选的组分d和组分f；
    其中，所述组分b为多异氰酸酯；所述组分c为亲水化合物，所述亲水化合物含有2-3个与NCO成反应活性的基团；所述组分d为不同于组分a的醇类扩链剂；所述组分f为数均分子量不超过500克/摩尔的多元胺；当所述组分c中不含有离子基团时，所述原料还包括组分e，所述组分e为能使组分c离子化的化合物；
    优选的，所述制备方法包括在60～90℃下反应得到端异氰酸酯的预聚体 的步骤。
  10. 一种软弹制品，其特征在于，所述软弹制品基于权利要求1-8任一项所述的聚氨酯-聚脲水分散体制得，优选的，所述软弹制品包括手套和/或安全套。
  11. 一种制备软弹制品的方法，其特征在于，包括将含有聚氨酯-聚脲水分散体的料液施加于制备软弹制品所需的模具中的步骤；优选的，所述软弹制品包括手套和/或安全套；所述聚氨酯-聚脲水分散体采用权利要求1-8任一项所述的聚氨酯-聚脲水分散体。
PCT/CN2022/107894 2022-07-26 2022-07-26 一种聚氨酯-聚脲水分散体及其制备方法和应用 WO2024020779A1 (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101508785A (zh) * 2008-02-15 2009-08-19 拜尔材料科学股份公司 分散体粘合剂
WO2010012400A2 (de) * 2008-07-29 2010-02-04 Bayer Materialscience Ag Kationische polyurethan-dispersionsklebstoffe
CN111566137A (zh) * 2018-01-18 2020-08-21 科思创德国股份有限公司 粘合剂

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101508785A (zh) * 2008-02-15 2009-08-19 拜尔材料科学股份公司 分散体粘合剂
WO2010012400A2 (de) * 2008-07-29 2010-02-04 Bayer Materialscience Ag Kationische polyurethan-dispersionsklebstoffe
CN111566137A (zh) * 2018-01-18 2020-08-21 科思创德国股份有限公司 粘合剂

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