WO2022057855A1 - 一种水性聚氨酯乳液及其制备方法和用途 - Google Patents

一种水性聚氨酯乳液及其制备方法和用途 Download PDF

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WO2022057855A1
WO2022057855A1 PCT/CN2021/118732 CN2021118732W WO2022057855A1 WO 2022057855 A1 WO2022057855 A1 WO 2022057855A1 CN 2021118732 W CN2021118732 W CN 2021118732W WO 2022057855 A1 WO2022057855 A1 WO 2022057855A1
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polyisocyanate
prepolymer
polyurethane emulsion
macromolecular
water
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PCT/CN2021/118732
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English (en)
French (fr)
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戴家兵
冯林林
刘斌
陈亮
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兰州科时西西里健康科技有限公司
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Priority to MX2023003225A priority Critical patent/MX2023003225A/es
Priority to EP21868677.2A priority patent/EP4215558A1/en
Priority to US18/245,774 priority patent/US20230323006A1/en
Publication of WO2022057855A1 publication Critical patent/WO2022057855A1/zh

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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the invention relates to the technical application field of water-based polyurethane, in particular to a water-based polyurethane emulsion and a preparation method and application thereof.
  • Condoms are the most widely used and simple devices for contraception and prevention of sexually transmitted diseases in the world.
  • the existing products mainly include natural latex rubber condoms and water-based polyurethane condoms.
  • polyurethane condoms on the market generally have low strength and poor resilience.
  • traditional water-based polyurethane emulsions are prepared by a three-step method or a one-step method, condoms made by this method have poor resilience and low strength. Therefore, starting from the polyurethane synthesis step, a high-resilience and high-strength water-based polyurethane condom is developed to further improve the performance advantages of polyurethane condom products compared with traditional latex condoms, which is of great market significance.
  • the present invention provides an aqueous polyurethane emulsion and a preparation method and application thereof.
  • the polyurethane condom prepared by the polyurethane emulsion of the present invention has the properties of high resilience and high strength.
  • the present invention first provides a method for preparing an aqueous polyurethane emulsion.
  • the method includes at least the following steps: heating and dehydrating a macromolecular polyol and reacting it with a first polyisocyanate to obtain a first prepolymer;
  • the prepolymer is reacted with the second polyisocyanate to obtain a second prepolymer;
  • the second prepolymer is reacted with a hydrophilic chain extender and a small molecule chain extender to obtain a third prepolymer;
  • a post-chain extender is added to emulsify and desolvate to obtain the polyurethane emulsion; wherein, the molar amount of the first polyisocyanate is less than the molar amount of the second polyisocyanate, and the The ratio of the molar amount of the first polyisocyanate to the molar amount of the macromolecular polyol is less than 1
  • the macromolecular polyol includes macromolecular diol and macromolecular triol, and the mass ratio of the macromolecular diol and macromolecular triol is (10-15): (1.5 ⁇ 3.5).
  • the molecular weight of the macromolecular diol is 1000-3000, and the molecular weight of the macromolecular triol is 600-6000.
  • the molar ratio of the macromolecular polyol, the first polyisocyanate and the second polyisocyanate is (1-1.5):(0.2-0.3):(2-2.5).
  • the molar ratio of the hydrophilic chain extender, the small molecule chain extender and the post-chain extender is: (1-1.3): (0.01-0.05): (0.5-0.9 ).
  • the R value in the aqueous polyurethane emulsion is 1.4-1.6, and the R value is the ratio of the number of moles of cyanate groups to the number of moles of hydroxyl groups in the aqueous polyurethane emulsion.
  • Another aspect of the present invention also provides an aqueous polyurethane emulsion prepared by the above method.
  • the waterborne polyurethane emulsion is an anionic waterborne polyurethane emulsion, and the solid content of the waterborne polyurethane emulsion is 30%-35%.
  • Another aspect of the present invention provides an aqueous polyurethane condom prepared from the above-mentioned polyurethane emulsion.
  • the water-based polyurethane condom includes any one or more of the following features:
  • the thickness is 0.015 ⁇ 0.025mm
  • the burst pressure is greater than or equal to 3.0kPa
  • the tensile strength is greater than or equal to 45N/mm 2 .
  • the present invention discloses a four-step method for synthesizing a polyurethane emulsion for high-elasticity and high-strength polyurethane condoms and a preparation method thereof.
  • the first step is divided into two steps in the traditional polyurethane resin synthesis process, and the soft segment in the macromolecular segment has more skeletons by using the polyisocyanate in two steps successively, thereby preparing a high-strength polymer , High resilience water-based polyurethane resin.
  • Figure 1 shows a schematic flow diagram of the preparation method of the present invention.
  • the present invention first provides a method for preparing a polyurethane emulsion.
  • the method can be realized by dipping the water-based polyurethane resin multiple times, and the method at least includes the steps of S1-S4:
  • the macromolecular polyol may include macromolecular diol and macromolecular triol
  • the heating dehydration may be performed in a four-necked flask, and the heating dehydration may be performed under vacuum conditions , the heating temperature can be 115-120°C, the vacuum condition can be -0.1MPa, the dehydration can be to dehydrate the polyol to a moisture content of less than 0.02%, the temperature can be lowered after the heating and dehydration, and the dehydration can be performed.
  • the cooling can be to lower the temperature to below 40°C, and after the cooling, the first polyisocyanate can be put into the four-necked flask for reaction, the temperature of the reaction can be 80 ⁇ 90°C, and the time of the reaction can be 2 ⁇ 90°C. After 3 hours, the temperature may be lowered after the reaction, and the temperature after the reaction may be lowered to below 40°C.
  • the first polyisocyanate may be one or more of isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate.
  • the molar ratio of the macromolecular polyol, the first polyisocyanate and the second polyisocyanate may be (1-1.5):(0.2-0.3):(2-2.5).
  • the macromolecular dihydric alcohol can be any one or a combination of the two in polyoxypropylene dihydric alcohol (PPG) and polytetrahydrofuran dihydric alcohol (PTMEG), and the molecular weight of the polyoxypropylene dihydric alcohol can be 1000 ⁇ 3000, such as 1000, 2000, 3000.
  • the molecular weight of the polytetrahydrofuran diol may be 1000-3000, such as 1000, 2000, 3000.
  • the macromolecular triol can be a polyoxypropylene triol, and the molecular weight of the polyoxypropylene triol can be 600-6000.
  • the use of this triol can improve the resilience performance of the water-based polyurethane and improve the strength of the condom at the same time. .
  • the use of the polyol with the above molecular weight in the present invention can ensure that the prepared waterborne polyurethane emulsion has good performance. If the molecular weight is too large, the resilience and breaking strength of the waterborne polyurethane emulsion will decrease after the film is formed. And the modulus is large.
  • the composition of the second polyisocyanate may be the same as the composition of the first polyisocyanate, the molar amount of the first polyisocyanate may be less than the molar amount of the second polyisocyanate, the first polyisocyanate
  • the molar amount of the first polyisocyanate is less than that of the second polyisocyanate, and the ratio of the molar amount of the first polyisocyanate to the molar amount of the macromolecular polyol is less than 1:3.
  • the present invention combines the molar amount of the first polyisocyanate and the macromolecular polyol. Controlling the molar amount of ions within the above range can better control the viscosity of the later reaction and avoid the risk of generating prepolymer gel.
  • the polyisocyanate is added in steps, and the amount of the polyisocyanate added for the first time is less than the quality of the polyisocyanate added for the second time, so that after the isocyanate is added for the first time, a single polyisocyanate can be sandwiched in the middle of the soft segment , instead of being distributed at both ends of the soft segment.
  • the reaction time may be 2-3 hours, the reaction temperature may be 80-90°C, and the temperature may be lowered after the reaction, and the temperature may be lowered to below 40°C.
  • the hydrophilic chain extender can be one or both of dimethylol propionic acid or dimethylol butyric acid, and the small molecule polyol chain extender can be selected from ethylene glycol , one or more of propylene glycol, butanediol or hexanediol, trimethylolpropane, the reaction time can be 3 ⁇ 4 hours, the reaction temperature can be 80 ⁇ 90 °C, the reaction finishes After the cooling, the temperature can be lowered to below 50°C.
  • a catalyst and a solvent can be added to carry out a catalytic reaction.
  • the temperature of the catalytic reaction can be 70 to 75°C, and the time of the catalytic reaction can be It is 2 to 3 hours. After the catalytic reaction is completed, the temperature can be lowered, and the temperature can be lowered to 15 to 20° C.
  • the solvent can be acetone.
  • steps S1 to S3 the reactions can be carried out under stirring conditions.
  • the catalyst may be selected from organotin.
  • the salt-forming agent can be triethylamine, and the water can be deionized water.
  • the post-chain extender can be a small molecular diamine, and the small molecular diamine can be selected from one or more of ethylene diamine, hexamethylene diamine or isophorone diamine.
  • the emulsification can be carried out in an emulsifier, and the emulsification can be carried out under stirring conditions, and the stirring speed can be 1000-1400 r/min.
  • the fraction can be 50-55%
  • the post-chain extender can be added after the ice-water mixture
  • the stirring speed after the post-chain extender is added can be 300-400r/min, for example 350r/min
  • the post-extender The chain agent reaction time can be 3 to 4 hours.
  • the temperature of the precipitation may be 40 ⁇ 45° C.
  • the pressure of the precipitation may be -0.07 ⁇ -0.09 MPa.
  • the present invention also provides a polyurethane emulsion prepared by the above method, the polyurethane emulsion is an anionic water-based polyurethane emulsion, and the solid content of the polyurethane emulsion is 30-35%.
  • the surface tension of the prepared polyurethane product is small and the viscosity is moderate.
  • the solid content of the polyurethane emulsion of the present invention cannot be too low, otherwise defects such as shrinkage cavities of the coating film will occur, and the pH value of the polyurethane emulsion can be 6.5-7.5.
  • the R value (cyano-hydroxyl ratio) of the polyurethane emulsion of the present invention can be controlled at about 1.4 to 1.6, such as 1.5, because the water resistance of the condom is relatively good at about 1.5, and the moisture absorption performance in the later stage is relatively good. The decline is not obvious. Because of the thickness of the condom, tiny defects are magnified.
  • the R value is less than 1.5, the viscosity of the system is large, the emulsification effect is not good, and the R value is small, and the soft segment content is high, so that the physical cross-linking points between macromolecules after film formation are less, and the water absorption is enhanced. If the R value is too large, the residual NCO content of the system will increase, and the particle size of the cross-linked emulsion formed by reacting with water will increase to a certain extent, which will affect the continuity of the later film formation.
  • the present invention also provides the use of the above-mentioned polyurethane emulsion.
  • the polyurethane emulsion of the present invention is an anionic water-based polyurethane emulsion, the solid content can be 30%-35%, and the pH value can be 6.5-7.5, which can be used for production safety.
  • Eco-friendly condoms The thickness of the condom may be 0.015-0.025 mm, the burst pressure may be greater than or equal to 3.0 kPa, and the tensile strength of the condom may be greater than or equal to 45 N/mm 2 .
  • the PPG (1000) of 7.5kg and the PTMEG (2000) of 15kg and the oxypropylene triol with molecular weight of 3000 are dropped into the reactor, heated to 110°C with stirring, and vacuum dehydrated to the moisture content of the oxypropylene triol under -0.1MPa condition Below 0.03%, the temperature was lowered to 40°C, 0.64kg of IPDI and 0.45kg of MDI were put in, the temperature was raised to 85°C with stirring, the reaction was kept for 2 hours, cooled to 40°C, 4.99kg of IPDI and 1.2kg of MDI were put in, and the stirring was carried out.
  • the above emulsion was heated to 40°C, and the acetone in the emulsion was removed under the condition of -0.09MPa to obtain the water-based polyurethane emulsion sample 1, and the R value of the sample 1 was 1.46.
  • the PPG1000 of 7.5kg and the PTMEG2000 of 15kg and the propylene oxide triol of molecular weight 3000 are put into the reaction kettle, stirred and heated to 110 ° C, vacuum dehydrated under the condition of -0.1MPa to the moisture content of the propylene oxide triol below 0.03%, cooled to 40 °C, drop into the IPDI of 0.64kg and the MDI of 0.45kg, stir and be warming up to 85 °C, insulation reaction 2 hours, be cooled to under 40 °C, drop into the IPDI of 4.6kg and the MDI of 1.2kg and the HMDI of 0.45kg, stir and be warming up to 85 °C °C, insulation reaction was cooled to 40 °C in 2 hours, dropped into the DMPA of 0.66kg and the acetone of 6.5kg, stirred and was warming up to 80 °C of reaction 2 hours, cooled to 50 °C, dropped into the catalyzer of 0.04kg and 4.3kg acetone, stirred and was
  • the above-mentioned emulsion was heated to 40°C, and the acetone in the emulsion was removed under the condition of -0.09MPa to obtain the water-based polyurethane emulsion sample 2.
  • the R value of the sample 2 was 1.46.
  • the present invention is further illustrated by performing performance tests on the water-based polyurethane condoms prepared by Samples 1-3 and Comparative Samples 1-4.
  • the test results are shown in Table 1.
  • the polyurethane condom of the present invention is prepared by the following method: cleaning the mold with pure water and drying at 100°C for 5 minutes; when the temperature of the mold drops to 40°C, soaking in a water-based polyurethane emulsion, placing it in an oven at 110°C for 4 minutes, and repeating this step 3 times, crimp the mold completed in the above steps to a suitable position, cool the mold after crimping to 20°C, immerse it in an aqueous solution mixed with 1% silica, take out and dry, drying temperature 140°C, drying time 20min, dry After cooling to room temperature and demoulding, the water-based polyurethane condom is obtained.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.
  • the above-mentioned embodiments merely illustrate the principles and effects of the present invention, but are not intended to limit the present invention.
  • anyone skilled in the art can make modifications or changes to the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed in the present invention should still be covered by the claims of the present invention.

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Abstract

本发明提供了一种水性聚氨酯乳液及其制备方法和用途，所述方法包括以下步骤：将大分子二元醇加热脱水后与第一多异氰酸酯进行反应，得到第一预聚体；将所述第一预聚体与第二多异氰酸酯进行反应，得到第二预聚体；将所述第二预聚体与亲水扩链剂、小分子扩链剂进行反应，得到第三预聚体；将所述第三预聚体与成盐剂反应后加入后扩链剂进行乳化、脱溶得到所述聚氨酯乳液；其中，所述第一多异氰酸酯的摩尔量小于第二多异氰酸酯的摩尔量，第一多异氰酸酯的摩尔量与所述大分子多元醇的摩尔量比值小于1∶3，使用本发明所述聚氨酯乳液制备得到的避孕套具有高弹高强的特点。

Description

一种水性聚氨酯乳液及其制备方法和用途 技术领域
本发明涉及水性聚氨酯技术应用领域，具体的涉及一种水性聚氨酯乳液及其制备方法和用途。
背景技术
避孕套是目前世界上应用最为广泛和简单的避孕以及防止性病传播的器具，现有产品主要有天然胶乳橡胶避孕套和水性聚氨酯避孕套。目前市面上的聚氨酯避孕套普遍强度较低，回弹较差，由于传统的水性聚氨酯乳液制备均由三步法或者一步法制成，此方法制成的避孕套均有回弹差，强度低等缺点，因此从聚氨酯合成步骤入手开发出一款高回弹高强度的水性聚氨酯避孕套，进一步提升聚氨酯避孕套产品相对于传统乳胶避孕套的性能优势，有十分重要的市场意义。
发明内容
为解决上述现有技术中存在的问题，本发明提供一种水性聚氨酯乳液及其制备方法和用途。通过本发明所述聚氨酯乳液制备得到的聚氨酯避孕套具有高回弹高强度性能。
本发明首先提供了一种水性聚氨酯乳液的制备方法，所述方法至少包括以下步骤：将大分子多元醇加热脱水后与第一多异氰酸酯进行反应，得到第一预聚体；将所述第一预聚体与第二多异氰酸酯进行反应，得到第二预聚体；将所述第二预聚体与亲水扩链剂、小分子扩链剂进行反应，得到第三预聚体；将所述第三预聚体与成盐剂反应后加入后扩链剂进行乳化、脱溶得到所述聚氨酯乳液；其中，所述第一多异氰酸酯的摩尔量小于第二多异氰酸酯的摩尔量，所述第一多异氰酸酯的摩尔量与所述大分子多元醇的摩尔量比值小于1∶3。
在一实施例中，所述大分子多元醇包括有大分子二元醇以及大分子三元醇，所述大分子二元醇和大分子三元醇的质量比为(10～15)：(1.5～3.5)。
在一实施例中，所述大分子二元醇的分子量为1000～3000，所述大分子三元醇的分子量为600～6000。
在一实施例中，所述大分子多元醇、所述第一多异氰酸酯以及所述第二多异氰酸酯的摩尔量比为(1～1.5)：(0.2～0.3)：(2～2.5)。
在一实施例中，所述亲水扩链剂、所述小分子扩链剂以及所述后扩链剂的摩尔量比为：(1～1.3)：(0.01～0.05)：(0.5～0.9)。
在一实施例中，所述水性聚氨酯乳液中R值为1.4～1.6，所述R值为所述水性聚氨酯乳液中氰酸酯基摩尔数与羟基摩尔数的比值。
本发明另一方面还提供了一种如上所述方法制备得到的水性聚氨酯乳液。
在一实施例中，所述水性聚氨酯乳液为阴离子型水性聚氨酯乳液，所述水性聚氨酯乳液的固含量为30％-35％。
本发明再一方面提供了一种如上所述的聚氨酯乳液制备得到的水性聚氨酯避孕套。
在一实施例中，所述水性聚氨酯避孕套包括以下特征中的任意一项或多项：
厚度为0.015～0.025mm；
爆破压力大于等于3.0kPa；
拉伸强度大于等于45N/mm 2。
如上所述，本发明公开了一种四步法合成高弹高强聚氨酯避孕套用聚氨酯乳液及其制备方法。本申请通过在传统聚氨酯树脂合成过程将第一步拆分为两步，利用先后两步投入多异氰酸酯使得大分子链段中的软段具有跟多的骨架，进而来制备一种具有较高强度、高回弹性的水性聚氨酯树脂。
附图说明
图1显示为本发明制备方法的流程示意图。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。注意，本发明所述聚氨酯树脂以及所述避孕套的性能测试分别参照国家标准GB/T1040.1-2006、GB7544-2009进行。如没有特别说明，本文中所示的“％”和“份”分别是指“质量％”和“质量份”。
请参阅图1。本发明首先提供了一种聚氨酯乳液的制备方法，所述方法可以包括采用多次浸渍水性聚氨酯树脂的方式来实现，所述方法至少包括S1-S4的步骤：
S1：将大分子多元醇加热脱水后与第一多异氰酸酯进行反应，得到第一预聚体；
S2：将所述第一预聚体与第二多异氰酸酯进行反应，得到第二预聚体；
S3：将所述第二预聚体与亲水扩链剂、小分子扩链剂进行反应，得到第三预聚体；
S4：将所述第三预聚体与成盐剂反应后加入后扩链剂进行乳化、脱溶得到所述聚氨酯乳液；其中，所述第一多异氰酸酯的摩尔量小于第二多异氰酸酯的摩尔量，第一多异氰酸酯的摩尔量与所述大分子多元醇的摩尔量比值小于1∶3。
在步骤S1中，所述大分子多元醇可以包括有大分子二元醇以及大分子三元醇，所述加热脱水可以是在四口烧瓶中进行，所述加热脱水可以是在真空条件下进行，所述加热的温度可以是115～120℃，所述真空条件可以是-0.1MPa，所述脱水可以是将多元醇脱水至含水率小于0.02％，所述加热脱水后可以进行降温，所述降温可以是降温至40℃以下，所述降温后可以给所述四口烧瓶中投入第一多异氰酸酯进行反应，所述反应的温度可以是80～90℃，所述反应的时间可以是2～3小时，所述反应结束后还可以进行降温，所述反应结束后的降温也可以是降温至40℃以下。
在步骤S1中，所述第一多异氰酸酯可以是异佛尔酮二异氤酸酯、二苯基甲烷二异氤酸酯、六亚甲基二异氰酸酯中的一种或几种。所述大分子多元醇、所述第一多异氰酸酯以及所述第二多异氰酸酯的摩尔量比可以是(1～1.5)：(0.2～0.3)：(2～2.5)。。所述大分子二元醇可以是聚氧化丙烯二元醇(PPG)以及聚四氢呋喃二元醇(PTMEG)中的任意一种或两种的组合，所述聚氧化丙烯二元醇的分子量可以是1000～3000，例如1000、2000、3000。所述聚四氢呋喃二元醇的分子量可以是1000～3000，例如1000、2000、3000。
所述大分子三元醇可以为聚氧化丙烯三醇，所述聚氧化丙烯三醇的分子量可以为600～6000，使用这种三元醇可以提高水性聚氨酯回弹性能，同时提高避孕套的强度。本发明采用上述分子量的多元醇可以保证制备得到的水性聚氨酯乳液性能良好，若分子量过大，水性聚氨酯乳液成膜后回弹性和断裂强度下降，如果分子量过小，水性聚氨酯乳液成膜易开裂，且模量大。
在步骤S2中，所述第二多异氰酸酯的成份可以和所述第一多异氰酸酯的成份相同，所述第一多异氰酸酯的摩尔量可以小于第二多异氰酸酯的摩尔量，所述第一多异氰酸酯的摩尔量小于第二多异氰酸酯的摩尔量，第一多异氰酸酯的摩尔量与所述大分子多元醇的摩尔量比值小于1：3，本发明将第一多异氰酸酯的摩尔量和大分子多元醇的摩尔量控制在以上范围内，可以较好的控制后期反应的粘度，避免产生预聚体凝胶的风险。
本发明通过分步加入多异氰酸酯，且第一次加入的多异氰酸酯的量小于第二次加入的多异氰酸酯质量，可以使得第一次加入异氰酸酯后有单个的多异氰酸酯可以被夹在软段的中间，而不是分布在软段的两端，再次加入异氰酸酯后，可以减少聚氨酯结构中异氰酸酯‐亲水扩链剂‐小分子醇这种长的硬段被夹在软段中间，进而使得软硬段的相分离降低，回弹较好。
在步骤S2中，所述反应时间可以是2～3小时，所述反应温度可以是80～90℃，所述反应结束后还可以进行降温，所述降温可以是降至40℃以下。在步骤S3中，所述亲水扩链剂可以为二羟甲基丙酸或二羟甲基丁酸中的一种或两种，所述小分子多元醇扩链剂可以选自乙二醇、丙二醇、丁二醇或己二醇、三羟甲基丙烷中的一种或几种，所述反应时间可以是3～4小时，所述反应温度可以是80～90℃，所述反应结束后可以进行降温，所述降温可以是降至50℃以下，所述降温后还可以加入催化剂和溶剂进行催化反应，所述催化反应的温度可以是70～75℃，所述催化反应的时间可以是2～3小时，所述催化反应结束后还可以进行降温，所述降温可以是降温至15～20℃，所述溶剂可以是丙酮。
在步骤S1至S3中，所述反应均可以是在搅拌的条件下进行。
在步骤S4中，所述催化剂可以是选自有机锡。所述成盐剂可以是三乙胺，所述的水可以是为去离子水。所述后扩链剂可以是小分子二元胺，所述小分子二元胺可以选自乙二胺、己二胺或异佛尔酮二胺中的一种或几种。所述乳化可以在乳化器中进行，所述乳化可以在搅拌的条件下进行，所述搅拌的速度可以是1000～1400r/min，所述乳化可以加入冰水混合物，所述冰水混合物的质量分数可以是50～55％，所述后扩链剂可以是在冰水混合物后加入，所述后扩链剂加入后搅拌速度可以是300～400r/min，例如350r/min，所述后扩链剂反应时间可以是3～4小时。所述脱溶的温度可以是40～45℃，所述脱溶的压力可以是-0.07～-0.09MPa。
本发明还提供了一种由上所述方法制备得到的聚氨酯乳液，所述聚氨酯乳液为阴离子型水性聚氨酯乳液，所述聚氨酯乳液的固含量为30～35％，采用上述固含量的聚氨酯乳液可以使得制备得到的聚氨酯产品表面张力较小，粘度适中。本发明所述聚氨酯乳液的固含量不能太低，不然会出现涂膜缩孔等缺陷，所述聚氨酯乳液的pH值可以是6.5～7.5。
在一实施例中，本发明所述聚氨酯乳液的R值(氰羟比)可以控制在1.4～1.6左右，例如1.5，这是由于在1.5左右避孕套的耐水性能相对较好，后期吸潮性能下降不明显。因为受避孕套厚度限制，微小的缺陷都会被放大。当R值小于1.5时体系粘度较大，乳化效果不好，而且R值小，软段含量高使得成膜后大分子间的物理交联点少，吸水性增强。若R值过大，体系残余NCO含量升高，与水反应生成一定程度交联乳液粒径会变大影响后期成膜的连续性。
本发明还提供了一种如上所述聚氨酯乳液的用途，本发明所述聚氨酯乳液为阴离子型水性聚氨酯乳液、固含量可以是30％～35％，pH值可以为6.5～7.5，可用于生产安全环保的避孕套。所述避孕套的厚度可以是0.015～0.025mm，爆破压力可以大于等于3.0kPa，所述避孕套的拉伸强度可以大于等于45N/mm 2。
以下将引入具体的实施例对本发明进行更为详细的说明。
实例
实施例1
将7.5kg的PPG(1000)和15kg的PTMEG(2000)以及分子量为3000的氧化丙烯三元醇投入反应釜，搅拌加热至110℃，-0.1MPa条件下真空脱水至氧化丙烯三元醇含水率在0.03％以下，降温至40℃,投入0.64kg的IPDI和0.45kg的MDI，搅拌升温至85℃，保温反应2小时，降温至40℃下，投入4.99kg的IPDI和1.2kg的MDI，搅拌升温至85℃,保温反应2小时降温至40℃下,投入0.66kg的DMPA和6.5kg的丙酮，搅拌升温至80℃反应2小时，降温至50℃，投入0.04kg的催化剂和4.3kg丙酮，搅拌升温至75℃反应3小时，然后降温至15℃，加入0.52kg的三乙胺和15kg的丙酮，搅拌15min，获得预聚体；
将预聚体转移至乳化器中，调整转盘转速至1300r/min高速搅拌下匀速将82kg的冰水混合物加入预聚体中，预聚体打开后继续搅拌5min，然后将转速调整至400r/min，加入0.3kg的乙二胺10倍水溶液，继续搅拌3小时，静置24小时；
将上述乳液升温至40℃，-0.09MPa条件下脱去乳液中的丙酮,制得水性聚氨酯乳液样品1，样品1的R值为1.46。
实施例2
将7.5kg的PPG1000和15kg的PTMEG2000以及分子量3000氧化丙烯三元醇投入反应釜，搅拌加热至110℃，-0.1MPa条件下真空脱水至氧化丙烯三元醇含水率在0.03％以下，降温至40℃，投入0.64kg的IPDI和0.45kg的MDI,搅拌升温至85℃,保温反应2小时，降温至40℃下，投入4.6kg的IPDI和1.2kg的MDI和0.45kg的HMDI，搅拌升温至85℃，保温反应2小时降温至40℃下，投入0.66kg的DMPA和6.5kg的丙酮，搅拌升温至80℃反应2小时，降温至50℃，投入0.04kg的催化剂和4.3kg丙酮，搅拌升温至75℃反应3小时，然后降温至15℃，加入0.52kg的三乙胺和15kg的丙酮，搅拌15min，获得预聚体；
将预聚体转移至乳化器中，调整转盘转速至1300r/min高速搅拌下匀速将82kg的冰水混合物加入预聚体中，预聚体打开后继续搅拌5min,然后将转速调整至400r/min,加入0.3kg的乙二胺10倍水溶液，继续搅拌3小时，静置24小时；
将上述乳液升温至40℃，-0.09MPa条件下脱去乳液中的丙酮，制得水性聚氨酯乳液样品2，样品2的R值为1.46。
对比例1
将实施例1的异氰酸酯一步加入得到对比样1。
对比例2
将实施例2的异氰酸酯一步加入，得到对比样2。
对比例3
将实施例1中第二次加入的IPDI量改为5.66得到对比样3，此时R值为1.6。
对比例4
将实施例1中第二次加入的IPDI量改为4.46得到对比样4，此时R值为1.35。
下面通过对样品1-3以及对比样1-4制备得到的水性聚氨酯避孕套进行性能测试以进一步说明本发明，测试结果见表1所示。本发明所述聚氨酯避孕套通过以下方法制备：将模具用纯水清洗干净，在100℃干燥5min；待模具温度降至40℃浸一道水性聚氨酯乳液，放入110℃烘箱干燥4min，重复此步骤3次，将上述步骤完成的模具卷边至合适位置，卷边后的模具降温至20℃，浸入掺有1％白炭黑的水溶液中，取出干燥，干燥温度140℃，干燥时间20min，干燥后冷却至室温脱模，即获得水性聚氨酯避孕套。
表1水性聚氨酯避孕套性能测试表
样品 厚度/mm 爆破压力/kPa 模量/MPa 断裂伸长率％ 拉升强度/Mpa
样品1 0.021 4.17 2.30 590 50
样品2 0.021 3.82 2.50 570 55
对比样1 0.021 3.66 2.10 612 45
对比样2 0.021 3.22 2.33 589 46
对比样3 0.021 3.98 2.75 532 51
对比样4 0.021 2.94 2.02 611 45.5
以下通过对实施例中的样品1-2以及对比样3-4放置一周后再次进行性能测试，测试结果如表2所示。
表2放置一周后水性聚氨酯避孕套性能测试表
样品 厚度/mm 爆破压力/kPa 模量/MPa 断裂伸长率％ 拉升强度/Mpa
样品1 0.021 4.13 2.20 594 49.6
样品2 0.021 3.93 2.50 575 55.5
对比样3 0.021 2.96 2.20 594 43
对比样4 0.021 2.21 1.72 645 38
由上表可知，对比样3和对比样4随着放置时间的延长，后期吸潮拉升强度下降明显。
所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

  1. 一种水性聚氨酯乳液的制备方法，其特征在于，所述方法至少包括以下步骤：
    将大分子多元醇加热脱水后与第一多异氰酸酯进行反应，得到第一预聚体；
    将所述第一预聚体与第二多异氰酸酯进行反应，得到第二预聚体；
    将所述第二预聚体与亲水扩链剂、小分子扩链剂进行反应，得到第三预聚体；
    将所述第三预聚体与成盐剂反应后加入后扩链剂进行乳化、脱溶得到所述聚氨酯乳液；
    其中，所述第一多异氰酸酯的摩尔量小于第二多异氰酸酯的摩尔量，所述第一多异氰酸酯的摩尔量与所述大分子多元醇的摩尔量比值小于1∶3。
  2. 根据权利要求1所述的方法，其特征在于：所述大分子多元醇包括有大分子二元醇以及大分子三元醇，所述大分子二元醇和大分子三元醇的质量比为(10～15)：(1.5～3.5)。
  3. 根据权利要求2所述的方法，其特征在于：所述大分子二元醇的分子量为1000～3000，所述大分子三元醇的分子量为600～6000。
  4. 根据权利要求1所述的方法，其特征在于：所述大分子多元醇、所述第一多异氰酸酯以及所述第二多异氰酸酯的摩尔量比为(1～1.5)：(0.2～0.3)：(2～2.5)。
  5. 根据权利要求1所述的方法，其特征在于：所述亲水扩链剂、所述小分子扩链剂以及所述后扩链剂的摩尔量比为(1～1.3)：(0.01～0.05)：(0.5～0.9)。
  6. 根据权利要求1所述的方法，其特征在于：所述水性聚氨酯乳液中R值为1.4～1.6，所述R值为所述水性聚氨酯乳液中氰酸酯基摩尔数与羟基摩尔数的比值。
  7. 一种根据权利要求1-6任意所述方法制备得到的水性聚氨酯乳液。
  8. 根据权利要求7所述的水性聚氨酯乳液，其特征在于：所述水性聚氨酯乳液为阴离子型水性聚氨酯乳液，所述水性聚氨酯乳液的固含量为30％-35％。
  9. 一种根据权利要求7-8任意所述水性聚氨酯乳液制备得到的水性聚氨酯避孕套。
  10. 根据权利要求9所述的聚氨酯避孕套，其特征在于：所述水性聚氨酯避孕套包括以下特 征中的任意一项或多项：
    厚度为0.015～0.025mm；
    爆破压力大于等于3.0kPa；
    拉伸强度大于等于45N/mm 2。
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