WO2022257317A1 - Résine de polyuréthane et son procédé de préparation - Google Patents

Résine de polyuréthane et son procédé de préparation Download PDF

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Publication number
WO2022257317A1
WO2022257317A1 PCT/CN2021/124692 CN2021124692W WO2022257317A1 WO 2022257317 A1 WO2022257317 A1 WO 2022257317A1 CN 2021124692 W CN2021124692 W CN 2021124692W WO 2022257317 A1 WO2022257317 A1 WO 2022257317A1
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WO
WIPO (PCT)
Prior art keywords
component
polyurethane resin
mpa
preparation
mixing
Prior art date
Application number
PCT/CN2021/124692
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English (en)
Chinese (zh)
Inventor
陈翠萍
潘念慈
宋维密
宋丽媛
李广佳
计成才
Original Assignee
道生天合材料科技(上海)股份有限公司
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Publication of WO2022257317A1 publication Critical patent/WO2022257317A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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

Definitions

  • the invention relates to the field of polyurethane, in particular to a polyurethane resin and a preparation method thereof.
  • Polyurethane is a high-molecular compound with rapid response and moderate tensile strength.
  • polyurethane resin it is widely used in larger-sized composite products, including composite pipes and utility poles in the winding production process, composite grids and bridge brackets in the pultrusion production process, and automobiles in the vacuum infusion process.
  • the production of large-scale composite products requires polyurethane resins to have a longer operating time to ensure that fiber reinforced materials such as glass fibers and carbon fibers have better wettability during the production process to achieve higher performance of composite materials.
  • the operating time of traditional polyurethane resins that is, the time for the viscosity of 175g polyurethane to increase to 500mPa.s at 30°C cannot be longer than 50min, and the thermal deformation temperature of the cast body is generally lower than 60°C, which makes it impossible to prepare more than 10 meters.
  • the invention provides a polyurethane resin and a preparation method thereof.
  • the preparation method of the polyurethane resin comprises mixing the first component and the second component to prepare the polyurethane resin.
  • said first component is formed by mixing at least one organic polyol, acrylate monomer and catalyst;
  • said second component is formed by mixing isocyanate and initiation aid; and controlling said first component and
  • the weight ratio of the second component is 100:(60-90), so that the prepared polyurethane resin has a viscosity of 20-300 mPa.s at 25 degrees Celsius and a polyurethane resin with an operating time of 50-200 minutes, and
  • the heat distortion temperature of the polyurethane resin cured at 70 degrees Celsius for 4 hours is greater than 60 degrees Celsius.
  • the invention provides a preparation method of a polyurethane resin to obtain a polyurethane resin with a viscosity of 20-300 mPa.s at 25 degrees Celsius and a working time of 50-200 minutes, and the polyurethane resin is cured at 70 degrees Celsius for 4 Hour heat distortion temperature greater than 60 degrees Celsius.
  • the preparation method of polyurethane resin of the present invention may further comprise the steps:
  • the first component is formed by mixing at least one organic polyol, acrylate monomer and catalyst;
  • the second component is formed by mixing isocyanate and initiator;
  • the weight ratio of the first component and the second component is controlled to be 100:(60-90).
  • the beneficial effect of the preparation method of the polyurethane resin of the present invention is that: the first component is formed by mixing at least one organic polyol, acrylate monomer and catalyst; the second component is composed of isocyanate and initiator agent, mix the first component and the second component, and control the weight ratio of the first component and the second component to be 100: (60-90), which is beneficial to A polyurethane resin with a viscosity of 20-300 mPa.s at 25 degrees Celsius and an operating time of 50-200 minutes is obtained, and the heat distortion temperature of the polyurethane resin cured at 70 degrees Celsius for 4 hours is greater than 60 degrees Celsius.
  • the operational time of the present invention is defined as: the time when the viscosity of every 175g of polyurethane resin increases to 500mPa.s at 30 degrees Celsius.
  • the viscosity of the polyurethane resin obtained by the preparation method of the present invention is 20-300 mPa.s at 25 degrees Celsius, and the operable time is 50-200 minutes.
  • the operable time of the polyurethane resin is 175 grams of the polyurethane resin. The time taken for the viscosity of the resin to increase to 500 mPa.s when treated in a water bath at 30°C.
  • the polyurethane resin has a viscosity of 60-90 mPa.s at 25 degrees Celsius.
  • the operable time of the polyurethane resin is 70-110 minutes.
  • the first component also includes enester compounds.
  • the beneficial effect is that it is beneficial to reduce the viscosity of the obtained polyurethane resin and improve the working time.
  • the general structural formula of the enester compound is:
  • R1 is a substituted or unsubstituted C2-C10 aliphatic alkyl group, a derivative of the substituted or unsubstituted C2-C10 aliphatic alkyl group, substituted or unsubstituted Any of a substituted alicyclic group, a derivative of the substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, and a derivative of the substituted or unsubstituted aryl group.
  • the general structural formula of the acrylate monomer is:
  • R2 is any of substituted or unsubstituted C2-C10 aliphatic group, substituted or unsubstituted alicyclic group and substituted or unsubstituted aromatic group
  • R3 is hydrogen, substituted or unsubstituted C1-C10 Any of the alkyl groups.
  • the substituted or unsubstituted C2-C10 aliphatic alkyl is methyl, ethyl, n-propyl, isobutyl, sec-butyl, 3-pentyl, 2-(2-methyl)butyl any one of pentyl, neopentyl, 2-(2-methyl)pentyl and hydroxymethyl.
  • the substituted or unsubstituted aryl group is any one of tolyl, phenyl, phenol, naphthyl, hydroxytolyl and thiophenyl.
  • the enester compound is allyl cyclohexylhexanoate
  • the acrylate monomer is hydroxypropyl methacrylate.
  • the cyclohexyl structure in the allyl cyclohexyl hexanoate increases the resistance of the interaction between molecules, and reduces the reaction rate when the first component and the second component are mixed;
  • the reaction of the claimed at least one organic polyol and isocyanate acts as an inhibitor.
  • the step of providing the first component and the second component includes: controlling the viscosity of the mixture obtained after mixing the first component at 25 degrees Celsius to be 10-200 mPa.s, and the hydroxyl value to be 200 -600 mg potassium hydroxide/g; and controlling the viscosity of the mixture obtained after mixing the second component to be 50-500 mPa.s at 25 degrees Celsius.
  • the viscosity of the mixture obtained after mixing the first component is controlled to be 10-200 mPa.s at 25 degrees Celsius, and the hydroxyl value is 250-400 mg potassium hydroxide/g.
  • the appearance of the first component is colorless or slightly yellow, and the viscosity of the mixture obtained after further adding coloring material and mixing at 25 degrees Celsius is 10-200 mPa.s, and the hydroxyl value is 250-400 mg potassium hydroxide /gram.
  • the step of controlling the viscosity of the mixture obtained after mixing the first component to be 10-200 mPa.s at 25 degrees Celsius, and the hydroxyl number to be 200-600 mg potassium hydroxide/g comprises: controlling the The weight ratio of the enyl ester compound to the at least one organic polyol is 1:(6-12).
  • the step of controlling the viscosity of the mixture obtained after mixing the first component to be 10-200 mPa.s at 25 degrees Celsius, and the hydroxyl number to be 200-600 mg potassium hydroxide/g comprises: controlling the The weight ratio of the acrylate monomer to the at least one organic polyol is 1:(1.7-2).
  • the step of controlling the viscosity of the mixture obtained after mixing the first component to be 10-200 mPa.s at 25 degrees Celsius, and the hydroxyl number to be 200-600 mg potassium hydroxide/g comprises: controlling the The catalyst accounts for 0.05-0.2% by weight of the total amount of the at least one organic polyol and the acrylate monomer.
  • the step of controlling the viscosity of the mixture obtained after mixing the first component to be 10-200 mPa.s at 25 degrees Celsius, and the hydroxyl number to be 200-600 mg potassium hydroxide/g comprises: controlling the The hydroxyl value of the at least one organic polyhydric alcohol is 100-700 mg potassium hydroxide/g, and the functionality is 2-4.
  • the step of controlling the viscosity of the mixture obtained after mixing the first component to be 10-200 mPa.s at 25 degrees Celsius, and the hydroxyl number to be 200-600 mg potassium hydroxide/g comprises: controlling the The hydroxyl value of the acrylate monomer is 390-410 mg potassium hydroxide/g.
  • the organic polyol is selected from at least one of polyether polyol, polyester polyol, polyether ester polyol, polymer polyol, polycarbonate polyol and polyether carbonate polyol.
  • polymer polyol also known as vinyl polymer grafted polyether polyol, referred to as POP
  • POP vinyl polymer grafted polyether polyol
  • the polyurethane foam has high bearing capacity and good resilience performance, and the cell structure and physical and mechanical properties of the foam are also improved.
  • Functionality polymer functionality, the average number of active functional groups on the polymer chain is called the functionality or average functionality of the polymer. Common active groups are hydroxyl-OH, carboxyl-COOH, allyl chloride, amino (amino)-NH2, etc.
  • the at least one organic polyol is (a) a polyether polyol with a functionality of 2 and (b) an organic polyol with a functionality of 3.
  • the weight ratio of (a) the polyether polyol with a functionality of 2 to (b) the organic polyol with a functionality of 3 is 1:(0.3-2).
  • polyether polyol with a functionality of 2 and (b) the organic polyol with a functionality of 3 described in this application are not specifically limited, and those skilled in the art can make a routine selection according to the description in this application.
  • the grades of (a) polyether polyols with a functionality of 2 include uranol D 204, Puranol D 210, Puranol D 220, Puranol D 230, Puranol D 240, Puranol D 280, Lupranol 1200 and the like.
  • the (b) grades of organic polyols with a functionality of 3 can be listed as Puranol G 303, Puranol G 303F, Puranol G 305, Puranol G 306, Puranol G 307, Puranol G 310, Puranol G 4030, Puranol G 5030 , Voranol CP 455, etc.
  • the catalyst is copper naphthenate.
  • the appearance of the second component is light yellow to dark brown, and different colorants can be added to change the color so that the viscosity is 50-500 cps.
  • the step of providing the first component and the second component comprises:
  • the step of controlling the viscosity of the mixture obtained after mixing the second component to be 50-500 mPa.s at 25 degrees Celsius includes: controlling the weight ratio of the isocyanate and the initiation aid to ( 47.5-50):1.
  • initiation aids described in this application are not particularly limited, and those skilled in the art can make routine choices.
  • the initiation aid is dibenzoyl peroxide.
  • the step of controlling the viscosity of the mixture obtained after mixing the second component to be 50-500 mPa.s at 25 degrees Celsius includes: controlling the isocyanate group content of the isocyanate to be 28-35% by weight %.
  • the isocyanate group content of the isocyanate is controlled to be 31.5% by weight.
  • the isocyanate is polyisocyanate.
  • polyisocyanates described in the present application are not particularly limited, and those skilled in the art can make routine selections according to the descriptions in the present application.
  • the preparation method of the polyurethane resin system comprises:
  • the first component and the second component are mixed to obtain the polyurethane resin.
  • the first component and the second component described herein are packaged separately.
  • Embodiments 1-5 of the present invention respectively provide a polyurethane resin system, the specific components of which are shown in Table 1, and the unit is parts by weight.
  • the preparation method of described polyurethane resin system is:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une résine de polyuréthane et son procédé de préparation. Le procédé de préparation de la résine de polyuréthane consiste à mélanger un premier constituant et un second constituant pour préparer la résine de polyuréthane, le premier constituant étant formé par mélange d'au moins un polyol organique, d'un monomère (méth)acrylate et d'un catalyseur, le second constituant étant formé par mélange d'un isocyanate et d'un initiateur, et le rapport en poids du premier constituant au second constituant étant régulé pour être de 100:(60 à 90), faisant de la résine de polyuréthane préparée une résine de polyuréthane ayant un temps de fonctionnement compris entre 50 et 200 minutes tandis que la viscosité est comprise entre 20 et 300 mPa.s à une température de 25 °C, et une température de déformation thermique de la résine de polyuréthane pendant le durcissement à une température de 70 °C pendant 4 heures est supérieure à 60 °C.
PCT/CN2021/124692 2021-06-08 2021-10-19 Résine de polyuréthane et son procédé de préparation WO2022257317A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110639816.9 2021-06-08
CN202110639816.9A CN113388074A (zh) 2021-06-08 2021-06-08 一种聚氨酯树脂系统及其制备方法

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113388074A (zh) * 2021-06-08 2021-09-14 道生天合材料科技(上海)股份有限公司 一种聚氨酯树脂系统及其制备方法
CN118647684A (zh) * 2022-01-29 2024-09-13 汉高股份有限及两合公司 两部分聚氨酯-(甲基)丙烯酸类混合粘合剂组合物
CN115181235B (zh) * 2022-06-14 2024-04-19 苏州贝彩纳米科技有限公司 一种ppc基的聚氨酯隔音降噪材料及其制备方法

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CN1505647A (zh) * 2001-04-12 2004-06-16 Dsmip�Ʋ����޹�˾ Lpa杂化物
CN104974502A (zh) * 2014-04-10 2015-10-14 拜耳材料科技(中国)有限公司 聚氨酯复合材料及其制备方法
CN105778005A (zh) * 2014-12-01 2016-07-20 科思创聚合物（中国）有限公司 可自由基聚合的聚氨酯组合物
CN110372823A (zh) * 2019-07-12 2019-10-25 万华化学集团股份有限公司 一种单组份热固化聚氨酯组合料
CN111051377A (zh) * 2017-09-12 2020-04-21 科思创德国股份有限公司 包含聚氨酯-聚丙烯酸酯树脂基质的复合材料
CN111825822A (zh) * 2019-04-15 2020-10-27 科思创德国股份有限公司 一种存储异氰酸酯反应性组分的方法
CN113388074A (zh) * 2021-06-08 2021-09-14 道生天合材料科技(上海)股份有限公司 一种聚氨酯树脂系统及其制备方法
CN113444223A (zh) * 2020-03-26 2021-09-28 科思创德国股份有限公司 多元醇配方及聚氨酯树脂

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670600A (en) * 1993-07-03 1997-09-23 Basf Lacke + Farben, Ag Aqueous two-component polyurethane coating composition, process for its preparation, and its use in processes for the production of a multicoat finish
CN1505647A (zh) * 2001-04-12 2004-06-16 Dsmip�Ʋ����޹�˾ Lpa杂化物
CN104974502A (zh) * 2014-04-10 2015-10-14 拜耳材料科技(中国)有限公司 聚氨酯复合材料及其制备方法
CN105778005A (zh) * 2014-12-01 2016-07-20 科思创聚合物（中国）有限公司 可自由基聚合的聚氨酯组合物
CN111051377A (zh) * 2017-09-12 2020-04-21 科思创德国股份有限公司 包含聚氨酯-聚丙烯酸酯树脂基质的复合材料
CN111825822A (zh) * 2019-04-15 2020-10-27 科思创德国股份有限公司 一种存储异氰酸酯反应性组分的方法
CN110372823A (zh) * 2019-07-12 2019-10-25 万华化学集团股份有限公司 一种单组份热固化聚氨酯组合料
CN113444223A (zh) * 2020-03-26 2021-09-28 科思创德国股份有限公司 多元醇配方及聚氨酯树脂
CN113388074A (zh) * 2021-06-08 2021-09-14 道生天合材料科技(上海)股份有限公司 一种聚氨酯树脂系统及其制备方法

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