CN104086743A - Preparation method of cardanol-base polyalcohols and polyurethanes thereof - Google Patents

Preparation method of cardanol-base polyalcohols and polyurethanes thereof Download PDF

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Publication number
CN104086743A
CN104086743A CN201410303176.4A CN201410303176A CN104086743A CN 104086743 A CN104086743 A CN 104086743A CN 201410303176 A CN201410303176 A CN 201410303176A CN 104086743 A CN104086743 A CN 104086743A
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cardanol
polylol
preparation
sulfydryl
vulcabond
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CN104086743B (en
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付长清
申亮
刘建成
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Jiangxi Science and Technology Normal University
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Jiangxi Science and Technology Normal University
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    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds

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

Abstract

The invention discloses a preparation method of two cardanol-base polyalcohols and polyurethanes thereof, which comprises the following steps: (1) directly carrying out sulfhydryl-alkene addition reaction on cardanol side chain unsaturated double bond and sulfhydryl monoalcohol under the irradiation of ultraviolet light to prepare the side chain cardanol-base polyalcohol with controllable hydroxyl number; (2) reacting hendecene acyl chloride and phenolic hydroxyl group of cardanol to prepare 10-undecylenic acid modified cardanol, reacting with sulfhydryl monoalcohol to prepare 10-undecylenic acid modified cardanol-base polyalcohol with controllable hydroxyl number; and (3) reacting the cardanol-base polyalcohol and 10-undecylenic acid modified cardanol-base polyalcohol with diisocyanate to prepare the cardanol-base polyurethanes. The method has the advantages of low cost, no environmental pollution and the like, and is renewable and biodegradable; and the generated polyurethane resin can be used as a resin for paints and adhesives.

Description

The preparation method of cardanol polylol and urethane thereof
Technical field
The present invention relates to the preparation method of bio-based polyurethane, be specifically related to the preparation method of two kinds of cardanol polylols and urethane thereof.
Background technology
Cardanol is a kind of abundant, inexpensive renewable non-edible plant oil resource of originating, and its molecular structure contains phenolic hydroxyl group and has 15 carbon side chains of different degrees of unsaturation.The molecular structure of this uniqueness is conducive to its chemical modification to prepare different functionalities chemical and macromolecular material, wherein with cardanol based surfactants and more containing the protective system research of cardanol.The reflecting point of chemical modification mainly concentrates on phenolic hydroxyl group, less to the modification of unsaturated double-bond on its side chain, only has a small amount of unsaturated terminal chain to be carried out to epoxidised research.Vegetable oil-based polyols is existing a large amount of application in the preparation of urethane resin, but because most vegetables oil is the tri-glyceride structure of lipid acid, adopting its urethane resin of preparing gained for polyvalent alcohol to lack hardness, during as coating resin, cause the wear resistance of coating and chemical resistance poor.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of cardanol polylol and urethane thereof.The method has been prepared the controlled cardanol polylol of hydroxy number by cardanol or 10 hendecenoic acid modification cardanol and sulfydryl single methanol by the addition reaction of sulfydryl alkene, and cardanol polylol makes cardanol based polyurethanes with di-isocyanate reaction again.Preparation method of the present invention is easy, reaction conditions gentleness.Prepared cardanol polylol hydroxy number is controlled, and gained cardanol based polyurethanes has the good performance advantage such as snappiness and biodegradable, can be used as coating and tackiness agent resin.
The inventor finds, contains this rigid radical of phenyl ring in cardanol, when phenyl ring is in main polymer chain structure instead of on side group, can give polymkeric substance good hardness.In the present invention taking the cardanol of cardanol, 10 hendecenoic acid modification and sulfydryl single methanol as raw material, can prepare the cardanol polylol of phenyl ring in chain by single step reaction and simple aftertreatment, and applied and the preparation of cardanol based polyurethanes, the synthetic method of this cardanol polylol and urethane does not have report at present.And replace polyester (ether) polyvalent alcohol from petroleum resources completely with cardanol polylol, synthetic cardanol based polyurethanes, the hardness of gained urethane is high and cost is low, meets day by day severe environmental regulation requirement.
The preparation method of cardanol polylol and urethane thereof, this polyvalent alcohol and urethane preparation method thereof realize as follows:
(1), by cardanol, sulfydryl single methanol and light trigger are dissolved in methylene dichloride and are placed on room temperature reaction under ultraviolet lamp, by controlling the reaction times, and the controlled cardanol polylol of preparation hydroxy number;
(2) hendecene acyl chlorides reacts with cardanol and prepares 10 hendecenoic acid modification cardanol; By 10 hendecenoic acid modification cardanol, sulfydryl single methanol and the light-initiated methylene dichloride that is dissolved in are placed on room temperature reaction under ultraviolet lamp, by controlling the reaction times, and the controlled 10 hendecenoic acid modification cardanol polylol of preparation hydroxy number;
(3) under organotin catalysts effect, cardanol polylol and 10 hendecenoic acid modification cardanol polylol are dissolved in DMF, be warming up to 60 DEG C of DMF solution that start to drip vulcabond; After adding, be warming up to 75 DEG C of reaction 4h and obtain cardanol based polyurethanes;
Described sulfydryl single methanol is 2 mercapto ethanol, 3-sulfydryl-1-propyl alcohol, 3-sulfydryl-1-hexanol, in 6-sulfydryl hexanol and 4-sulfydryl-n-butyl alcohol any one, preferably 2 mercapto ethanol, the one in 3-sulfydryl-1-propyl alcohol.
Described light trigger is the wherein a kind of of dimethoxybenzoin or 2-hydroxy-2-methyl-1-phenyl-1-acetone, preferably 2-hydroxy-2-methyl-1-phenyl-1-acetone, and the consumption of light trigger is total mass 1%～3%.
The power of described ultraviolet lamp is 1.8mw/cm 2.
The described reaction times is 10 ~ 50 hours.
2 ~ 3.3 of the cardanol polylol hydroxy number average out to that nuclear-magnetism is surveyed.
Described organotin catalysts is dibutyl tin laurate or stannous octoate; Be preferably dibutyl tin laurate.
Described vulcabond is fats vulcabond or aromatics vulcabond, be preferably 1,6-di-isocyanate, isophorone diisocyanate, tolylene diisocyanate, ditan-4, one or more mixtures in 4 '-vulcabond.
Compared with prior art, tool of the present invention has the following advantages:
(1) the present invention prepares cardanol polylol and 10 hendecenoic acid modification cardanol polylol taking renewable resources cardanol and 10 hendecenoic acid as raw material, and enrich in raw material cheapness, source, has the advantage such as environmental protection and biodegradable.
(2) in the cardanol polylol molecular structure that prepared by the present invention, contain phenyl ring and renewable chain alkyl simultaneously, there is excellent snappiness, hardness and good heat resistance.
(3) the present invention by efficiently, sulfydryl alkene addition reaction fast prepares cardanol polylol and 10 hendecenoic acid modification cardanol polylol; The method is easy, and reaction conditions gentleness and aftertreatment are simple.
Brief description of the drawings
Fig. 1 cardanol 1hNMR figure
Fig. 2 cardanol polyvalent alcohol (3.3 hydroxyls) 1hNMR figure
Fig. 3 is containing the 10 hendecenoic acid modification cardanol polylol of 3.3 hydroxyls 1hNMR figure.
Embodiment
Embodiment 1.
In the round-bottomed flask of 100ml, add respectively 20g cardanol, 23.5g 2 mercapto ethanol, 0.87g 2-hydroxy-2-methyl-1-phenyl-1-acetone and 50ml methylene dichloride, under room temperature and ultra violet lamp, to react 10 hours, water washing is used anhydrous MgSO 5-6 time afterwards 4dry, desolventize cardanol polylol, it is 2 that nuclear-magnetism records hydroxy number.
Embodiment 2.
In the round-bottomed flask of 100ml, add respectively 20g cardanol, 23.5g 2 mercapto ethanol, 0.87g 2-hydroxy-2-methyl-1-phenyl-1-acetone and 50ml methylene dichloride, under room temperature and ultra violet lamp, react 20 hours, water washing is used anhydrous MgSO 5-6 time afterwards 4dry, desolventize cardanol polylol, it is 2.5 that nuclear-magnetism records hydroxy number.
Embodiment 3.
In the round-bottomed flask of 100ml, add respectively 20g cardanol, 23.5g 2 mercapto ethanol, 0.87g 2-hydroxy-2-methyl-1-phenyl-1-acetone and 50ml methylene dichloride, under room temperature and ultra violet lamp, react 45 hours, water washing is used anhydrous MgSO 5-6 time afterwards 4dry, desolventize to obtain cardanol polylol, it is 3.3 that nuclear-magnetism records hydroxy number.
Cardanol 1hNMR figure is shown in Fig. 1, cardanol polyvalent alcohol (3.3 hydroxyls) 1hNMR figure is shown in Fig. 2.
Embodiment 4.
10 hendecenoic acid with sulfur oxychloride 90 DEG C of acidylates 2 hours; decompression rotation is removed sulfur oxychloride and is prepared hendecene acyl chlorides; cardanol and triethylamine drip the dry methylene chloride solution reaction 0.5 hour of hendecene acyl chlorides under ice bath after dissolving by dry methylene chloride; room temperature reaction is after 24 hours, respectively with using anhydrous MgSO after 10% NaOH solution, hydrochloric acid soln and water washing again 4dry, decompression rotation removes desolventizing and prepares 10 hendecenoic acid modification cardanol crude product.Crude product has silicagel column purifying (eluent: ethyl acetate/petroleum ether=2:1 volume ratio) to obtain 10 hendecenoic acid modification cardanol.
In the round-bottomed flask of 100ml, add respectively 20g 10 hendecenoic acid modification cardanol, 23.5g 2 mercapto ethanol, 0.87g light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone and 50ml methylene dichloride, under room temperature and ultra violet lamp, react 22 hours, water washing is used anhydrous MgSO 5-6 time afterwards 4dry, desolventize and obtain 10 hendecenoic acid modification cardanol polylol, it is 2.4 that nuclear-magnetism records hydroxy number.
Embodiment 5.
10 hendecenoic acid with sulfur oxychloride 90 DEG C of acidylates 2 hours; decompression rotation is removed sulfur oxychloride and is prepared hendecene acyl chlorides; cardanol and triethylamine drip the dry methylene chloride solution of hendecene acyl chlorides under ice bath after dissolving by dry methylene chloride; ice bath reaction 0.5 hour; room temperature reaction is after 24 hours, respectively with using anhydrous MgSO after 10%NaOH solution, hydrochloric acid soln and water washing again 4dry, decompression rotation removes desolventizing and prepares 10 hendecenoic acid modification cardanol crude product.Crude product has silicagel column purifying (eluent: ethyl acetate/petroleum ether=2:1 volume ratio) to obtain 10 hendecenoic acid modification cardanol.
In the round-bottomed flask of 100ml, add respectively 20g 10 hendecenoic acid modification cardanol, 23.5g 2 mercapto ethanol, 0.87g light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone and 50ml methylene dichloride, under room temperature and ultra violet lamp, react 50 hours, water washing is used anhydrous MgSO 5-6 time afterwards 4dry, desolventize to obtain 10 hendecenoic acid modification cardanol polylol, it is 3.3 that nuclear-magnetism records hydroxy number.Containing the 10 hendecenoic acid modification cardanol polylol of 3.3 hydroxyls 1hNMR figure is shown in Fig. 3.
Embodiment 6.
The preparation of cardanol based polyurethanes
Formula following (quality):
Cardanol polylol containing 2.5 hydroxyls: 12.20g
1,6-di-isocyanate (HDI): 6.08g
Dibutyl tin laurate (DBTDL): 0.16g
The cardanol based polyurethanes of the present embodiment, its concrete preparation process is as follows:
After cardanol polylol and organotin catalysts are dissolved with DMF, be warming up to 60 DEG C of DMF solution that start to drip 1,6-di-isocyanate; After adding, be warming up to 75 DEG C of reactions 4 hours.
Embodiment 7.
Cardanol based polyurethanes
Formula following (quality):
Cardanol polylol containing 3.3 hydroxyls: 11.22g
1,6-di-isocyanate (HDI): 6.49g
Dibutyl tin laurate (DBTDL): 0.16g
The cardanol based polyurethanes of the present embodiment, its concrete preparation process is as follows:
After cardanol polylol and organotin catalysts are dissolved with DMF, be warming up to 60 DEG C of DMF solution that start to drip 1,6-di-isocyanate; After adding, be warming up to 75 DEG C of reactions 4 hours.
Embodiment 8.
Cardanol based polyurethanes
Formula following (quality):
10 hendecenoic acid cardanol polylol containing 2.4 hydroxyls: 14.40g
1,6-di-isocyanate (HDI): 4.44g
Dibutyl tin laurate (DBTDL): 0.16g
The cardanol based polyurethanes of the present embodiment, its concrete preparation process is as follows:
After cardanol polylol and organotin catalysts are dissolved with DMF, be warming up to 60 DEG C of DMF solution that start to drip 1,6-di-isocyanate; After adding, be warming up to 75 DEG C of reactions 4 hours.
Embodiment 9.
Cardanol based polyurethanes
Formula following (quality):
10 hendecenoic acid modification cardanol polylol containing 3.3 hydroxyls: 14.40g
1,6-di-isocyanate (HDI): 5.49g
Dibutyl tin laurate (DBTDL): 0.16g
The cardanol based polyurethanes of the present embodiment, its concrete preparation process is as follows:
After the cardanol polylol of 10 hendecenoic acid modification and organotin catalysts are dissolved with DMF, be warming up to 60 DEG C of DMF solution that start to drip 1,6-di-isocyanate; After adding, be warming up to 75 DEG C of reactions 4 hours.

Claims (8)

1. the preparation method of cardanol polylol and urethane thereof, is characterized in that following preparation process:
(1), by cardanol, sulfydryl single methanol and light trigger are dissolved in methylene dichloride and are placed on room temperature reaction under ultraviolet lamp, by controlling the reaction times, and the controlled cardanol polylol of preparation hydroxy number;
(2) hendecene acyl chlorides reacts with cardanol and prepares 10 hendecenoic acid modification cardanol; By modification cardanol, sulfydryl single methanol and light trigger are dissolved in methylene dichloride and are placed on room temperature reaction under ultraviolet lamp, by controlling the reaction times, and the controlled 10 hendecenoic acid modification cardanol polylol of preparation hydroxy number;
(3) under organotin catalysts effect, cardanol polylol and 10 hendecenoic acid modification cardanol polylol are dissolved in DMF, be warming up to 60 DEG C of DMF solution that start to drip vulcabond; After adding, be warming up to 75 DEG C of reaction 4h and obtain cardanol based polyurethanes.
2. the preparation method of cardanol polylol according to claim 1, it is characterized in that described sulfydryl single methanol is 2 mercapto ethanol, 3-sulfydryl-1-propyl alcohol, 3-sulfydryl-1-hexanol, in 6-sulfydryl hexanol and 4-sulfydryl-n-butyl alcohol any one, preferably 2 mercapto ethanol, the one in 3-sulfydryl-1-propyl alcohol.
3. the preparation method of cardanol polylol according to claim 1, it is characterized in that described light trigger is the wherein a kind of of dimethoxybenzoin or 2-hydroxy-2-methyl-1-phenyl-1-acetone, preferably 2-hydroxy-2-methyl-1-phenyl-1-acetone, the consumption of light trigger is total mass 1%～3%.
4. the preparation method of cardanol polylol according to claim 1, the power that it is characterized in that described ultraviolet lamp is 1.8mw/cm 2.
5. the preparation method of cardanol polylol according to claim 1, is characterized in that the described reaction times is 10 ~ 50 hours.
6. the preparation method of cardanol polylol according to claim 1, is characterized in that cardanol polylol hydroxy number is controlled at 2 ~ 3.3 of average out to.
7. the preparation method of cardanol based polyurethanes according to claim 1, is characterized in that described organotin catalysts is dibutyl tin laurate or stannous octoate; Be preferably dibutyl tin laurate.
8. the preparation method of cardanol based polyurethanes according to claim 1, it is characterized in that described vulcabond is fats vulcabond or aromatics vulcabond, be preferably 1,6-di-isocyanate, isophorone diisocyanate, tolylene diisocyanate, ditan-4, one or more mixtures in 4 '-vulcabond.
CN201410303176.4A 2014-06-30 2014-06-30 The preparation method of cardanol polylol and urethane thereof Active CN104086743B (en)

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CN105001088A (en) * 2015-07-27 2015-10-28 江西科技师范大学 Method for preparing all-bio-based photocuring activated monomer and application of all-bio-based photocuring activated monomer
CN105237734A (en) * 2015-11-08 2016-01-13 福建师范大学 Synthesis method of cardanol-based epoxy resin
CN105367790A (en) * 2015-12-07 2016-03-02 江西科技师范大学 Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof
CN106519159A (en) * 2016-10-27 2017-03-22 江西科技师范大学 Limonene-based polyurethane with high water resistance and toluene resistance and preparation method thereof
CN110790882A (en) * 2019-11-13 2020-02-14 浩力森涂料（上海）有限公司 Organic silicon modified cardanol-based waterborne polyurethane and preparation method thereof
CN112358596A (en) * 2020-10-29 2021-02-12 中国林业科学研究院林产化学工业研究所 Cardanol-based shape memory polymer and preparation method thereof
CN113735749A (en) * 2021-09-26 2021-12-03 四川大学 Preparation method of binary primary alcohol for bio-based polyurethane with adjustable molecular weight
CN114106280A (en) * 2021-12-14 2022-03-01 上海华峰新材料研发科技有限公司 Aliphatic polyurethane resin and preparation method and application thereof
CN114245791A (en) * 2019-06-05 2022-03-25 Oms投资公司 Controlled release fertilizer compositions
CN116333314A (en) * 2023-04-12 2023-06-27 华南理工大学 Method for preparing degradable polyester based on solvent-free polymerization of 10-undecylenic acid

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Publication number Priority date Publication date Assignee Title
CN105001088A (en) * 2015-07-27 2015-10-28 江西科技师范大学 Method for preparing all-bio-based photocuring activated monomer and application of all-bio-based photocuring activated monomer
CN105237734A (en) * 2015-11-08 2016-01-13 福建师范大学 Synthesis method of cardanol-based epoxy resin
CN105237734B (en) * 2015-11-08 2017-06-09 福建师范大学 A kind of synthetic method of anacardol base epoxy
CN105367790B (en) * 2015-12-07 2018-03-27 江西科技师范大学 A kind of preparation method of the branched more membered ring carbonates of castor oil-base and its non-isocyanate polyurethane
CN105367790A (en) * 2015-12-07 2016-03-02 江西科技师范大学 Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof
CN106519159B (en) * 2016-10-27 2019-06-07 江西科技师范大学 Enhanced water resistance, resistance to toluene limonene based polyurethanes and preparation method thereof
CN106519159A (en) * 2016-10-27 2017-03-22 江西科技师范大学 Limonene-based polyurethane with high water resistance and toluene resistance and preparation method thereof
CN114245791A (en) * 2019-06-05 2022-03-25 Oms投资公司 Controlled release fertilizer compositions
CN110790882A (en) * 2019-11-13 2020-02-14 浩力森涂料（上海）有限公司 Organic silicon modified cardanol-based waterborne polyurethane and preparation method thereof
CN112358596A (en) * 2020-10-29 2021-02-12 中国林业科学研究院林产化学工业研究所 Cardanol-based shape memory polymer and preparation method thereof
CN112358596B (en) * 2020-10-29 2022-06-24 中国林业科学研究院林产化学工业研究所 Cardanol-based shape memory polymer and preparation method thereof
CN113735749A (en) * 2021-09-26 2021-12-03 四川大学 Preparation method of binary primary alcohol for bio-based polyurethane with adjustable molecular weight
CN113735749B (en) * 2021-09-26 2022-07-01 四川大学 Preparation method of binary primary alcohol for bio-based polyurethane with adjustable molecular weight
CN114106280A (en) * 2021-12-14 2022-03-01 上海华峰新材料研发科技有限公司 Aliphatic polyurethane resin and preparation method and application thereof
CN116333314A (en) * 2023-04-12 2023-06-27 华南理工大学 Method for preparing degradable polyester based on solvent-free polymerization of 10-undecylenic acid

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