CN104211931A - Pure plant oil based UV curable prepolymer - Google Patents
Pure plant oil based UV curable prepolymer Download PDFInfo
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- CN104211931A CN104211931A CN201410393867.8A CN201410393867A CN104211931A CN 104211931 A CN104211931 A CN 104211931A CN 201410393867 A CN201410393867 A CN 201410393867A CN 104211931 A CN104211931 A CN 104211931A
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Abstract
The invention belongs to the field of photosensitive polymer materials, and discloses a preparation method of a pure plant oil based UV curable prepolymer. The method comprises the following steps: (1) epoxidizing vegetable oil by hydrogen peroxide and benzoic acid; (2) adding an undecylenic acid ring opening epoxy group to the epoxidized vegetable oil, reacting at 170 DEG C for 8 h in the absence of solvent to prepare undecylenic acid modified vegetable oil based polyols; (3) mixing undecenoyl chloride and undecylenic acid modified vegetable oil based polyols prepared from undecylenic acid in ethyl acetate, adding triethylamine in ice bath, reacting for 2 h, then stirring for 24 h at room temperature, conducting pumping filtration, wash wiht 1% sodium hydroxide aqueous solution and distilled water, drying by magnesium sulfate to remove the solvent to obtain the product. The invention can reduce the dependence on oil resources, has the advantages of branching structure, low viscosity, UV curable double bonds at the end positions, high reactivity, a large amount of long chain alkanes contained and good flexibility.
Description
Technical field
The present invention relates to field of light-sensitive high molecular materials, particularly renewable resources is in the coating material solidified Application Areas of UV.
Background technology
UV curing technology refers to that, under UV effect, liquid-state oligomers and monomer form the process of solid product through crosslinking polymerization, is had the industrial technology of " 5E " feature because its fast setting, energy-and time-economizing, wide adaptability, energy economy & environment are friendly by being summarized as.Current UV curing system is primarily of acrylic ester prepolymer, monomer diluent and light trigger composition, and its performance determines primarily of prepolymer.The starting raw material of present stage UV curing formula is petroleum chemicals, when petroleum resources are day by day exhausted and price constantly rises, utilizes renewable resources to have important foundation research and economic implications for the novel UV of development of raw materials is coating material solidified.
Vegetables oil can be regenerated by photosynthesis, growth cycle is short, low price and polymer based on vegetables oil has biological degradation and eco-friendly feature, and therefore vegetables oil is one of oil replacement raw material of most potentiality.But due to the restriction of utilized renewable resources extremely derivative kind and constitutional features, prepolymer kind is few, renewable carbon content is lower and film performance is short of to some extent to cause plant oil based UV to solidify.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of renewable, source is wide, the pure plant oil based prepolymer of cost UV-curable that is low and easy preparation and preparation method thereof.
In the present invention with the derivative-undecylenic acid of vegetables oil and Viscotrol C for raw material, pure plant oil based UV solidification prepolymer can be prepared by high productivity by three-step reaction and simple aftertreatment, the synthesis that this plant oil based UV solidifies prepolymer is not reported at present, less at the consumption of preparation process solvent, productive rate is high and its cost is low, meets day by day severe environmental regulation requirement.
Pure plant oil based a kind of prepolymer of UV-curable provided by the present invention, its representational structural formula is:
Described vegetables oil is containing one or more the mixture in the vegetables oil of more than 2 or 2 unsaturated double-bonds, is preferably rapeseed oil, Semen Maydis oil, soybean oil, sweet oil, raisin seed oil, linseed oil seed oil and one or more mixture of tung oil., adding light trigger or do not adding light trigger; Under UV light presence or absence condition, with multi-thiol material at 20-30 DEG C of fast setting, highly cross-linked film can be obtained.
Described pure plant oil based UV-curable prepolymer, its preparation method mainly comprises following three steps: (1) adopts hydrogen peroxide and formic acid to carry out epoxidation to vegetables oil; (2) in epoxidized vegetable oil, add undecylenic acid open loop epoxide group, under solvent-free existence, within 8 hours, prepare the vegetable oil-based polyols of undecylenic acid modification in 170 DEG C of reactions; (3) the hendecene acyl chlorides obtained by undecylenic acid is mixed in ethyl acetate with the vegetable oil-based polyols of undecylenic acid modification, and under ice bath, add triethylamine react 2 hours, then room temperature (20-30 DEG C) stirs 24 hours, aqueous sodium hydroxide solution and distilled water wash respectively with 1% after suction filtration, removes desolventizing after dried over mgso and obtains product.
Described pure plant oil based UV-curable prepolymer, the content of its renewable carbon atom is 100%.
Described pure plant oil based UV-curable prepolymer has branched structure, and the degree of branching is relevant to the number of unsaturated double-bond on vegetable oil raw materials, double key number object 1 ~ 2 times contained by vegetables oil.
Described pure plant oil based UV-curable prepolymer, its unsaturated functionality is relevant to the number of unsaturated double-bond on vegetable oil raw materials, double key number object 1 ~ 2 times contained by vegetables oil.On vegetable oil raw materials, the number of unsaturated double-bond is 2 ~ 8.
Described pure plant oil based UV-curable prepolymer, its molecular weight is 1672 ~ 3868 g.mol
-1.
Described pure plant oil based UV-curable prepolymer, is adding light trigger or is not adding light trigger; Under UV light presence or absence condition, all can with multi-thiol material at room temperature (20-30 DEG C) fast setting, obtain highly cross-linked film.
Described multi-thiol material is the material containing 2 and above sulfydryl, as 1.6-ethanthiol, tetramethylolmethane tri-thiol propionic ester or tetramethylolmethane four mercaptopropionic acid ester etc.
Compared with prior art, the present invention has following beneficial effect: the raw materials used vegetables oil of the present invention and undecylenic acid are entirely renewable resources, the content (%BRC) preparing the renewable carbon of gained prepolymer is 100%, alleviates the dependence to petroleum resources; Prepare gained prepolymer and have branched structure, the material of viscosity ratio same molecular amount is low; The UV-curable double bond prepared contained by gained prepolymer is in end position, reactive high; To prepare in gained prepolymer containing a large amount of long alkane chain, the snappiness that UV solidified coating is good can be given, can be used for the coating material solidified and sizing agent of UV.
Accompanying drawing explanation
Fig. 1 Rap Oil-based UV-curable prepolymer preparation process Raw and intermediate product nucleus magnetic hydrogen spectrum figure (A: rapeseed oil B: epoxy rapeseed oil C: undecylenic acid open loop epoxy rapeseed oil D: Rap Oil-based prepolymer)
Fig. 2 Rap Oil-based UV-curable prepolymer preparation process Raw and intermediate product nucleus magnetic hydrogen spectrum figure (A: rapeseed oil B: epoxy rapeseed oil C: undecylenic acid open loop epoxy rapeseed oil D: Rap Oil-based prepolymer).
Embodiment
In order to better explain the present invention, illustrate main contents of the present invention further below in conjunction with specific embodiment, but the present invention is not only confined to following examples.
Embodiment 1
1) get rapeseed oil 5g, the hydrogen peroxide 12g of 30% and formic acid 5.36g, in flask, is placed in after magnetic stirring apparatus reacts 24h, adds 10ml ethyl acetate, 10ml distilled water, leave standstill 10min layering under room temperature.Get the washing of upper organic phase sodium carbonate solution to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve and steam except desolventizing, obtain epoxy rapeseed oil;
2) mixed with undecylenic acid 1.47g (epoxy and carboxyl mol ratio are 1:1) by obtained epoxy rapeseed oil 2.0g, at 170 DEG C, reaction obtains the Rap Oil-based polyvalent alcohol of undecylenic acid modification for 8 hours;
3) undecanoyl chlorine 3.2g, triethylamine 1.6g and ethyl acetate 5ml are joined in the Rap Oil-based polyvalent alcohol 3.47g of undecylenic acid modification, react under ice bath after 2 hours and be warming up to room temperature reaction 24 hours, suction filtration.Liquid phase uses aqueous sodium hydroxide solution and the distilled water wash of 1% respectively, after anhydrous magnesium sulfate drying, suction filtration, revolves steaming, obtains the Rap Oil-based prepolymer (overall yield is 85%) of UV-curable;
Rap Oil-based UV-curable prepolymer preparation process Raw and intermediate product nucleus magnetic hydrogen spectrum figure are shown in Fig. 1, Fig. 2.The content (%BRC) preparing the renewable carbon of gained prepolymer is 100%, alleviates the dependence to petroleum resources; Prepare gained prepolymer and have branched structure, the material of viscosity ratio same molecular amount is low; The UV-curable double bond prepared contained by gained prepolymer is in end position, reactive high; To prepare in gained prepolymer containing a large amount of long alkane chain, the snappiness that UV solidified coating is good can be given, can be used for the coating material solidified and sizing agent of UV.
Embodiment 2
1) get Semen Maydis oil 5g, the hydrogen peroxide 12g of 30% and formic acid 5.36g, in flask, is placed in magnetic stirring apparatus and reacts 24h, adds 10ml ethyl acetate, 10ml removes distilled water, leaves standstill 10min layering.Get the washing of upper organic phase sodium carbonate solution to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve and steam except desolventizing, obtain epoxy Semen Maydis oil;
2) mixed with undecylenic acid 1.5g (epoxy and carboxyl mol ratio are 1:1) by the epoxy Semen Maydis oil 2.0g obtained above, at 170 DEG C, reaction obtains the Semen Maydis oil polylol of undecylenic acid modification for 8 hours;
3) undecanoyl chlorine 3.6g, triethylamine 1.8g and ethyl acetate 5ml are joined in the Rap Oil-based polyvalent alcohol 3.5g of undecylenic acid modification, react 2 hours under ice bath, be warming up to room temperature reaction 24 hours, suction filtration, liquid phase uses aqueous sodium hydroxide solution and the distilled water wash of 1% respectively, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain the Semen Maydis oil based prepolymers (overall yield is 83%) of UV-curable.
Embodiment 3
1) get sweet oil 5g, the hydrogen peroxide 8.4g of 30% and formic acid 3.75g, in flask, is placed in magnetic stirring apparatus and reacts 24h, adds 10ml ethyl acetate, 10ml distilled water, leaves standstill 10min layering.Get the washing of upper organic phase sodium carbonate solution to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain epoxy sweet oil;
2) mixed with undecylenic acid 1.1g (epoxy and carboxyl mol ratio are 1:1) by the epoxy sweet oil 2.0g obtained above, at 170 DEG C, reaction obtains the sweet oil polylol of undecylenic acid modification for 8 hours;
3) undecanoyl chlorine 2.4g, triethylamine 1.2g and ethyl acetate 5ml are added in the sweet oil polylol 3.1g of undecylenic acid modification, react 2 hours under ice bath, be warming up to room temperature reaction 24 hours, suction filtration.Liquid phase uses aqueous sodium hydroxide solution and the distilled water wash of 1% respectively, after anhydrous magnesium sulfate drying, suction filtration, revolves steaming, obtains the sweet oil based prepolymers (overall yield is 88%) of UV-curable.
Embodiment 4
1) get linseed oil 5g, the hydrogen peroxide 18g of 30% and formic acid 8g, in flask, is placed in magnetic stirring apparatus and reacts 24h, adds 15ml ethyl acetate, 15ml distilled water, leaves standstill 10min layering.Get the washing of upper organic phase sodium carbonate solution to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain epoxy linseed oil;
2) the epoxy linseed oil 2.0g obtained above is mixed with undecylenic acid 2.2g (with oxirane value and undecylenic acid mol ratio for 1:1), at 170 DEG C, react the linseed oil polylol of undecylenic acid modification in 8 hours;
3) undecanoyl chlorine 4.8g, triethylamine 2.4g and ethyl acetate 10ml are joined in the linseed oil polylol 4.2g of undecylenic acid modification, react 2 hours under ice bath, be warming up to room temperature reaction 24 hours, suction filtration.Get aqueous sodium hydroxide solution and distilled water wash that liquid phase uses 1% respectively, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain the linseed oil based prepolymers (overall yield is 81%) of UV-curable.
Claims (9)
1. a pure plant oil based polyenoid class UV-curable prepolymer, is characterized in that: its general structure is as follows:
, adding light trigger or do not adding light trigger; Under UV light presence or absence condition, with multi-thiol material at 20-30 DEG C of fast setting, highly cross-linked film can be obtained.
2. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, it is characterized in that described vegetables oil is containing one or more the mixture in the vegetables oil of more than 2 or 2 unsaturated double-bonds, be preferably rapeseed oil, Semen Maydis oil, soybean oil, sweet oil, raisin seed oil, linseed oil seed oil and one or more mixture of tung oil.
3. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, its preparation method mainly comprises following three steps: (1) adopts hydrogen peroxide and formic acid to carry out epoxidation to vegetables oil; (2) in epoxidized vegetable oil, add undecylenic acid open loop epoxide group, under solvent-free existence, within 8 hours, prepare the vegetable oil-based polyols of undecylenic acid modification in 170 DEG C of reactions; (3) the hendecene acyl chlorides obtained by undecylenic acid is mixed in ethyl acetate with the vegetable oil-based polyols of undecylenic acid modification, and under ice bath, add triethylamine react 2 hours, then 20-30 DEG C is stirred 24 hours, aqueous sodium hydroxide solution and distilled water wash respectively with 1% after suction filtration, removes desolventizing after dried over mgso and obtains product.
4. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, is characterized in that the content of renewable carbon atom is 100%.
5. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, have branched structure, the degree of branching is relevant to the number of unsaturated double-bond on vegetable oil raw materials, double key number object 1 ~ 2 times contained by vegetables oil.
6. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, its unsaturated functionality is relevant to the number of unsaturated double-bond on vegetable oil raw materials, double key number object 1 ~ 2 times contained by vegetables oil.
7. the pure plant oil based polyenoid class UV-curable prepolymer according to claim 4 and 5, on described vegetable oil raw materials, the number of unsaturated double-bond is 2 ~ 8.
8. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, its molecular weight is 1672 ~ 3868 g/mol.
9. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, described multi-thiol compound is the material containing 2 and above sulfydryl, is preferably 1.6-ethanthiol, tetramethylolmethane tri-thiol propionic ester or tetramethylolmethane four mercaptopropionic acid ester.
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Cited By (4)
| 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 |
| CN109666303A (en) * | 2019-01-25 | 2019-04-23 | 付远 | A kind of visible light 3D printing technique of epoxidized vegetable oil |
| WO2021135222A1 (en) * | 2019-12-30 | 2021-07-08 | 华南农业大学 | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use 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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| US6433121B1 (en) * | 1998-11-06 | 2002-08-13 | Pittsburg State University | Method of making natural oil-based polyols and polyurethanes therefrom |
| CN1837181A (en) * | 2006-04-16 | 2006-09-27 | 南京红宝丽股份有限公司 | Bio-based polyhydric alcohol prepared by using rape seed oil |
| CN101583651A (en) * | 2006-09-04 | 2009-11-18 | 生物能源株式会社 | Polyester polyol |
| CN101641324A (en) * | 2007-01-12 | 2010-02-03 | 陶氏环球技术公司 | Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use |
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2014
- 2014-08-12 CN CN201410393867.8A patent/CN104211931B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6433121B1 (en) * | 1998-11-06 | 2002-08-13 | Pittsburg State University | Method of making natural oil-based polyols and polyurethanes therefrom |
| CN1837181A (en) * | 2006-04-16 | 2006-09-27 | 南京红宝丽股份有限公司 | Bio-based polyhydric alcohol prepared by using rape seed oil |
| CN101583651A (en) * | 2006-09-04 | 2009-11-18 | 生物能源株式会社 | Polyester polyol |
| CN101641324A (en) * | 2007-01-12 | 2010-02-03 | 陶氏环球技术公司 | Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use |
Non-Patent Citations (1)
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| LEILA HOJABRI ET AL.: "Fatty Acid-Derived Diisocyanate and Biobased Polyurethane Produced from Vegetable Oil: Synthesis, Polymerization, and Characterization", 《BIOMACROMOLECULES》 * |
Cited By (4)
| 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 |
| CN109666303A (en) * | 2019-01-25 | 2019-04-23 | 付远 | A kind of visible light 3D printing technique of epoxidized vegetable oil |
| WO2021135222A1 (en) * | 2019-12-30 | 2021-07-08 | 华南农业大学 | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use 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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| CN104211931B (en) | 2016-05-11 |
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Effective date of registration: 20180425 Address after: 512400 Pearl Industrial Park, Nanxiong, Shaoguan, Guangdong Patentee after: Nanxiong USTC Technology Co., Ltd. Address before: 330013 605 Fenglin Road, Nanchang Economic Development Zone, Jiangxi Patentee before: Jiangxi Science & Technology Normal University |
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