CN105601828A - Castor-oil-based polyurethane-acrylate emulsion preparation method - Google Patents
Castor-oil-based polyurethane-acrylate emulsion preparation method Download PDFInfo
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- CN105601828A CN105601828A CN201510950633.3A CN201510950633A CN105601828A CN 105601828 A CN105601828 A CN 105601828A CN 201510950633 A CN201510950633 A CN 201510950633A CN 105601828 A CN105601828 A CN 105601828A
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- castor oil
- acrylic acid
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08G18/08—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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty 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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
- C08G18/65—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
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
Abstract
The present invention discloses a castor-oil-based polyurethane-acrylate emulsion preparation method which is as follows: under dry nitrogen atmosphere protection, first, an oligomer polyol and castor oil are dehydrated, polyisocyanate is added, after reaction, a hydrophilic chain extender, a chain extender, a catalyst and a solvent are added the reaction to a theory stoichiometric point, and castor-oil-based aqueous polyurethane can be obtained by cooling, emulsion and solvent removal under reduced pressure; and the castor-oil-based aqueous polyurethane is used as seed emulsion, a vinyl monomer and an initiator solution are added dropwise for emulsion polymerization to obtain castor-oil-based polyurethane-acrylate emulsion. Cheap castor oil polyol is introduced into the materials, so that the compatibility, degree of crosslinking and hydrophobicity of the materials are markedly improved, and the castor-oil-based polyurethane-acrylate emulsion can be widely used in the fields of coatings, adhesives and the like.
Description
Technical field
The present invention relates to a kind of preparing technical field of macromolecular material, be specifically related to a kind of preparation method of polyurethane based on castor oil-acrylic acid ester emulsion.
Background technology
Aqueous polyurethane-acrylate (PUA) is to substitute using water the modified polymer material that organic solvent grows up as decentralized medium. It is mainly prepared by seeded emulsion polymerization technology, it have concurrently polyurethane wear-resistant, can cutting and the characteristic such as the hardness of polyacrylate is high, good weatherability, and use safe, nontoxic, do not fire, the advantage such as non-environmental-pollution. Therefore, be described as " third generation aqueous polyurethane ". At present, it is first to synthesize end-vinyl PU emulsion mostly that chemical copolymerization is prepared PUA emulsion, and then, taking this PU emulsion as seed, the seeded emulsion polymerization that carries out acrylate forms. Wait people using polyurethane (PU) emulsion of hydroxy propyl methacrylate (HPMA) end-blocking as seed emulsion as University of Anhui poplar is for army building, taking ammonium persulfate as initator, adopt Emulsifier-free Emulsion Polymerization Technology to synthesize polymerization of acrylic modified polyurethane emulsion (textile journal, the 27th volume, the 1st phase). CN102153712 discloses the preparation method of a kind of water-based polyurethane-acrylate emulsion and redispersable latex powder prepared therefrom, this patent is carried out end-blocking with HPMA, hydroxyethyl methacrylate (HEMA) to polyurethane, first prepare the polyaminoester emulsion with unsaturated bond, then by emulsion polymerization synthesis of polyurethane-acrylic acid ester emulsion. Due to the impact of polyurethane segment on terminal double bond, cause PA percent grafting not high, and obtain by this method polyurethane-polyacrylate composite emulsion mostly be linear block copolymers, in material compatibility, resistance to water and mechanical strength also have very large deficiency.
Castor-oil plant main body of oil is the glyceride of castor oil acid, castor oil acid (9-thiazolinyl-12-kamalolenic acid) contains hydroxyl, carboxyl and carbon-carbon double bond, the hydroxyl average functionality of castor oil is 2.7, castor oil is replaced to polyethers (or polyester) polyalcohol, synthetic water based polyurethane, can improve the degree of cross linking of aqueous polyurethane. Unsaturated carbon-carbon double bond in castor oil and coupled methylene (CH thereof2-) active site of aqueous polyurethane and acrylic monomers graft copolymerization can be provided, its remaining carbon-carbon double bond also can, by oxidation cross-linked, improve the degree of cross linking of polymer, improves film performance. Castor oil is as a kind of natural reproducible resource, cheap, and has excellent cryogenic property and water resistance.
Summary of the invention
The object of the invention is to propose a kind of preparation method of polyurethane based on castor oil-acrylic acid ester emulsion, to overcome the defect in prior art.
The preparation method of polyurethane based on castor oil-acrylic acid ester emulsion of the present invention, it is characterized in that: under dry nitrogen protection, by the oligomer polyol after vacuum dehydration, castor oil, polyisocyanates adds in reactor, at 80 ~ 100 DEG C of reaction 1 ~ 2h, add again hydrophily chain extender, chain extender, catalysts and solvents, continue reaction 2 ~ 4h in 50 ~ 75 DEG C, obtain polyurethane based on castor oil ionomer, cool to 20 ~ 40 DEG C, under the high speed shear of 800 ~ 8000 revs/min, add nertralizer, water carries out emulsion dispersion, decompression desolvation, obtain polyurethane based on castor oil seed emulsion, get above-mentioned emulsion and be placed in the reactor with reflux condensing tube, thermometer, nitrogen conduit, add deionized water, vinyl monomer, the initiator solution of metering, be warming up under the mixing speed of 70 ~ 85 DEG C in 60 ~ 130 revs/min, reaction 1 ~ 2h, drip remaining monomer, initiator solution, in 2～3h, drip off, after dripping off, be warming up to 90 ~ 95 DEG C, continue reaction 0.5h, filter and obtain polyurethane based on castor oil-acrylic acid ester emulsion.
Taking the ionomeric quality of polyurethane based on castor oil as benchmark, the mass fraction of each component is:
Oligomer polyol 50%-75%; Isocyanates 20%-45%; Chain extender 1%-10%; Hydrophilic chain extender 3-8%; Catalyst 0.1-0.5%; Solvent 10-20%; Vinyl monomer 10-60%.
Described oligomer polyol is polyester-diol, PTMEG, PCDL, the polycaprolactone glycol of number-average molecular weight 1000 ~ 4000.
Described vulcabond is selected from toluene di-isocyanate(TDI), IPDI, dicyclohexyl methyl hydride diisocyanate.
Described hydrophily chain extender is selected from dihydromethyl propionic acid, dimethylolpropionic acid.
Described chain extender is selected from BDO, 1,6-hexylene glycol, ethylene glycol, hydroxymethyl-cyclohexane, quinhydrones-bis-(beta-hydroxyethyl) ether, diglycol.
Described vinyl monomer is selected from methyl methacrylate, acrylic acid, methyl ester butyl acrylate, acrylic acid methyl, hydroxypropyl acrylate, styrene.
Described initator is potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide.
Compared with prior art, the present invention has the following advantages:
1, the present invention taking castor oil as graft copolymerization point, acrylate monomer percent grafting is high, the polymer obtaining is comb-shaped polymer, between polyurethane and acrylate, compatibility is high.
2, the present invention adopts Emulsifier-free Emulsion Polymerization Technology, has avoided the impact of small-molecular emulsifier on material property.
3, the introducing of castor oil has significantly improved lower temperature resistance, compatibility, resistance to water and the degree of cross linking of material.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1: the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion
In there-necked flask at 250ml with reflux condensing tube and thermometer, add the polyhexamethylene adipate glycol 100g that number-average molecular weight after toluene di-isocyanate(TDI) (TDI) 34g, vacuum dehydration is 2000, hydroxyl value equals 55mgKOH/g, castor oil 30g, under mechanical agitation in 90 DEG C of isothermal reaction 1.5h; Be cooled to 80 DEG C, add dihydromethyl propionic acid (DMPA) 5.0g, diglycol (DEG) 7.5g, dibutyltin dilaurate 0.1g, acetone 50ml, reacts to NCO content and reaches theoretical value (adopt standard di-n-butylamine titration determine) in 60 DEG C; Be cooled to 30 DEG C of left and right, under 1800 revs/min of high shear, add triethylamine 3.7g in and 2min, add several times the about 340g of deionized water, stir 2min, then the lower desolvation acetone of decompression, obtaining solid content is 45%, the translucent polyurethane based on castor oil emulsion of PH ≈ 7.
Get above-mentioned emulsion and be placed in the reactor with reflux condensing tube, thermometer, nitrogen conduit, add deionized water, vinyl monomer, the initiator solution of metering, be warming up under the mixing speed of 70 ~ 85 DEG C in 60 ~ 130 revs/min, reaction 1 ~ 2h, drip remaining monomer, initiator solution, in 2～3h, drip off, after dripping off, be warming up to 90 ~ 95 DEG C, continue reaction 0.5h, filter and obtain polyurethane based on castor oil-acrylic acid ester emulsion.
Embodiment 2: the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion
In there-necked flask at 250ml with reflux condensing tube and thermometer, add the polyoxypropyleneglycol 100g that number-average molecular weight after IPDI (IPDI) 45g, vacuum dehydration is 2000, hydroxyl value equals 55mgKOH/g, castor oil 35g, under mechanical agitation in 90 DEG C of isothermal reaction 1.5h; Be cooled to 80 DEG C, add dihydromethyl propionic acid (DMPA) 6.0g, diglycol (DEG) 7.0g, dibutyltin dilaurate 0.1g, acetone 50ml, reacts to NCO content and reaches theoretical value (adopt standard di-n-butylamine titration determine) in 60 DEG C; Be cooled to 30 DEG C of left and right, under 1800 revs/min of high shear, add triethylamine 3.7g in and 2min, add several times the about 340g of deionized water, stir 2min, then the lower desolvation acetone of decompression, obtaining solid content is 45%, the translucent polyurethane based on castor oil emulsion of PH ≈ 7.
Get above-mentioned emulsion and be placed in the reactor with reflux condensing tube, thermometer, nitrogen conduit, add deionized water, vinyl monomer, the initiator solution of metering, be warming up under the mixing speed of 70 ~ 85 DEG C in 60 ~ 130 revs/min, reaction 1 ~ 2h, drip remaining monomer, initiator solution, in 2～3h, drip off, after dripping off, be warming up to 90 ~ 95 DEG C, continue reaction 0.5h, filter and obtain polyurethane based on castor oil-acrylic acid ester emulsion.
Claims (8)
1. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion, it is characterized in that: under dry nitrogen protection, by the oligomer polyol after vacuum dehydration, castor oil, polyisocyanates adds in reactor, at 80 ~ 100 DEG C of reaction 1 ~ 2h, add again hydrophily chain extender, chain extender, catalysts and solvents, continue reaction 2 ~ 4h in 50 ~ 75 DEG C, obtain polyurethane based on castor oil ionomer, cool to 20 ~ 40 DEG C, under the high speed shear of 800 ~ 8000 revs/min, add nertralizer, water carries out emulsion dispersion, decompression desolvation, obtain polyurethane based on castor oil seed emulsion, get above-mentioned emulsion and be placed in the reactor with reflux condensing tube, thermometer, nitrogen conduit, add deionized water, vinyl monomer, the initiator solution of metering, be warming up under the mixing speed of 70 ~ 85 DEG C in 60 ~ 130 revs/min, reaction 1 ~ 2h, drip remaining monomer, initiator solution, in 2～3h, drip off, after dripping off, be warming up to 90 ~ 95 DEG C, continue reaction 0.5h, filter and obtain polyurethane based on castor oil-acrylic acid ester emulsion.
2. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion according to claim 1, is characterized in that, taking the ionomeric quality of polyurethane based on castor oil as benchmark, the mass fraction of each component is:
Oligomer polyol 50%-75%; Isocyanates 20%-45%; Chain extender 1%-10%; Hydrophilic chain extender 3-8%; Catalyst 0.1-0.5%; Solvent 10-20%; Vinyl monomer 10-60%.
3. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion according to claim 1, is characterized in that:
Described oligomer polyol is polyester-diol, PTMEG, PCDL, the polycaprolactone glycol of number-average molecular weight 1000 ~ 4000.
4. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion according to claim 1, is characterized in that: described vulcabond is selected from toluene di-isocyanate(TDI), IPDI, dicyclohexyl methyl hydride diisocyanate.
5. the preparation method of a kind of organic-silicon-modified cross-linked polyurethane emulsion according to claim 1, is characterized in that: described hydrophily chain extender is selected from dihydromethyl propionic acid, dimethylolpropionic acid.
6. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion according to claim 1, it is characterized in that: described chain extender is selected from 1,4-butanediol, 1,6-hexylene glycol, ethylene glycol, hydroxymethyl-cyclohexane, quinhydrones-bis-(beta-hydroxyethyl) ether, diglycol.
7. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion according to claim 1, is characterized in that: described vinyl monomer is selected from methyl methacrylate, acrylic acid, methyl ester butyl acrylate, acrylic acid methyl, hydroxypropyl acrylate, styrene.
8. the preparation method of polyurethane based on castor oil-acrylic acid ester emulsion according to claim 1, is characterized in that: described initator is potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059716A (en) * | 2018-01-09 | 2018-05-22 | 佳化化学（茂名）有限公司 | The polyurethane based on castor oil elastomer of its preparation of castor oil composite material and application |
| CN109562633A (en) * | 2016-08-01 | 2019-04-02 | 路博润先进材料公司 | Coating composition for gloss ink-absorbing medium |
| CN111187392A (en) * | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Preparation of alcohol scrubbing resistant and acid and alkali resistant waterborne polyurethane |
| CN111848067A (en) * | 2020-07-30 | 2020-10-30 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
| CN112358575A (en) * | 2020-10-29 | 2021-02-12 | 上海世壮新能源科技有限公司 | Environment-friendly polyurethane-acrylate hybrid emulsion and preparation method thereof |
| CN114395822A (en) * | 2021-09-01 | 2022-04-26 | 长春工业大学 | Preparation method of physical and chemical synergetic super-hydrophobic waterborne polyurethane film |
| CN114605598A (en) * | 2022-03-31 | 2022-06-10 | 长兴化学（天津）有限公司 | Bio-based dispersant, preparation method and application thereof |
| CN114958133A (en) * | 2022-04-19 | 2022-08-30 | 铁科腾跃科技有限公司 | Bio-based modified low-temperature-resistant quick-setting asphalt emulsion coating and preparation method thereof |
| CN116265536A (en) * | 2023-03-13 | 2023-06-20 | 上海欧畅新材料科技有限公司 | Water-based ink for PVC (polyvinyl chloride) substrate and preparation and application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109562633A (en) * | 2016-08-01 | 2019-04-02 | 路博润先进材料公司 | Coating composition for gloss ink-absorbing medium |
| CN109562633B (en) * | 2016-08-01 | 2021-07-23 | 路博润先进材料公司 | Coating composition for glossy ink-receptive media |
| CN108059716B (en) * | 2018-01-09 | 2020-07-07 | 佳化化学（茂名）有限公司 | Castor oil composite material and castor oil-based polyurethane elastomer prepared by using same |
| CN108059716A (en) * | 2018-01-09 | 2018-05-22 | 佳化化学（茂名）有限公司 | The polyurethane based on castor oil elastomer of its preparation of castor oil composite material and application |
| CN111187392A (en) * | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Preparation of alcohol scrubbing resistant and acid and alkali resistant waterborne polyurethane |
| CN111848067A (en) * | 2020-07-30 | 2020-10-30 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
| CN111848067B (en) * | 2020-07-30 | 2022-02-01 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
| CN112358575B (en) * | 2020-10-29 | 2023-08-15 | 上海世壮新能源科技有限公司 | Environment-friendly polyurethane-acrylate hybrid emulsion and preparation method thereof |
| CN112358575A (en) * | 2020-10-29 | 2021-02-12 | 上海世壮新能源科技有限公司 | Environment-friendly polyurethane-acrylate hybrid emulsion and preparation method thereof |
| CN114395822A (en) * | 2021-09-01 | 2022-04-26 | 长春工业大学 | Preparation method of physical and chemical synergetic super-hydrophobic waterborne polyurethane film |
| CN114605598A (en) * | 2022-03-31 | 2022-06-10 | 长兴化学（天津）有限公司 | Bio-based dispersant, preparation method and application thereof |
| CN114605598B (en) * | 2022-03-31 | 2024-03-01 | 长兴化学（天津）有限公司 | Bio-based dispersing agent and preparation method and application thereof |
| CN114958133A (en) * | 2022-04-19 | 2022-08-30 | 铁科腾跃科技有限公司 | Bio-based modified low-temperature-resistant quick-setting asphalt emulsion coating and preparation method thereof |
| CN114958133B (en) * | 2022-04-19 | 2022-12-13 | 铁科腾跃科技有限公司 | Bio-based modified low-temperature-resistant quick-setting asphalt emulsion coating and preparation method thereof |
| CN116265536A (en) * | 2023-03-13 | 2023-06-20 | 上海欧畅新材料科技有限公司 | Water-based ink for PVC (polyvinyl chloride) substrate and preparation and application thereof |
| CN116265536B (en) * | 2023-03-13 | 2024-03-12 | 上海欧畅新材料科技有限公司 | Water-based ink for PVC (polyvinyl chloride) substrate and preparation and application thereof |
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