CN102617812A - Preparation method of anionic water-based polyurethane/poly (phenethylene-acrylate-acrylonitrile) hybrid emulsion - Google Patents
Preparation method of anionic water-based polyurethane/poly (phenethylene-acrylate-acrylonitrile) hybrid emulsion Download PDFInfo
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Abstract
The invention discloses a preparation method of an anionic water-based polyurethane/poly (phenethylene-acrylate-acrylonitrile) hybrid emulsion. The preparation method comprises two stages, namely anionic water-based polyurethane seeded emulsion synthesis and seeded emulsion polymerization. According to the invention, synthetic anionic water-based polyurethane is used as seeded emulsion for the synthesis of ASA resin, and a seeded emulsion polymerization method can be well utilized to organically combine the synthetic anionic water-based polyurethane and the ASA resin, so that the water resistance, the oil resistance and the heat resistance of water-based polyurethane resin as well as the impact resistance of the ASA resin are improved.
Description
One, technical field
The invention belongs to the seeded emulsion polymerization field, be specifically related to the synthetic of anion-type water-thinned polyurethane emulsion and utilize it, carry out the synthetic aqueous polyurethane of graft copolymerization/the gather preparation method of (cinnamic acrylic ester-vinyl cyanide) resin as seed emulsion.
Two, background technology
Urethane (PU) is meant and contains the multiple amino-formate bond (general name of family macromolecule material NHCOO-) in the molecular structure.Superperformances such as polyurethane material has that high gloss, lower temperature resistance are good, high-wearing feature, snappiness, weather-proof and chemical proofing are widely used as plastics, rubber, coating, fiber etc.Water-based PU has not only kept the superperformance of common solvent type PU on performance, and owing to make water as dispersion medium, and is nontoxic during use, pollution-free, do not burn, be prone to advantages such as modification, smell be little, become the focus of world's polyurethane material research.Yet owing in molecular chain, introduced hydrophilic radical, so the water tolerance of resin, oil-proofness and thermotolerance are bad.In order to improve these shortcomings of aqueous polyurethane, people have done the improvement of a lot of aspects.Often the various resin copolymerization of aqueous polyurethane and other are formed copolymer resin, not only can overcome the defect problem of above-mentioned aqueous polyurethane, also combine the performance of other resins simultaneously.
Gather (cinnamic acrylic ester-vinyl cyanide) (ASA) ternary graft copolymer of forming by vinyl cyanide, vinylbenzene, propenoate of resin; It is rubber phase with the polyacrylic ester, the thermoplastic elastomer that is formed mutually as plastics by vinylbenzene and acrylonitrile monemer graft copolymerization.The ASA resin is a kind of physical and mechanical properties and the similar engineering plastics of ABS.Because ASA replaces the divinyl rubber part that contains unsaturated double-bond in the ABS resin with the acrylic elastomer that does not contain unsaturated double-bond just; Therefore the ASA resin singly can not resisted degraded that uviolizing causes, wear out, fades; Simultaneously work in-process can heat-resisting oxygen effect, prevents to decompose and variable color.So its ageing-resistant performance is more than 10 times of ABS resin.The ASA resin can be widely used in fields such as automobile, electronics, daily necessities, outdoor decoration material and material of construction.
Therefore; Utilize the lower temperature resistance of polyurethane material good, high-wearing feature, snappiness wait the modified ASA resin; Both excellent properties are combined; Then possibly obtain a kind of excellent weather-proof Ginkgo Biloba Leaf Extract that has, good low-temperature resistance and shock resistance have the macromolecular material of good heat resistance simultaneously concurrently.So not only improve the impact property of ASA resin, and improved the water resistance of waterborne polyurethane resin.But at first need solve both problems of consistency before.
Three, summary of the invention
The present invention aims to provide a kind of anion-type water-thinned polyurethane/gather preparation method of (cinnamic acrylic ester-vinyl cyanide) composite emulsion; Technical problem to be solved is the compatibility problem that solves ASA resin and waterborne polyurethane resin; Make the two altogether, thereby make the synthetic composite emulsion have water-fast, oil resistant, resistance toheat and stronger impact property simultaneously through chemical bonded refractory.
The present invention as seed emulsion, carries out the synthetic aqueous polyurethane of graft copolymerization/gather (cinnamic acrylic ester-vinyl cyanide) composite emulsion with the anion-type water-thinned polyurethane emulsion.
Technical solution problem of the present invention adopts following technical scheme:
The preparation method of anion-type water-thinned polyurethane of the present invention/gather (cinnamic acrylic ester-vinyl cyanide) composite emulsion comprises the preparation of anion-type water-thinned polyurethane seed emulsion and each unit process of preparation of composite emulsion:
The preparation of said anion-type water-thinned polyurethane seed emulsion is the tolylene diisocyanate mixing with the polyether Glycols of 20-40 weight part and 35-60 weight part; Reacted 2.5 hours at 70 ℃ under the nitrogen protection; Add then the 3-10 weight part dimethylol propionic acid (DMPA), 3-10 weight part 1; The catalyzer dibutyl tin laurate (DBTDL) of 4-butyleneglycol (BDO) and 0.5-3 weight part; Continue down reaction 3h in 80 ℃, be cooled to 60-70 ℃ and add 3-10 parts by weight of acrylic hydroxyl ethyl ester (HEA) reaction 1.5h subsequently, then be cooled to 40 ℃ and add the triethylamine neutralization reaction 25min of 3-10 weight part; Add the deionized water emulsification 20-30min of 100-150 weight part at last, obtain the anion-type water-thinned polyurethane seed emulsion;
The preparation of said composite emulsion is that the anion-type water-thinned polyurethane seed emulsion with the 20-60 weight part is warming up to 60-80 ℃ of insulation 0.5h; Drip the pre-emulsified propenoate mixture of 20-30 weight part then; About 1-3h drips off; Drip off continued insulation reaction 1.5h; The pre-emulsified vinylbenzene of Dropwise 5 0-100 weight part and acrylonitrile mixture are carried out graft polymerization reaction subsequently, and about 3-5h drips off, and drip off continued insulation reaction 3h and obtain anion-type water-thinned polyurethane/gather (cinnamic acrylic ester-vinyl cyanide) composite emulsion.
The composite emulsion of the present invention preparation is obtained anion-type water-thinned polyurethane/gather (cinnamic acrylic ester-vinyl cyanide) resin through breakdown of emulsion, flocculation, washing, centrifugal and drying process successively; The salt that uses during breakdown of emulsion is selected from one or more in calcium chloride, sal epsom, sodium sulfate, the magnesium chloride.
Said polyether Glycols is selected from polyether Glycols N210 or polyether Glycols N220.
Said pre-emulsified propenoate mixture constitutes by weight: propenoate 35-45 part, emulsifying agent 0.5-2.5 part, initiator 0.1-0.35 part, pH value regulator 0.1-0.35 part, linking agent 1.5-3 part, deionized water 55-65 part;
Said propenoate is selected from Bing Xisuandingzhi, ethyl propenoate, the Isooctyl acrylate monomer one or more, if ratio is any when multiple;
Said emulsifying agent is selected from anionic emulsifier and/or nonionic emulsifying agent, if ratio is any when multiple;
Said initiator is selected from one or both in Potassium Persulphate, ammonium persulphate, the Diisopropyl azodicarboxylate, if ratio is any when multiple;
Said pH value regulator is selected from one or both in yellow soda ash, sodium hydrogencarbonate, the Sodium phosphate, dibasic, if ratio is any when multiple;
Said linking agent select oneself glycol two propylene esters (HDDA) and/or tri (propylene glycol) diacrylate (TPGDA) are if ratio is any when multiple.
Said pre-emulsified vinylbenzene and acrylonitrile mixture constitute by weight: mixture 35-45 part of vinylbenzene and vinyl cyanide; Emulsifying agent 0.5-2.5 part; Initiator 0.1-0.35 part, molecular weight regulator tert-dodecyl mercaptan 0.1-1.2 part, deionized water 55-65 part;
Said emulsifying agent is selected from anionic emulsifier and/or nonionic emulsifying agent, if ratio is any when multiple;
Said initiator is selected from one or both in Potassium Persulphate, ammonium persulphate, the Diisopropyl azodicarboxylate, if ratio is any when multiple;
Said pH value regulator is selected from one or both in yellow soda ash, sodium hydrogencarbonate, the Sodium phosphate, dibasic, if ratio is any when multiple.
Said anionic emulsifier is selected from sodium lauryl sulphate, X 2073 or polyethers NP amber sulfonate; Said nonionic emulsifying agent is selected from polyoxyethylene nonylphenol or polyoxyethylene octylphenol ether.
The present invention adopts Hydroxyethyl acrylate as the bridge joint material, utilizes cyanic acid reaction in hydroxyl and the aqueous polyurethane in its molecule, generates the end-sealed type aqueous polyurethane emulsion that has two keys; Carry out seeded emulsion polymerization then; Because the two keys in the Hydroxyethyl acrylate molecule are participated in propenoate, vinyl cyanide and cinnamic copolyreaction; So the molecular chain of aqueous polyurethane and ASA resin reaches the purpose of blend through chemical bonded refractory altogether, has increased the consistency between the two.
The present invention utilizes self-emulsification synthetic anionic aqueous polyurethane emulsion; It as seed emulsion, is dripped in advance the good Butyl Acrylate Monomer mixture of emulsification in advance, carry out the seeded emulsion polymerization reaction; The particle diameter of seed emulsion is increased, and the latex that is polymerized has multimodal or bimodal particle size distribution.In addition; Institute's synthetic anion-type water-thinned polyurethane emulsion is that Hydroxyethyl acrylate (HEA) is end capped; When carrying out Raolical polymerizable, two keys in the molecular chain and acrylic polymer form chemical b `, drip good vinylbenzene of preparatory emulsification and acrylonitrile monemer mixture then; Be adsorbed on and carry out the emulsion graft copolymerization reaction on the seed emulsion particle, the percentage of grafting of this graft copolymerization is higher.
The present invention utilizes the synthetic anion-type water-thinned polyurethane as seed emulsion, carries out the synthetic of ASA resin, can well utilize the seeded emulsion polymerization method, and the two is organically combined.Not only improve the Waterproofing/oilproofing resistance toheat of waterborne polyurethane resin, and improved the impact property of ASA resin.
Four, description of drawings
Fig. 1 is for passing through self-emulsification synthetic anion-type water-thinned polyurethane distribution of particle size of emulsion figure.The particle diameter that can be known aqueous polyurethane emulsion by Fig. 1 is unimodal distribution, and median size is about 50nm.
Fig. 2 is for dripping the distribution of particle size of emulsion figure after pre-emulsified propenoate mixture carries out seeding polymerization.Can be known with aqueous polyurethane by Fig. 2 and to carry out polyreaction as seed emulsion, the latex that is polymerized has multimodal or bimodal particle size distribution.The median size at first peak is about 37nm, and the median size at second peak is about 220nm.
Fig. 3 carries out distribution of particle size of emulsion figure after the graft polymerization for dripping pre-emulsified vinylbenzene and acrylonitrile mixture.As can be seen from Figure 3 drip styrene and acrylonitrile mixture are carried out emulsion graft copolymerization reaction back particle diameter and are increased very greatly, and median size is a 311nm left side stone.
Five, embodiment
In order to explain that better the present invention, spy enumerate following embodiment, but the present invention is not limited in following embodiment.
Embodiment 1:
(1) preparation of anion-type water-thinned polyurethane seed emulsion: the polyether Glycols N21036.72g adding after will dewatering is equipped with in the there-necked flask of TM, whisking appliance, prolong, drips the 17.46g tolylene diisocyanate, logical nitrogen protection; Be warming up to 70 ℃ of reaction 1.5-2.0h and obtain performed polymer, add proper amount of acetone dilution performed polymer, add 3.67g hydrophilic chain extender DMPA, 3.40g small molecule chain extender BDO and 3 catalyzer DBTDL then; React 3h down in 80 ℃; Be cooled to 65-70 ℃ and add the HEA of 1.38g, reaction 1.5h, the viscosity of available small amount of acetone regulation system in reaction process then; Be cooled to 40 ℃ subsequently; Add 2.78g triethylamine neutralization reaction 0.5h, under high-speed stirring, slowly drip deionized water emulsification 0.5h, obtain blue transparent anion-type water-thinned polyurethane seed emulsion.
(2) preparation of pre-emulsified propenoate mixture: the 1.60g sodium lauryl sulphate is put in the 250.23g deionized water; After stirring is fully dissolved it; The mix monomer that slowly adds 80.30g Bing Xisuandingzhi and ethyl propenoate (mass ratio 3: 1), 0.5g Potassium Persulphate, 1.4g bicarbonate of ammonia and 4.5g pinakon two propylene esters stirs and got final product in 30 minutes.
(3) preparation of pre-emulsified vinylbenzene and acrylonitrile mixture: the 6.41g sodium lauryl sulphate is put in the 431.23g deionized water; After stirring is fully dissolved it; Slowly add the mix monomer of 194.12g vinylbenzene and 96.10g vinyl cyanide, stir and obtained pre-emulsion in 30 minutes.
(4) preparation of composite emulsion: the anion-type water-thinned polyurethane seed emulsion of step (1) preparation is added in the 2000ml four-hole bottle that TM, whisking appliance and reflux condensing tube are housed; Agitator also is warming up to 60 ℃; 0.5h after be warming up to 78 ℃; Begin to drip the pre-emulsified propenoate mixture of step (2) preparation, drip off insulation reaction 1.5h about 2.0-3.0h; Add the 0.9g Potassium Persulphate subsequently, drip the pre-emulsified vinylbenzene and the acrylonitrile mixture of step (3) preparation, drip off about 4.0-5.0h, add tert-dodecyl mercaptan 0.6g, insulation reaction 3h obtains composite emulsion again.
(5) anion-type water-thinned polyurethane/the gather preparation of (cinnamic acrylic ester-vinyl cyanide) resin
The composite emulsion that the NaCl solution of 5wt% is added step (4) preparation carries out breakdown of emulsion, after operations such as flocculation, washing, drying, grinding, promptly gets anion-type water-thinned polyurethane/gather (cinnamic acrylic ester-vinyl cyanide) resin.
Embodiment 2:
Utilize synthetic anion-type water-thinned polyurethane emulsion among the embodiment 1, carry out the seeded emulsion polymerization reaction.Change the content and the kind of the propenoate that adds, and when carrying out the graft emulsion copolymerization, change the content that adds vinylbenzene and vinyl cyanide mix monomer, all the other steps are identical with embodiment 1.Obtain anion-type water-thinned polyurethane and the modified resin that gathers (cinnamic acrylic ester-vinyl cyanide) resin different ratios.
Claims (5)
1. an anion-type water-thinned polyurethane/gather the preparation method of (cinnamic acrylic ester-vinyl cyanide) composite emulsion comprises the preparation of anion-type water-thinned polyurethane seed emulsion and each unit process of preparation of composite emulsion, it is characterized in that:
The preparation of said anion-type water-thinned polyurethane seed emulsion is the tolylene diisocyanate mixing with the polyether Glycols of 20-40 weight part and 35-60 weight part; Reacted 2.5 hours at 70 ℃ under the nitrogen protection; Add then the 3-10 weight part dimethylol propionic acid, 3-10 weight part 1; The catalyzer dibutyl tin laurate of 4-butyleneglycol and 0.5-3 weight part; Continue down reaction 3h in 80 ℃, be cooled to 60-70 ℃ and add 3-10 parts by weight of acrylic hydroxyl ethyl ester reaction 1.5h subsequently, then be cooled to 40 ℃ and add the triethylamine neutralization reaction 20-30min of 3-10 weight part; Add the deionized water emulsification 25min of 100-150 weight part at last, obtain the anion-type water-thinned polyurethane seed emulsion;
The preparation of said composite emulsion is that the anion-type water-thinned polyurethane seed emulsion with the 20-60 weight part is warming up to 60-80 ℃ of insulation 0.5h; Drip the pre-emulsified propenoate mixture of 20-30 weight part then; Drip off continued insulation reaction 1.5h; The pre-emulsified vinylbenzene and the acrylonitrile mixture of Dropwise 5 0-100 weight part drip off continued insulation reaction 3h and get final product subsequently.
2. preparation method according to claim 1 is characterized in that: said polyether Glycols is selected from polyether Glycols N210 or polyether Glycols N220.
3. preparation method according to claim 1; It is characterized in that: said pre-emulsified propenoate mixture constitutes by weight: propenoate 35-45 part; Emulsifying agent 0.5-2.5 part, initiator 0.1-0.35 part, pH value regulator 0.1-0.35 part; Linking agent 1.5-3 part, deionized water 55-65 part;
Said propenoate is selected from Bing Xisuandingzhi, ethyl propenoate, the Isooctyl acrylate monomer one or more;
Said emulsifying agent is selected from anionic emulsifier and/or nonionic emulsifying agent;
Said initiator is selected from one or both in Potassium Persulphate, ammonium persulphate, the Diisopropyl azodicarboxylate;
Said pH value regulator is selected from one or both in yellow soda ash, sodium hydrogencarbonate, the Sodium phosphate, dibasic;
Said linking agent glycol two propylene ester and/or the tri (propylene glycol) diacrylates of selecting oneself.
4. preparation method according to claim 1; It is characterized in that: said pre-emulsified vinylbenzene and acrylonitrile mixture constitute by weight: mixture 35-45 part of vinylbenzene and vinyl cyanide; Emulsifying agent 0.5-2.5 part; Initiator 0.1-0.35 part, molecular weight regulator tert-dodecyl mercaptan 0.1-1.2 part, deionized water 55-65 part;
Said emulsifying agent is selected from anionic emulsifier and/or nonionic emulsifying agent;
Said initiator is selected from one or both in Potassium Persulphate, ammonium persulphate, the Diisopropyl azodicarboxylate;
Said pH value regulator is selected from one or both in yellow soda ash, sodium hydrogencarbonate, the Sodium phosphate, dibasic.
5. according to claim 3 or 4 described preparing methods, it is characterized in that:
Said anionic emulsifier is selected from sodium lauryl sulphate, X 2073 or polyethers NP amber sulfonate; Said nonionic emulsifying agent is selected from polyoxyethylene nonylphenol or polyoxyethylene octylphenol ether.
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Cited By (5)
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| CN104293073A (en) * | 2014-05-13 | 2015-01-21 | 中国林业科学研究院木材工业研究所 | Aqueous elastic paint and its preparation method |
| CN105647047A (en) * | 2016-01-21 | 2016-06-08 | 天津中财型材有限责任公司 | Chemical modification ASA resin and preparation method and application thereof |
| CN106674437A (en) * | 2016-12-31 | 2017-05-17 | 佛山市顺德区巴德富实业有限公司 | Polyurethane-acrylate hybrid emulsion and preparation method thereof |
| CN109651571A (en) * | 2018-12-28 | 2019-04-19 | 四川中物材料股份有限公司 | A kind of HI high impact ASA graft copolymer and synthetic method |
| CN115302600A (en) * | 2022-09-01 | 2022-11-08 | 广东大自然家居科技研究有限公司 | Modified solid wood floor and manufacturing method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293073A (en) * | 2014-05-13 | 2015-01-21 | 中国林业科学研究院木材工业研究所 | Aqueous elastic paint and its preparation method |
| CN104293073B (en) * | 2014-05-13 | 2018-11-06 | 中国林业科学研究院木材工业研究所 | A kind of aqueous elastic paint and preparation method thereof |
| CN105647047A (en) * | 2016-01-21 | 2016-06-08 | 天津中财型材有限责任公司 | Chemical modification ASA resin and preparation method and application thereof |
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| CN106674437A (en) * | 2016-12-31 | 2017-05-17 | 佛山市顺德区巴德富实业有限公司 | Polyurethane-acrylate hybrid emulsion and preparation method thereof |
| CN109651571A (en) * | 2018-12-28 | 2019-04-19 | 四川中物材料股份有限公司 | A kind of HI high impact ASA graft copolymer and synthetic method |
| CN109651571B (en) * | 2018-12-28 | 2019-11-05 | 四川中物材料股份有限公司 | A kind of HI high impact ASA graft copolymer and synthetic method |
| CN115302600A (en) * | 2022-09-01 | 2022-11-08 | 广东大自然家居科技研究有限公司 | Modified solid wood floor and manufacturing method thereof |
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