CN1473863A - Process for preparing water dispersion of crosslinking vinyl resin/polyurethane hybrid resin - Google Patents
Process for preparing water dispersion of crosslinking vinyl resin/polyurethane hybrid resin Download PDFInfo
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- CN1473863A CN1473863A CNA021363927A CN02136392A CN1473863A CN 1473863 A CN1473863 A CN 1473863A CN A021363927 A CNA021363927 A CN A021363927A CN 02136392 A CN02136392 A CN 02136392A CN 1473863 A CN1473863 A CN 1473863A
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Abstract
During the copolymerizing of ethylene monomer emulsion or into water dispersed emulsion of vinyl resin copolymer, hydrophilic or non-hydrophilic polyurethane pre-polymer is added, so that hydroxy, carboxylic and other group in the vinyl polymer chain segment and the NCO or OH end radical in polyurethane pre-polymer react to graft polyurethane chain segment onto vinyl copolymer structure. The product is then mixed with isocyanate to prepare water dispersion of crosslinked vinyl copolymer resin/polyurethane hybrid resin. The resin may be used as paint and adhesive used in automobile, building, timber and other industries.
Description
The present invention is the preparation method of crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.
Along with improving constantly of Economic development and environmental requirement, the research of green material gets more and more people's extensive concerning day by day, therefore is that the material of dispersion medium replaces the inexorable trend that traditional solvent-dispersed materials is the Materials science development with water.Each state as aqueous polyurethane, waterborne polyester, aqueous epoxy resins etc., is applied to fields such as coating, tackiness agent all competitively studying waterborne polymeric in recent years.Aqueous polyurethane (PU) is as research in the water-base resin and the kind that is most widely used, and extremely people paid close attention in recent years.As far back as nineteen forty-two, Schlack has successfully prepared cation-type water-thinned polyurethane first.But after self-emulsification occurs, just make synthetic polyaminoester emulsion stability and film forming properties be improved, make it to obtain great industrial application value.Bayer companies in 1967 carry out the industrial production of aqueous polyurethane first.Entered since the eighties, advanced countries such as the U.S., Germany, Britain, Japan have successively released the water-based PU of the multiple trade mark, as the Neoraz of ICI company, the SpensolL of Reichold company and the Witcobond of Witco company etc., water-based PU is widely used in fields such as coating, binding agent, hide finishes and printing ink, the research-and-development activity of water-based PU has obtained development rapidly, at present, the patent of relevant water-based PU has reached more than 2000 piece.
U.S. Pat 5173526 has been described a kind of method for preparing water dispersible polyurethane/vinyl polymer dispersion.The steps include: the end capped base polyurethane prepolymer for use as of isocyano of a kind of carboxylic water-dispersion of (a) preparation; (b) add vinyl monomer and form performed polymer/monomer mixture; (c) add a kind of tertiary amine in the mixture; (d) this performed polymer/monomer mixture is distributed in the water; (e) introduce oil-soluble initiator and chainextender in the system; (f) polymerization of vinyl monomer and the chain extension of base polyurethane prepolymer for use as are finished in heating.European patent has reported that a class contains the two component systems of improvement of the polymkeric substance and the polyisocyanates of crosslinkable hydroxy, refers in particular to the hybrid of a kind of hydroxy acrylate and the dispersible polyisocyanates of water.Its preparation process is similar with US5173526, different is will add at least a acrylate monomer that contains a hydroxyl in (b) to form performed polymer/monomer mixture, (c) by a kind of azanol hydroxyl is introduced in the base polyurethane prepolymer for use as structure in, (e) chainextender that adds a kind of hydroxyl in, after polymerization and chain extension are finished, this is mixed dispersion liquid mix at last with water dispersible polyisocyanate.Compare with acrylate resin with pure urethane, hybrid resin has been taken into account the performance and the price of product, and promptly it not only combines urethane, acrylate resin characteristics separately, also may produce new performance advantage, form the effect of 1+1＞2, also reduced cost simultaneously.
In vinyl polymer emulsions such as vinyl acetate emulsion, acrylic ester emulsion, styrene-butadiene latex, the organic solution of polyisocyanates is disperseed the aqueous adhesive that forms, be called the aqueous vinyl polyurethane adhesive.General merchandise vinyl urethane tackiness agent is a two-component adhesive, with aqueous vinyl resin, filler and surfactant mixtures is host, and the mixture that has polyisocyanates, solvent or the stablizer of two above NCO groups with polymeric MDI etc. is a linking agent.Isocyanate solution can well disperse in Vinylite solution, and after moisture evaporation process and drying, isocyanic ester and water-base resin and water reaction produce water-fast, heat-stable cured article.The isocyanic ester that can be used for making the aqueous vinyl polyurethane adhesive has: PAPI, MDI, TDI, TDI-TMP affixture, triphenylmethane triisocyanate, HDI, IPDI, polyisocyanates such as XDI, H12MDI, and the performed polymer of the end NCO group made of they and polyethers or polyester, that the most frequently used is poly methylene poly phenyl poly isocyanate (PAPI).This type of tackiness agent be 1974 by the exploitation of Japanese Koyo Sangyo Ltd., be mainly used in wood adhesive.The whole world existing number state company more than ten buys its patented technology so far, produces the aqueous vinyl polyurethane adhesive.Formaldehydeless emitting is free from environmental pollution during such adhesive solidification.It is reported that before and after 1985, this type of tackiness agent annual production of Japan reaches 10,000 tons.
The aqueous vinyl polyurethane adhesive is mainly used in wood working (as glued board, shaving board manufacturing, various adhesive bonding of wood), also can be used for the bonding of materials such as metal sheet, paper, PVC plastics, synthetic plate, porous plastics, concrete.Its advantage is: cost is low than the solvent borne polyurethane tackiness agent, has excellent water-resistance, and adhering speed is fast, and shortcoming is to add that shorten working life behind the isocyanic ester component.
The present invention is in vinyl monomer emulsion copolymerization process or directly introduces hydrophilic or not hydrophilic base polyurethane prepolymer for use as in the Vinylite aqueous dispersions, NCO or the reaction of OH end group by group such as the hydroxyl on the vinyl polymer segment, carboxyl and amide group and polyurethane prepolymer produce chemical bond, thereby the urethane segment is grafted in the ethylenic copolymer structure, mix preparation crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions again with polyisocyanates or aminoresin.Different with the existing method for preparing Vinylite/polyurethane hybrid aqueous dispersions such as US5173526 and EP0742239A1, the present invention is that the dispersed polyurethane performed polymer carries out chemical precrosslink in the ethylenic copolymer aqueous dispersions.Compare with traditional aqueous vinyl urethane resin, owing to adopted precrosslink, this aqueous vinyl multipolymer/polyurethane hybrid resin has higher cross-linking density, thereby behind its crosslinking curing, the water tolerance of film, solvent resistance, intensity significantly improve.And precrosslink has promoted to form interpenetrating(polymer)networks between ethylenic copolymer and urethane, thereby can better bring into play urethane and Vinylite performance advantage separately, and in addition, soft section that base polyurethane prepolymer for use as comprises will be improved the toughness of material significantly.This crosslinking type aqueous hybrid resin can be used as coating, tackiness agent, is applied in fields such as automobile, building, wood working.Especially as tackiness agent, not only have the characteristics that the Vinylite initial bonding strength is high and the urethane applicable base materials is wide, bonding force is strong, the aqueous vinyl polyurethane adhesive that special its water tolerance, bonding strength and snappiness are all more general is higher, thereby has wide market application prospect.
Details are as follows in the present invention:
(1) used vinyl monomer is vinyl acetate, (methyl) acrylate, (methyl) vinylformic acid, (methyl) vinylformic acid hydroxyl second (third) ester, the basic acrylamide of hydroxyl first (second), toxilic acid diethyl (fourth) ester, fumaric acid diethyl (fourth) ester, vinylbenzene etc.;
(2) mixture of vinyl monomer is added dropwise in the deionized water that contains emulsifying agent, initiator, 70-90 ℃ was reacted 4-8 hour, preparation ethylenic copolymer emulsion;
(3) polyether glycol or polyester polyol and isocyanate-monomer (comprising HDI, IPDI, TDI etc.) reacted 4-6 hour down in 70-100 ℃, make-NCO or-the end capped base polyurethane prepolymer for use as of OH, or introducing part dimethylol propionic acid, after prepolymerization reaction is finished, be dispersed in the water through neutralization, get the base polyurethane prepolymer for use as aqueous dispersions;
(4) base polyurethane prepolymer for use as or its aqueous dispersions are joined in the ethylenic copolymer emulsion, 70-90 ℃ was reacted 1-3 hour, or prepare urethane (PU) or polyurethane/polyacrylate (PUA) aqueous dispersions by US5173526, with the blend of ethylenic copolymer aqueous dispersions, prepare the Vinylite aqueous dispersions of polyurethane chemistry modification again;
(5) polyisocyanate solution is dispersed in the above-mentioned hybrid resin aqueous dispersions, polyisocyanates comprises tripolymer and the polymer of PAPI, MDI, TDI-TMP affixture, HDI biuret, HDI, IPDI, MDI, TDI, or the polyisocyanates of process hydrophilic treatment, or with-the end capped base polyurethane prepolymer for use as solution of NCO is linking agent, preparation crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.As tackiness agent its working life be 8-16 hour;
(6) polyisocyanate solution or non-aqueous base polyurethane prepolymer for use as solution solvent for use are aliphatics or aromatic hydro carbons, ketone, ester class etc. in the step (5), as acetone, butanone, N-Methyl pyrrolidone, 1-Methoxy-2-propyl acetate etc., solid content is 30-100%, be generally 60-90%, NCO content is 5-25%, is generally 10-20%.
The present invention is described in detail for following example, but content of the present invention is not subjected to the restriction of embodiment.
Example one
In the four-hole boiling flask of reflux exchanger is housed, certain proportion adds deionized water, polyvinyl alcohol 1799, polyxyethylated alkylphenol nonionic emulsifier OS, anionic emulsifier IS, be warming up to 80 ℃, begin to drip mixture of vinyl monomer, comprise vinyl acetate, dibutyl maleate and vinylformic acid, isothermal reaction 5-7 hour, add 10% persulfate aqueous solution during this time in batches, the ethylenic copolymer emulsion.
Polyethylene glycol adipate (molecular weight 2000) vacuum hydro-extraction (90-100 ℃) 1.5hr; add dimethylol propionic acid (DMPA), N-Methyl pyrrolidone (NMP), isophorone diisocyanate (IPDI) under the argon shield successively; be warming up to 70-90 ℃ of reaction 3-5 hour; add the triethylamine neutralization;-the end capped aqueous polyurethane performed polymer of OH, its solid content is 80%.Under the high degree of agitation, be dispensed in the above-mentioned ethylenic copolymer emulsion, 80-90 ℃ was reacted 1-2 hour, made the Vinylite aqueous dispersions of polyurethane chemistry modification.
Above-mentioned modified vinyl resin aqueous dispersions is mixed with HDI tripolymer solution by a certain percentage, make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.The each component prescription is as follows:
Table 1
The raw materials quality umber
Deionized water 140
Polyvinyl alcohol 1,799 5
Nonionic emulsifying agent OS 3
Anionic emulsifier IS 1
Vinyl acetate 69
Dibutyl maleate 23
Vinylformic acid 8
Persulfate aqueous solution (10%) 6
Hydrophilic base polyurethane prepolymer for use as 50
HDI tripolymer (80% solid content) 15
Example two
Prepare ethylenic copolymer emulsion (solid content 50%) and hydrophilic base polyurethane prepolymer for use as by example one method, this base polyurethane prepolymer for use as is dispersed in the deionized water, get performed polymer aqueous dispersions (solid content 45%), be dispensed into then in the above-mentioned ethylenic copolymer emulsion, 80-90 ℃ was reacted 1-2 hour, made the Vinylite aqueous dispersions of polyurethane chemistry modification.This modified vinyl resin aqueous dispersions is mixed with HDI tripolymer solution by a certain percentage, make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.The each component prescription is as follows:
Table 2
The raw materials quality umber
Deionized water 140
Polyvinyl alcohol 1,799 7
Nonionic emulsifying agent OS 3.9
Anionic emulsifier IS 1.3
Vinyl acetate 90
Dibutyl maleate 30
Vinylformic acid 10
Persulfate aqueous solution (10%) 8
Base polyurethane prepolymer for use as aqueous dispersions 140
HDI tripolymer (80% solid content) 20
Example three
Polyester vacuum hydro-extraction in the example one (90-100 ℃) 1.5hr; add N-Methyl pyrrolidone (NMP), isophorone diisocyanate (IPDI) under the argon shield successively; be warming up to 70-90 ℃ of reaction 3-5 hour ,-the end capped base polyurethane prepolymer for use as of OH, its solid content is 80%.Replace the aqueous polyurethane performed polymer with this nonaqueous base polyurethane prepolymer for use as, make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.
Example four
The composition of vinyl monomer changes in the example one: vinyl acetate, butyl acrylate, vinylformic acid, hydroxyethyl methylacrylate make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.The each component prescription is:
Table 3
The raw materials quality umber
Deionized water 150
Nonionic emulsifying agent OS 2.7
Anionic emulsifier IS 0.9
Vinyl acetate 75
Butyl acrylate 20
Hydroxyethyl methylacrylate 5
Vinylformic acid 10
Persulfate aqueous solution (10%) 7
Hydrophilic base polyurethane prepolymer for use as 50
HDI tripolymer (80% solid content) 20
Example five
The composition of vinyl monomer changes in the example one: vinyl acetate, dibutyl maleate, methacrylic acid, n-methylolacrylamide make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.The each component prescription is:
Table 4
The raw materials quality umber
Deionized water 150
Polyvinyl alcohol 1,799 5
Nonionic emulsifying agent OS 2.7
Anionic emulsifier IS 0.9
Vinyl acetate 65
Butyl acrylate 20
N-methylolacrylamide 5
Methacrylic acid 10
Persulfate aqueous solution (10%) 7
Hydrophilic base polyurethane prepolymer for use as 45
HDI tripolymer (80% solid content) 20
Example six
Mixture of vinyl monomer dropwise adds and carries out pre-emulsification in the deionized water that is dissolved with initiator, emulsifying agent, pre-emulsion with 1/10 joins in second half deionized water, be warming up to 80 ℃, reacted 30 minutes, and began to drip remaining pre-emulsion, after 4-6 hour, add base polyurethane prepolymer for use as, 80-90 ℃ of constant temperature 1 hour mixes with HDI tripolymer solution after the cooling again, makes the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.Prescription is with table 1.
Example seven
100 parts and 20 parts deionized waters of base polyurethane prepolymer for use as aqueous dispersions in the example two mix, in 4-6 hour, at the uniform velocity be added drop-wise to the pre-emulsion in the example six in the system, 70-90 ℃ of isothermal reaction, all the other make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions with example six.
Example eight
12 parts of polyethylene glycol adipates (molecular weight 2000), IPDI6 part, NMP4 part, 90 ℃ were reacted 3-5 hour, and made-the end capped base polyurethane prepolymer for use as solution of NCO.This base polyurethane prepolymer for use as linking agent, is mixed with the Vinylite aqueous dispersions of the polyurethane chemistry modification of example one gained, make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.
Example nine
9 parts of polyethylene glycol adipates (molecular weight 2000), DMPA1 part, IPDI8 part, NMP4 part, 90 ℃ were reacted 3-5 hour, and made-the end capped hydrophilic base polyurethane prepolymer for use as of NCO solution.This hydrophilic base polyurethane prepolymer for use as linking agent, is mixed with the Vinylite aqueous dispersions of the polyurethane chemistry modification of example one gained, make the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.
Example ten
With part methyl-etherified melamine resin (CYMEL373) is linking agent, with the Vinylite aqueous dispersions of the polyurethane chemistry modification of the example one gained mixed by 1: 6, makes the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.
Claims (10)
1. the preparation method of a class crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions, preparation process is as follows:
(1) preparation Vinylite aqueous dispersions;
(2) preparation vinyl resin/polyurethane hybrid resin aqueous dispersions;
(3) preparation crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions.
2. according to the described method for preparing the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions of claim 1 (1), it is characterized in that containing emulsifying agent or having preparation Vinylite aqueous dispersions under the monomer condition of hydrophilic radical, hydrophilic radical wherein comprises carboxyl, hydroxyl, amido, amide group, ether or the like.
3. according to claim 1 (1), the 2 described methods that prepare the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions, it is characterized in that vinyl monomer is vinyl acetate, (methyl) acrylate, (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, (hydroxyl) acrylamide, maleic acid ester, fumarate, vinylbenzene etc.Wherein the ratio of vinyl acetate is 20-100%.
4. according to the described method for preparing the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions of claim 1 (2), it is characterized in that base polyurethane prepolymer for use as can add in the vinyl monomer polymerization process, can directly be scattered in the Vinylite emulsion, also can be with polyurethane aqueous dispersion and the blend of Vinylite aqueous dispersions.
5. according to claim 1 (2), the 4 described methods that prepare the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions, it is characterized in that urethane can utilize hydrophilic radical self-emulsifying or the outer emulsification of emulsifying agent, has the chemically crosslinked of part between the carboxyl in the hydroxyl on the polyurethane molecular chain, carboxyl and the Vinylite structure, hydroxyl.
6. according to claim 1 (2), 4, the 5 described methods that prepare the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions, it is characterized in that urethane is polyether-type or polyester type, hydroxyl value is 30-250mgKOH/g, be generally 50-120mgKOH/g, ratio in hybrid resin is 10-90%, is generally 20-60%.
7. according to the described method for preparing the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions of claim 1 (3), it is characterized by additional crosslink agent is that polyisocyanates, aminoresin or end group are the base polyurethane prepolymer for use as of NCO.
8. according to claim 1 (3), the 7 described methods that prepare the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions, it is characterized by tripolymer and polymer that polyisocyanates comprises HDI biuret, TDI, HDI, IPDI, MDI.
9. according to claim 1 (3), 7, the 8 described methods that prepare the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions, it is characterized by the dilution of linking agent useable solvents, solvent for use is ketone, ester class, alcohols isopolarity solvent, and consumption is the 10-50% of linking agent.
10. the method for preparing the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions according to claim 1, the solid content that it is characterized by the crosslinking vinyl resin/polyurethane hybrid resin aqueous dispersions is 20-60%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010040844A1 (en) * | 2008-10-09 | 2010-04-15 | Nuplex Resins B.V. | Aqueous hybrid dispersions |
| CN101724371B (en) * | 2009-12-18 | 2012-09-26 | 中钞特种防伪科技有限公司 | Hot melt adhesive composition and application thereof |
| CN101945906B (en) * | 2007-12-13 | 2014-07-16 | 帝斯曼知识产权资产管理有限公司 | Aqueous coating composition comprising polyurethanes and vinyl polymers |
| CN106316156A (en) * | 2016-07-29 | 2017-01-11 | 安徽丹凤集团桐城玻璃纤维有限公司 | Impregnating agent for coating glass fiber surface |
| CN111051265A (en) * | 2017-09-12 | 2020-04-21 | 竹本油脂株式会社 | Dispersion maintaining agent for hydraulic composition |
| CN111471269A (en) * | 2019-01-23 | 2020-07-31 | 山东卓远装饰材料有限公司 | Water rate precise control polymer composite material for plate modification and preparation method thereof |
| EP3755753B1 (en) * | 2018-02-21 | 2022-07-27 | Basf Se | Method for producing articles coated with adhesive |
-
2002
- 2002-08-06 CN CNA021363927A patent/CN1473863A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101945906B (en) * | 2007-12-13 | 2014-07-16 | 帝斯曼知识产权资产管理有限公司 | Aqueous coating composition comprising polyurethanes and vinyl polymers |
| WO2010040844A1 (en) * | 2008-10-09 | 2010-04-15 | Nuplex Resins B.V. | Aqueous hybrid dispersions |
| US8288468B2 (en) | 2008-10-09 | 2012-10-16 | Nuplex Resins B.V. | Aqueous hybrid dispersions |
| CN102239195B (en) * | 2008-10-09 | 2014-03-12 | 树脂核动力工业有限公司 | Aqueous hybrid dispersions |
| CN101724371B (en) * | 2009-12-18 | 2012-09-26 | 中钞特种防伪科技有限公司 | Hot melt adhesive composition and application thereof |
| CN106316156A (en) * | 2016-07-29 | 2017-01-11 | 安徽丹凤集团桐城玻璃纤维有限公司 | Impregnating agent for coating glass fiber surface |
| CN111051265A (en) * | 2017-09-12 | 2020-04-21 | 竹本油脂株式会社 | Dispersion maintaining agent for hydraulic composition |
| CN111051265B (en) * | 2017-09-12 | 2020-12-08 | 竹本油脂株式会社 | Dispersion maintaining agent for hydraulic composition |
| EP3755753B1 (en) * | 2018-02-21 | 2022-07-27 | Basf Se | Method for producing articles coated with adhesive |
| CN111471269A (en) * | 2019-01-23 | 2020-07-31 | 山东卓远装饰材料有限公司 | Water rate precise control polymer composite material for plate modification and preparation method thereof |
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