CN101469055A - Active organosilicon-polyurethane performed polymer and solvent-free active organosilicon-polyurethane emulsion prepared thereby - Google Patents

Active organosilicon-polyurethane performed polymer and solvent-free active organosilicon-polyurethane emulsion prepared thereby Download PDF

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CN101469055A
CN101469055A CNA2007103002846A CN200710300284A CN101469055A CN 101469055 A CN101469055 A CN 101469055A CN A2007103002846 A CNA2007103002846 A CN A2007103002846A CN 200710300284 A CN200710300284 A CN 200710300284A CN 101469055 A CN101469055 A CN 101469055A
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organosilicon
preferred
polyurethane prepolymer
emulsion
base polyurethane
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Inventor
阚成友
侯昭升
谢伟
赵志清
张勇
T·F·利姆
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Henkel AG and Co KGaA
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Priority to CNA2007103002846A priority Critical patent/CN101469055A/en
Priority to PCT/EP2008/066351 priority patent/WO2009080441A1/en
Publication of CN101469055A publication Critical patent/CN101469055A/en
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to an active organic silicon-polyurethane prepolymer and a solvent free active organic silicon-polyurethane emulsion prepared by the same. The preparation process comprises the following steps: using active organic silicon compound, isocyanate, polyether, hydrophilic monomer and the like as main raw materials to synthesize active organic silicon-polyurethane prepolymer through a bulk polymerization reaction, and then using the prepolymer to prepare the organic silicon-polyurethane emulsion with high stability through phase inversion emulsification technology without adding any organic solvent; and the emulsion can quick cross link along with volatilization of moisture at room temperature to form an emulsion film with good property. The preparation method has the advantages of little equipment investment, simple process and low production cost; and the prepared emulsion product can be widely applied to producing environment-friendly hydrophobic seal gum and water paint, and can also be used in the fields of leather processing, papermaking, textile dressing, and the like.

Description

Active organosilicon-base polyurethane prepolymer for use as and solvent-free active organosilicon-polyaminoester emulsion prepared therefrom
Technical field
The invention belongs to material science, more specifically, the present invention relates to a kind of active organosilicon-base polyurethane prepolymer for use as and preparation method thereof and utilize described organosilicon-base polyurethane prepolymer for use as to disperse the solvent-free active organosilicon-polyaminoester emulsion that obtains and the preparation method of described emulsion.
Background technology
Aqueous polyurethane (WPU) has obtained widespread use since eighties of last century the seventies has product to come out, and has shown good prospects for application.Because WPU is medium with water, compliance with environmental protection requirements not only, and can save the resource and the energy, thereby more and more be subjected to people's attention.Simultaneously, because WPU viscosity and mobile molecular weight with polymkeric substance are irrelevant, thereby can arrive desired horizontal with molecular-weight adjusting, and the influence of factors such as viscosity when using without worry about or flowability, so its range of application is constantly widened.WPU now has been widely used in leather processing, papermaking, textile finishing, fabric coating, tackiness agent, oil field with fields such as chemical.Reactive organosilicon compounds is incorporated among the WPU, can makes material have the performance of organosilicon and urethane concurrently.Organic siloxane modified WPU product has short film formation time usually, and in good work-ing life, its cementability, intensity, toughness, wear resistance and water tolerance and solvent resistance are also very excellent.
1997, (J.Coat.Technol., 1997,69 (870): 43-51 such as Chen; 1997,69 (875): 49-55) utilize the silane that contains epoxy group(ing) to come modifying cinepazid emulsion and polyurethane aqueous dispersion body as additive, the gained aqueous polymer emulsion has good package stability, and in use can very fast crosslinked film forming.Discover that this method of modifying can significantly improve the work-ing life of weathering resistance, solvent resistance, cementability and the latex film of latex film.
(polymer journal, 2000 (3): 319-324 such as Wang actor playing a martial role in Chinese operas; Polymer material science and engineering, 2001,17 (3): 102-105) having obtained solid content by steps such as solution polymerization, water-dispersion and steaming desolventize is the organic silicon modified aqueous polyurethane dispersion of 30wt%.But hydrolytic condensation takes place in this urethane aqueous based dispersions that contains terminal silicon alkoxyl group when at room temperature placing, and forms the waterbased urethane microgel.
(European Polymer J., 2004,40 (12): 2745-2755 such as Subramani; Progress in Organic Coatings, 2004,51 (4): 329-338) in the presence of organic solvent, adopt the isocyanic ester sealing technique to prepare and contain the segmental organic silicon modified aqueous polyurethane emulsion of Diacetylmonoxime, but this emulsion must make the isocyanate group deblocking through heating in use, the organo-silicon coupling agent that also will add siliceous alkoxyl group simultaneously makes the active isocyanate radical reaction that generates behind organosilicon and the deblocking, to realize hydrolytic crosslinking.Though the package stability of this dual-component aqueous polyurethane system is fine, need optional equipment in use, and mixed system is shorter work-ing life.
(J.Appl.Polym.Sci. such as nearest Subramani, 2005,98 (2): 620-631) with Toluene-2,4-diisocyanate, 4-vulcabond, polyoxyethylene glycol and 2, the 2-dimethylol propionic acid is a raw material, is solvent with acetone, synthesized isocyanate-terminated base polyurethane prepolymer for use as, add γ-An Bingjisanjiayangjiguiwan after neutralization and water-dispersion, vacuum is steamed and is removed acetone then, obtains organosilicon-polyurethane aqueous dispersion body.
In a word, acetone and other organic solvent has all been used in the preparation of the active organosilicon-polyaminoester emulsion of bibliographical information, though the most of solvent in the system can remove its steaming by vacuumizing, but the harm that residual solvent causes environment and the loss of solvent recuperation remain a problem demanding prompt solution, and the vacuum of solvent steams to remove simultaneously also can increase extra technology and bring a large amount of energy consumptions.
In addition, in order to keep the stability of emulsion, the active organosilicon component concentration of these active organosilicon-polyaminoester emulsions is lower usually, may only account for the 2-5wt% of dispersion solid content, and the performance of the content of active organosilicon and latex film is closely related.
Summary of the invention
On the one hand, the invention provides a kind of active organosilicon-base polyurethane prepolymer for use as and preparation method thereof, on the other hand, the present invention also provides and utilizes the described active organosilicon-solvent-free active organosilicon-polyaminoester emulsion of base polyurethane prepolymer for use as dispersion acquisition and the preparation method of described emulsion.
Active organosilicon of the present invention-base polyurethane prepolymer for use as adopts the preparation of mass polymerization technology, and the content of the active organosilicon part of this active organosilicon-base polyurethane prepolymer for use as can improve than prior art greatly up to 15wt%.
Solvent-free active organosilicon of the present invention-polyaminoester emulsion adopts the preparation of phase reversion emulsifying technology, and its technology is simple, processing ease, and production cost is low.
According to the present invention, described solvent-free active organosilicon-polyaminoester emulsion does not contain any organic solvent, therefore helps environmental protection; The solid content of this emulsion reaches as high as 55wt%, and latex particle size can reach about 200nm, and these all have obvious improvement than prior art; This emulsion has good package stability and freeze-thaw stability, and particularly, this emulsion at room temperature can be stablized and stores more than 180 days and can stablize storage 50 ℃ under more than 150 days.
This solvent-free active organosilicon-polyaminoester emulsion of the present invention not only can be directly used in fields such as leather processing, papermaking, textile finishing, and can be widely used in the production of environmental friendliness aqueous sealant and water-borne coatings.
In addition, the minimum film-forming temperature of solvent-free active organosilicon-polyaminoester emulsion of the present invention can be lower than 0 ℃, it at room temperature can very fast crosslinked film forming with the volatilization of moisture, and its crosslinking degree can reach about 90wt%, and rate of film build is also far away from common aqueous polyurethane emulsion; And the latex film that is obtained has the good mechanical performance, as has extraordinary sticking power, snappiness, shock strength etc.
Particularly, the invention provides a kind of active organosilicon-base polyurethane prepolymer for use as, the weight-average molecular weight of wherein said organosilicon-base polyurethane prepolymer for use as is 3000-200000, preferred 5000-100000, most preferably 8000-50000 and have following schematic general formula:
Figure A200710300284D00091
Wherein, n is 0 or 1, and m is the integer of 5-1000, R 1, R 2Be methyl or ethyl independently respectively, R 3For methylene radical or-(CH 2) 3-, R 4Be H or phenyl, R 5For-(CH 2) 6-,
Figure A200710300284D00092
Figure A200710300284D00093
Or R 6Be methyl or hydrogen, condition is R 6All be not hydrogen, R 7Be methyl, ethyl, propyl group, butyl or benzyl, and R 8Be methyl and/or ethyl.
According to the present invention, the content of active organosilicon part can reach 15wt% in described active organosilicon-base polyurethane prepolymer for use as, is preferably 9-12.5wt%.
The present invention also provides the preparation method of described active organosilicon-base polyurethane prepolymer for use as, and this method utilizes the mass polymerization technology to carry out, and comprises the steps:
A. vulcabond, polyethers and hydrophilic monomer are mixed, heat up then, and fully stirring makes it fusion;
B. in the molten mixture of step a, add catalyzer and make it abundant polymerization;
C. in the reaction mixture of step b, add tertiary amine and continue stirring reaction for some time; With
D. in the reaction mixture of step c, add the active organosilicon monomer, continue isothermal reaction for some time, obtain active organosilicon-base polyurethane prepolymer for use as at last.
More specifically, according to the present invention, in the step a of the method for preparing organosilicon-urethane (SPU) performed polymer:
Raw materials used vulcabond is selected from Toluene-2,4-diisocyanate, 4-vulcabond (TDI), ditan-2,4 '-vulcabond (MDI), 1,6-hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) and their mixture;
Described polyethers is selected from the blend of polyoxyethylene (PEO), polyoxytrimethylene (PPO), ethylene oxide propylene oxide copolymer (PEO-co-PPO) and polyoxyethylene and polyoxytrimethylene, with control this polyethers molecular weight ranges at 200-40000, preferred 200-20000, most preferably 300-10000; With
Described hydrophilic monomer is selected from 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylolpropionic acid (DMBA) and their mixture;
In addition, the mol ratio of described polyethers and vulcabond is 1/1.05-1/5, preferred 1/1.1-1/3, most preferably 1/1.2-1/2; With
The mol ratio of described hydrophilic monomer and polyethers is 1/1-1/10, preferred 1/2-1/8, most preferably 1/2-1/4;
In addition, in step a, after described raw material is mixed in proportion, make mixture be warming up to 35-120 ℃, preferred 50-95 ℃, made it to stir fusion 5 minutes-10 hours, preferred 10 minutes-4 hours, most preferably 15 minutes-1 hour, make the complete fusion of described mixture and mix.
According to the present invention, in the step b of the method for preparing organosilicon-urethane (SPU) performed polymer:
Employed catalyzer is the organic tin compound, is selected from dibutyltin dilaurate (DBTDL) and stannous octoate (SO), and/or is tertiary amines, is selected from triethylamine and Trimethylamine 99; Be preferably the organic tin compound; This catalyst consumption is the 0.01-5wt% of total monomer weight, preferred 0.01-3wt%, most preferably 0.05-1.5wt%; After adding catalyzer, make described molten mixture polymerization (preferred constant temperature polymerization) 0.5-24 hour, preferred 0.5-12 hour, most preferably 1.5-4 hour.
According to the present invention, in the step c of the method for preparing organosilicon-urethane (SPU) performed polymer: the tertiary amine that is added is selected from Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine and contains the tertiary amine of benzyl, preferred Trimethylamine 99 and triethylamine, most preferably triethylamine; This tertiary amine preferably adopts the dropping mode to add, and the mol ratio of its add-on and hydrophilic monomer is 0.8/1-3/1, preferred 1/1-2/1, most preferably 1/1-1.5/1; Continued stirring reaction 5 minutes-10 hours after adding tertiary amine, preferred 10 minutes-3 hours, most preferably 15 minutes-1.5 hours.
According to the present invention, in the steps d of the method for preparing organosilicon-urethane (SPU) performed polymer:
The active organosilicon monomer that is added is selected from γ-An Bingjisanyiyangjiguiwan (APTES), γ-aminopropyl methyldiethoxysilane (APMDES), γ-An Bingjisanjiayangjiguiwan (APTMS), γ-aminopropyl methyl dimethoxysilane (APMDMS), anilinomethyl triethoxysilane (PAMTES), anilinomethyl methyldiethoxysilane (PAMMDES), anilinomethyl trimethoxy silane (PAMTMS) and anilinomethyl methyl dimethoxysilane (PAMMDMS);
The mol ratio of monomeric add-on of this active organosilicon and vulcabond is 1/1.1-1/5, preferred 1/1.2-1/4, most preferably 1/1.5-1/2.5;
Continue isothermal reaction 10 minutes-24 hours after adding the organosilicon reactive monomer, preferred 20 minutes-10 hours, most preferably 30 minutes-4 hours, obtain organosilicon-base polyurethane prepolymer for use as at last.
The present invention also provides a kind of solvent-free active organosilicon-polyaminoester emulsion; it is included in the above-mentioned organosilicon-base polyurethane prepolymer for use as of dispersive and protective colloid and emulsifying agent in the water; the solid content of this emulsion is 25-55wt%; preferred 30-45wt%; latex particle size is less than 500nm, preferred 100-300nm.
The present invention further provides the preparation method of described solvent-free active organosilicon-polyaminoester emulsion, this method adopts the phase reversion emulsifying process under the organic solvent-free existence to carry out, and comprises the steps:
A1. in organosilicon-base polyurethane prepolymer for use as of the present invention, add protective colloid, and stirring makes it to mix;
B1. make the mixed system naturally cooling of step a1, then under agitation to wherein adding emulsifier aqueous solution; With
C1. stirring fully disperses organosilicon-base polyurethane prepolymer for use as, with the pH value of dilute acid solution regulation system, obtains organosilicon-polyaminoester emulsion then.
More specifically, according to the present invention, in the step a1 of the method for preparing solvent-free active organosilicon-polyaminoester emulsion:
The mixing temperature of organosilicon-base polyurethane prepolymer for use as and protective colloid is the polymerization temperature of the described organosilicon-base polyurethane prepolymer for use as of preparation, the time that mixes is 5-240 minute, preferred 10-120 minute, most preferably 15-60 minute, make organosilicon-base polyurethane prepolymer for use as and protective colloid thorough mixing;
The consumption of described protective colloid is the 0.1-20wt% of system solid content, preferred 0.5-10wt%, most preferably 1-7wt%; With
Described protective colloid is polyether-modified polysiloxane, and its schematic general formula is as follows:
Figure A200710300284D00121
Wherein, x is the integer of 10-10000, and y is the integer of 0-10000, and n is the integer of 5-2000, and m is that integer and the R of 0-2000 is H, CH 3, C 2H 5Or OCCH 3
In the present invention, the preparation of the method for described protective colloid reference (Cai Zhenyun etc., organosilicon material, 2005,19 (4): 20-22).
According to the present invention, in the step b1 of the method for preparing solvent-free active organosilicon-polyaminoester emulsion:
Make the mixed system naturally cooling that forms among the step a1, system temperature is controlled at 20-90 ℃, this temperature generally is lower than the polymerization temperature of the described organosilicon-base polyurethane prepolymer for use as of preparation, adopts the mode that drips or add in batches to add emulsifier aqueous solution then in system;
Described emulsifying agent is the mixture of anionic emulsifier or anionic emulsifier and nonionic emulsifying agent, described anionic emulsifier is selected from aliphatic sulphate, aromatic sulfonic acid salt, aliphatic sulfonate and aromatic sulphonate, preferred aliphat vitriol such as sodium lauryl sulphate (SDS), described nonionic emulsifying agent is selected from polyoxyethylene alkyl ester, polyethylene oxide alkyl ethers and polyoxyethylene aryl ethers, preferred polyoxyethylene aryl ethers such as polyoxyethylene nonyl phenyl Vinyl Ether (OP-10); With when for mixture, wherein the weight ratio of anionic emulsifier and nonionic emulsifying agent is 1/50-1/5, preferred 1/35-1/10, most preferably 1/30-1/15; With
The consumption of described emulsifying agent is the 0.1-10wt% of system solid content, preferred 0.5-7.5wt%, most preferably 1-4wt%.
According to the present invention, in the step c1 of the method for preparing solvent-free active organosilicon-polyaminoester emulsion:
Initial stir speed (S.S.) is 5-100rpm, preferred 5-75rpm, most preferably 10-50rpm, along with the dispersion of organosilicon-base polyurethane prepolymer for use as in water, improve stir speed (S.S.) gradually, final stir speed (S.S.) is 150-3000rpm, preferred 200-2500rpm, most preferably 200-2000rpm;
After treating that organosilicon-base polyurethane prepolymer for use as fully disperses, under agitation dropwise add the pH=5-9 of the diluted acid regulation system of 2-10wt%, preferred pH=5.5-8.5, pH=6-8 most preferably, described diluted acid is mineral acids such as dilute hydrochloric acid, dilute sulphuric acid, also can be organic acids such as dilute acetic acid, preferred dilute hydrochloric acid.
According to the present invention; in the process of the described organosilicon-base polyurethane prepolymer for use as of preparation and organosilicon-polyaminoester emulsion, all do not use any organic solvent; therefore these preparation methods are cost savings and energy-conserving and environment-protective; and the molecular weight of described organosilicon-base polyurethane prepolymer for use as; wetting ability and rigidity etc. can be by the raw materials used and controls recently that feeds intake; in addition; owing to when carrying out described organosilicon-base polyurethane prepolymer for use as phase reversion emulsification, used protective colloid, thereby the freeze-thaw stability and the package stability under room temperature and 50 ℃ of described organosilicon-polyaminoester emulsion have obviously been improved.
Embodiment
Below by embodiment, the present invention is described in further detail, described embodiment only is to describe the present invention rather than restriction the present invention.
In following all embodiment: the emulsion solid content gravimetric determination; Latex particle size is measured down in 25 ℃ on the Britain Zetasize-3000HS of Malvern company laser particle size analyzer; Emulsion viscosity is measured down at 25 ℃ with homemade NDJ-8S digital display rotational viscosimeter; The freeze-thaw stability of emulsion is measured by State Standard of the People's Republic of China GB9268-88 method; Adopt static method in climatic chamber, to measure with the package stability of emulsion under room temperature and 50 ℃.
In following all embodiment: latex film is by the preparation of State Standard of the People's Republic of China GB1727-92 method; The sticking power of latex film, snappiness and resistance to impact shock are measured by State Standard of the People's Republic of China GB1720-79, GB/T1731-93 and GB/T1732-93 method respectively; Temperature during latex film weightlessness 1wt% is measured in nitrogen atmosphere on U.S. Universal company's T GA2050 thermogravimetric analyzer with thermogravimetry, and temperature rise rate is 20 ℃/minute; With by being solvent extraction 24 hours with the butanone with soxhlet extraction with latex film, the mass percent of the polymkeric substance that is got off by extracting is not defined as the crosslinking degree of latex film.
Embodiment 1
Synthesizing of organosilicon-base polyurethane prepolymer for use as: 7.5g MDI (chemical pure), 15.0gPPO-1000 (technical grade) and 0.74g DMBA (chemical pure) are added in the there-necked flask, be warming up to 90 ℃, made it to stir fusion 30 minutes; Add 0.2g catalyzer DBTDL, isothermal reaction 100 minutes; Add in the 0.71g triethylamine (TEA, analytical pure) and the carboxyl on the performed polymer side chain, continued stirring reaction 25 minutes; Then, add 3.23g APTES (technical pure), continue isothermal reaction 80 minutes, obtain organosilicon-base polyurethane prepolymer for use as.
The emulsification of organosilicon-base polyurethane prepolymer for use as: under 90 ℃, adding 1.5g protective colloid in 27.2g organosilicon-base polyurethane prepolymer for use as (in its schematic general formula: x=500, y=100, m=0, n=300 and R are CH 3) and mixed 20 minutes; After making described mixture naturally cool to about 50 ℃, the control stir speed (S.S.) adds the deionized water that 30ml is dissolved with 0.45g sodium lauryl sulphate (SDS, chemical pure) then in system about 50rpm; After 20 minutes, divide three times and add the 30ml deionized water, each 10ml, 15 minutes at interval, in this process, improve stir speed (S.S.) gradually to about 400rpm, stir after 10 minutes, the dilute hydrochloric acid of Dropwise 5-10wt% in system, the pH value of regulating emulsion is about 6-8, obtains the oyster white target product at last.
The character of gained emulsion and corresponding latex film sees Table 1 and table 2 respectively.
Embodiment 2
Synthesizing of organosilicon-base polyurethane prepolymer for use as: 5.22g TDI (chemical pure), 20.0gPPO-2000 (technical grade), 6.0g PEO-2000 (chemical pure) and 0.74g DMBA (chemical pure) are added in the there-necked flask, be warming up to 70 ℃, made it to stir fusion 60 minutes; Add 0.1g catalyzer DBTDL, isothermal reaction 180 minutes; Add among the 0.71g TEA (analytical pure) and the carboxyl on the performed polymer side chain, continued stirring reaction 45 minutes; Then, add 4.30g PAMTES (technical pure), continue isothermal reaction 150 minutes, obtain organosilicon-base polyurethane prepolymer for use as.
The emulsification of organosilicon-base polyurethane prepolymer for use as: under 70 ℃, adding 1.5g protective colloid in 40.7g organosilicon-base polyurethane prepolymer for use as (in its schematic general formula: x=500, y=100, m=100, n=700 and R are CH 3) and mixed 40 minutes; After making described mixture naturally cool to about 35 ℃, the control stir speed (S.S.) is about 40rpm, in system, drip the deionized water that 60ml is dissolved with 1.0g Sodium dodecylbenzene sulfonate (SDBS, chemical pure) and 0.8g polyoxyethylene nonyl phenyl Vinyl Ether (OP-10, chemical pure) then; After dropwising, improve stir speed (S.S.) gradually, stir after 10 minutes to about 500rpm, the dilute hydrochloric acid of Dropwise 5-10wt% in system, the pH value of regulating emulsion is about 6-8, obtains the oyster white target product at last.
The character of gained emulsion and corresponding latex film sees Table 1 and table 2 respectively.
Embodiment 3
Synthesizing of organosilicon-base polyurethane prepolymer for use as: 5.22g TDI (chemical pure), 19.5gPPO-1500 (technical grade) and 0.67g DMPA (chemical pure) are added in the there-necked flask, be warming up to 75 ℃, made it to stir fusion 50 minutes; Add 0.07g catalyst S O, isothermal reaction 90 minutes; Add in the 0.36g Trimethylamine 99 (TMA, analytical pure) and the carboxyl on the performed polymer side chain, continued stirring reaction 40 minutes; Then, add 2.61g APTMS (technical pure), continue isothermal reaction 120 minutes, obtain organosilicon-base polyurethane prepolymer for use as.
The emulsification of organosilicon-base polyurethane prepolymer for use as: under 75 ℃, adding 1.5g protective colloid in 27.7g organosilicon-base polyurethane prepolymer for use as (in its schematic general formula: x=500, y=300, m=100, n=700 and R are OCCH 3) and mixed 40 minutes; After making described mixture naturally cool to room temperature (about 25 ℃), the control stir speed (S.S.) drips the deionized water that 60ml is dissolved with 1.20g SDS (chemical pure) then in system about 60rpm; After dropwising, improve stir speed (S.S.) gradually, stir after 10 minutes to about 700r pm, the dilute hydrochloric acid of Dropwise 5-10wt% in system, the pH value of regulating emulsion is about 6-8, obtains the oyster white target product at last.
The character of gained emulsion and corresponding latex film sees Table 1 and table 2 respectively.
Embodiment 4
Synthesizing of organosilicon-base polyurethane prepolymer for use as: 7.5g MDI (chemical pure), 24gPPO-2000 (technical grade) and 0.89g DMBA (chemical pure) are added in the there-necked flask, be warming up to 80 ℃, made it to stir fusion 45 minutes; Add 0.15g catalyzer DBTDL, isothermal reaction 150 minutes; Add among the 0.81g TEA (analytical pure) and the carboxyl on the performed polymer side chain, continued stirring reaction 40 minutes; Then, add 3.44g APTES (technical pure), continue isothermal reaction 120 minutes, obtain organosilicon-base polyurethane prepolymer for use as.
The emulsification of organosilicon-base polyurethane prepolymer for use as: under 80 ℃, adding 2.3g protective colloid in 38.56g organosilicon-base polyurethane prepolymer for use as (in its schematic general formula: x=500, y=0, m=700, n=700 and R are OCCH 3) and mixed 40 minutes; Make described mixture naturally cool to about 30 ℃, the control stir speed (S.S.) adds the deionized water that 30ml is dissolved with 2.60g SDS (chemical pure) then in system about 40rpm; After 20 minutes, divide three times and add the 30ml deionized water, each 10ml, 15 minutes at interval, in this process, improve stir speed (S.S.) gradually to about 800rpm, stir after 10 minutes, the dilute hydrochloric acid of Dropwise 5-10wt% in system, the pH value of regulating emulsion is about 6-8, obtains the oyster white target product at last.
The character of gained emulsion and corresponding latex film sees Table 1 and table 2 respectively.
Embodiment 5
Synthesizing of organosilicon-base polyurethane prepolymer for use as: 7.5g MDI (chemical pure), 15gPEO-co-PPO-1000 (technical grade) and 0.81g DMPA (chemical pure) are added in the there-necked flask, be warming up to 95 ℃, made it to stir fusion 30 minutes; Add 0.1g catalyzer DBTDL, isothermal reaction 120 minutes; Add among the 0.41g TEA (analytical pure) and the carboxyl on the performed polymer side chain, continued stirring reaction 30 minutes; Then, add 3.0g APTES (technical pure), continue isothermal reaction 90 minutes, obtain organosilicon-base polyurethane prepolymer for use as.
The emulsification of organosilicon-base polyurethane prepolymer for use as: under 95 ℃, adding 1.0g protective colloid in 27.02g organosilicon-base polyurethane prepolymer for use as (in its schematic general formula: x=1000, y=0, m=1000, n=1000 and R are C 2H 5) and mixed 25 minutes; Make described mixture naturally cool to about 55 ℃, the control stir speed (S.S.) adds the deionized water that 30ml is dissolved with 0.8g SDBS (chemical pure) and 0.8g 0P-10 then in system about 50rpm; After 20 minutes, divide three times and add the 30ml deionized water, each 10ml, 15 minutes at interval, improve stir speed (S.S.) then gradually to about 800rpm, stir after 10 minutes, the dilute hydrochloric acid of Dropwise 5-10wt% in system, the pH value of regulating emulsion is about 6-8, obtains the oyster white target product at last.
The character of gained emulsion and corresponding latex film sees Table 1 and table 2 respectively.
Embodiment 6
Synthesizing of organosilicon-base polyurethane prepolymer for use as: 5.22g TDI (chemical pure), 26gPEO-co-PPO-2000 (technical grade) and 0.89g DMBA (chemical pure) are added in the there-necked flask, be warming up to 80 ℃, made it to stir fusion 40 minutes; Add 0.12g catalyzer DBTDL, isothermal reaction 180 minutes; Add among the 0.71g TEA (analytical pure) and the carboxyl on the performed polymer side chain, continued stirring reaction 30 minutes; Then, add 4.30g PAMTMS (technical pure), continue isothermal reaction 120 minutes, obtain organosilicon-base polyurethane prepolymer for use as.
The emulsification of organosilicon-base polyurethane prepolymer for use as: under 80 ℃, adding 2.0g protective colloid in 36.3g organosilicon-base polyurethane prepolymer for use as (in its schematic general formula: x=1000, y=500, m=0, n=2000 and R are H) and mixed 30 minutes; Make described mixture naturally cool to about 60 ℃, the control stir speed (S.S.) drips the deionized water that 60ml is dissolved with 1.20g SDS (chemical pure) then in system about 40rpm; After dropwising, improve stir speed (S.S.) gradually, stir after 10 minutes to about 800rpm, the dilute hydrochloric acid of Dropwise 5-10wt% in system, the pH value of regulating emulsion is about 6-8, obtains the oyster white target product at last.
The character of gained emulsion and corresponding latex film sees Table 1 and table 2 respectively.
Table 1 is the character of organosilicon-polyaminoester emulsion prepared among the embodiment 1-6
The character of the organosilicon-polyaminoester emulsion for preparing among each embodiment of table 1.
Figure A200710300284D00171
* account for the mass percent of system solid content.
Table 2 is a character of utilizing the latex film of organosilicon prepared among the embodiment 1-6-polyaminoester emulsion acquisition
The character of the latex film of organosilicon-polyaminoester emulsion among each embodiment of table 2.
Figure A200710300284D00181
By the data of table 1 and table 2 as can be seen, the solid content height of organosilicon-polyaminoester emulsion that the present invention obtained, little, the active organosilicon theoretical content height of latex particle size, and have good package stability and freeze-thaw stability, and utilize crosslinking degree height, the decomposition temperature height of the latex film of described organosilicon-polyaminoester emulsion acquisition, and have the good mechanical performance, as have extraordinary sticking power, snappiness, shock strength etc.

Claims (37)

1. active organosilicon-base polyurethane prepolymer for use as, the weight-average molecular weight of wherein said organosilicon-base polyurethane prepolymer for use as is 3000-200000, preferred 5000-100000, most preferably 8000-50000 and have following schematic general formula:
Figure A200710300284C00021
Wherein, n is 0 or 1, and m is the integer of 5-1000, R 1, R 2Be methyl or ethyl independently respectively, R 3For methylene radical or-(CH 2) 3-, R 4Be H or phenyl, R 5For-(CH 2) 6-,
Figure A200710300284C00022
Figure A200710300284C00023
Or
Figure A200710300284C00024
R 6Be methyl or hydrogen, condition is R 6All be not hydrogen, R 7Be methyl, ethyl, propyl group, butyl or benzyl, and R 8Be methyl and/or ethyl.
2. active organosilicon-the base polyurethane prepolymer for use as of claim 1, the content of active organosilicon part can reach 15wt% in wherein said organosilicon-base polyurethane prepolymer for use as.
3. claim 1 or active organosilicon-base polyurethane prepolymer for use as of 2, the content of active organosilicon part is 9-12.5wt% in wherein said organosilicon-base polyurethane prepolymer for use as.
4. each the preparation method of active organosilicon-base polyurethane prepolymer for use as of claim 1-3, this method utilizes the mass polymerization technology to carry out, and comprises the steps:
A. vulcabond, polyethers and hydrophilic monomer are mixed, heat up then, and fully stirring makes it fusion;
B. in the molten mixture of step a, add catalyzer and make it abundant polymerization;
C. in the reaction mixture of step b, add tertiary amine and continue stirring reaction for some time; With
D. in the reaction mixture of step c, add the active organosilicon monomer, continue isothermal reaction for some time, obtain active organosilicon-base polyurethane prepolymer for use as at last.
5. the method for claim 4 wherein makes mixture be warming up to 35-120 ℃ among the step a, and preferred 50-95 ℃ and to stir the fused time be 5 minutes-10 hours, preferred 10 minutes-4 hours, most preferably 15 minutes-1 hour.
6. claim 4 or 5 method, wherein employed catalyzer is the organic tin compound among the step b, is selected from dibutyltin dilaurate and stannous octoate; And/or be tertiary amine compounds, be selected from triethylamine and Trimethylamine 99, wherein be preferably the machine tin compound.
7. each method of claim 4-6, constant temperature polymerase 10 .5-24 hour among the step b wherein, preferred 0.5-12 hour, most preferably 1.5-4 hour.
8. each method of claim 4-7, wherein the adding mode of tertiary amine adopts dropping technology among the step c.
9. each method of claim 4-8, wherein the reaction times among the step c is 5 minutes-10 hours, preferred 10 minutes-3 hours, most preferably 15 minutes-1.5 hours.
10. each method of claim 4-9, wherein the isothermal reaction time in the steps d is 10 minutes-24 hours, preferred 20 minutes-10 hours, most preferably 30 minutes-4 hours.
11. each method of claim 4-10, wherein said vulcabond is selected from Toluene-2,4-diisocyanate, 4-vulcabond, ditan-2,4 '-vulcabond, 1,6-hexamethylene-diisocyanate, isophorone diisocyanate and their mixture.
12. each method of claim 4-11, wherein said polyethers is selected from the blend of polyoxyethylene, polyoxytrimethylene, ethylene oxide and propylene oxide copolymer and polyoxyethylene and polyoxytrimethylene.
13. each method of claim 4-12, wherein said hydrophilic monomer is selected from 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid and their mixture.
14. each method of claim 4-13, wherein said active organosilicon monomer is selected from γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyldiethoxysilane, γ-An Bingjisanjiayangjiguiwan, γ-aminopropyl methyl dimethoxysilane, anilinomethyl triethoxysilane, anilinomethyl methyldiethoxysilane, anilinomethyl trimethoxy silane and anilinomethyl methyl dimethoxysilane.
15. each method of claim 4-14, wherein the described tertiary amine among the step c is selected from Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine and contains the tertiary amine of benzyl, preferred Trimethylamine 99 and triethylamine, most preferably triethylamine.
16. each method of claim 4-15, wherein:
The mol ratio of polyethers and vulcabond is 1/1.05-1/5, preferred 1/1.1-1/3, most preferably 1/1.2-1/2;
The mol ratio of hydrophilic monomer and polyethers is 1/1-1/10, preferred 1/2-1/8, most preferably 1/2-1/4;
The tertiary amine among the step c and the mol ratio of hydrophilic monomer are 0.8/1-3/1, preferred 1/1-2/1, most preferably 1/1-1.5/1;
The mol ratio of active organosilicon monomer and vulcabond is 1/1.1-1/5, preferred 1/1.2-1/4, most preferably 1/1.5-1/2.5; With
Employed catalyst consumption is the 0.01-5wt% of total monomer weight among the step b, preferred 0.01-3wt%, most preferably 0.05-1.5wt%.
17. each method of claim 4-16, the molecular weight of wherein controlling described polyethers is 200-40000, preferred 200-20000, most preferably 300-10000.
18. a solvent-free active organosilicon-polyaminoester emulsion, it is included in dispersive in the water by each organosilicon-base polyurethane prepolymer for use as or each organosilicon-base polyurethane prepolymer for use as and the protective colloid and the emulsifying agent of method preparation of claim 4-17 of claim 1-3.
19. the solvent-free active organosilicon-polyaminoester emulsion of claim 18, the solid content of wherein said emulsion are 25-55wt%.
20. the solvent-free active organosilicon-polyaminoester emulsion of claim 18 or 19, the solid content of wherein said emulsion are 30-45wt%.
21. each solvent-free active organosilicon-polyaminoester emulsion of claim 18-20, the latex particle size of wherein said emulsion is less than 500nm.
22. each solvent-free active organosilicon-polyaminoester emulsion of claim 18-21, the latex particle size of wherein said emulsion is 100-300nm.
23. each solvent-free active organosilicon-polyaminoester emulsion of claim 18-22, the content of wherein said protective colloid is the 0.1-20wt% of system solid content, preferred 0.5-10wt%, most preferably 1-7wt%.
24. each solvent-free active organosilicon-polyaminoester emulsion of claim 18-23, wherein said protective colloid is polyether-modified polysiloxane, and it has following schematic general formula:
Figure A200710300284C00051
Wherein, x is the integer of 10-10000, and y is the integer of 0-10000, and n is the integer of 5-2000, and m is that integer and the R of 0-2000 is H, CH 3, C 2H 5Or OCCH 3
25. each solvent-free active organosilicon-polyaminoester emulsion of claim 18-24, the content of wherein said emulsifying agent is the 0.1-10wt% of system solid content, preferred 0.5-7.5wt%, most preferably 1-4wt%.
26. each solvent-free active organosilicon-polyaminoester emulsion of claim 18-25, wherein said emulsifying agent is the mixture of anionic emulsifier or anionic emulsifier and nonionic emulsifying agent, with when the time for mixture, wherein the weight ratio of anionic emulsifier and nonionic emulsifying agent is 1/50-1/5, preferred 1/35-1/10, most preferably 1/30-1/15.
27. the solvent-free active organosilicon-polyaminoester emulsion of claim 26, wherein said anionic emulsifier is selected from aliphatic sulphate, aromatic sulfonic acid salt, aliphatic sulfonate and aromatic sulphonate, preferred aliphat vitriol such as sodium lauryl sulphate; Described nonionic emulsifying agent is selected from polyoxyethylene alkyl ester, polyethylene oxide alkyl ethers and polyoxyethylene aryl ethers, preferred polyoxyethylene aryl ethers such as polyoxyethylene nonyl phenyl Vinyl Ether.
28. the preparation method of a solvent-free active organosilicon-polyaminoester emulsion, this method adopt the phase reversion emulsifying process under the organic solvent-free existence to carry out, and comprise the steps:
A1. to claim 1-3 each organosilicon-base polyurethane prepolymer for use as or each the organosilicon-base polyurethane prepolymer for use as of method preparation of claim 4-17 in add protective colloid, and stir and make it to mix;
B1. make the mixed system naturally cooling of step a1, then under agitation to wherein adding emulsifier aqueous solution; With
C1. stirring fully disperses organosilicon-base polyurethane prepolymer for use as, with the pH value of dilute acid solution regulation system, obtains organosilicon-polyaminoester emulsion then.
29. the method for claim 28, wherein the mixing temperature of step a1 is 5-240 minute for the polymerization temperature and the time of mixing in this step of the described organosilicon-base polyurethane prepolymer for use as of preparation, preferred 10-120 minute, and most preferably 15-60 minute.
30. the method for claim 28 or 29, wherein said protective colloid are polyether-modified polysiloxane, it has following schematic general formula:
Figure A200710300284C00061
Wherein, x is the integer of 10-10000, and y is the integer of 0-10000, and n is the integer of 5-2000, and m is that integer and the R of 0-2000 is H, CH 3, C 2H 5Or OCCH 3
31. each method of claim 28-30, the consumption of wherein said protective colloid is the 0.1-20wt% of system solid content, preferred 0.5-10wt%, most preferably 1-7wt%.
32. each method of claim 28-31 wherein makes the mixed system of step a1 naturally cool to 20-90 ℃ among the step b1.
33. each method of claim 28-31, wherein said emulsifier aqueous solution adopts the mode that drips or add in batches to add, wherein said emulsifying agent is the mixture of anionic emulsifier or anionic emulsifier and nonionic emulsifying agent, with when the time for mixture, wherein the weight ratio of anionic emulsifier and nonionic emulsifying agent is 1/50-1/5, preferred 1/35-1/10, most preferably 1/30-1/15.
34. the method for claim 33, wherein: described anionic emulsifier is selected from aliphatic sulphate, aromatic sulfonic acid salt, aliphatic sulfonate and aromatic sulphonate, preferred aliphat vitriol such as sodium lauryl sulphate; Described nonionic emulsifying agent is selected from polyoxyethylene alkyl ester, polyethylene oxide alkyl ethers and polyoxyethylene aryl ethers, preferred polyoxyethylene aryl ethers such as polyoxyethylene nonyl phenyl Vinyl Ether.
35. each method of claim 28-34, the consumption of wherein said emulsifying agent is the 0.1-10wt% of system solid content, preferred 0.5-7.5wt%, most preferably 1-4wt%.
36. each method of claim 28-35, wherein the initial stir speed (S.S.) among the step c1 is 5-100rpm, preferred 5-75rpm, 10-50rpm most preferably, with along with the dispersion of organosilicon-base polyurethane prepolymer for use as in water, improve stir speed (S.S.) gradually, final stir speed (S.S.) is 150-3000rpm, preferred 200-2500rpm, most preferably 200-2000rpm.
37. each method of claim 28-36, wherein used dilute acid concentration is 2-10wt% among the step c1, this diluted acid under agitation dropwise adds, be selected from dilute hydrochloric acid, dilute sulphuric acid and dilute acetic acid with this diluted acid, preferred dilute hydrochloric acid, be adjusted to 5-9 with the pH value of final emulsion, preferred 5.5-8.5, most preferably 6-8.
CNA2007103002846A 2007-12-26 2007-12-26 Active organosilicon-polyurethane performed polymer and solvent-free active organosilicon-polyurethane emulsion prepared thereby Pending CN101469055A (en)

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