CN102093703A - Method for preparing chitin whisker modified waterborne polyurethane - Google Patents
Method for preparing chitin whisker modified waterborne polyurethane Download PDFInfo
- Publication number
- CN102093703A CN102093703A CN 201110005529 CN201110005529A CN102093703A CN 102093703 A CN102093703 A CN 102093703A CN 201110005529 CN201110005529 CN 201110005529 CN 201110005529 A CN201110005529 A CN 201110005529A CN 102093703 A CN102093703 A CN 102093703A
- Authority
- CN
- China
- Prior art keywords
- chitin
- preparation
- chitin whisker
- polyisocyanate
- polyester polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002101 Chitin Polymers 0.000 title claims abstract description 119
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 74
- 239000004814 polyurethane Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 42
- 229920000570 polyether Polymers 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 38
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 32
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 150000003384 small molecules Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract 10
- 150000003077 polyols Chemical class 0.000 claims abstract 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 40
- 150000002009 diols Chemical class 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920005749 polyurethane resin Polymers 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 62
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- 229920000728 polyester Polymers 0.000 description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 31
- 239000002131 composite material Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 18
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 150000002334 glycols Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 238000005266 casting Methods 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 2
- 230000001851 biosynthetic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000018 Callose Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acetylhexosamine Chemical compound CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种甲壳素晶须改性聚氨酯树脂的制备方法，其特征在于：以多异氰酸酯与聚酯多元醇或/和聚醚多元醇为原料制得聚氨酯预聚物后，再加入小分子扩链剂并降粘，在已经乳化完成的水性聚氨酯乳液中添加甲壳素晶须，制得甲壳素晶须改性水性聚氨酯。本发明中甲壳素晶须的加入量为：多异氰酸酯、聚酯多元醇或/和聚醚多元醇、小分子扩链剂三种原料总质量的1-5%。本发明方法所得到的甲壳素晶须改性水性聚氨酯材料的拉伸强度和杨氏模量相对改性前都有明显的提高，而且保持了比较高的断裂伸长率。本发明工艺简单，材料来源广泛，而且生产成本低且具有环保、可生物降解的特点，可用作膜、涂料、胶黏剂等材料。The invention relates to a preparation method of chitin whisker-modified polyurethane resin, which is characterized in that: after preparing polyurethane prepolymer with polyisocyanate and polyester polyol or/and polyether polyol as raw materials, adding small molecules A chain extender and a viscosity reducer, adding chitin whiskers to the emulsified water-based polyurethane emulsion to obtain chitin whisker-modified water-based polyurethane. The amount of chitin whiskers added in the present invention is: 1-5% of the total mass of the three raw materials: polyisocyanate, polyester polyol or/and polyether polyol, and small molecule chain extender. The tensile strength and Young's modulus of the chitin whisker modified water-based polyurethane material obtained by the method of the invention are significantly improved compared with those before modification, and relatively high elongation at break is maintained. The invention has the advantages of simple process, wide source of materials, low production cost, environmental protection and biodegradability, and can be used as materials such as films, coatings and adhesives.
Description
Technical field
The invention belongs to the biological nano field of compound material, relate to the preparation method of modified polyurethane resin, be specifically related to a kind of preparation method of chitin whisker modified aqueous polyurethane.
Background technology
Chitin (chitin) be in the animal and plant body through biosynthetic a kind of multi-polysaccharide natural macromolecule compound, output is only second to Mierocrystalline cellulose, nearly 10,000,000,000 tons of the annual biosynthetic chitins of nature are a kind of very abundant natural resource.Chitin is elementary composition by C, H, four kinds of O, N, and chemical formula is (C
8H
13NO
5) n.Chitin is the polysaccharide that is formed by connecting with β-1,4 glycosidic link form by N-acetyl-2-amino-2-deoxy-D-glucose, is called (1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-callose by the systematic nomenclature chitin.Chitin and derivative thereof not only have excellent biological compatibility, low toxicity and biological degradability, also have many biomedical functions and drug effect.Many chitins and the commercialization already of derivative product thereof, about the international academic monograph " Advance in Chitin Science " of chitin also in last century the nineties start publication.Chitin and derivative thereof have formed new research and development focus in fields such as life science, functional materialss.
Nanoparticle also is ultrafine particle, refers generally to the particle of size between 1 ~ 1000nm, is the transitional region that is in cluster and macro object boundary.Nanoparticle has: surface effects, small-size effect and macro quanta tunnel effect promptly have the character of special light, electromagnetism, mechanics and chemical aspect.Chitin whisker (chitin whiskers) is to be that raw material obtains with the abundant chitin of originating, with respect to inorganic nano-particle, chitin whisker has following characteristics: great amount of hydroxy group and amino are contained in its surface, can carry out chemical reaction or form strong intermolecular interaction; Secondly, it has biodegradable, physiologically acceptable and advantages of environment protection, helps protecting people's health and environment.At present, the research that chitin whisker is used for filled polymer developing material new bio nano composite material receives much concern.Utilized the successful modification of chitin whisker natural rubber, soybean proteins etc. have improved intensity, hardness and the wear resistance of product.
Urethane is meant the multifunctional macromolecule synthetic materials that contains the carbamate base class in the molecular chain.It is divided into solvent borne polyurethane and aqueous polyurethane again, and wherein aqueous polyurethane more and more is subject to people's attention owing to have premium propertiess such as nontoxic, pollution-free.The aqueous polyurethane that contains single polyurethane structural for the performance that makes its film forming matter satisfies practical application more widely, needs further to improve mechanical property, and for this reason, it is necessary that aqueous polyurethane is carried out modification.
The present invention has overcome present most of modification technology and can only rely on and sacrifice elongation at break fully and improve tensile strength, and modification technology preparation process complicated technology defective, a kind of preparation method of chitin whisker modified aqueous polyurethane is provided, its technology is simple, the starting material wide material sources, and have environmental protection, advantage such as biodegradable.
Summary of the invention
The invention provides a kind of preparation method of chitin whisker modified aqueous polyurethane, it is characterized in that, in turn include the following steps:
1) by polyisocyanates and raw material polyester polyol or/and polyether glycol stirs through mixing, obtain polyurethane prepolymer after the reaction;
2) add small molecule chain extender in the polyurethane prepolymer that in step 1), obtains, stirring reaction, and use the acetone viscosity reduction;
3) with step 2) reaction product that obtains is cooled to below 40 ℃, adds neutralization reagent then, the adjusting pH value is 6-8, in and after 5-10 minute, water-dispersion on the rocks again, aqueous polyurethane emulsion; Add the chitin whisker blend in described aqueous polyurethane emulsion, vacuumize then and remove acetone, the mass percent of control solid content is 5-40%, gets described chitin whisker modified aqueous polyurethane.
In the step 1) of the present invention, or/and polyether glycol when mixing, its mass percent is: polyisocyanates is 65-90% when described polyisocyanates and described polyester polyol, and polyester polyol is or/and polyether glycol is 10-35%; Wherein, when described polyisocyanates mixed with the pure and mild polyether glycol of described polyester polyols, described polyester polyol and polyether glycol mass percent between the two was any proportioning.
In the step 1) of the present invention, mixing the temperature that stirs is 70-90 ℃, and the reaction times is 2-3 hour.
Step 2 of the present invention) carry out under 70-90 ℃, the add-on of described small molecule chain extender is the 10-50% of polyisocyanates quality, and the stirring reaction time is 1-2 hour.Described step 2) add-on of acetone is that polyisocyanates, polyester polyol are or/and the 10-30% of polyether glycol and small molecule chain extender three total mass in.
In the step 3) of the present invention, the add-on of described chitin whisker is that polyisocyanates, polyester polyol are or/and the 1-5% of polyether glycol and small molecule chain extender three total mass.
Among the present invention, the polyisocyanates in the described step 1) comprises diphenylmethanediisocyanate, tolylene diisocyanate.The pure and mild polyether glycol of polyester polyols in the step 1) comprises: polycaprolactone glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, polypropylene glycol.
The object of the present invention is to provide the preparation method of a kind of tensile strength height, chitin whisker modified aqueous polyurethane that elongation at break is high.
To achieve these goals, the technical solution adopted in the present invention is as follows:
1) by any one of polyisocyanates and following three kinds of raw materials: raw material polyester polyol or raw material polyether glycol or raw material polyether glycol and polyester polyols alcohol mixture, mixed stirring reaction 2-3 hour down at 70-90 ℃, obtain polyurethane prepolymer;
Wherein, when polyisocyanates mixes with the mixture of polyester polyol or polyether glycol or polyether glycol and polyester polyol, the mass percent of the mixture of polyisocyanates and polyester polyol or polyether glycol or polyether glycol and polyester polyol is respectively: polyisocyanates is 65-90%, and the mixture of polyester polyol or polyether glycol or polyether glycol and polyester polyol is 10-35%.
Wherein, when polyisocyanates mixed with the mixture material of the pure and mild polyether glycol of polyester polyols, the pure and mild polyether glycol of polyester polyols wherein mass percent between the two was any proportioning;
2) under 70-90 ℃, added the small molecule chain extender stirring reaction 1-2 hour in the polyurethane prepolymer that in step 1), obtains, and use the acetone viscosity reduction; Wherein, the add-on of small molecule chain extender is the 10-50% of polyisocyanates quality; The add-on of acetone is: polyisocyanates, polyester polyol are or/and the 10-30% of polyether glycol, three kinds of raw materials quality sums of small molecule chain extender;
3) with step 2) reaction product that obtains is cooled to below 40 ℃, adds neutralization reagent then, the adjusting pH value is 6-8, in and after 5-10 minute, water-dispersion on the rocks again, aqueous polyurethane emulsion; Add the chitin whisker blend in the aqueous polyurethane emulsion, the add-on of chitin whisker is: polyisocyanates, polyester polyol are or/and the 1-5% of polyether glycol and three kinds of raw materials quality sums of small molecule chain extender; Vacuumize then and remove acetone, the mass percent of control solid content is 5-40%, promptly makes the chitin whisker modified aqueous polyurethane.
Described small molecule chain extender is any one or any one the above mixing in dibasic alcohol, diamine, trivalent alcohol, the tertiary amine, is any proportioning during any one above mixing.
Described chitin whisker gets the described sulphuric acid hydrolysis that is hydrolyzed to by the chitin hydrolysis.
The preparation method of described chitin whisker is: chitin is stirred in ebullient 5 wt%KOH solution removed deproteinize in 6 hours.The suspension that obtains at room temperature stirs a night, filters, with distilled water wash for several times.NaCl with the 17g/L of the sodium acetate buffer that contains 0.3M
2The aqueous solution was bleached 6 hours down at 80 ℃.Suspension keeps removing in 48 hours residual protein in 5 wt%KOH solution.In 3600 rev/mins whizzer centrifugal 15 minutes afterwards, the acidolysis under boiling state of the corresponding lg chitin of 3N/30mlHCI was stirred 90 minutes.With the muddy liquid distilled water diluting of gained, 3600 rev/mins of recentrifuge 15 minutes (3 times).The 2 hours dialysed overnight in distilled water again of afterwards muddy liquid being dialysed in flowing water reach 4 up to pH value.Obtain dispersion liquid with supersound process then.At last, add the sodiumazide bacteria growing inhibiting, dispersion liquid is placed in 6 ℃ of environment.Described chitin is mainly derived from shrimp shell, crab shell etc., and content is up to 58%-85%.
The present invention is by adding chitin whisker in the building-up process of aqueous polyurethane emulsion, and the mechanical property that its emulsion is solidified the mould material that the back forms significantly improves, and it can keep improving tensile strength simultaneously than high elongation at tear.Chitin whisker among the present invention is to be got by the chitin hydrolysis, and chitin is mainly derived from shrimp shell and crab shell, and is with low cost, the source is abundant, and the processing condition of preparation, chitin extraction whisker are simple.Aqueous polyurethane is a kind of ep-type material, that the present invention will originate will be abundant, the simple chitin whisker of technology combines the using value that the material that has not only obtained improved performance has also improved chitin with environment-friendly water-based polyurethane, expanded its use range, its low production cost and have environmental protection, biodegradable characteristics simultaneously, and technology of the present invention is simple, therefore has higher scientific and technological content.The mechanical property of the resulting chitin whisker modified aqueous polyurethane of this method is significantly improved, and can be used as materials such as film, coating, sizing agent.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.Under the spirit and scope that do not deviate from inventive concept, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection domain with the appending claims.
Embodiment 1:
A kind of preparation method of chitin whisker modified aqueous polyurethane, it comprises the steps:
1) with polyester diol (polycaprolactone glycol, the PCL of calculated amount
2000, Mn is 2000) and be blended in 70 ℃ of following stirring reactions 2 hours with diphenylmethanediisocyanate (MDI), get polyurethane prepolymer; The mass percent of polyester diol and diphenylmethanediisocyanate is: polyester diol 30%, diphenylmethanediisocyanate 70%;
Among the present invention, polyisocyanates can be diphenylmethanediisocyanate or tolylene diisocyanate; The pure and mild polyether glycol of polyester polyols can be polycaprolactone glycol, poly-hexanodioic acid-1,4-butanediol ester glycol or polypropylene glycol.
2) under 85 ℃, in polyurethane prepolymer, add small molecule chain extender: 2,2 '-dimethylol propionic acid (DMPA), the add-on of small molecule chain extender DMPA is 20% of a diphenylmethanediisocyanate quality, stirring reaction 1 hour, and use the acetone viscosity reduction, the add-on of acetone be polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 10%;
3) after reaction was finished, temperature dropped to (as 0-39 ℃) below 40 ℃, and addings waits in the triethylamine (TEA) of DMPA molar weight and salify 5 minutes again, the add-on of triethylamine identical with the amount of DMPA (the adjusting pH value is within the 6-8 scope); Under high-speed stirring (2000-4000 rev/min), chitin whisker frozen water solution added disperses, the chitin whisker add-on be polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 1%.The chitin whisker add-on can be in the scope of 0.1-30%.Vacuumize then and remove acetone and obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion); The solid content of chitin whisker composite aqueous polyurethane emulsion is controlled by the water yield that adds at 20%();
4) under 60 ℃, with chitin whisker composite aqueous polyurethane emulsion casting film-forming on polyfluortetraethylene plate.
After mould material is cut into sheet, be 35%, place after 7 days under the room temperature and carry out performance test at constant humidity.The mechanical property of the sheet material of preparation sees Table 1.Mechanical property is with reference to State Standard of the People's Republic of China GB4456-84, newly thinks carefully in Shenzhen on the CMT6503 instrument of testing tool company to record, and rate of extension is 200 mm/min.
Embodiment 2:
A kind of preparation method of chitin whisker modified aqueous polyurethane, it comprises the steps:
1) polyester diol (polycaprolactone glycol, Mn are 2000) of calculated amount and the mixture and the diphenylmethanediisocyanate (MDI) of polyether Glycols (polypropylene glycol) are blended in 70 ℃ of following stirring reactions 2 hours, get polyurethane prepolymer; The mass percent of polyester diol and diphenylmethanediisocyanate is: the mixture 35% of the pure and mild polyether Glycols of polyester binary, diphenylmethanediisocyanate 65%;
2) under 85 ℃, in polyurethane prepolymer, add small molecule chain extender: 2,2 '-dimethylol propionic acid (DMPA), the add-on of small molecule chain extender DMPA is 20% of a diphenylmethanediisocyanate quality, stirring reaction 1 hour, and use the acetone viscosity reduction, the add-on of acetone be the pure and mild polyether Glycols of polyester binary mixture, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 20%;
3) after reaction was finished, temperature dropped to (as 0-39 ℃) below 40 ℃, and addings waits in the triethylamine (TEA) of DMPA molar weight and salify 5 minutes again, the add-on of triethylamine identical with the amount of DMPA (the adjusting pH value is within the 6-8 scope); Under high-speed stirring (2000-4000 rev/min), the adding of chitin whisker frozen water solution is disperseed, the chitin whisker add-on be the pure and mild polyether Glycols of polyester binary mixture, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 1%; Vacuumize then and remove acetone and obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion); The solid content of chitin whisker composite aqueous polyurethane emulsion is controlled by the water yield that adds at 30%();
4) under 60 ℃, with chitin whisker composite aqueous polyurethane emulsion casting film-forming on polyfluortetraethylene plate.
After mould material is cut into sheet, be 35%, place after 7 days under the room temperature and carry out performance test at constant humidity.The mechanical property of the sheet material of preparation sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 3:
Substantially the same manner as Example 1, difference is: the chitin whisker of interpolation is polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 2%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 4:
Substantially the same manner as Example 2, difference is: the chitin whisker of interpolation is mixture, the diphenylmethanediisocyanate and 2 of the pure and mild polyether Glycols of polyester binary, 2 '-the dimethylol propionic acid total mass 2%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 5:
A kind of preparation method of chitin whisker modified aqueous polyurethane, it comprises the steps:
1) polyester diol (polycaprolactone glycol, Mn are 2000) of calculated amount and the mixture and the diphenylmethanediisocyanate (MDI) of polyether Glycols (polypropylene glycol) are blended in 70 ℃ of following stirring reactions 2 hours, get polyurethane prepolymer; The mass percent of polyester diol and diphenylmethanediisocyanate is: the pure and mild polyether Glycols mixture 25% of polyester binary, diphenylmethanediisocyanate 75%;
2) under 85 ℃, in polyurethane prepolymer, add small molecule chain extender: 2,2 '-dimethylol propionic acid (DMPA), the add-on of small molecule chain extender DMPA is 20% of a diphenylmethanediisocyanate quality, stirring reaction 1 hour, and use the acetone viscosity reduction, the add-on of acetone be the pure and mild polyether Glycols of polyester binary mixture, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 30%;
3) after reaction was finished, temperature dropped to (as 0-39 ℃) below 40 ℃, and addings waits in the triethylamine (TEA) of DMPA molar weight and salify 5 minutes again, the add-on of triethylamine identical with the amount of DMPA (the adjusting pH value is within the 6-8 scope); Under high-speed stirring (2000-4000 rev/min), the adding of chitin whisker frozen water solution is disperseed, the chitin whisker add-on be the pure and mild polyether Glycols of polyester binary mixture, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 1%; Vacuumize then and remove acetone and obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion); The solid content of chitin whisker composite aqueous polyurethane emulsion is controlled by the water yield that adds at 15%();
4) under 60 ℃, with chitin whisker composite aqueous polyurethane emulsion casting film-forming on polyfluortetraethylene plate.
After mould material is cut into sheet, be 35%, place after 7 days under the room temperature and carry out performance test at constant humidity.The mechanical property of the sheet material of preparation sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 6:
Substantially the same manner as Example 1, difference is: the chitin whisker of interpolation is polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 3%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 7:
Substantially the same manner as Example 5, difference is: the chitin whisker of interpolation is mixture, the diphenylmethanediisocyanate and 2 of the pure and mild polyether Glycols of polyester binary, 2 '-the dimethylol propionic acid total mass 3%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 8:
A kind of preparation method of chitin whisker modified aqueous polyurethane, it comprises the steps:
1) polyester diol (polycaprolactone glycol, Mn are 2000) with calculated amount is blended in 70 ℃ of following stirring reactions 2 hours with diphenylmethanediisocyanate (MDI), gets polyurethane prepolymer; The mass percent of polyester diol and diphenylmethanediisocyanate is: polyester diol 20%, diphenylmethanediisocyanate 80%;
2) under 85 ℃, in polyurethane prepolymer, add small molecule chain extender: 2,2 '-dimethylol propionic acid (DMPA), the add-on of small molecule chain extender DMPA is 20% of a diphenylmethanediisocyanate quality, stirring reaction 1 hour, and use the acetone viscosity reduction, the add-on of acetone be polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 20%;
3) after reaction was finished, temperature dropped to (as 0-39 ℃) below 40 ℃, and addings waits in the triethylamine (TEA) of DMPA molar weight and salify 5 minutes again, the add-on of triethylamine identical with the amount of DMPA (the adjusting pH value is within the 6-8 scope); Under high-speed stirring (2000-4000 rev/min), chitin whisker frozen water solution added disperses, the chitin whisker add-on be polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 2%; Vacuumize then and remove acetone and obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion); The solid content of chitin whisker composite aqueous polyurethane emulsion is controlled by the water yield that adds at 10%();
4) under 60 ℃, with chitin whisker composite aqueous polyurethane emulsion casting film-forming on polyfluortetraethylene plate.
After mould material is cut into sheet, be 35%, place after 7 days under the room temperature and carry out performance test at constant humidity.The mechanical property of the sheet material of preparation sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 9:
Substantially the same manner as Example 1, difference is: the chitin whisker of interpolation is polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 4%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 10:
Substantially the same manner as Example 8, difference is: the chitin whisker of interpolation is polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 4%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 11:
A kind of preparation method of chitin whisker modified aqueous polyurethane, it comprises the steps:
1) polyester diol (PBA2000, Mn are 2000 for poly-hexanodioic acid-1,4-butanediol ester glycol) with calculated amount is blended in 70 ℃ of following stirring reactions 2 hours with tolylene diisocyanate (TDI), gets polyurethane prepolymer; The mass percent of polyester diol and diphenylmethanediisocyanate is: polyester diol 15%, diphenylmethanediisocyanate 85%;
2) under 85 ℃, in polyurethane prepolymer, add small molecule chain extender: 2,2 '-dimethylol propionic acid (DMPA), the add-on of small molecule chain extender DMPA is 20% of a tolylene diisocyanate quality, stirring reaction 1 hour, and use the acetone viscosity reduction, the add-on of acetone be polyester diol, tolylene diisocyanate and 2,2 '-the dimethylol propionic acid total mass 10%;
3) after reaction was finished, temperature dropped to (as 0-39 ℃) below 40 ℃, and addings waits in the triethylamine (TEA) of DMPA molar weight and salify 5 minutes again, the add-on of triethylamine identical with the amount of DMPA (the adjusting pH value is within the 6-8 scope); Under high-speed stirring (2000-4000 rev/min), chitin whisker frozen water solution added disperses, the chitin whisker add-on be polyester diol, tolylene diisocyanate and 2,2 '-the dimethylol propionic acid total mass 5%; Vacuumize then and remove acetone and obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion); The solid content of chitin whisker composite aqueous polyurethane emulsion is controlled by the water yield that adds at 30%();
4) under 60 ℃, with chitin whisker composite aqueous polyurethane emulsion casting film-forming on polyfluortetraethylene plate.
After mould material is cut into sheet, be 35%, place after 7 days under the room temperature and carry out performance test at constant humidity.The mechanical property of the sheet material of preparation sees Table 1.Mechanics Performance Testing is with embodiment 1.
Embodiment 12:
Substantially the same manner as Example 1, difference is: the chitin whisker of interpolation is polyester diol, diphenylmethanediisocyanate and 2,2 '-the dimethylol propionic acid total mass 5%, obtain chitin whisker modified aqueous polyurethane (or claim chitin whisker composite aqueous polyurethane emulsion).The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
Implement 13:
Substantially the same manner as Example 1, difference is: do not add chitin whisker, obtain aqueous polyurethane emulsion.The mechanical property of preparation sheet material sees Table 1.Mechanics Performance Testing is with embodiment 1.
More than show:
With embodiment 13 relatively, other have used the mechanical property (tensile strength, Young's modulus) of the product chitin whisker composite aqueous polyurethane that preparation method's of the present invention embodiment makes to be significantly improved, but also have kept higher elongation at break.
2. can be found relatively by the experimental result of embodiment 13,1,3,6 that along with the increase of chitin whisker content, the tensile strength of its product increases gradually, elongation at break decreases;
3. relatively can find by the experimental result of embodiment 3,6,9,12, continuation increase along with chitin whisker content, the product that the tensile strength contrast traditional method of its product makes still has remarkable increase, but it is no longer in rising trend that it increases effect, and its product elongation at break will further reduce;
4. can find relatively by the experimental result of embodiment 13,1,3,6,9,12 that along with the increase of chitin whisker content, the Young's modulus of its product increases always.
The interpolation chitin whisker that the present invention proposes innovation carries out the preparation method of modified aqueous polyurethane, wherein, the addition of chitin whisker can be controlled in polyisocyanates, polyester polyol or/and the 1-5% of polyether glycol, three kinds of raw materials quality sums of small molecule chain extender.
Above experimental result as seen, not adding the method that chitin whisker prepares aqueous polyurethane with tradition compares, adopt the inventive method to prepare the chitin whisker modified aqueous polyurethane, when the addition of chitin whisker during at 1-5%, mechanical properties such as the tensile strength of the modified aqueous polyurethane that the inventive method makes, Young's modulus all are optimized, and have kept higher elongation at break.As seen, preparation method of the present invention has actual application value preferably.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110005529 CN102093703A (en) | 2011-01-12 | 2011-01-12 | Method for preparing chitin whisker modified waterborne polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110005529 CN102093703A (en) | 2011-01-12 | 2011-01-12 | Method for preparing chitin whisker modified waterborne polyurethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102093703A true CN102093703A (en) | 2011-06-15 |
Family
ID=44126978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110005529 Pending CN102093703A (en) | 2011-01-12 | 2011-01-12 | Method for preparing chitin whisker modified waterborne polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102093703A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709364A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Preparation method of quaternary ammonium salt chitosan and organic silicon composite modified cationic water-based polyurethane fixing agent |
| CN107129676A (en) * | 2017-06-15 | 2017-09-05 | 天津大学 | Cation aqueous polyurethane-chitosan blend thing and preparation method thereof |
| CN108396559A (en) * | 2018-02-05 | 2018-08-14 | 广西大学 | A kind of bagasse base film and preparation method thereof |
| CN112957278A (en) * | 2021-02-19 | 2021-06-15 | 杭州协合医疗用品有限公司 | Chitin whisker modified water-based nail polish and preparation method thereof |
| CN114736646A (en) * | 2021-12-03 | 2022-07-12 | 广西至善新材料科技有限公司 | Preparation method of nano chitin reinforced waterborne polyurethane adhesive |
| CN115304735A (en) * | 2022-09-19 | 2022-11-08 | 广东睿鹏材料科学有限公司 | Nano chitin-based polyurethane and preparation method thereof |
| CN115572379A (en) * | 2022-10-17 | 2023-01-06 | 黄山中泽新材料有限公司 | Preparation method of azide-containing polyester polyol and application of azide-containing polyester polyol in post-crosslinking single-component waterborne polyurethane |
| CN116004110A (en) * | 2023-01-13 | 2023-04-25 | 上海正欧实业有限公司 | Wear-resistant polyurethane floor coating with self-lubricating function and preparation method thereof |
| CN117304551A (en) * | 2023-09-01 | 2023-12-29 | 贵州省材料产业技术研究院 | Preparation method of modified chitin whisker reinforced and toughened PBAT micro-foaming composite material |
| CN118006212A (en) * | 2024-04-10 | 2024-05-10 | 天津双安劳保橡胶有限公司 | Preparation method and application of chitin-modified waterborne polyurethane composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6491931B1 (en) * | 1999-07-08 | 2002-12-10 | L'ORéAL S.A. | Cosmetic composition comprising fibers and a film forming polymer |
| CN1974662A (en) * | 2006-11-21 | 2007-06-06 | 中国地质大学（武汉） | Composite elastic chitin whisker material and its prepn and use |
| CN101230189A (en) * | 2008-01-29 | 2008-07-30 | 武汉理工大学 | A kind of preparation method of polysaccharide nanocrystalline grafted polyester modified polyurethane material |
-
2011
- 2011-01-12 CN CN 201110005529 patent/CN102093703A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6491931B1 (en) * | 1999-07-08 | 2002-12-10 | L'ORéAL S.A. | Cosmetic composition comprising fibers and a film forming polymer |
| CN1974662A (en) * | 2006-11-21 | 2007-06-06 | 中国地质大学（武汉） | Composite elastic chitin whisker material and its prepn and use |
| CN101230189A (en) * | 2008-01-29 | 2008-07-30 | 武汉理工大学 | A kind of preparation method of polysaccharide nanocrystalline grafted polyester modified polyurethane material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709364A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Preparation method of quaternary ammonium salt chitosan and organic silicon composite modified cationic water-based polyurethane fixing agent |
| CN107129676A (en) * | 2017-06-15 | 2017-09-05 | 天津大学 | Cation aqueous polyurethane-chitosan blend thing and preparation method thereof |
| CN108396559A (en) * | 2018-02-05 | 2018-08-14 | 广西大学 | A kind of bagasse base film and preparation method thereof |
| CN112957278A (en) * | 2021-02-19 | 2021-06-15 | 杭州协合医疗用品有限公司 | Chitin whisker modified water-based nail polish and preparation method thereof |
| CN112957278B (en) * | 2021-02-19 | 2022-11-08 | 杭州协合医疗用品有限公司 | Chitin whisker modified water-based nail polish and preparation method thereof |
| CN114736646A (en) * | 2021-12-03 | 2022-07-12 | 广西至善新材料科技有限公司 | Preparation method of nano chitin reinforced waterborne polyurethane adhesive |
| CN115304735A (en) * | 2022-09-19 | 2022-11-08 | 广东睿鹏材料科学有限公司 | Nano chitin-based polyurethane and preparation method thereof |
| CN115572379A (en) * | 2022-10-17 | 2023-01-06 | 黄山中泽新材料有限公司 | Preparation method of azide-containing polyester polyol and application of azide-containing polyester polyol in post-crosslinking single-component waterborne polyurethane |
| CN115572379B (en) * | 2022-10-17 | 2024-03-12 | 黄山中泽新材料有限公司 | Preparation method of azido-containing polyester polyol and application of azido-containing polyester polyol in post-crosslinking single-component waterborne polyurethane |
| CN116004110A (en) * | 2023-01-13 | 2023-04-25 | 上海正欧实业有限公司 | Wear-resistant polyurethane floor coating with self-lubricating function and preparation method thereof |
| CN117304551A (en) * | 2023-09-01 | 2023-12-29 | 贵州省材料产业技术研究院 | Preparation method of modified chitin whisker reinforced and toughened PBAT micro-foaming composite material |
| CN118006212A (en) * | 2024-04-10 | 2024-05-10 | 天津双安劳保橡胶有限公司 | Preparation method and application of chitin-modified waterborne polyurethane composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093703A (en) | Method for preparing chitin whisker modified waterborne polyurethane | |
| Santamaria-Echart et al. | Advances in waterborne polyurethane and polyurethane-urea dispersions and their eco-friendly derivatives: A review | |
| Gogoi et al. | Biobased biodegradable waterborne hyperbranched polyurethane as an ecofriendly sustainable material | |
| Zhang et al. | Semi-interpenetrating polymer networks prepared from castor oil-based waterborne polyurethanes and carboxymethyl chitosan | |
| El-Naggar et al. | Exploration of a novel and efficient source for production of bacterial nanocellulose, bioprocess optimization and characterization | |
| CN100404576C (en) | Preparation method of starch nanocrystal modified waterborne polyurethane | |
| Madbouly | Waterborne polyurethane dispersions and thin films: biodegradation and antimicrobial behaviors | |
| Gu et al. | Multiple hydrogen bonding enables strong, tough, and recyclable soy protein films | |
| Siqueira et al. | Gelatin and galactomannan-based scaffolds: Characterization and potential for tissue engineering applications | |
| JP7349079B2 (en) | Method for producing paramylon resin | |
| JP7490182B2 (en) | Biodegradable composite material containing cellulose nanofibers and biodegradable resin | |
| CN103476803B (en) | Celluosic resin and manufacture method thereof | |
| Haida et al. | Starch-reinforced vinylogous urethane vitrimer composites: an approach to biobased, reprocessable, and biodegradable materials | |
| KR101725238B1 (en) | Protein-polymer-graphene oxide nanocomposites and nanocomposite films comprising them | |
| DE19750846C1 (en) | Process for the production of a component for the production of polymer mixtures based on starch | |
| Jayalath et al. | Bio-based polyurethane materials: Technical, environmental, and economic insights | |
| WO2012137622A1 (en) | Cellulose resin and method for producing same | |
| CN109810484B (en) | Preparation method of polylactic acid modified material | |
| Klongklaew et al. | Characterization and application in natural rubber of Leucaena leaf and its extracted products | |
| CN108034225B (en) | Method for preparing chitosan/thermoplastic polyurethane elastomer composite material | |
| JP7495676B2 (en) | Paramylon-based resin, molding material, molded body, and method for producing paramylon-based resin | |
| Zhou et al. | Bio-based polyurethane aqueous dispersions | |
| CN110698824B (en) | Degradable plastic and production process thereof | |
| CN118652410A (en) | A bio-based polyurethane material and its preparation method and application | |
| Tajeddin | Packaging composite materials from renewable resources |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110615 |