CN101230107A - Method for preparing konjac glucomannan grafted polyesters - Google Patents
Method for preparing konjac glucomannan grafted polyesters Download PDFInfo
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- CN101230107A CN101230107A CNA2008100468209A CN200810046820A CN101230107A CN 101230107 A CN101230107 A CN 101230107A CN A2008100468209 A CNA2008100468209 A CN A2008100468209A CN 200810046820 A CN200810046820 A CN 200810046820A CN 101230107 A CN101230107 A CN 101230107A
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Abstract
The invention relates to a preparation method of biodegradable material. A preparation method of konjac glucomannan grafting polyester is characterized in that preparation method comprises the following steps: firstly, according to the mass ratio of konjac glucomannan and polymeric monomer of 1:300 to 1:1, the mass of plasticizer is 0.01 to 3 percent of the mass of the polymeric monomer, the mass of konjac glucomannan to the volume ratio of solvent is 1g : 20 ml to 80 ml, and the konjac glucomannan, the polymeric monomer and catalyst and the solvent are chosen; the konjac glucomannan, the solvent and magneton are put into a reactor; secondly, the reactor is put into an oil bath, nitrogen is charged for one hour and then added with the catalyst, the reaction temperature is at 80 to 120 DEG C, and the reaction time lasts for 2 to10 hours; thirdly, the polymeric monomer is added, the polymerization temperature is at 80 to 120 DEG C, the reaction time lasts for 4-80 hours, and after the reaction stops, compound material solution is obtained; fourthly, through deposition, filter and drying, the konjac glucomannan grafting polyester is obtained. The invention has the advantages of low cost, strong operability, environmental protection, complete biodegradation and simple process.
Description
Technical field
The present invention relates to a kind of preparation method of konjac glucomannan grafted polyesters, belong to the natural macromolecular material field, also belong to the ecological environment material nd field.
Background technology
Konjaku, Bie Ming Amorphophalus rivieri, Betel taro, numb taro, belong to the Araeceae per nnial herb.The whole world is known 130 kinds, and wherein, China is one of topmost in the world konjaku producing country.Some kind stem tubers of Amorphophallus are rich in konjac polysaccharide, and especially white konjaku, elephant-foot yam kind content are up to 50-65%.Konjac polysaccharide claims Rhizoma amorphophalli glucomannan again, be by numerous seminoses and glucose, with β-1, the linear polymer that the 4-glycosidic link couples together, the molecular ratio of glucose and seminose are 1: 1.5-1.7, and molecular weight can be up to 106 dalton, the viscosity extra-high-speed, water-soluble, turgidity is especially big in water, has specific biological activity.Have multiple unique physical and chemical properties such as water-soluble, water holding thickening, stable, suspension, gelling, bonding, film forming has it to use and develop value widely owing to Rhizoma amorphophalli glucomannan.Can be widely used in drink industry, meat product, bean product, frozen product, jelly, pudding, fruit grain freeze, chocolate freezes, jam, candy, fields such as flour products.In addition, konjac polysaccharide all has been widely used at aspects such as weaving, printing and dyeing, cosmetic, pottery, fire-fighting, environmental protection, military project, oil productions, as can be used as papermaking slurry and wrapping material, even aspect such as protective foods.These konjac polysaccharide all have cheap, renewable and advantages of environment protection.
Recently, because growing tension, crude oil price continuous rise and the problem of environmental pollution of petroleum resources, be subjected to people based on the poly-STUDY ON POLYSACHAROSE of renewable resources and application and extensively pay attention to, also be significant for the poly-polysaccharide of development and utilization simultaneously.Also there is the shortcoming of some aspect of performances in natural polysaccharide, and, poor water resistance low as intensity etc. by graft polymerization graftomer segment on macromolecular chain, to improve its performance, can satisfy service requirements.Link agent and chemical promotor and other auxiliary agents of being connected as in the mixture of synthetic macromolecule and natural polymer, adding chemistry, intensity greatly improved when the plastics that make connected than the nothing chemistry, and have biology, a dual degradation property of light, and between composition, form chemical bonding each other, therefore this system forms homogeneous and continuous phase structure, shows excellent mechanical property and processing characteristics (Chinese patent application number: 96122161; Chinese patent application number: 200510026627).Simultaneously, this class natural polymer and synthetic macromolecule can be used as the expanding material of synthetic macromolecule and natural polymer blended material by the mixture that covalent linkage forms, and promote consistency between the two to realize high mechanical property and thermal characteristics.In addition, utilizing the microwave polymerization process to come synthetic macromolecule, also is a nearest big focus of research, as passing through microwave polymerization synthesizing polylactic acid (Chinese patent application number: 200410013681).Thermopolymerization be a kind of substantially the most also be most important polymerization process, as by thermopolymerization g-polycaprolactone (Carbohydrate Polymers 2005,60,103) on W-Gum, but utilize konjac glucomannan grafted polyesters also not have bibliographical information.
Degradation material is by various ways such as photodegradation, chemical degradation, biological degradations, material degradation is become the small-molecule substance of environmental sound, as water, carbonic acid gas, preparation has practical and well behaved novel degradable synthetic materials is a kind of effective way that solves environmental problem.Biodegradable material comprises natural materials and synthetic materials, natural materials comprises starch, Mierocrystalline cellulose, chitin and their derivative, the degradable synthetic materials contain usually hydrolyzable functional group (as, ester bond, urea key, amido linkage, ehter bond etc.), as poly(lactic acid), polycaprolactone etc.The natural biological degradative plastics is an example with pure starch plastic, and the starch strongly hydrophilic makes the plastics of its preparation very responsive to humidity, and in the low-humidity environment, softening agent can diffuse out from product, and product is become fragile; During high humidity environment, water can diffuse into product, changes shape of product, reduces mechanical property.In addition, elasticity is low and the nerve height also is the weakness of starch.Some hydrophobic aliphatic polyesters (as, polycaprolactone, poly(lactic acid) etc.) have excellent water tolerance, mechanical property and a processing stability, can degrade by hydrolysis, biodegradable in soil, but production cost is higher than conventional plastic (as polyethylene, polystyrene etc.) far away.And the Biodegradable polyester compound system of cheap starch and excellent property becomes performance and this method to contradiction of cost of solving.
Summary of the invention
The object of the present invention is to provide the preparation method of the konjac glucomannan grafted polyesters of a kind of degraded with low cost, easy, environmental protection.
To achieve these goals, the technical solution adopted in the present invention is as follows: a kind of preparation method of konjac glucomannan grafted polyesters is characterized in that comprising the steps:
1). the mass ratio by Rhizoma amorphophalli glucomannan and polymerization single polymerization monomer is 1: 300-1: 1, the quality of catalyzer is the 0.01-3% of polymerization single polymerization monomer quality, the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 20ml-80ml, choose Rhizoma amorphophalli glucomannan, polymerization single polymerization monomer, catalyzer, solvent; Rhizoma amorphophalli glucomannan and solvent and magneton are put into reactor; 2). then reactor is put into oil bath pan, under the magneton effect, Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor, and logical nitrogen added catalyzer after 1 hour, temperature of reaction is 80-120 ℃, reaction times 2-10 hour (for the reaction times behind the adding catalyzer); 3). add polymerization single polymerization monomer, continue the magneton stirring and lead to nitrogen, polymerization temperature is 80-120 ℃, and polymerization time is 4-80 hour, and reaction stops, and gets matrix material solution; 4). the volume ratio by solvent and precipitation agent is 1: 4-8, matrix material solution is joined in the precipitation agent precipitation (to come out the polymer precipitation in the matrix material solution with precipitation agent, intact polymerization single polymerization monomer and the catalyzer of unreacted then stayed in the solution), suction filtration, with drying precipitate, get konjac glucomannan grafted polyesters.
Described polymerization single polymerization monomer is rac-Lactide or caprolactone etc.Form polymer chains such as polylactide or polycaprolactone.
Described catalyzer is the organic tin catalyzer, mainly is stannous octoate or the tin protochloride of checking by U.S. food medicine office.
Described solvent is a toluene.Described precipitation agent is an alcohols, comprises methyl alcohol or ethanol etc.
The present invention adopts Rhizoma amorphophalli glucomannan, by thermopolymerization method grafting biodegradable polyesters (polylactide or polycaprolactone) polymer chain on Rhizoma amorphophalli glucomannan, obtains konjac glucomannan grafted polyesters.Main raw material(s) adopts Rhizoma amorphophalli glucomannan, has with low cost, environmental friendliness, advantage such as biodegradable; The present invention adopts the method for thermopolymerization, has environmental protection, simple, quick, the characteristics of high efficiency of technology.The material environment close friend of preparation, be easy to degraded, can straight forming processing, as wrapping material and engineering plastics etc., also can be used for the expanding material of Polymer Blending System.
The present invention has following beneficial effect: with low cost, strong operability, environmental protection, fully biodegradable, technology are simple.
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.
Embodiment 1:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 40; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the volume ratio of the quality of Rhizoma amorphophalli glucomannan and solvent (toluene) is 1g: 40ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours (for the reaction times behind the adding catalyzer).Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 8 hours; after reaction stops; matrix material solution, be 1: 4 by the volume ratio of solvent and precipitation agent, matrix material solution is joined in the methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation is got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
With dried konjac glucomannan grafted polyesters at injection moulding machine (HAAKE MiniJet, Germany Haake company) carries out injection moulding on, injection temperature is 70 ℃, injection time is 3min, injection pressure is 5bar, and film tool temperature is 30 ℃, and the dwell time is 2min, the sheet material that obtains is 35% at constant humidity, places after 7 days under the room temperature and carries out performance test.The mechanical property of the sheet material of preparation sees Table 1.Mechanical property thinks carefully newly in Shenzhen with reference to State Standard of the People's Republic of China GB4456-84 on the CMT6503 instrument of testing tool company and records that rate of extension is 10mm/min.
Annotate: magneton is a kind of thing that has magnetic, has stirring action, and the branch of size is arranged, and shapes such as fusiform and rectangle are also arranged, and when it can rotate in magnetic stirring apparatus effect following time, thereby reaches the stirring purpose.
Embodiment 2:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 60; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 40ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours (for the reaction times behind the adding catalyzer).Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 8 hours; after reaction stops; matrix material solution, be 1: 4 by the volume ratio of solvent and precipitation agent, matrix material solution is joined in the methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation is got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.The mechanical property of the sheet material of preparation sees Table 1.The injecting condition of sheet material and Mechanics Performance Testing are with embodiment 1.
Embodiment 3:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 80; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours (for the reaction times behind the adding catalyzer).Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 8 hours; after reaction stops; matrix material solution, be 1: 4 by the volume ratio of solvent and precipitation agent, matrix material solution is joined in the methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation is got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.The mechanical property of the sheet material of preparation sees Table 1.The injecting condition of sheet material and Mechanics Performance Testing are with embodiment 1.
Embodiment 4:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 200; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 80 ℃, and the reaction times is 8 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 80 ℃, and polymerization time is 60 hours; after reaction stops; matrix material solution, be 1: 6 by the volume ratio of solvent and precipitation agent, matrix material solution is joined in the methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation is got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 5:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 1; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 30ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 0.75% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 100 ℃, and the reaction times is 4 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 100 ℃, and polymerization time is 80 hours; after reaction stops; matrix material solution, be 1: 6 by the volume ratio of solvent and precipitation agent, matrix material solution is joined in the methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation is got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 6:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 300; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 80ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 0.75% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 100 ℃, and the reaction times is 4 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 100 ℃, and polymerization time is 40 hours; after reaction stops; matrix material solution, be 1: 6 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 7:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 40; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 0.5% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 24 hours; after reaction stops; matrix material solution, be 1: 8 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 8:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 40; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 0.5% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 48 hours; after reaction stops; matrix material solution, be 1: 8 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 9:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 100; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 2% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 6 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 50 hours; after reaction stops; matrix material solution, be 1: 8 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 10:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of caprolactone monomer are 1: 150; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 2% of caprolactone quality that stannous octoate adds quality; temperature of reaction is 100 ℃, and the reaction times is 2 hours.Reach after the reaction times; add caprolactone (U.S. Aldrich company) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 100 ℃, and polymerization time is 70 hours; after reaction stops; matrix material solution, be 1: 8 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 11:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 60; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 100 ℃, and the reaction times is 4 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 100 ℃, and polymerization time is 20 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 12:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 100; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 10 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 13:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 200; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 80ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 80 ℃, and the reaction times is 6 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 80 ℃, and polymerization time is 50 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 14:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 300; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 80ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 1% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 80 ℃, and the reaction times is 6 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 80 ℃, and polymerization time is 70 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 15:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 80; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 0.5% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 8 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 16:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 100; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 3% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 120 ℃, and the reaction times is 2 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 8 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 17:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 1; Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor; then reactor is put into oil bath pan; under the magneton effect; Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor; the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 20ml; logical nitrogen adds stannous octoate (Shanghai chemical reagents corporation of Chinese Medicine group) again and makees catalyzer after 1 hour; it is 0.01% of rac-Lactide quality that stannous octoate adds quality; temperature of reaction is 80 ℃, and the reaction times is 10 hours.Reach after the reaction times; add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer; continue the magneton stirring and lead to nitrogen, polymerization temperature is 80 ℃, and polymerization time is 80 hours; after reaction stops; matrix material solution, be 1: 5 by the volume ratio of solvent and precipitation agent, will in the matrix material solution adding methyl alcohol (Shanghai chemical reagents corporation of Chinese Medicine group) polymer precipitation be got off; suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 18:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 100, Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor, then reactor is put into oil bath pan, under the magneton effect, Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor, the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 60ml, logical nitrogen adds tin protochloride again and makees catalyzer after 1 hour, it is 3% of rac-Lactide quality that tin protochloride adds quality, temperature of reaction is 120 ℃, and the reaction times is 2 hours.Reach after the reaction times, add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer, continue the magneton stirring and lead to nitrogen, polymerization temperature is 120 ℃, and polymerization time is 8 hours, after reaction stops, matrix material solution, be 1: 4 by the volume ratio of solvent and precipitation agent (ethanol), will in the matrix material solution adding ethanol polymer precipitation be got off, suction filtration, drying promptly get konjac glucomannan grafted polyesters.
Embodiment 19:
A kind of preparation method of konjac glucomannan grafted polyesters, it comprises the steps:
The quality of Rhizoma amorphophalli glucomannan and the mass ratio of lactide monomer are 1: 1, Rhizoma amorphophalli glucomannan (Wuhan strong gloomy konjak products company limited) and toluene (Dihua worker company limited is won in Tianjin) and magneton are put into reactor, then reactor is put into oil bath pan, under the magneton effect, Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor, the volume ratio of the quality of Rhizoma amorphophalli glucomannan and solvent (toluene) is 1g: 20ml, logical nitrogen adds tin protochloride again and makees catalyzer after 1 hour, it is 0.01% of rac-Lactide quality that tin protochloride adds quality, temperature of reaction is 80 ℃, and the reaction times is 10 hours.Reach after the reaction times, add rac-Lactide (Shenzhen City Guanghua Weiye Industry Co.,Ltd) and do polymerization single polymerization monomer, continue the magneton stirring and lead to nitrogen, polymerization temperature is 80 ℃, and polymerization time is 80 hours, after reaction stops, matrix material solution, be 1: 8 by the volume ratio of solvent and precipitation agent (ethanol), will in the matrix material solution adding ethanol polymer precipitation be got off, suction filtration, drying promptly get konjac glucomannan grafted polyesters.
The konjac glucomannan grafted product mechanical property of table 1.
| Numbering | Young's modulus/MPa | Tensile strength/MPa | Elongation at break/% |
| Embodiment 1 | 1430.86 | 51.41 | 5.39 |
| Embodiment 2 | 1154.21 | 54.41 | 52.99 |
| Embodiment 3 | 1438.85 | 56.45 | 6.86 |
Illustrate: other embodiment that does not enumerate its mechanical property in this table does not mean that it can not injection moulding.
By embodiment 1,2,3 can find, when other thermal polymerization condition is identical, mass ratio increase along with caprolactone monomer and Rhizoma amorphophalli glucomannan, the Young's modulus of the direct injection moulding resulting sheet of its graft product reduces afterwards earlier and increases, tensile strength increases always, elongation at break then increases afterwards earlier and reduces, wherein embodiment 2 has maximum elongation at break, be 52.99%, its corresponding Young's modulus and tensile strength are respectively 1154.21MPa and 54.41MPa, embodiment 3 has maximum Young's modulus and tensile strength, is respectively 1438.85MPa and 56.45MPa, and its corresponding elongation at break is 6.86%.
Can find that to sum up embodiment 2 has good comprehensive mechanical properties in the thermopolymerization.
Claims (7)
1. the preparation method of a konjac glucomannan grafted polyesters is characterized in that comprising the steps:
1). the mass ratio by Rhizoma amorphophalli glucomannan and polymerization single polymerization monomer is 1: 300-1: 1, the quality of catalyzer is the 0.01-3% of polymerization single polymerization monomer quality, the quality of Rhizoma amorphophalli glucomannan and the volume ratio of solvent are 1g: 20ml-80ml, choose Rhizoma amorphophalli glucomannan, polymerization single polymerization monomer, catalyzer, solvent; Rhizoma amorphophalli glucomannan and solvent and magneton are put into reactor; 2). then reactor is put into oil bath pan, under the magneton effect, Rhizoma amorphophalli glucomannan and solvent constantly stir in reactor, and logical nitrogen added catalyzer after 1 hour, and temperature of reaction is 80-120 ℃, reaction times 2-10 hour; 3). add polymerization single polymerization monomer, continue the magneton stirring and lead to nitrogen, polymerization temperature is 80-120 ℃, and polymerization time is 4-80 hour, and reaction stops, and gets matrix material solution; 4). the volume ratio by solvent and precipitation agent is 1: 4-8, matrix material solution joined in the precipitation agent precipitates, suction filtration, with drying precipitate, konjac glucomannan grafted polyesters.
2. the preparation method of a kind of konjac glucomannan grafted polyesters according to claim 1, it is characterized in that: described polymerization single polymerization monomer is rac-Lactide or caprolactone.
3. the preparation method of a kind of konjac glucomannan grafted polyesters according to claim 1, it is characterized in that: described catalyzer is the organic tin catalyzer.
4. the preparation method of a kind of konjac glucomannan grafted polyesters according to claim 3, it is characterized in that: the organic tin catalyzer is stannous octoate or tin protochloride.
5. the preparation method of a kind of konjac glucomannan grafted polyesters according to claim 1, it is characterized in that: described solvent is a toluene.
6. the preparation method of a kind of konjac glucomannan grafted polyesters according to claim 1, it is characterized in that: described precipitation agent is an alcohols.
7. the preparation method of a kind of konjac glucomannan grafted polyesters according to claim 6, it is characterized in that: alcohols is methyl alcohol or ethanol.
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