CN103834072A - Modified nature latex, preparation method and use thereof - Google Patents
Modified nature latex, preparation method and use thereof Download PDFInfo
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- CN103834072A CN103834072A CN201210470393.3A CN201210470393A CN103834072A CN 103834072 A CN103834072 A CN 103834072A CN 201210470393 A CN201210470393 A CN 201210470393A CN 103834072 A CN103834072 A CN 103834072A
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Abstract
The invention belongs to the technical field of rubber chemical modification, and relates to a preparation method and a use of a modified nature latex. The modified nature latex is prepared from the following components by weight: 100 parts of nature latex, and 10-30 parts of sericin grafted aqueous polyurethane emulsion. According to the present invention, the modified rubber has advantages of surface functionalization, good biocompatibility and the like; the mechanical property and the allergy of the nature latex gloves are improved; and the traditional method that the protein removing method is adopted to solve the allergy of the latex product is changed, the allergy problem is solved without reduction of the protein content, and the physical and mechanical properties of the latex product are ensured.
Description
Technical field
The invention belongs to rubber chemistry modification technology field, relate to a kind of preparation method and its usage of modified natural emulsion.
Background technology
A kind of natural polymer globular preteins that silk gum is made up of 18 seed amino acids such as Serine, aspartic acid, because amino acid contains hydroxyl, amino and the stronger side group of carboxyl isopolarity, the characteristics such as the fabulous wetting ability of silk gum and chemically reactive and the special moisture retention to skin, oxidation-resistance and biocompatibility are given.Silk gum can carry out grafting, blending reaction and obtain with other polymer the material of excellent performance.The research of silk gum in recent years more and more comes into one's own, and silk gum and modified product are widely used in makeup, food, textiles and high molecular products.
Aqueous polyurethane be a kind ofly do not fire, environment-friendly materials nontoxic, free from environmental pollution, there is the advantages such as hardness is high, strong adhesion, corrosion-resistant, solvent resistance is good, its goods have good surperficial slipping, and can be coated in latex product surface increases the comfortableness of its wearing.
Natural emulsion has good physical and mechanical properties, is the raw material of many medical articles and daily necessities, but its goods exist, the irritated and surperficial adhesion of human body skin is dressed to the problems such as uncomfortable.Wherein contain the protein of some sensitization, easily bring out contact dermatitis, anaphylaxis conjunctivitis, allergic rhinitis, urticaria, allergic asthma and the anaphylaxis of the shock constant speed property sent out.The research solving in recent years and improve latex protein allergy more and more comes into one's own, the main terms of settlement of report has deproteinated, enzyme decomposition, surface chlorination etc. at present, but these methods exist cost higher, the difficult problems such as complex process, and the minimizing of protein can cause latex product mechanical property to reduce greatly.
Therefore, develop and be a kind ofly conducive to keep latex performance, can not cause allergic reaction, dress comfortable natural rubber latex production method, become the active demand of this area.
Summary of the invention
The defect the object of the invention is to for overcoming prior art provides natural emulsion of a kind of silk gum grafting aqueous polyurethane emulsion modification and its production and use.
For achieving the above object, the technical solution used in the present invention is as follows:
For the deficiencies in the prior art, the present invention utilizes the good feature such as biocompatibility and oxidation-resistance of silk gum, in conjunction with the good mechanical property of aqueous polyurethane, synthesize silk gum grafting aqueous polyurethane emulsion (SPU), by the method for heterocoagulation the emulsion of grafting and natural emulsion blend, the polarity segment of SPU molecule is preferential to be combined under hydrogen bonded etc. acts on latex protein molecule, form the supramolecular structure system that multiple bonding exists, under the solidification of natural rubber, most of SPU Mobility of the chain segments is to the surface and interface of the microfacies of rubber, form SPU protective layer securely on rubber matrix surface, make modified rubber there is the advantages such as surface-functionalized and good biocompatibility, improve mechanical property and the supersensitivity of natural emulsion gloves.
A kind of modified natural emulsion, is made by the component that comprises following weight part:
100 parts of natural emulsions,
Silk gum grafting aqueous polyurethane emulsion 10-30 part.
Described natural emulsion is the concentrated natural emulsion of ammoniacal liquor, and wherein the content of natural rubber is 50.0-71.0%, and surplus is ammoniacal liquor.
Described silk gum grafting aqueous polyurethane emulsion is made up of the component that comprises following weight part:
Oligomer polyol 38.81-35.07 part,
Wetting ability chainextender 1.50-2.00 part,
N-Methyl pyrrolidone 10-18 part,
Polyisocyanates 12.21-15.54 part,
Catalyzer 0.1-0.3 part,
Solvent acetone 15.0-30.0 part,
Neutralizing agent 1.13-1.51 part,
Silk gum aqueous solution 90.0-250.0 part.
Described oligomer polyol is polyether glycol, preferably polypropylene glycol 2000, polyoxypropyleneglycol or PTMG.
Described wetting ability chainextender is dimethylol propionic acid, dihydroxyl half ester, second diamino ethyl sulfonic acid sodium, diethylenetriamine etc.
Described polyisocyanates be in aliphatic isoflurane chalcone diisocyanate, hexamethylene diisocyanate and aromatic tolylene diisocyanate, diphenylmethanediisocyanate etc. any.
Described catalyzer is dibutyl tin laurate, in stannous octoate etc. any.
Described neutralizing agent be in triethylamine, ammoniacal liquor, epoxy chloropropane etc. any.
Above-mentioned middle N-Methyl pyrrolidone and acetone are all as solvent.
The concentration of the described silk gum aqueous solution is 11.9 ~ 28.9%, and wherein solute silk gum is commercially available silk cocoon, and solvent is deionized water, and its preparation method is:
(1) silk cocoon is cut into 0.5-1.5cm
3bulk, take 50-80 part and carry out oscillating washing, then use deionized water rinsing;
(2) add 300-500 part deionized water after cleaning, put into reactor and be heated to 100-110 ℃, after boiling, keep stopping after boiling state 2-4h heating;
(3), while hot after suction filtration, by the lyophilize of gained solution, drying temperature is-30--50 ℃ that the time is 12-24h, makes 13.5-24.4 part silk gum powder;
(4) deionized water that adds 60-100 part in 13.5-24.4 part silk gum powder, uniform stirring fully dissolves it, obtains concentration and be 11.9 ~ 28.9% the silk gum aqueous solution, and stir speed (S.S.) is 150-250r/min.
A preparation method for above-mentioned modified natural emulsion, comprises the following steps:
(1) taking weight part by said ratio is natural emulsion and 10-30 part silk gum grafting aqueous polyurethane emulsion of 100 parts,
(2) heterocoagulation blend, temperature is 20-30 ℃, stirring velocity is 100-200r/min, stirs 2-4h, and both are mixed.
In described step (1), the preparation method of silk gum grafting aqueous polyurethane emulsion, comprises the following steps:
(1) in reactor, 38.81-35.07 part oligomer polyol, 1.50-2.00 part wetting ability chainextender, 10-18 part solvent N-Methyl pyrrolidone are mixed, be warming up to 110-130 ℃, constant temperature 1-2h, makes wetting ability chainextender dissolve rear slow cooling completely to 40-60 ℃;
(2) in the product of step (1), drip 12.21-15.54 part polyisocyanates, 0.1-0.3 part catalyzer, 15.0-30.0 part acetone, be slowly warming up to 70-90 ℃, constant temperature 2-3h, is then cooled to 40-60 ℃;
(3) in the product of step (2), add 1.13-1.51 part neutralizing agent, and 90.0-250.0 part silk gum aqueous solution is slowly dropped in reactor, adopt high speed shear 5000-12000r/ minute, emulsification 5-8 minute, under normal pressure, distill out acetone, obtain silk gum grafting end-blocking aqueous polyurethane emulsion.
Above-mentioned modified natural emulsion for example, as a purposes for dipped goods material, medical latex glove.
Described dipped goods is medical latex glove, nuclear industry special type protection gloves, sebific duct, medical catheter, balloon, condom, baby nipple or fingerstall; Be preferably medical latex glove, its moulding process is the manufacture craft of conventional medical latex glove.
The present invention compared with prior art, has the following advantages and beneficial effect:
1, the present invention utilizes the good feature such as biocompatibility and oxidation-resistance of silk gum, in conjunction with the good mechanical property of aqueous polyurethane, synthesize silk gum grafting aqueous polyurethane emulsion (SPU), by the method for heterocoagulation the emulsion of grafting and natural emulsion blend, the polarity segment of SPU molecule is preferential to be combined under hydrogen bonded etc. acts on latex protein molecule, form the supramolecular structure system that multiple bonding exists, under the solidification of natural rubber, most of SPU Mobility of the chain segments is to the surface and interface of the microfacies of rubber, form SPU protective layer securely on rubber matrix surface, make modified rubber there is the advantages such as surface-functionalized and good biocompatibility, improve mechanical property and the supersensitivity of natural emulsion gloves.
2, the present invention changes tradition by removing the way of method of protein solution latex product allergy, under the condition that does not reduce protein content, solves allergic problem, has guaranteed the physical and mechanical properties of latex product.
3, except there is allergic problem in natural rubber, and also, because containing unsaturated double-bond in molecule, its heat oxygen aging resistance, organic solvent-resistant and uviolresistance are all poor, and these shortcomings also become the obstacle of its development day by day.The oxidation-resistance of silk gum is by a large amount of studies confirm that, is expected to improve the characteristics such as heat oxygen aging resistance with silk gum modified natural rubber, thus for the development of rubber industry brings new knowledge growth point and point of economic increase.
4, China is silk big country, and original silk processing industry is dyed etc. in production process in filature, refining, has a large amount of silk gum waste liquid discharges, has not only caused Biological resources waste, the environment of having gone back severe contamination.When exploitation silk gum waste resource recycling, protect environment.Silk gum is a kind of degradable biomaterial with green concept, has huge application prospect.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Natural emulsion in following examples, is the concentrated natural emulsion of ammoniacal liquor, purchased from Hainan Mei Lianxiangshun rubber company limited,
Silk cocoon in following examples is commercially available.
Embodiment 1
(1) prepare the silk gum aqueous solution:
Commercially available silk cocoon is cut into general 0.5cm
3bulk after, take 50 parts and carry out oscillating washing, then use deionized water rinsing;
After cleaning, add 300 parts of deionized waters, put into flask and carry out 100 ℃ of water-baths, after boiling, keep after boiling state 3h, stop heating;
After suction filtration, by the lyophilize of gained solution, drying temperature is-30 ℃ while hot, and the time is 24h, makes 13.5 parts, silk gum powder;
In 13.5 parts of silk gum powder, add 100 parts of deionized waters, uniform stirring 10min(stir speed (S.S.) is 150r/min) it is fully dissolved, obtain concentration and be 11.9% the silk gum aqueous solution, for subsequent use;
(2) prepare silk gum grafting aqueous polyurethane emulsion:
Being equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and dropping funnel, drop into oligomer polyol polypropylene glycol 2,000 38.81 weight parts, wetting ability chainextender dimethylol propionic acid 1.50 weight parts and solvent N-Methyl pyrrolidone 10 weight parts, slowly be warming up to 110 ℃ of left and right, constant temperature 1 hour, dissolves wetting ability chainextender completely; Slow cooling to 40 ℃;
Drip isoflurane chalcone diisocyanate 12.21 weight parts, catalyzer dibutyl tin laurate 0.1 weight part and acetone 15.0 weight parts by formula, be more slowly warming up to 70 ℃ of left and right, constant temperature 2 hours, is then cooled to 40 ℃;
Add neutralizing agent triethylamine 1.13 weight parts, by the silk gum aqueous solution 90.0 weight parts, slowly drop in flask, adopt high speed shear (5000r/ minute), emulsification 5 minutes, distills out acetone under normal pressure, obtains silk gum grafting end-blocking aqueous polyurethane emulsion.
(3) prepare silk gum grafting aqueous polyurethane emulsion modified natural emulsion
By 100 parts of natural emulsions (mass content of natural rubber is 50.0%) and 10 parts of silk gum grafting aqueous polyurethane emulsions obtained above;
Natural emulsion and silk gum grafting aqueous polyurethane emulsion are carried out to heterocoagulation blend, and temperature is 20 ℃, and stirring velocity is 100r/min, stirs 2h, and both are mixed; Obtain the natural emulsion 1# of silk gum grafting aqueous polyurethane emulsion modification.
Natural emulsion 1# is adopted to the manufacture craft of conventional medical latex glove, make medical latex glove, the performance of this emulsion products refers to table 1.
Embodiment 2
(1) prepare the silk gum aqueous solution:
Commercially available silk cocoon is cut into general 1.0cm
3bulk after, take 50 parts and carry out oscillating washing, then use deionized water rinsing;
After cleaning, add 400 parts of deionized waters, put into flask and carry out 105 ℃ of water-baths, after boiling, keep after boiling state 4h, stop heating;
After suction filtration, by the lyophilize of gained solution, drying temperature is-40 ℃ while hot, and the time is 18h, makes 14.3 parts, silk gum powder;
In 14.3 parts of silk gum powder, add 100 parts of deionized waters, uniform stirring 10min(stir speed (S.S.) is 200r/min) it is fully dissolved, obtain concentration and be 12.5% the silk gum aqueous solution, for subsequent use;
(2) prepare silk gum grafting aqueous polyurethane emulsion:
Being equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and dropping funnel, drop into oligomer polyol PTMG 38.81 weight parts, wetting ability chainextender dihydroxyl half ester 1.50 weight parts and solvent N-Methyl pyrrolidone 15 weight parts, slowly be warming up to 120 ℃ of left and right, constant temperature 1.5 hours, dissolves wetting ability chainextender completely; Slow cooling to 50 ℃;
Drip hexamethylene diisocyanate 13.32 weight parts, catalyzer dibutyl tin laurate 0.2 weight part and acetone 20.0 weight parts by formula, be more slowly warming up to 80 ℃ of left and right, constant temperature 2.5 hours, is then cooled to 50 ℃;
Add neutralizing agent triethylamine 1.13 weight parts, by the silk gum aqueous solution 150.0 weight parts, slowly drop in flask, adopt high speed shear (8000r/ minute), emulsification 6 minutes, distills out acetone under normal pressure, obtains silk gum grafting end-blocking aqueous polyurethane emulsion;
(3) prepare silk gum grafting aqueous polyurethane emulsion modified natural emulsion
100 parts of natural emulsions (mass content of natural rubber is 60.0%) and 15 parts of silk gum grafting aqueous polyurethane emulsions obtained above are carried out to heterocoagulation blend, and temperature is 25 ℃, and stirring velocity is 150r/min, stirs 2.5h, and both are mixed.Obtain the natural emulsion 2# of silk gum grafting aqueous polyurethane emulsion modification.
Natural emulsion 2# is adopted to the manufacture craft of conventional medical latex glove, make medical latex glove, the performance of this emulsion products refers to table 1.
Embodiment 3
(1) prepare the silk gum aqueous solution:
Commercially available silk cocoon is cut into general 1.5cm
3bulk after, take 70 parts and carry out oscillating washing, then use deionized water rinsing;
After cleaning, add 500 parts of deionized waters, put into flask and carry out 110 ℃ of water-baths, after boiling, keep after boiling state 3.5h, stop heating;
After suction filtration, by the lyophilize of gained solution, drying temperature is-50 ℃ while hot, and the time is 12h, makes 20.9 parts, silk gum powder;
In 20.9 parts of silk gum powder, add 100 parts of deionized waters, uniform stirring 10min(stir speed (S.S.) is 250r/min) it is fully dissolved, obtain concentration and be 17.3% the silk gum aqueous solution, for subsequent use;
(2) prepare silk gum grafting aqueous polyurethane emulsion:
Being equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and dropping funnel, drop into oligomer polyol polyoxypropyleneglycol 35.07 weight parts, wetting ability chainextender dimethylol propionic acid 2.00 weight parts and solvent N-Methyl pyrrolidone 18 weight parts, slowly be warming up to 130 ℃ of left and right, constant temperature 2 hours, dissolves wetting ability chainextender completely; Slow cooling to 60 ℃;
Drip diphenylmethanediisocyanate 14.43 weight parts, sub-tin 0.3 weight part of octoate catalyst and acetone 25.0 weight parts by formula, be more slowly warming up to 90 ℃ of left and right, constant temperature 3 hours, is then cooled to 60 ℃;
Add neutralizing agent epoxy chloropropane 1.51 weight parts, by the silk gum aqueous solution 200.0 weight parts, slowly drop in flask, adopt high speed shear (10000r/ minute), emulsification 7 minutes, distills out acetone under normal pressure, obtains silk gum grafting end-blocking aqueous polyurethane emulsion.
(3) prepare silk gum grafting aqueous polyurethane emulsion modified natural emulsion
100 parts of natural emulsions (mass content of natural rubber is 71.0%) and 20 parts of silk gum grafting aqueous polyurethane emulsions obtained above are carried out to heterocoagulation blend, and temperature is 30 ℃, and stirring velocity is 200r/min, stirs 3h, and both are mixed.Obtain the natural emulsion 3# of silk gum grafting aqueous polyurethane emulsion modification.
Natural emulsion 3# is adopted to the manufacture craft of conventional medical latex glove, make medical latex glove, the performance of this emulsion products refers to table 1.
Embodiment 4
(1) prepare the silk gum aqueous solution:
Commercially available silk cocoon is cut into general 1.0cm
3bulk after, take 80 parts and carry out oscillating washing, then use deionized water rinsing;
After cleaning, add 300 parts of deionized waters, put into flask and carry out 110 ℃ of water-baths, after boiling, keep after boiling state 4h, stop heating;
After suction filtration, by the lyophilize of gained solution, drying temperature is-50 ℃ while hot, and the time is 18h, makes 24.4 parts, silk gum powder;
In silk gum powder, add 60ml deionized water, uniform stirring 10min(stir speed (S.S.) is 180r/min) it is fully dissolved, obtain concentration and be 28.9% the silk gum aqueous solution, for subsequent use;
(2) prepare silk gum grafting aqueous polyurethane emulsion:
Being equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and dropping funnel, drop into oligomer polyol polypropylene glycol 2,000 35.07 weight parts, wetting ability chainextender second diamino ethyl sulfonic acid sodium 2.00 weight parts and solvent N-Methyl pyrrolidone 16 weight parts, slowly be warming up to 120 ℃ of left and right, constant temperature 2 hours, dissolves wetting ability chainextender completely; Slow cooling to 50 ℃;
Drip tolylene diisocyanate 15.54 weight parts, sub-tin 0.2 weight part of octoate catalyst and acetone 30.0 weight parts by formula, be more slowly warming up to 85 ℃ of left and right, constant temperature 3 hours, is then cooled to 50 ℃;
Add neutralizing agent triethylamine 1.51 weight parts, by the silk gum aqueous solution 250.0 weight parts, slowly drop in flask, adopt high speed shear (12000r/ minute), emulsification 8 minutes, distills out acetone under normal pressure, obtains silk gum grafting end-blocking aqueous polyurethane emulsion;
(3) prepare silk gum grafting aqueous polyurethane emulsion modified natural emulsion
100 parts of natural emulsions (mass content of natural rubber is 65.0%) and 25 parts of silk gum grafting aqueous polyurethane emulsions obtained above are carried out to heterocoagulation blend, and temperature is 28 ℃, and stirring velocity is 180r/min, stirs 4h, and both are mixed.Obtain the natural emulsion 4# of silk gum grafting aqueous polyurethane emulsion modification.
Natural emulsion 4# is adopted to the manufacture craft of conventional medical latex glove, make medical latex glove, the performance of this emulsion products refers to table 1.
Table 1
As seen from the above table, in the prepared latex product of the present invention, can overflow protein content and greatly reduce, greatly reduce thus the anaphylaxis phenomenon of rubber item to small white mouse.This emulsion particle after just because of heterocoagulation blend is nucleocapsid structure, silk gum grafting aqueous polyurethane particle has wrapped natural emulsion particle, the albumen on natural emulsion surface is also wrapped thereupon, add the raising of upper film cross-linking density, the macromolecule protein on natural emulsion surface is firmly locked in the inside, can in water, not be degraded into the low molecular protein of allergen, therefore the leachable protein content of the film after modification is very low, correspondingly greatly improve hypersensitive problem yet.With the composition that the film surface of skin contact contains silk gum, it has many characteristics such as friendly, moisture retention, oxidation-resistance to skin, can have maintenance function to skin.
In addition, the mechanical property of finding out the natural latex products of this kind of method modification from the tensile strength of upper table does not only reduce and is slightly improved, this is because with respect to natural emulsion, aqueous polyurethane has more been given prominence to the essence of its rigid structure, all large compared with natural emulsion of the intensity of its goods and hardness, this also just this method be better than the simple benefit of removing method of protein of tradition.
Embodiment 5
(1) prepare the silk gum aqueous solution:
Commercially available silk cocoon is cut into general 1.0cm
3bulk after, take 70 parts and carry out oscillating washing, then use deionized water rinsing;
After cleaning, add 400 parts of deionized waters, put into flask and carry out 100 ℃ of water-baths, after boiling, keep after boiling state 3h, stop heating;
After suction filtration, by the lyophilize of gained solution, drying temperature is-30 ℃ while hot, and the time is 24h, makes 15.4 parts, silk gum powder;
In 15.4 parts of silk gum powder, add 100ml deionized water, uniform stirring 10min(stir speed (S.S.) is 230r/min) it is fully dissolved, obtain concentration and be 13.3% the silk gum aqueous solution, for subsequent use;
(2) prepare silk gum grafting aqueous polyurethane emulsion:
Being equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and dropping funnel, drop into oligopolymer PTMG 38.81 weight parts, wetting ability chainextender diethylenetriamine 1.50 weight parts and solvent N-Methyl pyrrolidone 18 weight parts, slowly be warming up to 115 ℃ of left and right, constant temperature 2 hours, dissolves wetting ability chainextender completely; Slow cooling to 60 ℃;
Drip isoflurane chalcone diisocyanate 13.32 weight parts, sub-tin 0.3 weight part of octoate catalyst and acetone 25.0 weight parts by formula, be more slowly warming up to 80 ℃ of left and right, constant temperature 3 hours, is then cooled to 50 ℃;
Add neutralizing agent ammoniacal liquor 1.13 weight parts, by the silk gum aqueous solution 200.0 weight parts, slowly drop in flask, adopt high speed shear (10000r/ minute), emulsification 5 minutes, distills out acetone under normal pressure, obtains silk gum grafting end-blocking aqueous polyurethane emulsion;
(3) prepare silk gum grafting aqueous polyurethane emulsion modified natural emulsion
100 parts of natural emulsions (mass content of natural rubber is 58.0%) and 30 parts of silk gum grafting aqueous polyurethane emulsions obtained above are carried out to heterocoagulation blend, and temperature is 22 ℃, and stirring velocity is 130r/min, stirs 3.5h, and both are mixed.Obtain the natural emulsion 5# of silk gum grafting aqueous polyurethane emulsion modification.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a modified natural emulsion, is characterized in that: be made up of the component that comprises following weight part:
100 parts of natural emulsions,
Silk gum grafting aqueous polyurethane emulsion 10-30 part.
2. modified natural emulsion according to claim 1, is characterized in that: described natural emulsion is the concentrated natural emulsion of ammoniacal liquor, and wherein the content of natural rubber is 50.0-71.0%, and surplus is ammoniacal liquor.
3. modified natural emulsion according to claim 1, is characterized in that: described silk gum grafting aqueous polyurethane emulsion is made up of the component that comprises following weight part:
Oligomer polyol 38.81-35.07 part,
Wetting ability chainextender 1.50-2.00 part,
N-Methyl pyrrolidone 10-18 part,
Polyisocyanates 12.21-15.54 part,
Catalyzer 0.1-0.3 part,
Solvent acetone 15.0-30.0 part,
Neutralizing agent 1.13-1.51 part,
Silk gum aqueous solution 90.0-250.0 part.
4. modified natural emulsion according to claim 3, is characterized in that: described oligomer polyol is polyether glycol, preferably polypropylene glycol 2000, polyoxypropyleneglycol or PTMG;
Or described wetting ability chainextender is dimethylol propionic acid, dihydroxyl half ester, second diamino ethyl sulfonic acid sodium, diethylenetriamine.
5. modified natural emulsion according to claim 3, is characterized in that: described polyisocyanates is isoflurane chalcone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or diphenylmethanediisocyanate;
Or described catalyzer is dibutyl tin laurate or stannous octoate;
Or described neutralizing agent is triethylamine, ammoniacal liquor or epoxy chloropropane.
6. modified natural emulsion according to claim 3, is characterized in that: the concentration of the described silk gum aqueous solution is 11.9 ~ 28.9%, and wherein solute silk gum is silk cocoon, and solvent is deionized water, and its preparation method is:
(1) silk cocoon is cut into 0.5-1.5cm
3bulk, take 50-80 part and carry out oscillating washing, then use deionized water rinsing;
(2) add 300-500 part deionized water after cleaning, put into reactor and be heated to 100-110 ℃, after boiling, keep stopping after boiling state 2-4h heating;
(3), while hot after suction filtration, by the lyophilize of gained solution, drying temperature is-30--50 ℃ that the time is 12-24h, makes 13.5-24.4 part silk gum powder;
(4) deionized water that adds 60-100 part in 13.5-24.4 part silk gum powder, uniform stirring fully dissolves it, obtains concentration and be 11.9 ~ 28.9% the silk gum aqueous solution, and stir speed (S.S.) is 150-250r/min.
7. a preparation method for arbitrary described modified natural emulsion in the claims 1-6, is characterized in that: comprise the following steps:
(1) taking weight part by proportioning claimed in claim 1 is natural emulsion and 10-30 part silk gum grafting aqueous polyurethane emulsion of 100 parts,
(2) heterocoagulation blend, temperature is 20-30 ℃, is uniformly mixed.
8. preparation method according to claim 7, is characterized in that: in described step (1), the preparation method of silk gum grafting aqueous polyurethane emulsion, comprises the following steps:
(1) in reactor, 38.81-35.07 part oligomer polyol, 1.50-2.00 part wetting ability chainextender, 10-18 part solvent N-Methyl pyrrolidone are mixed, be warming up to 110-130 ℃, constant temperature 1-2h, makes wetting ability chainextender dissolve rear slow cooling completely to 40-60 ℃;
(2) in the product of step (1), drip 12.21-15.54 part polyisocyanates, 0.1-0.3 part catalyzer, 15.0-30.0 part acetone, be slowly warming up to 70-90 ℃, constant temperature 2-3h, is then cooled to 40-60 ℃;
(3) in the product of step (2), add 1.13-1.51 part neutralizing agent, and 90.0-250.0 part silk gum aqueous solution is slowly dropped in reactor, adopt high speed shear 5000-12000r/ minute, emulsification 5-8 minute, under normal pressure, distill out acetone, obtain silk gum grafting end-blocking aqueous polyurethane emulsion.
9. the preparation method described in 7 as requested, is characterized in that: in described step (2), stirring velocity is 100-200r/min, stirs 2-4h.
In a claims 1-6 arbitrary described modified natural emulsion as the purposes of dipped goods material.
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| CN105384977A (en) * | 2015-12-16 | 2016-03-09 | 中国工程物理研究院材料研究所 | Powder-free gloves and preparation method thereof |
| CN106317960A (en) * | 2016-09-21 | 2017-01-11 | 云南师范大学 | Method for immobilizing proteins in natural rubber latex by aid of modified tannin extract |
| CN106519335A (en) * | 2016-11-17 | 2017-03-22 | 无锡市长安曙光手套厂 | Medical latex film |
| CN107501913A (en) * | 2017-07-20 | 2017-12-22 | 兰州科天健康科技股份有限公司 | A kind of preparation method for being used to prepare the natural emulsion modified aqueous polyurethane of condom |
| CN111072907A (en) * | 2019-12-31 | 2020-04-28 | 江苏领瑞新材料科技有限公司 | Preparation method of waterborne polyurethane for bulletproof armor plate |
| CN112143214A (en) * | 2020-10-10 | 2020-12-29 | 天长市恒生医疗器械有限公司 | Latex gloves |
| CN112625426A (en) * | 2020-12-16 | 2021-04-09 | 江苏必得科技股份有限公司 | Thermoplastic foamed polyurethane material applied to rail transit and preparation method thereof |
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