CN114685922B - Bio-based itaconate rubber glove and preparation method thereof - Google Patents
Bio-based itaconate rubber glove and preparation method thereof Download PDFInfo
- Publication number
- CN114685922B CN114685922B CN202011560370.2A CN202011560370A CN114685922B CN 114685922 B CN114685922 B CN 114685922B CN 202011560370 A CN202011560370 A CN 202011560370A CN 114685922 B CN114685922 B CN 114685922B
- Authority
- CN
- China
- Prior art keywords
- itaconate
- groups
- rubber
- parts
- glove
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/52—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/4842—Outerwear
- B29L2031/4864—Gloves
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to the technical field of rubber, in particular to a bio-based itaconate rubber glove and a preparation method thereof. The invention adopts the itaconate latex from the biological base and replaces the traditional natural latex and petrochemical base latex to prepare the glove, so that the dependence on hevea brasiliensis and petrochemical energy sources can be reduced, and simultaneously, the itaconate rubber does not contain protein, and the allergy and shock risks in the process of wearing the glove can be reduced.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to a bio-based itaconate rubber glove and a preparation method thereof.
Background
The natural latex glove has the advantages of good elasticity, acid and alkali resistance, durability and the like, but is easy to cause allergy, even has the death case caused by the allergy, and the natural latex comprises rubber hydrocarbon, water and a small amount of non-rubber substances such as protein, resin, sugar, inorganic salt and the like. Natural latex gloves have been used for over a century and market demand has been vigorous. However, natural latex gloves expose safety risks to human health in use, including protein allergy to some users, potential risk of nitrosamines generated during processing to human body induced tumors, and the use of powderous gloves in the medical field can lead to respiratory tract inflammation or allergy, dermatitis, wound infections, etc. (Li Zhifeng, lv Mingzhe, li Yongzhen, liu Yunhao. Development of natural latex gloves and synthetic latex gloves [ J/OL ]. Rubber industry: 1-7[2020-12-22 ]). The natural latex used in the world is almost completely derived from hevea brasiliensis, and the hevea brasiliensis is relatively harsh in planting environment, is only suitable for growing in tropical areas, and is threatened by leaf blight of south america in recent years; so the price of the natural latex rises year by year, the cost rises, and the problems greatly limit the popularization of the natural latex glove. The nitrile latex is prepared by polymerizing acrylonitrile and butadiene through processes such as dipping coagulant, nitrile latex, vulcanization, surface treatment and the like, has the advantages of little allergy, good ductility, chemical resistance, lasting wear and the like, and can provide good protection for users (Chinese patent CN110317380A, liu Wenjing, sun Chuanzhi, zhang Mucun, cao Yuan and Zong Qiuyue, liu Hongming, a nitrile glove and a preparation method [ P ]). However, the nitrile glove on the market has poorer flexibility and higher price than that of the latex product, and the waste of the nitrile latex glove can generate harmful substances and pollute the environment.
Disclosure of Invention
In order to solve the technical problems, the itaconate derived from the biological group and butadiene are copolymerized to obtain the biological group itaconate latex, and the biological group itaconate latex is used for replacing the traditional natural latex and petrochemical group latex to prepare the glove, so that the dependence on hevea brasiliensis and petrochemical energy sources can be reduced, and simultaneously, the itaconate rubber does not contain protein, and the allergy and shock risks in the process of wearing the glove can be reduced.
The invention aims at providing a biobased itaconate rubber glove which comprises blended biobased itaconate rubber, a vulcanizing agent and an accelerator.
Wherein the vulcanizing agent is selected from sulfur; the vulcanizing agent can promote the vulcanization reaction of the bio-based itaconate rubber;
the accelerator is at least one selected from dithiocarbamates and thiazoles, preferably at least one selected from 2-mercaptobenzothiazole, zinc di-n-butyldithiocarbamate and zinc diethyl dithiocarbamate;
the amount of the vulcanizing agent is 0.5 to 5 parts by weight, the amount of the accelerator is 0.1 to 5 parts by weight, and preferably, the amount of the vulcanizing agent is 1 to 2 parts by weight, and the amount of the accelerator is 0.5 to 1 part by weight, based on 100 parts by weight of the bio-based itaconate rubber;
the rubber glove also contains at least one of potassium hydroxide, zinc oxide and filler; the amount of potassium hydroxide is 0.01 to 1 part, the amount of zinc oxide is 0.5 to 10 parts, and the amount of filler is 0 to 20 parts by weight based on 100 parts by weight of the bio-based itaconate rubber; preferably, the amount of potassium hydroxide is 0.01 to 1 part, the amount of zinc oxide is 0.5 to 10 parts, and the amount of filler is 0 to 10 parts, based on 100 parts by weight of the bio-based itaconate rubber.
In the bio-based itaconate rubber glove, the bio-based itaconate rubber is obtained by copolymerizing an itaconate monomer and a diene compound;
wherein, the mole ratio of the itaconic acid ester monomer and the diene compound is 1 (1-7), preferably 1 (1.9-4.5);
the itaconate monomer is at least one selected from monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monopropyl itaconate, dipropyl itaconate, monobutyl itaconate, dibutyl itaconate, monopentyl itaconate, monopexyl itaconate, dihexyl itaconate, shan Gengzhi itaconate, diheptyl itaconate, monooctyl itaconate, dioctyl itaconate, monononyl itaconate, dinonyl itaconate, monodecyl itaconate and didecyl itaconate, preferably at least one selected from dimethyl itaconate, diethyl itaconate, dipropyl itaconate and dibutyl itaconate;
the diene compound is at least one selected from butadiene and isoprene, preferably butadiene.
The second object of the invention is to provide a preparation method of the bio-based itaconate rubber glove, which comprises the following steps:
uniformly stirring components comprising the itaconate rubber, a vulcanizing agent and an accelerator, and standing to obtain slurry;
step two, immersing the glove model in a coagulant solution, and taking out and drying;
and step three, dipping the glove model obtained after the step two in the slurry obtained in the step one, and obtaining the bio-based itaconate rubber glove after vulcanization reaction and demoulding.
Specifically, at least one of potassium hydroxide, zinc oxide and filler is also added in the first step; the added KOH is used for adjusting the pH value of the prepared itaconate latex slurry, enhancing the stability of the latex, and simultaneously, promoting the tensile strength of the itaconate glove; the added zinc oxide can promote the pre-vulcanization of the itaconate rubber glove, and shorten the pre-vulcanization reaction time; the filler is at least one selected from white carbon black, calcium carbonate and barium sulfate, and is preferably water slurry added with the filler, and the mechanical property of the itaconate glove can be further improved by the added filler.
The stirring temperature in the first step is 20-30 ℃, and the stirring time is 1-2 h;
the standing time in the first step is 12-24 hours, and the mixture is kept at room temperature;
the coagulant in the second step is selected from soluble metal salts, preferably at least one of calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, zinc nitrate and zinc chloride;
the mass percentage concentration of the coagulant in the coagulant solution in the second step is 15-25%;
the dipping temperature in the second step is 25-55 ℃, and the dipping time is 5-15 s;
the drying temperature in the second step is 60-80 ℃ and the drying time is 10-30 min;
before dipping, the glove model is subjected to acid washing, alkali washing, rinsing and drying treatment; wherein the solution adopted for acid washing is at least one selected from nitric acid solution and hydrochloric acid solution, and the pH value of the solution adopted for acid washing is 3-5; the solution used for alkaline washing is at least one selected from sodium hydroxide solution and potassium hydroxide solution, and the pH value of the solution used for alkaline washing is 9-12; the rinsing can be performed in a common rinsing mode, and the water is used for rinsing; the drying treatment can also be carried out in a conventional manner, for example, at 60-80 ℃ for 20-30 min.
The dipping temperature in the third step is 25-35 ℃ and the dipping time is 1-6 min; the glove model dried in the third step is immersed in the slurry and then further comprises a drop operation, and a drop method commonly used in the field can be adopted;
the vulcanization reaction temperature in the step three is 110-140 ℃, and the vulcanization reaction time is 0.5-1 h;
after the vulcanization reaction in the step three, leaching, curling, cleaning and drying are also needed; the glove model after the drying treatment can be immersed in the slurry again, the operation process of the third step is repeated, and the operation is repeated for 2 to 5 times. The above-described leaching, hemming and drying processes may all be accomplished using procedures commonly used in the art.
In the preparation method, the bio-based itaconate rubber is prepared by polymerization of components including itaconate monomers and diene compounds, and preferably comprises the following steps:
step 1, adding deionized water, an emulsifying agent, electrolyte, an activating agent, an antioxidant and an itaconate monomer into a reaction container, and uniformly mixing;
step 2, adding a diene compound into the mixture obtained in the step 1, adding an initiator after pre-emulsification, and then carrying out polymerization reaction;
and step 3, after the reaction is finished, adding a terminator into the reaction container, and stirring to obtain the bio-based itaconate rubber.
Wherein the itaconate monomer is at least one selected from monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monopropyl itaconate, dipropyl itaconate, monobutyl itaconate, dibutyl itaconate, monopentyl itaconate, dipentyl itaconate, monohexyl itaconate, dihexyl itaconate Shan Gengzhi, diheptyl itaconate, monooctyl itaconate, dioctyl itaconate, monononyl itaconate, dinonyl itaconate, monodecyl itaconate and didecyl itaconate, preferably at least one selected from dimethyl itaconate, diethyl itaconate, dipropyl itaconate and dibutyl itaconate;
the diene compound is at least one selected from butadiene and isoprene, preferably selected from butadiene;
the emulsifier is selected from disproportionated potassium abietate and sodium stearate, and preferably has a mass ratio of 10.1:1, a mixture of potassium disproportionated abietate and sodium stearate;
the electrolyte is at least one selected from disodium ethylenediamine tetraacetate and potassium chloride;
the activator is at least one selected from ferrous sulfate and formaldehyde sodium bisulfate (sodium metabisulfite);
the terminator is selected from hydroxylamine;
the antioxidant is selected from sodium dithionite;
the initiator is at least one selected from tert-butyl hydroperoxide and p-menthane hydroperoxide;
the pre-emulsification temperature is 5-25 ℃, and the pre-emulsification time is 1-4 h;
the polymerization reaction temperature is 5-10 ℃, and the polymerization reaction time is 4-8 h;
the polymerization reaction is completed under the protection of inert gas.
The weight of the itaconic acid ester is calculated as 100 weight parts, the dosage of the diene compound is 65-70 weight parts, the dosage of the emulsifier is 7.5-8.0 weight parts, the dosage of the electrolyte is 1.0-1.5 weight parts, the dosage of the activating agent is 0.1-0.5 weight part, the dosage of the terminating agent is 0.6-0.8 weight part, the dosage of the antioxidant is 0.01-0.05 weight part, and the dosage of the initiating agent is 0.05-0.08 weight part.
When the bio-based itaconate rubber glove is prepared, the process of stirring the slurry containing the bio-based itaconate rubber, the vulcanizing agent, the accelerator, the potassium hydroxide and the zinc oxide is a pre-vulcanization process, the pre-vulcanization can lead latex to react in advance before dipping the glove, shorten the vulcanization time of the glove in the processing process, reduce the energy consumption and improve the product performance, wherein the added potassium hydroxide is used for adjusting the pH value of the prepared itaconate latex slurry, enhancing the stability of the latex and simultaneously has an accelerating effect on improving the tensile strength of the itaconate glove; the added zinc oxide can promote the pre-vulcanization of the itaconate rubber glove and shorten the pre-vulcanization time. And (3) mixing the components to obtain slurry, immersing the glove model pretreated in advance in a coagulant solution, taking out, drying, immersing in the slurry, vulcanizing and demolding to obtain the bio-based itaconate rubber glove.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts itaconic acid ester from biological base resource as comonomer to copolymerize with diene compound to obtain itaconic acid ester latex;
2. the itaconic acid ester raw material has wide sources, and can reduce the dependence on hevea brasiliensis and petrochemical energy sources;
3. the itaconate rubber contains no protein, so that the risk of allergy and shock in the process of wearing the glove can be reduced;
4. the bio-based itaconate rubber glove provided by the invention has better biodegradability, is more environment-friendly, and has wider application prospect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
the glove sample was cut into dumbbell-shaped specimens using a cutter, and the specimens were subjected to tensile testing according to ASTM D412 using a CMT 4104 type electronic tensile machine to obtain tensile strength, elongation at break, elongation at elongation. The test stretch rate was 500mm/min.
The raw materials and sources used in the examples are as follows:
sulfur, zinc oxide, zinc di-n-butyl dithiocarbamate (BZ), calcium carbonate aqueous slurry (50%), white carbon black aqueous slurry (20%), dongguan, pentaceae latex Co., ltd; potassium hydroxide, sodium hydroxide, calcium chloride, aletin; nitric acid, tianjin, meta-Chemie, inc.
Example 1
Preparation of itaconate latex:
respectively adding an emulsifier, deionized water, electrolyte, an activating agent, an antioxidant and an itaconate monomer into a reaction kettle, and then sealing the reaction device to replace the reaction kettle with nitrogen atmosphere;
butadiene was added to the autoclave, pre-emulsified at 25℃for one hour, cooled down during this period, and then initiator was added, and polymerization was carried out at 8℃for 8 hours. After the reaction is completed, a terminator is injected into the reaction kettle to obtain itaconate latex (the mole ratio of itaconate monomer to butadiene is 1:3). The raw materials, amounts and sources used are listed in Table 1.
TABLE 1 raw materials, amounts and sources used in EXAMPLE 1
Preparation of biobased itaconate rubber glove:
adding 0.1 part by weight of KOH, 5 parts by weight of ZnO, 1 part by weight of sulfur and 0.5 part by weight of BZ-promoting agent into 100 parts by weight of itaconate latex, slowly stirring for 1h at 25 ℃, and standing for 24h to obtain slurry;
pretreatment is carried out on the glove model: firstly, cleaning a glove model in a nitric acid solution with a pH value of 3, then cleaning the glove model in a sodium hydroxide aqueous solution with a pH value of 12, then rinsing the glove model, and drying the glove model in a 75 ℃ oven;
preparing a coagulant solution: adding 15 parts by weight of calcium chloride and 85 parts by weight of deionized water into a batching barrel, and uniformly stirring to obtain a coagulant solution;
dipping the pretreated glove model in a coagulant solution at 25 ℃ for 5 seconds, dripping, drying at 70 ℃, dipping in the slurry at 25 ℃ for 6 minutes, drying, leaching and curling, placing in a vulcanizing tank at 110 ℃, heating and vulcanizing for 30 minutes, leaching, drying and demolding to obtain the bio-based itaconate rubber glove. The performance test is shown in Table 4.
Example 2
Preparation of itaconate latex:
respectively adding an emulsifier, deionized water, electrolyte, an activating agent, an antioxidant and an itaconate monomer into a reaction kettle, and then sealing the reaction device to replace the reaction kettle with nitrogen atmosphere;
butadiene was added to the autoclave, pre-emulsified at 25℃for one hour, cooled down during this period, and then initiator was added, and polymerization was carried out at 8℃for 8 hours. After the reaction, a terminator is injected into the reaction kettle to obtain itaconate latex (the mole ratio of itaconate monomer to butadiene is 1:1.9). The raw materials, amounts and sources used are listed in Table 2.
TABLE 2 raw materials, amounts and sources used in EXAMPLE 2
Preparation of biobased itaconate rubber glove:
adding 0.3 weight part of KOH, 7 weight parts of ZnO, 2 weight parts of sulfur and 1.5 weight parts of BZ-promoting agent into 100 weight parts of itaconate latex, slowly stirring for 1h at 25 ℃, adding 15 weight parts of calcium carbonate aqueous slurry (50%), stirring for 2h, and standing for 24h to obtain slurry;
pretreatment is carried out on the glove model: firstly, cleaning a glove model in a nitric acid solution with a pH value of 3, then cleaning the glove model in a sodium hydroxide aqueous solution with a pH value of 12, then rinsing the glove model, and drying the glove model in a 75 ℃ oven;
preparing a coagulant solution: adding 25 parts by weight of calcium chloride and 75 parts by weight of deionized water into a batching barrel, and uniformly stirring to obtain a coagulant solution;
dipping the pretreated glove model in a coagulant solution at 55 ℃ for 15 seconds, dripping, drying at 70 ℃, dipping in the slurry at 35 ℃ for 5 minutes, drying, leaching and curling, placing in a vulcanizing tank at 140 ℃, heating and vulcanizing for 1 hour, leaching, drying and demolding to obtain the calcium carbonate/itaconic acid ester rubber glove. The performance test is shown in Table 4.
Example 3
Preparation of itaconate latex:
respectively adding an emulsifier, deionized water, electrolyte, an activating agent, an antioxidant and an itaconate monomer into a reaction kettle, and then sealing the reaction device to replace the reaction kettle with nitrogen atmosphere;
butadiene was added to the autoclave, pre-emulsified at 25℃for one hour, cooled down during this period, and then initiator was added, and polymerization was carried out at 8℃for 8 hours. After the reaction, a terminator was injected into the reaction vessel to obtain an itaconate latex (mole ratio of itaconate monomer to butadiene was 1:4.5). The raw materials, amounts and sources used are listed in Table 3.
TABLE 3 raw materials, amounts and sources used in EXAMPLE 3
Preparation of biobased itaconate rubber glove:
adding 0.2 part by weight of KOH, 5 parts by weight of ZnO, 1 part by weight of sulfur and 0.5 part by weight of BZ-promoting agent into 100 parts by weight of itaconate latex, slowly stirring for 1h at 25 ℃, adding 10 parts by weight of white carbon black aqueous slurry (50%), stirring for 2h, and standing for 24h to obtain slurry;
pretreatment is carried out on the glove model: firstly, cleaning a glove model in a nitric acid solution with a pH value of 3, then cleaning the glove model in a sodium hydroxide aqueous solution with a pH value of 12, then rinsing the glove model, and drying the glove model in a 75 ℃ oven;
preparing a coagulant solution: adding 20 parts by weight of calcium chloride and 80 parts by weight of deionized water into a batching barrel, and uniformly stirring to obtain a coagulant solution;
dipping the pretreated glove model in a coagulant solution at 30 ℃ for 10 seconds, dripping, drying at 70 ℃, dipping in the slurry at 30 ℃ for 6 minutes, drying, leaching and curling, placing in a vulcanizing tank at 140 ℃, heating and vulcanizing for 1 hour, leaching, drying and demolding to obtain the itaconate rubber glove. The performance test is shown in Table 4.
Comparative example 1
Adding 0.1 part by weight of KOH, 5 parts by weight of ZnO, 1 part by weight of sulfur and 0.5 part by weight of BZ-promoting agent into 100 parts by weight of natural latex, slowly stirring for 1h, and standing for 24h to obtain slurry;
pretreatment is carried out on the glove model: firstly, cleaning a glove model in a nitric acid solution with a pH value of 3, then cleaning the glove model in a sodium hydroxide aqueous solution with a pH value of 12, then rinsing the glove model, and drying the glove model in a 75 ℃ oven;
preparing a coagulant solution: adding 15 parts by weight of calcium chloride and 85 parts by weight of deionized water into a batching barrel, and uniformly stirring to obtain a coagulant solution;
dipping the pretreated glove model in a coagulant solution at 25 ℃ for 5s, dripping, drying, dipping in the slurry at 25 ℃ for 30s, drying, leaching and curling, placing in a vulcanizing tank at 110 ℃, heating and vulcanizing for 30min, leaching, drying and demolding to obtain the natural latex glove. The performance test is shown in Table 4.
Comparative example 2
Adding 0.1 part by weight of KOH, 5 parts by weight of ZnO, 1 part by weight of sulfur and 0.5 part by weight of BZ-promoting agent into 100 parts by weight of nitrile latex, slowly stirring for 1h, and standing for 24h to obtain slurry;
pretreatment is carried out on the glove model: firstly, cleaning a glove model in a nitric acid solution with a pH value of 3, then cleaning the glove model in a sodium hydroxide aqueous solution with a pH value of 12, then rinsing the glove model, and drying the glove model in a 75 ℃ oven;
preparing a coagulant solution: adding 15 parts by weight of calcium chloride and 85 parts by weight of deionized water into a batching barrel, and uniformly stirring to obtain a coagulant solution;
dipping the pretreated glove model in a coagulant solution at 25 ℃ for 5s, dripping, drying, dipping in the slurry at 25 ℃ for 30s, drying, leaching and curling, placing in a vulcanizing tank at 110 ℃, heating and vulcanizing for 30min, leaching, drying and demolding to obtain the butyronitrile glove. The performance test is shown in Table 4.
TABLE 4 Performance test results for examples 1-3 and comparative examples 1-2
As can be seen from the performance test results of examples 1-3 and comparative examples 1-2, the tensile strength of the itaconate rubber glove provided by the invention reaches more than 3.4MPa, and the elongation at break is higher than that of the natural latex rubber glove and the nitrile glove. In example 2, calcium carbonate was added to the latex, the glove performance was improved, the cost was reduced, the tensile strength of the glove was increased to 3.5MPa, and in example 3, white carbon black was added to the latex, the tensile strength of the glove was 8.0MPa, because calcium carbonate and white carbon black were dispersed as a filler in the system, and the interaction between the filler and the rubber was increased. Therefore, the itaconate rubber glove provided by the invention has better mechanical properties, is more environment-friendly, and has wider application prospect as a novel bio-based rubber glove.
Claims (14)
1. A biobased itaconate rubber glove comprises blended biobased itaconate rubber, a vulcanizing agent and an accelerator, wherein the biobased itaconate rubber is obtained by copolymerizing an itaconate monomer and a diene compound, the diene compound is selected from butadiene, and the mole ratio of the itaconate monomer to the diene compound is 1 (1-7); the rubber glove also comprises potassium hydroxide, zinc oxide and filler, wherein the dosage of the potassium hydroxide is 0.01-1 part, the dosage of the zinc oxide is 0.5-10 parts and the dosage of the filler is 0-20 parts by taking the biobased itaconate rubber as 100 parts by weight.
2. A rubber glove according to claim 1, wherein,
the vulcanizing agent is selected from sulfur; and/or the number of the groups of groups,
the accelerator is at least one selected from dithiocarbamates and thiazoles; and/or the number of the groups of groups,
the amount of the vulcanizing agent is 0.5 to 5 parts by weight and the amount of the accelerator is 0.1 to 5 parts by weight based on 100 parts by weight of the bio-based itaconate rubber.
3. A rubber glove according to claim 2, wherein,
the accelerator is at least one selected from 2-mercaptobenzothiazole, zinc di-n-butyl dithiocarbamate and zinc diethyl dithiocarbamate; and/or the number of the groups of groups,
the amount of the vulcanizing agent is 1-2 parts by weight based on 100 parts by weight of the bio-based itaconate rubber, and the amount of the accelerator is 0.5-1 part by weight.
4. A rubber glove according to claim 2, wherein,
the filler is at least one selected from white carbon black, calcium carbonate and barium sulfate.
5. The rubber glove according to claim 4, wherein,
the amount of potassium hydroxide is 0.01 to 1 part, the amount of zinc oxide is 0.5 to 10 parts, and the amount of filler is 0 to 10 parts by weight based on 100 parts by weight of the bio-based itaconate rubber.
6. A rubber glove according to claim 1, wherein,
the mole ratio of the itaconate monomer and the diene compound is 1 (1.9-4.5); and/or the number of the groups of groups,
the itaconate monomer is at least one selected from monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monopropitaconate, dipropyl itaconate, monobutyl itaconate, dibutyl itaconate, monopentyl itaconate, monopexyl itaconate, dihexyl itaconate, shan Gengzhi itaconate, diheptyl itaconate, monooctyl itaconate, dioctyl itaconate, monononyl itaconate, dinonyl itaconate, monodecyl itaconate and didecyl itaconate.
7. The rubber glove according to claim 6, wherein,
the itaconate monomer is at least one selected from dimethyl itaconate, diethyl itaconate, dipropyl itaconate and dibutyl itaconate.
8. A method for preparing the bio-based itaconate rubber glove according to any one of claims 1 to 7, which comprises the following steps:
uniformly stirring components comprising the bio-based itaconate rubber, a vulcanizing agent and an accelerator, and standing to obtain slurry; potassium hydroxide, zinc oxide and filler are also added in the first step;
step two, immersing the glove model in a coagulant solution, and taking out and drying;
and step three, dipping the glove model obtained after the step two in the slurry obtained in the step one, and obtaining the bio-based itaconate rubber glove after vulcanization reaction and demoulding.
9. The method according to claim 8, wherein,
the stirring temperature in the first step is 20-30 ℃, and the stirring time is 1-2 h; and/or the number of the groups of groups,
the standing time in the first step is 12-24 hours; and/or the number of the groups of groups,
the coagulant in the second step is selected from soluble metal salts; and/or the number of the groups of groups,
the mass percentage concentration of the coagulant in the coagulant solution in the second step is 15-25%; and/or the number of the groups of groups,
the dipping temperature in the second step is 25-55 ℃, and the dipping time is 5-15 s; and/or the number of the groups of groups,
the drying temperature in the second step is 60-80 ℃ and the drying time is 10-30 min; and/or the number of the groups of groups,
before dipping, the glove model in the second step is subjected to acid washing, alkali washing, rinsing and drying treatment; and/or the number of the groups of groups,
the dipping temperature in the third step is 25-35 ℃ and the dipping time is 1-6 min; and/or the number of the groups of groups,
the vulcanization reaction temperature in the step three is 110-140 ℃, and the vulcanization reaction time is 0.5-1 h; and/or the number of the groups of groups,
and (3) after the vulcanization reaction in the step three, leaching, curling, cleaning and drying are also needed.
10. The method according to claim 9, wherein,
the coagulant in the second step is at least one selected from calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, zinc nitrate and zinc chloride.
11. The method according to claim 9, wherein,
the solution used for pickling is at least one selected from nitric acid solution and hydrochloric acid solution; and/or the number of the groups of groups,
the pH value of the pickling solution is 3-5; and/or the number of the groups of groups,
the solution used for alkaline washing is at least one selected from sodium hydroxide solution and potassium hydroxide solution; and/or the number of the groups of groups,
the pH value of the alkaline washing solution is 9-12.
12. The preparation method of claim 8, wherein the bio-based itaconate rubber is obtained by polymerization of components including itaconate monomers and diene compounds, and specifically comprises the following steps:
step 1, adding deionized water, an emulsifying agent, electrolyte, an activating agent, an antioxidant and an itaconate monomer into a reaction container, and uniformly mixing;
step 2, adding a diene compound into the mixture obtained in the step 1, adding an initiator after pre-emulsification, and then carrying out polymerization reaction;
and step 3, after the reaction is finished, adding a terminator into the reaction container, and stirring to obtain the bio-based itaconate rubber.
13. The method according to claim 12, wherein,
the itaconate monomer is at least one selected from monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monopropyl itaconate, dipropyl itaconate, monobutyl itaconate, dibutyl itaconate, monopentyl itaconate, monopexyl itaconate, dihexyl itaconate, shan Gengzhi itaconate, diheptyl itaconate, monooctyl itaconate, dioctyl itaconate, monononyl itaconate, dinonyl itaconate, monodecyl itaconate and didecyl itaconate; and/or the number of the groups of groups,
the diene compound is selected from butadiene; and/or the number of the groups of groups,
the emulsifier is selected from disproportionated potassium abietate and sodium stearate; and/or the number of the groups of groups,
the electrolyte is at least one selected from disodium ethylenediamine tetraacetate and potassium chloride; and/or the number of the groups of groups,
the activator is at least one selected from ferrous sulfate and formaldehyde sodium bisulfate; and/or the number of the groups of groups,
the terminator is selected from hydroxylamine; and/or the number of the groups of groups,
the antioxidant is selected from sodium dithionite; and/or the number of the groups of groups,
the initiator is at least one selected from tert-butyl hydroperoxide and p-menthane hydroperoxide; and/or the number of the groups of groups,
the pre-emulsification temperature is 5-25 ℃, and the pre-emulsification time is 1-4 h; and/or the number of the groups of groups,
the polymerization reaction temperature is 5-10 ℃, and the polymerization reaction time is 4-8 h; and/or the number of the groups of groups,
the polymerization reaction is completed under the protection of inert gas.
14. The method of claim 13, wherein the process comprises,
the itaconate monomer is at least one selected from dimethyl itaconate, diethyl itaconate, dipropyl itaconate and dibutyl itaconate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011560370.2A CN114685922B (en) | 2020-12-25 | 2020-12-25 | Bio-based itaconate rubber glove and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011560370.2A CN114685922B (en) | 2020-12-25 | 2020-12-25 | Bio-based itaconate rubber glove and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114685922A CN114685922A (en) | 2022-07-01 |
| CN114685922B true CN114685922B (en) | 2023-06-13 |
Family
ID=82130934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011560370.2A Active CN114685922B (en) | 2020-12-25 | 2020-12-25 | Bio-based itaconate rubber glove and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114685922B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945817A (en) * | 2015-06-15 | 2015-09-30 | 北京化工大学 | Itaconate/butadiene copolymer type bioengineering rubber and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084514A (en) * | 1990-11-14 | 1992-01-28 | Reichhold Chemicals, Inc. | Latex gloves with improved donnability |
| US6870019B2 (en) * | 2000-12-12 | 2005-03-22 | Nippon A & L Inc. | Latex for dip molding and a dip molded product |
| JP5472286B2 (en) * | 2009-02-28 | 2014-04-16 | 日本ゼオン株式会社 | DIP MOLDING COMPOSITION AND DIP MOLDED BODY |
| CN102558578B (en) * | 2011-12-26 | 2013-11-13 | 北京化工大学 | Itaconate/isoprene copolymer type bio-based engineering elastomer and preparation method thereof |
| CN102558437B (en) * | 2011-12-26 | 2013-11-13 | 北京化工大学 | Method for preparing itaconic ester/isoprene copolymer type bio-based engineering elastomer through low temperature emulsion polymerization |
| JP6006326B2 (en) * | 2012-01-18 | 2016-10-12 | エルジー・ケム・リミテッド | Latex composition for dip molding |
| KR20170098852A (en) * | 2014-12-25 | 2017-08-30 | 니폰 제온 가부시키가이샤 | Latex composition for dip molding and dip-molded article |
| KR102081765B1 (en) * | 2016-09-07 | 2020-02-26 | 주식회사 엘지화학 | Latex composition for dip-forming and the product prepared thereby |
-
2020
- 2020-12-25 CN CN202011560370.2A patent/CN114685922B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945817A (en) * | 2015-06-15 | 2015-09-30 | 北京化工大学 | Itaconate/butadiene copolymer type bioengineering rubber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Xinxin Zhou et al..A solvent-less green synthetic route toward a sustainable bio-based elastomer: design, synthesis, and characterization of poly(dibutyl itaconate-cobutadiene).《Polymer Chemitry》.2019,第10卷第6131-6144页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114685922A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101211230B1 (en) | Carboxylic acid modified-nitrile based copolymer latex, latex composition for dip-forming comprising the same | |
| KR101424856B1 (en) | Carboxylic acid modified-nitrile based copolymer latex for dip-forming, latex composition for dip-forming comprising the same, and the product thereof | |
| KR101920009B1 (en) | Carboxylic acid modified nitrile based copolymer latex compotision, method for preparing the copolymer latex composition, latex composition for dip-forming comprising the copolymer latex composition and article formed by the composition | |
| US20140329956A1 (en) | Latex for dip molding, composition for dip molding, preparation method of dip molded product, and dip molded product prepared thereby | |
| CN107075141B (en) | Latex composition for dip forming and dip-formed article made therefrom | |
| KR101599583B1 (en) | Carboxylic acid modified-nitrile based copolymer latex composition and dip-forming comprising the same | |
| KR20160046166A (en) | Latex composition for dip-forming comprising carboxylic acid modified-nitrile copolymer latex and dip-forming article produced by thereof | |
| CN104053716B (en) | Latex composition for dip forming | |
| CN107429001B (en) | Rubber composition and use thereof | |
| CN115124653B (en) | Bio-based rubber and preparation method thereof | |
| JP3496292B2 (en) | Composites of nitrile group-containing highly saturated copolymer rubber and fiber | |
| CN109071886A (en) | Latex composition and moulded products prepared therefrom for dip forming | |
| KR101467020B1 (en) | Carboxylic acid modified-nitrile based copolymer latex for dip-forming, latex composition for dip-forming comprising the same, and products thereof | |
| KR102069828B1 (en) | Latex composition for dip-forming and the product prepared thereby | |
| CN112159497B (en) | Preparation method of fluorine-silicon modified butyronitrile latex applied to medical butyronitrile gloves | |
| CN114685922B (en) | Bio-based itaconate rubber glove and preparation method thereof | |
| KR101421322B1 (en) | Non-foaming vinyl chloride-based resin paste resin and a method for producing thereof | |
| KR101687866B1 (en) | Carboxylic acid modified-nitrile based copolymer latex composition and latex composition for dip-forming comprising thereof | |
| KR20120086927A (en) | Carboxylic acid modified-nitrile based copolymer latex for dip-forming, latex composition for dip-forming comprising the same, and the product thereof | |
| KR101573980B1 (en) | Carbonic acid modified nitrile based copolymer latex composition and composition for dip molding | |
| CN107922677B (en) | Latex composition for dip molding and molded article prepared therefrom | |
| KR101779295B1 (en) | Latex composition for dip-forming and dip-forming article produced therefrom | |
| KR20120129367A (en) | Composition comprising the carboxylic acid modified-nitrile based copolymer latex and dip-formed article for dip-forming comprising the same | |
| KR20210043344A (en) | Latex compositon for dip-forming, mehtod for preparing the composion and article formed by the composition | |
| KR20170041092A (en) | Latex for Dip-Forming, Composition for Dip-Forming, Method of Manufacturing Dip-Formed Article and the Dip-Formed Article manufactured by using the Method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |