CN103965556A - Infusion bottle used sulfur-free and zinc-free rubber plug and preparation method thereof - Google Patents

Infusion bottle used sulfur-free and zinc-free rubber plug and preparation method thereof Download PDF

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Publication number
CN103965556A
CN103965556A CN201410146657.9A CN201410146657A CN103965556A CN 103965556 A CN103965556 A CN 103965556A CN 201410146657 A CN201410146657 A CN 201410146657A CN 103965556 A CN103965556 A CN 103965556A
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China
Prior art keywords
parts
free
zinc
temperature
infusion bottle
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Pending
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CN201410146657.9A
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Chinese (zh)
Inventor
叶明支
叶显保
王洁然
肖尚军
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ANHUI HUANENG MEDICAL RUBBER PRODUCTS Co Ltd
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ANHUI HUANENG MEDICAL RUBBER PRODUCTS Co Ltd
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Priority to CN201410146657.9A priority Critical patent/CN103965556A/en
Publication of CN103965556A publication Critical patent/CN103965556A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283Halogenated homo- or copolymers of iso-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)

Abstract

The invention discloses an infusion bottle used sulfur-free and zinc-free rubber plug and a preparation method thereof. The infusion bottle used sulfur-free and zinc-free rubber plug is prepared from the following raw materials in parts by weight: 70-90 parts of chlorinated butyl rubber, 15-25 parts of butadiene-acrylonitrile rubber, 10-15 parts of dimethyl silicone rubber, 2-3 parts of N,N-m-phenylene bismaleimide, 3-5 parts of polyethylene wax, 12-18 parts of silicon powder, 60-80 parts of organic bentonite, 0.3-0.5 part of carbon black N6600, 2.5-4.5 parts of mineral oil, 5-10 parts of precipitated barium carbonate, 8-12 parts of light calcium powder, 0.5-1 part of an accelerant H and 10-15 parts of modified packing. According to the infusion bottle used sulfur-free and zinc-free rubber plug, as N,N-m-phenylene bismaleimide is adopted and the vulcanization system such as sulfur and zinc oxide is replaced by the accelerant H, which is easy to disperse and operate in the formula; as the accelerant H is non-toxic and pollution-free, the cleanliness of the rubber plug is greatly improved and medicines are prevented from being polluted; moreover, the rubber plug has excellent physical mechanical property, chemical stability, medium resistance, air tightness, age resistance, heat resistance and the like and the infusion bottle used sulfur-free and zinc-free rubber plug is widely applied in opening sealing in various medical infusion bottles.

Description

A kind of infusion bottle is used without sulphur without zinc plug and preparation method thereof
Technical field
The present invention relates generally to a kind of plug and preparation method thereof, relates in particular to a kind of infusion bottle and uses without sulphur without zinc plug and preparation method thereof.
Background technology
Plug is the important component part of sealing material in infusion bottle, be the main sealed piece of infusion bottle and lead a mouthful part, because he directly contacts with medicine, therefore may be by mode and medicine generation cross reactions such as absorption, absorption, infiltration and extractings, thereby impact and pollution medicine, so pharmacopoeia of each country and related standards have all been made extremely strict regulation to the use of plug and performance.Isoprene-isobutylene rubber replaces natural rubber with its higher physical strength, good resistance to air loss, low-permeability and the performance such as ageing-resistant and is widely used and makes to produce medical rubber plug, but on market, the vulcanization system of existing butyl rubber stoppers is generally sulphur, sulfur-donor and zinc oxide vulcanization system, zinc oxide, sulphur have bad impact to medical rubber plug, the cleanliness factor cleanliness factor of these vulcanization systems can not meet the strict demand of various pharmacopeia, therefore, being badly in need of a kind of infusion bottle of exploitation uses without sulphur without zinc plug, to meet the requirement of infusion bottle rubber plug high-cleanness, high.
Summary of the invention
The object of the invention is just to provide a kind of infusion bottle and uses without sulphur without zinc plug and preparation method thereof, improves the cleanliness factor of butyl rubber stoppers.
For achieving the above object, the present invention adopts following technical scheme:
Infusion bottle is used without sulphur without a zinc plug, and it is to be made by the raw material of following weight parts:
Chlorinated butyl rubber 70-90, paracril 15-25, dimethyl silicone rubber 10-15, N, N '-penylene bismaleimides 2-3, polyethylene wax 3-5, the beautiful powder 12-18 of silicon, organobentonite 60-80, carbon black N6600.3-0.5, white oil 2.5-4.5, precipitated barium carbonate 5-10, light calcium carbonate powder 8-12, vulkacit H 0.5-1, modified filler 10-15;
The preparation method of described modified filler is as follows: a, get the raw material of following weight part: fibrolite 12-18, peridotites 10-15, phosphatic rock 5-10, Low Density Polyethylene 15-20, voltalef 8-14, ethene-vinyl acetate-carbonyl terpolymer 6-12, magnesium oxide 2-3, stearic acid 1-2, bamboo charcoal powder 2.5-4.5, tourmaline powder 2-3, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 1-2, epoxy soybean oil 4-8, low molecular weight polycaprolactone butylene 3-6; B, to get fibrolite, peridotites, apatites mixed even, 660-720 ℃ of calcining 2-3h, naturally cool to room temperature, pulverize, cross 100-150 mesh sieve, then add sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, epoxy soybean oil, low molecular weight polycaprolactone butylene, magnesium oxide, stearic acid, bamboo charcoal powder, tourmaline powder, 1000-1500rpm speed lapping 10-15min, stand-by; B, get Low Density Polyethylene, voltalef, ethene-vinyl acetate-carbonyl terpolymer and drop into melt blending in twin screw extruder, after it melts completely, add above-mentioned ground compound, extruding pelletization, naturally cool to room temperature, be modified filler.
Infusion bottle preparation method without zinc plug without sulphur, comprises the following steps:
(1) chlorinated butyl rubber, paracril, dimethyl silicone rubber are dropped in milling machine to pressurization 0.6-0.8MPa, temperature 50-60 ℃, mixing 1-1.5min, then drop into N, other raw material beyond a N '-penylene bismaleimides, vulkacit H, pressurization 0.6-0.8MPa, temperature 80-90 ℃, mixing 2-4min, then drop into N, a N '-penylene bismaleimides, vulkacit H, pressurization 0.6-0.8MPa, temperature 100-110 ℃, mixing 1.5-2.5min, discharge;
(2) mill roll spacing is adjusted to 4-6mm, and the sizing material that milling machine is got rid of drops into thin-pass in mill, until roller temperature, reaches after 55-65 ℃, continues thin-pass 20-30min, waits after the sticky rear roller of film, becomes atresia woven design shape to get final product blanking, places 24-36h;
(3) the above-mentioned film making is injected to sulfidization molding after cooling, cut-parts, curing temperature is 190-210 ℃, and sulfide stress is 25-30MPa, and screw tube temperature is 70-80 ℃, and injection tube temperature is 85-95 ℃, and cold runner temperature is 85-95 ℃;
(4) film of moulding gets product through die-cut, screening, cleaning, silication, dry, test package.
Advantage of the present invention is:
The present invention adopts N, a N '-penylene bismaleimides, vulkacit H replace the vulcanization systems such as sulphur, zinc oxide, easily dispersion, easy to operate in formula, nontoxic pollution-free, can greatly improve the cleanliness factor of plug, avoid drug contamination, and the plug making has the performances such as good physical and mechanical properties, chemical stability, resistance to medium, resistance to air loss, ageing resistance, thermotolerance, can be widely used in the sealing of various medical transfusion bottlenecks.
Embodiment
Embodiment 1
Infusion bottle is used without sulphur without a zinc plug, and it is to be made by the raw material of following weight (kg):
Chlorinated butyl rubber 80, paracril 20, dimethyl silicone rubber 15, N, a N '-penylene bismaleimides 2.5, polyethylene wax 4, the beautiful powder 16 of silicon, organobentonite 70, carbon black N6600.4, white oil 3.5, precipitated barium carbonate 8, light calcium carbonate powder 10, vulkacit H 0.8, modified filler 15;
The preparation method of described modified filler is as follows: a, get the raw material of following weight (kg): fibrolite 15, peridotites 12, phosphatic rock 8, Low Density Polyethylene 16, voltalef 12, ethene-vinyl acetate-carbonyl terpolymer 8, magnesium oxide 2.5, stearic acid 1, bamboo charcoal powder 3, tourmaline powder 3, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 1.5, epoxy soybean oil 6, low molecular weight polycaprolactone butylene 4; B, to get fibrolite, peridotites, apatites mixed even, 660 ℃ of calcining 3h, naturally cool to room temperature, pulverize, cross 150 mesh sieves, then add sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, epoxy soybean oil, low molecular weight polycaprolactone butylene, magnesium oxide, stearic acid, bamboo charcoal powder, tourmaline powder, 1000rpm speed lapping 10min, stand-by; B, get Low Density Polyethylene, voltalef, ethene-vinyl acetate-carbonyl terpolymer and drop into melt blending in twin screw extruder, after it melts completely, add above-mentioned ground compound, extruding pelletization, naturally cool to room temperature, be modified filler.
Infusion bottle preparation method without zinc plug without sulphur, comprises the following steps:
(1) chlorinated butyl rubber, paracril, dimethyl silicone rubber are dropped in milling machine to pressurization 0.7MPa, 55 ℃ of temperature, mixing 1min, then drop into N, other raw material beyond a N '-penylene bismaleimides, vulkacit H, pressurization 0.7MPa, 85 ℃ of temperature, mixing 3min, then drop into N, a N '-penylene bismaleimides, vulkacit H, pressurization 0.7MPa, 105 ℃ of temperature, mixing 2min, discharge;
(2) mill roll spacing is adjusted to 5mm, and the sizing material that milling machine is got rid of drops into thin-pass in mill, until roller temperature, reaches after 60 ℃, continues thin-pass 25min, waits after the sticky rear roller of film, becomes atresia woven design shape to get final product blanking, places 24-36h;
(3) the above-mentioned film making is injected to sulfidization molding after cooling, cut-parts, curing temperature is 200 ℃, and sulfide stress is 30MPa, and screw tube temperature is 75 ℃, and injection tube temperature is 90 ℃, and cold runner temperature is 90 ℃;
(4) film of moulding gets product through die-cut, screening, cleaning, silication, dry, test package.
The performance test results is as following table:

Claims (2)

1. infusion bottle is used without sulphur without a zinc plug, it is characterized in that, it is to be made by the raw material of following weight parts:
Chlorinated butyl rubber 70-90, paracril 15-25, dimethyl silicone rubber 10-15, N, N '-penylene bismaleimides 2-3, polyethylene wax 3-5, the beautiful powder 12-18 of silicon, organobentonite 60-80, carbon black N660 0.3-0.5, white oil 2.5-4.5, precipitated barium carbonate 5-10, light calcium carbonate powder 8-12, vulkacit H 0.5-1, modified filler 10-15;
The preparation method of described modified filler is as follows: a, get the raw material of following weight part: fibrolite 12-18, peridotites 10-15, phosphatic rock 5-10, Low Density Polyethylene 15-20, voltalef 8-14, ethene-vinyl acetate-carbonyl terpolymer 6-12, magnesium oxide 2-3, stearic acid 1-2, bamboo charcoal powder 2.5-4.5, tourmaline powder 2-3, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester 1-2, epoxy soybean oil 4-8, low molecular weight polycaprolactone butylene 3-6; B, to get fibrolite, peridotites, apatites mixed even, 660-720 ℃ of calcining 2-3h, naturally cool to room temperature, pulverize, cross 100-150 mesh sieve, then add sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, epoxy soybean oil, low molecular weight polycaprolactone butylene, magnesium oxide, stearic acid, bamboo charcoal powder, tourmaline powder, 1000-1500rpm speed lapping 10-15min, stand-by; B, get Low Density Polyethylene, voltalef, ethene-vinyl acetate-carbonyl terpolymer and drop into melt blending in twin screw extruder, after it melts completely, add above-mentioned ground compound, extruding pelletization, naturally cool to room temperature, be modified filler.
2. infusion bottle as claimed in claim 1 preparation method without zinc plug without sulphur, is characterized in that comprising the following steps:
(1) chlorinated butyl rubber, paracril, dimethyl silicone rubber are dropped in milling machine to pressurization 0.6-0.8MPa, temperature 50-60 ℃, mixing 1-1.5min, then drop into except N other raw material beyond a N '-penylene bismaleimides, vulkacit H, pressurization 0.6-0.8MPa, temperature 80-90 ℃, mixing 2-4min, then drop into N, a N '-penylene bismaleimides, vulkacit H, pressurization 0.6-0.8MPa, temperature 100-110 ℃, mixing 1.5-2.5min, discharge;
(2) mill roll spacing is adjusted to 4-6mm, and the sizing material that milling machine is got rid of drops into thin-pass in mill, until roller temperature, reaches after 55-65 ℃, continues thin-pass 20-30min, waits after the sticky rear roller of film, becomes atresia woven design shape to get final product blanking, places 24-36h;
(3) the above-mentioned film making is injected to sulfidization molding after cooling, cut-parts, curing temperature is 190-210 ℃, and sulfide stress is 25-30MPa, and screw tube temperature is 70-80 ℃, and injection tube temperature is 85-95 ℃, and cold runner temperature is 85-95 ℃;
(4) film of moulding gets product through die-cut, screening, cleaning, silication, dry, test package.
CN201410146657.9A 2014-04-11 2014-04-11 Infusion bottle used sulfur-free and zinc-free rubber plug and preparation method thereof Pending CN103965556A (en)

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Application Number Priority Date Filing Date Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105440358A (en) * 2015-12-16 2016-03-30 宁国天运橡塑制品有限公司 Corrosion resistant and wear resistant rubber material for oil sealing
CN105482280A (en) * 2016-01-14 2016-04-13 武夷学院 Sulfur-free aldehyde-free rubber plug and preparation method thereof
CN109679240A (en) * 2018-12-28 2019-04-26 江阴市海华橡塑有限公司 A kind of medicinal chlorinated butyl rubber plug and its production technology

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101104700A (en) * 2007-08-18 2008-01-16 青岛科技大学 Radiation vulcanizing method for environment-friendly type medical rubber products
CN102702574A (en) * 2012-06-04 2012-10-03 郑州市翱翔医药包装有限公司 Vulcanizing system and medical chlorinated butyl rubber plug
CN102977477A (en) * 2012-11-16 2013-03-20 北京橡胶工业研究设计院 High temperature vulcanization halogenated butyl rubber composition and applications thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101104700A (en) * 2007-08-18 2008-01-16 青岛科技大学 Radiation vulcanizing method for environment-friendly type medical rubber products
CN102702574A (en) * 2012-06-04 2012-10-03 郑州市翱翔医药包装有限公司 Vulcanizing system and medical chlorinated butyl rubber plug
CN102977477A (en) * 2012-11-16 2013-03-20 北京橡胶工业研究设计院 High temperature vulcanization halogenated butyl rubber composition and applications thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105440358A (en) * 2015-12-16 2016-03-30 宁国天运橡塑制品有限公司 Corrosion resistant and wear resistant rubber material for oil sealing
CN105482280A (en) * 2016-01-14 2016-04-13 武夷学院 Sulfur-free aldehyde-free rubber plug and preparation method thereof
CN105482280B (en) * 2016-01-14 2017-11-24 武夷学院 One kind is without sulphur without aldehyde plug and preparation method thereof
CN109679240A (en) * 2018-12-28 2019-04-26 江阴市海华橡塑有限公司 A kind of medicinal chlorinated butyl rubber plug and its production technology

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Address after: 238371 Yao Gou Industrial Zone, Wuhu, Anhui, Wuwei County

Applicant after: ANHUI HUANENG MEDICAL RUBBER PRODUCTS CO., LTD.

Address before: 238371 Yao Gou Industrial Zone, Wuhu, Anhui, Wuwei County

Applicant before: Anhui Huaneng Medical Rubber Products Co., Ltd.

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Application publication date: 20140806

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