CN109593280A - A kind of chlorinated butyl rubber bung formula and preparation method - Google Patents
A kind of chlorinated butyl rubber bung formula and preparation method Download PDFInfo
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- CN109593280A CN109593280A CN201811604482.6A CN201811604482A CN109593280A CN 109593280 A CN109593280 A CN 109593280A CN 201811604482 A CN201811604482 A CN 201811604482A CN 109593280 A CN109593280 A CN 109593280A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions 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
- C08L23/28—Compositions 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
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The present invention relates to a kind of chlorinated butyl rubber bung formula and preparation methods, belong to medical grade rubber accessories technical field.This method can be under the premise of the chemical assistants such as not newly-increased activating agent, promotor, under the premise of selecting suitable vulcanizing system, and taking using the method for a small amount of white carbon black replacement equivalent clay improves the compatibility of chlorinated butyl rubber plug and drug.White carbon black used in inventive formulation is precipitated hydrated silica, under the premise of not reducing rubber mobility energy, improve the curing temperature of sizing material, it is more come out by the high temperature vulcanized moisture made in sizing material and small-molecule substance, reduce the moisture and small-molecule substance contained in chlorinated butyl rubber plug, improve the compatibility of chlorinated butyl rubber plug and drug, to meet the higher requirement in pharmaceutical factory.
Description
Technical field
The present invention relates to a kind of chlorinated scoline formula and preparation methods, belong to medical grade rubber accessories technical field.
Background technique
Halogenated butyl rubber plug is due to good inherent cleanliness, chemical stability, air-tightness, biological property, quilt
It is widely used in medical package field.Although halogenated butyl rubber itself is cleaner, because of the complexity of rubber plug formula, in rubber plug
Process in need joined a variety of chemical assistants, and need to can just produce the medicine having use value by sulfidation
With butyl rubber plug, thus inevitably inside rubber plug some reaction residuals not being chemically bound of remaining, be not involved in
The substance of reaction, the product of thermal decomposition and vulcanization product.These small-molecule substances are directly contacted in rubber plug with drug, may
It is interacted by the modes such as absorption, absorption, infiltration, leaching, release, migration and drug, influences drug safety.
Since chlorinated scoline activity is relatively low, vulcanizing system selects limitation slightly larger, production technology requirement
Harshness, current most domestic chlorination rubber plug product are all curing resin systems, and a variety of chemical assistants, and resin are contained in formula
The rubber plug curing temperature of system is low, and most of moisture and small-molecule substance cannot adequately be precipitated in vulcanization, remains in rubber plug
In product, remaining moisture and small-molecule substance are easy gradually to migrate out in rubber plug after powder charge, influence phase of the rubber plug with drug
Capacitive.Especially some relative consistencies require stringent drug, Market Feedback and complaint often occur.
The curing temperature of resin system chlorination rubber plug formula is 174 DEG C -177 DEG C, most moisture in sizing material when vulcanization
It cannot be precipitated with small-molecule substance, however it remains in rubber plug, cause the moisture content of rubber plug product is higher not to be able to satisfy to water
Divide the use of more demanding drug, simultaneously because small-molecule substance precipitation is not thorough the compatibility for affecting drug and rubber plug.
It would generally be changed by reducing the dosage of activating agent to improve the compatibility rubber plug manufacturer of chlorinated butyl rubber plug and drug
The kind compatibility with drug, but be easy to appear rubber plug vulcanization in this way and be not thorough, the new quality problems such as hardness deficiency.Improve sulphur
Change temperature to realize, but improving curing temperature can make the mobile performance of sizing material that can reduce, and occur rubber plug production in vulcanization outer
See defect.The open defect of rubber plug can lead to the performance that the serious consequences such as rubber plug air-tightness forfeiture directly affect packaging drug,
Open defect also can influence indirectly the compatibility of rubber plug and drug by influencing rubber plug internal performance simultaneously.
Summary of the invention
The objective for implementation that technical solution of the present invention is directed to is the chlorinated butyl rubber bung formula of resin system.That selects is white
Carbon black is the white carbon black for precipitating legal system, need to meet medical package materials'use requirement.Because white carbon black partial size is smaller, it is not easy to disperse,
The used in amounts of white carbon black adjusts according to the actual situation.A small amount of white carbon black is used in technical solution of the present invention, is carried out with clay
Equivalent replacement.Newly-designed chlorinated butyl formula curing temperature is obvious compared with the curing temperature variation of original formulation.
The present invention replaces part clay after the suitable vulcanizing system of selection, softening agent, by using white carbon black, so that chlorine
The technique dump temperature fluctuation range for changing butyl rubber bung formula becomes 125 ± 10 DEG C from 120 ± 5 DEG C, rubber vulcanization temperature by
174 DEG C -177 DEG C rise to 185 DEG C -190 DEG C, and the curing temperature of sizing material is improved while not influencing rubber mobility energy,
In the case where high temperature vulcanized by sizing material moisture and small-molecule substance exclude more thoroughly, improve rubber plug product it is pure
Degree and the compatibility with drug, greatly meet the needs of client.
It is an object of the invention to improve the compatibility of chlorinated butyl rubber plug and drug.Titanium dioxide is hydrated by using precipitating
Silicon (white carbon black) chlorinated scoline does not reduce mixed with can not increase new activating agent, promotor newly under new vulcanizing system
Compound physical mechanical performance is refined, under the premise of keeping sizing material superior fluidity energy, the curing temperature of glue stuff compounding is improved, makes sizing material
In moisture and small-molecule substance be precipitated as far as possible, improve and the compatibility of drug.
Concrete scheme is a kind of chlorinated butyl rubber bung formula, including the following raw material:
40-60 parts of chlorinated scoline, 30-40 parts of clay, 0.5-2 parts of titanium dioxide, 0.01-0.5 parts of semi-reinforcing hydrocarbon black, oxygen
Zinc 0.5-3 parts of change, 0.1-1 parts of stearic acid, 0.1-1 parts of alkyl phenol disulfide, 0.1-2 parts of dimethicone, white carbon black 1-5
Part.
In preferred embodiment, 50 parts of the chlorinated scoline, 35 parts of clay, 1 part of titanium dioxide, 0.1 part of semi-reinforcing hydrocarbon black,
2 parts of zinc oxide, 0.25 part of stearic acid, 0.25 part of alkyl phenol disulfide, 1 part of dimethicone, 3.0 parts of white carbon black.
Chlorinated butyl rubber bung formula of the present invention, includes the following steps:
A, cooperate: weighing various raw material according to formula and mixed；
B, be kneaded preforming: by the mixture in step a, dumping, mixing produce 8-15min at 120-130 DEG C；It sets again
In open mill after the mill of 9-11min, rubber compound is obtained, is put into extruder after cooling, squeezes out sizing material through calender pressure
Cooling is delayed, then carries out cut-parts according to vulcanization process demand, film is stored, for use；
C, vulcanize: by the film cut out in vulcanizer, the sulfidization molding under 185 DEG C of -190 DEG C of hot conditions is obtained same
One specificationPowder needle rubber plug；
D, be punched: the product after sulfidization molding is punched to single butyl rubber plug by bicker；
E, it cleans: being cleaned according to normal wash technique, sampling does finished product detection and compared with drug compatibility.
Technical solution of the present invention: by selecting suitable vulcanizing agent, white carbon black is added, the mode of plasticizer is replaced, mentions
The curing temperature of high sizing material, and then improve the compatibility of chlorinated butyl rubber plug and drug.Present invention uses precipitatings to be hydrated dioxy
SiClx replaces a small amount of filler clay, replaces the mode of resin curative to break elite tree resin system using alkyl phenol disulfide
Limitation of the rubber compound dump temperature no more than 125 DEG C, makes maximum technique dump temperature can achieve 135 DEG C, while sizing material sulphur
Change temperature and rises to 185 DEG C -190 DEG C by 174 DEG C -177 DEG C.It is thorough by the high temperature vulcanized moisture made in sizing material and small-molecule substance
Bottom is precipitated, and reduces the content of moisture and small-molecule substance in rubber plug, the compatibility of Lai Gaishan chlorinated butyl rubber plug and drug.Hard charcoal
Black to belong to inorganic material, partial size is smaller, is not easy to disperse, and the selection of the number and type of dosage influences whether the performance of rubber compound.
Specific design process is as follows:
1, the selection of white carbon black: white carbon black is mainly used as reinforcing agent in rubber industry.White carbon black by preparation method not
It is divided into two kinds together: vapor phase method and the precipitation method.Fume colloidal silica partial size is minimum, about 15-25nm, and specific surface area is up to 50-
400m2/ g, impurity are few.Precipitated silica partial size is larger, about 20-40nm, and purity is lower, reinforcing poor compared with vapor phase method, but
Processing performance is good.There is stronger adsorptivity on white carbon black surface, can be combined with water with hydrogen bond formation, forms polymolecular adsorption layer；
Small molecule organic compound can also be adsorbed, special efficacy absorption is occurred to aniline, formaldehyde etc..This special efficacy suction-operated can be strong suction
Chemical assistant in attached sizing compound formula, to occur to postpone sulfation.This law is exactly to be reached using the suction-operated of white carbon black
The purpose of chlorinated butyl rubber plug curing temperature is improved, to improve the compatibility of chlorinated butyl rubber plug and drug.Vapor phase method hard charcoal
Black partial size is carefully not easy to disperse in sizing material, therefore selects the biggish precipitation method hard charcoal for meeting medicinal butyl rubber bung and using of partial size
It is black.The performance indicator of the precipitated hydrated silica (white carbon black) of selection should meet table 1.
The performance indicator of 1 precipitated hydrated silica of table (white carbon black)
2, the dosage design of white carbon black: white carbon black as a kind of inorganic supporting material, dosage number influence whether rubber plug
The physical mechanical properties such as hardness, ash content, the tensile strength of product；And since white carbon black has the phenomenon that delay vulcanizes, in order to
Avoid such case can be using the dosage for improving activating agent and promotor, but activating agent, promotor are organic material, to rubber plug
Chemical property can have an impact, and influence the compatibility of rubber plug and drug；The partial size of white carbon black is much smaller than clay partial size, it is not easy to point
It dissipates, the open defects such as apparent white line, white point occurs in the improper sizing material that will lead to of dosage.
The present invention replaces the clay of equivalent with a small amount of white carbon black, to white carbon black after fixing the dosage of other raw material
Dosage optimizes.Mixing time fixes 10min, and dump temperature is set to 125 DEG C, and passes through glue stuff compounding curing curve, physics
Mechanical performance, film appearances evaluate the dosage of white carbon black.Different white carbon black dosages are under 125 DEG C of mixing binder removals
Rubber compound curing curve characteristic and physical mechanical property are specifically shown in Table 2, table 3.
125 DEG C of 2 dump temperature of table, the curing curve of different component white carbon black dosages
125 DEG C of 3 dump temperature of table, the physical mechanical property of different component white carbon black dosages
Remarks: ash content detection foundation is YBB00262005-2015 rubber Ash determination method；Pull apart strength Mpa detection foundation
GB/T528-2009；Elongation at break % detects foundation: GB/T528-2009；Hardness/Shao A detection is according to GB/T531.1-
2008；300% stretches detection according to GB/T528-2009 surely；Film appearances range estimation.
As seen from the results in Table 2, gradually increasing with white carbon black dosage, in the premise for not influencing glue stuff compounding mobile performance
Under, curing temperature has been increased to 190 DEG C by 174 DEG C, the high temperature vulcanized precipitation conducive to moisture and small-molecule substance in sizing material.But
After white carbon black dosage reaches 12 parts, dispersion of the white carbon black in sizing material is affected, and glue stuff compounding has apparent appearance to lack
Fall into: white point, white line are not able to satisfy the production of rubber plug product.
As seen from the results in Table 3, gradually increasing with white carbon black dosage, the physical mechanical property of glue stuff compounding has significantly
It is promoted, the addition of white carbon black does not have an adverse effect to the physical property of butyl rubber plug, meets the design of butyl rubber plug formula
It is required that.
The curing curve of comprehensive glue stuff compounding, sulfuration process, physical mechanical property, the shadow of the Multiple factors such as film appearances
It rings, the dosage of white carbon black is the most suitable at 6-9 parts, and specific dosage is adjusted according to the actual situation.
3, the selection of vulcanizing agent: chlorinated scoline formula vulcanizing agent usually selects resin, alkyl phenol disulfide body
System, resin cure generate C-O-C cross-bond and HO-C-OH cross-bond, and under alkaline environment, Yi Fasheng scission of link is caused in rubber plug
The wash-off of substance, to influence drug quality；And alkyl phenol disulfide is vulcanized, and stable C-C key and single sulphur are generated
Scission of link will not occur under alkaline environment for key.Therefore alkyl phenol disulfide is selected.
4, the selection of plasticizer: current chlorinated scoline formula, which commonly softens system, polyethylene wax, vaseline, silicon
Oil etc., wherein some researches show that when rubber plug is in contact with drug, lower-molecular substance polyethylene wax is readily migrate into drug, shadow
Ring drug compatibility.For improvement and drug compatibility, softening agent of the dimethicone as this chlorinated scoline formula is selected.
The present invention has following benefit:
1, the curing temperature of chlorinated scoline is promoted by 174 DEG C -177 DEG C to 185 DEG C -190 DEG C, does not influence sizing material
Mobile performance.
2, the high temperature vulcanized moisture that can make in sizing material and small-molecule substance are precipitated as far as possible, improve chlorinated butyl rubber plug
With the compatibility of drug, drug safety is improved.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1: a kind of curing temperature of chlorinated butyl rubber bung formula used online is improved using the present invention, is improved
With the compatibility of drug, by control cure curve, physical mechanical property, finished product detection performance and with the compatibility of drug into
Row verifying.Specific embodiment is as follows:
B, cooperate: requiring to weigh various raw material according to formula table, formula table is shown in Table 4.Formula A changes compared with original formulation,
Resin is changed to alkyl phenol disulfide, and polyethylene wax is replaced using dimethicone,
Newly-increased part white carbon black, there is no variations for remaining various component.Specifically it is shown in Table 4.
4 original formulation table of table and improvement formula table
B, it is kneaded preforming: according to banburying process 10min, 125 DEG C of progress mixing productions of dump temperature；It is placed in open mill again
After the mill of 9-11min, the rubber compound of two formulas is obtained.Rubber compound after cooling is put into extruder, sizing material is squeezed out
It is cooling after calender rolls, cut-parts then are carried out according to vulcanization process demand, film is stored, for use.
C, vulcanize: the conditions of vulcanization parameter determined according to rheometer, by the film cut out in vulcanizer high temperature and pressure
Sulfidization molding under appointed condition obtains same specificationPowder needle rubber plug.
D, be punched: the product after sulfidization molding is punched to single butyl rubber plug by bicker.
E, it cleans: being cleaned according to normal wash technique, sampling does finished product detection and compared with drug compatibility.
F, rubber compound performance verification: rubber compound carries out sulphur varied curve performance verification and rubber compound Physical Mechanical is able to verify that.
(1) rubber compound rheological property detects: rubber compound curing curve is detected using rheometer, and testing result is shown in Table 5.
5 rubber compound sulphur of table is denaturalized energy
Being denaturalized by rubber compound sulphur can be it can be seen that original formulation A ML under 174 DEG C of conditions of vulcanization be lower, and sizing material has good
Good mobile performance, and when curing temperature is 188 DEG C, the mobile performance of ML higher, sizing material are affected, and when vulcanization is easy to appear
Open defect causes product unqualified；Formula A is changed under 174 DEG C of conditions of vulcanization, and ML is only that 4.51 rubber mobilities can be good
It is good, but TC10, TC90 higher, curingprocess rate reduce rapidly, production efficiency is unable to satisfy the demand of butyl rubber plug manufacturer,
And under 188 DEG C of conditions of vulcanization, ML and formula A it is almost the same in 174 DEG C of conditions of vulcanization, the mobile performance of sizing material not by
, can be under conditions of high temperature vulcanized to large effect, the crosslinking degree of glue stuff compounding is improved, and product can be normal
Production.
(2) detection of physical mechanical property, testing result have been carried out to rubber compound and has been shown in Table 6.By rubber compound Physical Mechanical
The comparison of energy can be seen that formula A, which changes, negatively affects physical mechanical property product, have not been changed the physical property of rubber plug.
6 rubber compound Physical Mechanical performance of table
H, rubber plug water content detection:
Detection method (thermogravimetry): taking rubber plug several (total weight about 10g), be placed in the weighing bottle of constant weight, and precision claims
It is fixed, it is subsequently placed in accurately weighed again after 105 DEG C of dry 2h, less loss weight is rubber plug moisture divided by initial weight.It is formulated A and matches
Square A changes 5 groups of data of each Parallel testing, and specific detection data is shown in Table 7.
7 rubber plug water content detection data of table
| Formula | Data 1 | Data 2 | Data 3 | Data 4 | Data 5 | Mean value |
| It is formulated A | 0.41% | 0.42% | 0.40% | 0.41% | 0.42% | 0.41% |
| Formula A changes | 0.22% | 0.23% | 0.21% | 0.22% | 0.22% | 0.22% |
According to 7 result of table it is found that newly the rubber plug moisture content that changes of formula A have compared with the rubber plug moisture of original formulation A it is bright
Aobvious reduction fully meets the use for the drug for having particular/special requirement to moisture.
I, rubber plug and drug compatibility result verification:
Choose the cefoperazone sodium sulbactam sodium of the auspicious pharmaceutical manufacturing in east, * 10 bottles of bottle of specification 1g/；Shandong Shandong medicine share
The Ceftriaxone Sodium of Co., Ltd, * 10 bottles of bottle of specification 1g/；The brizolina of Lukang Medical Co., Ltd., Shandong, specification
* 10 bottles of 1g/ bottle.It gets out sufficient amount of cleaning qualified formula A and formula A and changes rubber plug.
Accelerated test: original encapsulation aluminium-plastic cap and rubber plug are removed in sled on superclean bench, changes ready test immediately
Rubber plug, and aluminium lid is pricked, carry out mark.Every battery of tests rubber plug encapsulates 5 bottles of drug.Injection is drawn using clean syringe after encapsulation
Water, alignment rubber plug acupuncture ring carry out puncture water filling, every bottle of water filling 10mL, and appropriate shaking dissolves drug.By dissolved drug
Be inverted in a stainless steel pallet, be placed in temperature 60 C ± 2 DEG C, relative humidity 75% ± 5% constant temperature and humidity incubator in,
It places for 24 hours.
The detection of NTU value: the drug that accelerated test is completed takes out, and is cooled to room temperature, every group of test drug, which takes 1, directly to be made
The detection of NTU value is carried out with nephelometer (U.S. Hach, 2100AN).Various drugs and the specific detection data of rubber plug compatibility are shown in Table
8。
8 NTU value detection data of table
Data analysis: the NTU value of table 8 shows that formula A, which changes, is substantially better than formula A and 3 kinds of medicines with the compatibility of 3 kinds of drugs
The compatibility of product, the high temperature vulcanized compatibility to resinae chlorinated butyl rubber plug of experiment results proved improve significantly.
J, end properties detect: to original formulation and the rubber plug (powder needle rubber plug) for improving formula production referring to national standard
YBB00052005-2015 is detected, and testing result is shown in Table 7, and on the basis of original formulation, the rubber plug finished product for adding white carbon black is each
Item testing result is all satisfied requirements of the national standard.
7 rubber plug performance indicator of table and testing result
For above-described embodiment by contrast and experiment, raising can be passed through by demonstrating neoteric chlorinated scoline formula
The mode of curing temperature by sizing material moisture and small-molecule substance be precipitated it is more thorough, so as to improve the compatibility with drug, mention
High drug safety.
Claims (3)
1. a kind of chlorinated butyl rubber bung formula, which is characterized in that the raw material including following parts by weight:
40-60 parts of chlorinated scoline, 30-40 parts of clay, 0.5-2 parts of titanium dioxide, 0.01-0.5 parts of semi-reinforcing hydrocarbon black, zinc oxide
0.5-3 parts, 0.1-1 parts of stearic acid, 0.1-1 parts of alkyl phenol disulfide, 0.1-2 parts of dimethicone, 1-5 parts of white carbon black.
2. chlorinated butyl rubber bung formula according to claim 1, which is characterized in that the raw material including following parts by weight:
50 parts of chlorinated scoline, 35 parts of clay, 1 part of titanium dioxide, 0.1 part of semi-reinforcing hydrocarbon black, 2 parts of zinc oxide, 0.25 part of stearic acid, alkane
0.25 part of base phenol disulfide, 1 part of dimethicone, 3.0 parts of white carbon black.
3. the preparation method of chlorinated butyl rubber bung formula according to claim 1 or 2, which is characterized in that including as follows
Step:
A, cooperate: weighing various raw material according to formula and mixed；
B, be kneaded preforming: by the mixture in step a, dumping, mixing produce 8-15min at 120-130 DEG C；
It is placed in open mill again after the mill of 9-11min, obtains rubber compound, is put into extruder after cooling, squeeze out sizing material warp
It is cooling after calender calendering, cut-parts then are carried out according to vulcanization process demand, film is stored, for use；
C, vulcanize: by the film cut out in vulcanizer, the sulfidization molding under 185 DEG C of -190 DEG C of hot conditions obtains same rule
The 20 powder needle rubber plug of φ of lattice；
D, be punched: the product after sulfidization molding is punched to single butyl rubber plug by bicker；
E, it cleans: being cleaned according to normal wash technique, sampling does finished product detection and compared with drug compatibility.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288180A (en) * | 2021-12-22 | 2022-04-08 | 湖北华强科技股份有限公司 | Piston for pen type injector of explosion-proof plug |
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| CN107254109A (en) * | 2017-06-09 | 2017-10-17 | 湖北华强科技有限责任公司 | A kind of alkaline drug butyl rubber bung and preparation method thereof |
| CN108226455A (en) * | 2017-12-25 | 2018-06-29 | 湖北华强科技有限责任公司 | A kind of fast appraisement method of butyl rubber plug and lyophilized preparation drug compatibility |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5839436A (en) * | 1981-09-03 | 1983-03-08 | Showa Gomme Kk | Rubber plug |
| CN101851377A (en) * | 2009-12-31 | 2010-10-06 | 山东省药用玻璃股份有限公司 | Novel medical powder injection rubber plug and manufacturing method thereof |
| CN106009341A (en) * | 2016-07-06 | 2016-10-12 | 湖北华强科技有限责任公司 | Formula of halogenated butyl rubber plug capable of achieving low-temperature vulcanization |
| CN106084515A (en) * | 2016-07-06 | 2016-11-09 | 湖北华强科技有限责任公司 | One has puncture plug and preparation method |
| CN107254109A (en) * | 2017-06-09 | 2017-10-17 | 湖北华强科技有限责任公司 | A kind of alkaline drug butyl rubber bung and preparation method thereof |
| CN108226455A (en) * | 2017-12-25 | 2018-06-29 | 湖北华强科技有限责任公司 | A kind of fast appraisement method of butyl rubber plug and lyophilized preparation drug compatibility |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288180A (en) * | 2021-12-22 | 2022-04-08 | 湖北华强科技股份有限公司 | Piston for pen type injector of explosion-proof plug |
| CN114288180B (en) * | 2021-12-22 | 2024-05-17 | 湖北华强科技股份有限公司 | Piston for pen-type injector of explosion-proof plug |
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