CN113969100A - Coating composition containing molecular sieve catalyst, coating liquid for non-silicification rubber plug, preparation method of coating liquid and preparation method of non-silicification rubber plug - Google Patents

Coating composition containing molecular sieve catalyst, coating liquid for non-silicification rubber plug, preparation method of coating liquid and preparation method of non-silicification rubber plug Download PDF

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CN113969100A
CN113969100A CN202010704506.6A CN202010704506A CN113969100A CN 113969100 A CN113969100 A CN 113969100A CN 202010704506 A CN202010704506 A CN 202010704506A CN 113969100 A CN113969100 A CN 113969100A
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curing
rubber plug
catalyst
weight
parts
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CN113969100B (en
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李建华
钟林
安婷婷
王镭
宋小飞
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2323/22—Copolymers of isobutene; butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to the technical field of production of medicinal rubber plugs, and discloses a coating composition containing a molecular sieve catalyst, which contains the following components stored in a mixing way or independently: blocked polydimethylsiloxane, catalyst and coupling agent, and optionally containing an organic solvent; wherein the catalyst is a ZSM-5 molecular sieve catalyst; relative to 100 parts by weight of the blocked polydimethylsiloxane, the content of the catalyst is 0.01-3 parts by weight, the content of the coupling agent is 20-250 parts by weight, and the content of the organic solvent is 0-2000 parts by weight. The preparation process of the siliconized free rubber plug provided by the invention is simple, does not influence the quality of the rubber plug, does not need repeated treatment, is easy to implement and has obvious effect.

Description

Coating composition containing molecular sieve catalyst, coating liquid for non-silicification rubber plug, preparation method of coating liquid and preparation method of non-silicification rubber plug
Technical Field
The invention relates to the technical field of production of medicinal rubber plugs, in particular to a coating composition containing a molecular sieve catalyst, a method for preparing coating liquid for a non-silicification rubber plug, the coating liquid for the non-silicification rubber plug prepared by the method, and a method for preparing the non-silicification rubber plug.
Background
In the rubber plug production process, rubber plugs are usually subjected to silicification treatment by rubber plug production enterprises, namely a layer of silicone oil is sprayed on the surfaces of the rubber plugs. The lubricating property of the silicone oil can prevent the rubber plugs from being bonded in the production and transportation processes, reduce particles generated by mutual friction of the rubber plugs and ensure that the rubber plugs are normally operated and pressed on a pharmaceutical filling machine.
However, the technical defects brought by the siliconizing treatment are that the medicine needs to be sterilized under high pressure with a plug after being filled, and the silicone oil residue is released from the rubber plug and dissolved into the medicine in the process; additionally, silicidation can also result in insoluble particles and visible foreign matter being rejected for inspection and rework or scrapping.
There is therefore a need for a new plug which overcomes the disadvantages of the siliconized plugs described above.
Therefore, a lot of work is being done at home and abroad. For example: the full tectorial membrane or neck tectorial membrane on plug surface, but the tectorial membrane plug mainly to the higher pharmaceutical packaging of pH valve, easily appear that the membrane material adhesion is not strong moreover, the membrane easily drops, and membrane material elasticity is poor, and tectorial membrane plug hardness is great, easily appears the self sealedly poor, the acupuncture performance subalternation problem, and the price is also more expensive simultaneously.
For example, CN2768773Y discloses a siliconization-free medical rubber plug, which is formed by laminating a film on the top end surface and the peripheral wall of the crown portion of the rubber plug to prevent the rubber plug from being contaminated by siliconization, but when the rubber plug is used, the film is punctured by a needle, and then the medical liquid contacts with the rubber plug, which still can cause contamination to the medical liquid.
The improved technical scheme CN105907298A discloses a grafting type rubber plug spraying liquid, which adopts catalysts such as dibutyltin dilaurate and dibutyltin dilaurate, is harmful to human bodies and environment, and is difficult to separate in the reaction.
The improved technical scheme CN107629240A discloses a preparation process of a siliconized free rubber plug, which adopts homogeneous catalysts such as titanate and the like, is difficult to recover and reuse after reaction, and is easy to hydrolyze and deactivate; in addition, the coating is cured by adopting a high-temperature thermosetting mode, the curing period is longer, and the curing temperature is higher.
Therefore, there is a need to optimize and improve the prior art method for preparing silicone-free rubber plugs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a coating composition containing a molecular sieve catalyst, which can obtain a coating solution for a non-silicification rubber plug with low viscosity of a spraying solvent, easy operation and low surface friction coefficient.
In order to achieve the above object, a first aspect of the present invention provides a coating composition containing a molecular sieve catalyst, the composition containing two or more of the following components stored in admixture or separately:
blocked polydimethylsiloxane, catalyst and coupling agent, and optionally containing an organic solvent;
wherein the catalyst is a ZSM-5 molecular sieve catalyst;
relative to 100 parts by weight of the blocked polydimethylsiloxane, the content of the catalyst is 0.01-3 parts by weight, the content of the coupling agent is 20-250 parts by weight, and the content of the organic solvent is 0-2000 parts by weight.
The invention provides a method for preparing coating liquid for a siliconized free rubber plug, wherein the coating liquid is prepared from the composition, and the method comprises the following steps: and (3) carrying out contact reaction on each component in the component A containing the blocked polydimethylsiloxane, the catalyst and the coupling agent in the presence of an organic solvent.
The third aspect of the invention provides the coating liquid for the siliconized free rubber plug prepared by the method.
The fourth aspect of the present invention provides a method for preparing a silicone-free rubber plug, comprising:
(1) mixing and contacting the coating liquid for the siliconized free rubber plug prepared by the method with a curing agent and/or a photoinitiator to obtain a spraying liquid;
(2) coating the spraying liquid on at least part of the area of the rubber plug to be sprayed to obtain the sprayed rubber plug;
(3) and curing the sprayed rubber plug.
The preparation process of the siliconized free rubber plug provided by the invention is simple, does not influence the quality of the rubber plug, does not need repeated treatment, is easy to implement and has obvious effect.
In addition, the rubber plug obtained by the invention has low surface friction coefficient, good ultraviolet resistance, chemical resistance and aging resistance, can avoid the silicification process in the rubber plug production process, can isolate the rubber plug from medicines and liquid medicines, avoids mutual diffusion and permeation, reduces particle pollution, protects the stability of the medicines, meets the requirement of the resistance of the rubber plug and the medicines, and has very reliable biological safety and biological stability.
Further, it can be seen from the results of the examples of the present invention that, compared with the conventional silicone oil silicone rubber plug, the rubber plug of the present invention has better resistance to common drugs such as chlorpromazine hydrochloride because the coating layer on the surface of the rubber plug does not fall off.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, normal pressure means one atmospheric pressure unless otherwise specified.
Herein, unless otherwise specified, the component a mentioned below is different from the coating film composition for the silicone-free plug only in whether or not an organic solvent is contained.
As described above, the first aspect of the present invention provides a coating composition containing a molecular sieve catalyst, which contains two or more of the following components stored in admixture or independently:
blocked polydimethylsiloxane, catalyst and coupling agent, and optionally containing an organic solvent;
wherein the catalyst is a ZSM-5 molecular sieve catalyst;
relative to 100 parts by weight of the blocked polydimethylsiloxane, the content of the catalyst is 0.01-3 parts by weight, the content of the coupling agent is 20-250 parts by weight, and the content of the organic solvent is 0-2000 parts by weight.
Preferably, the content of the organic solvent is 100-2000 parts by weight.
Preferably, the catalyst is an H-type ZSM-5 molecular sieve catalyst. The beta-molecular sieve catalyst is preferably in the shape of a cylinder, a cloverleaf or other special shapes, and also comprises ZSM-5 molecular sieves in various shapes prepared by extruding powdered ZSM-5 molecular sieves. The H-type ZSM-5 molecular sieve is preferably an H-type ZSM-5 molecular sieve catalyst obtained by performing ammonia exchange, acid treatment or other treatment methods on a Na-type ZSM-5 molecular sieve catalyst.
According to a preferred embodiment of the present invention, the H-type ZSM-5 molecular sieve catalyst has a silica to alumina molar ratio of 25 to 300. In the embodiment, the coated composition for the non-silicification rubber plug prepared by the catalyst containing the silica-alumina molar ratio is more beneficial to preparing the rubber plug with low surface friction coefficient.
Preferably, the end-capped polydimethylsiloxane is selected from at least one of amino-end-capped polydimethylsiloxane, hydroxyl-end-capped polydimethylsiloxane, alpha-hydro-omega-hydroxyl-polydimethylsiloxane, and alkoxy-end-capped polydimethylsiloxane. In the end-capped polydimethylsiloxane, the alkoxy comprises a linear alkoxy, a branched alkoxy or a cycloalkoxy, and the total number of carbon atoms of the alkoxy is 1-20.
According to a preferred embodiment of the invention, the viscosity of the blocked polydimethylsiloxane is 750-. Under the embodiment, the prepared film coating composition is applied to the rubber plug coating liquid, so that the rubber plug has a lower surface friction coefficient. In the present invention, the viscosity is measured at normal pressure and 20 ℃.
Preferably, the coupling agent is selected from at least one of an aminosilane coupling agent, an epoxy silane coupling agent, and an alkyl alkoxy silane coupling agent. More preferably, the coupling agent is selected from the group consisting of gamma-methacryloxypropyltrimethoxysilane (KH-570), g-aminopropyltrimethoxysilane (KH-551), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560).
Preferably, the organic solvent is selected from at least one of acetone, butanone, n-hexane, n-heptane, cycloheptane and toluene.
As described above, the second aspect of the present invention provides a method for preparing a coating liquid for a silicone-free rubber plug, the coating liquid being prepared from the above composition, the method comprising: and (3) carrying out contact reaction on each component in the component A containing the blocked polydimethylsiloxane, the catalyst and the coupling agent in the presence of an organic solvent.
In the present invention, the organic solvent is essential for solution preparation before coating, but when the product of the present invention is sold as a commercial product, the combination a may be stored separately from the organic solvent for easy transportation and storage, and may be mixed before coating application.
The types of the components involved in the second aspect of the present invention are the same as the types of the components in the composition described in the first aspect of the present invention, and in order to avoid repetition, the present invention will not be described herein again, and those skilled in the art will not be understood as limiting the present invention.
According to the present invention, preferably, the conditions of the contact reaction include: the temperature is 80-130 ℃ and the time is 2-15 h.
Preferably, the catalyst is used in an amount of 0.01 to 3 parts by weight, the coupling agent is used in an amount of 20 to 250 parts by weight, and the organic solvent is used in an amount of 100 to 2000 parts by weight, relative to 100 parts by weight of the blocked polydimethylsiloxane.
Preferably, the method further comprises: and carrying out solid-liquid separation on the mixture obtained after the contact reaction to obtain the coating liquid for the non-silicification rubber plug.
The step of the solid-liquid separation in the present invention is not particularly limited, and may be a conventional choice in the art as long as the purpose of spatially separating the liquid and the solid in the mixture obtained after the contact reaction can be achieved. The purpose of the solid-liquid separation in the present invention is to separate the catalyst from the mixture obtained after the contact reaction. Preferably, the means of solids separation is centrifugation and/or filtration. The equipment for carrying out said centrifugation and/or filtration can be chosen by the person skilled in the art according to the actual needs.
As described above, the third aspect of the present invention provides the coating liquid for the silicone-free rubber plug prepared by the above method.
As previously mentioned, a fourth aspect of the present invention provides a method for preparing a siliconized free plug, the method comprising:
(1) mixing and contacting the coating liquid for the siliconizing-free rubber plug with a curing agent and/or a photoinitiator to obtain a spraying liquid;
(2) coating the spraying liquid on at least part of the area of the rubber plug to be sprayed to obtain the sprayed rubber plug;
(3) and curing the sprayed rubber plug.
According to the present invention, the areas to be coated by the spraying liquid in the process of preparing the rubber plug are well known to those skilled in the art, and the partial areas include, but are not limited to, the crown surface, the neck surface and the bottom surface of the rubber plug, and the coating can be performed by those skilled in the art according to the actual needs.
According to the present invention, it is well known to those skilled in the art that the preparation process of the rubber plug further includes, but is not limited to, the following steps before the spraying liquid is coated with the rubber plug: mixing rubber, discharging rubber sheets, molding, vulcanizing, cutting, cleaning and drying. Further, if necessary, the method for preparing the silicone-free rubber plug provided by the invention can further comprise the following steps: and (3) punching, cleaning, sterilizing and the like the cured rubber plug.
Preferably, in step (1), the conditions of the mixing contact include: the temperature is 20-40 deg.C, and the time is 10-60 min.
Preferably, the curing agent is selected from at least one of aromatic polyamine, acid anhydride, resol, amino resin, dicyandiamide, and hydrazide; preferably, the curing agent is selected from at least one of aromatic polyamine and acid anhydride.
Preferably, the photoinitiator is selected from at least one of benzoin and derivatives thereof, benzil compounds, alkyl phenone compounds, acyl phosphorus oxide, benzophenone compounds and thioxanthone compounds; preferably, the photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone (photoinitiator 1173), 1-hydroxy-cyclohexyl-phenyl ketone (photoinitiator 184), 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (TPO), and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819).
Preferably, the curing agent and the photoinitiator are used in amounts such that the total amount of curing agent and photoinitiator in the spray fluid is from 1 to 8 wt%, preferably from 1 to 5 wt%. When only the curing agent or the photoinitiator is contained, the single content is also within the above range.
Preferably, the curing treatment is performed by at least one selected from the group consisting of thermal curing and ultraviolet curing. The curing treatment is carried out in at least one mode, which means that thermal curing or ultraviolet curing can be adopted, and dual curing of thermal curing and ultraviolet curing can also be adopted. In the present invention, the thermal curing is carried out in the presence of a curing agent; the UV curing is carried out in the presence of a photoinitiator.
According to a preferred embodiment, the curing treatment is carried out by means of thermal curing.
According to a preferred embodiment of the invention, the method further comprises: before the thermal curing, the sprayed rubber plug is dried; preferably, the temperature for drying is 100-160 ℃.
The thermal curing may for example be carried out at a constant temperature, for example at a temperature of 100-250 ℃; it is also possible to carry out the curing in stages at different temperatures, for example, first at from 0 to 90 ℃ and then at from 90 to 250 ℃.
According to a preferred embodiment of the present invention, the thermal curing includes sequentially performing low-temperature curing at a temperature of 20-40 ℃ and high-temperature curing at a temperature of 150-200 ℃. Under the preferred embodiment, the rubber plug cured by stages has lower surface friction coefficient, and better ultraviolet resistance, chemical resistance and aging resistance.
Preferably, the time of low-temperature curing is 12-36h, and the time of high-temperature curing is 2-10 min.
According to the present invention, preferably, the curing treatment is performed by means of ultraviolet light curing.
Preferably, the uv curing is performed using a medium pressure mercury lamp.
According to a preferred embodiment of the present invention, the conditions of the uv curing include: the power of the medium-pressure mercury lamp is 300-2000W, the irradiation distance is 10-50cm, and the curing time is 60-300 s. In the present invention, the uv curing may be performed in an inert atmosphere or an oxygen-containing atmosphere, and in order to reduce the production cost, the uv curing is performed in the air. Under the preferred embodiment, the rubber plug cured by ultraviolet light has lower surface friction coefficient, and has better ultraviolet resistance, chemical resistance and aging resistance.
Preferably, the curing treatment is carried out by using a dual curing mode of ultraviolet curing and thermal curing. Further preferably, step (3) comprises: and (3) firstly carrying out ultraviolet curing on the sprayed rubber plug, and then carrying out thermal curing. More preferably, when the dual curing mode is adopted, the conditions of the ultraviolet curing include: the power of the medium-pressure mercury lamp is 300-; the conditions for the thermal curing include: the temperature is 150 ℃ and 200 ℃, and the curing time is 1-8 min.
Preferably, the material of the rubber plug to be sprayed is selected from at least one of isoprene rubber, butyl rubber and halogenated butyl rubber.
Compared with the prior art, the invention also has the following advantages:
the invention improves the traditional preparation method of the rubber plug, so that the invention has the advantage of environmental protection and greatly shortens the curing time. The rubber plug obtained by curing has low surface friction coefficient, good ultraviolet resistance, chemical resistance and aging resistance, can avoid the silicification process in the rubber plug production process, and can isolate the rubber plug from medicines and liquid medicines, thereby avoiding interdiffusion and permeation, and realizing the purposes of reducing particle pollution and protecting the stability of the medicines. The rubber plug provided by the invention meets the compatibility requirement of the rubber plug and medicines, and has very reliable biological safety and biological stability.
The present invention will be described in detail below by way of examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and should not be taken as limiting the scope of the present invention.
In the following examples, the following examples are given,
the rubber plug is made of the following materials: the brominated butyl rubber and the chlorinated butyl rubber are purchased from Anhui Huafeng medical rubber and plastic Limited company with the trade marks of HFG-08B, HFG-10 respectively;
end-capped polydimethylsiloxane: hydroxyl-terminated polydimethylsiloxane, alpha-hydro-omega-hydroxy-polydimethylsiloxane, respectively, were purchased from carbofuran technologies ltd, beijing;
ZSM-5 molecular sieves were purchased from Tianjin south China catalyst Ltd;
coupling agent: KH-570, KH-551 and KH-560, all available from Bailingwei technologies, Beijing;
photoinitiator (2): photoinitiators 1173, 819, TPO, 184 were purchased from Bailingwei technologies, Beijing;
curing agent: n, N-dimethylbenzylamine, available from Bailingwei technologies, Beijing
Chlorpromazine hydrochloride was purchased from Beijing Bailingwei science and technology Co., Ltd;
the ultraviolet curing machine is a product which is purchased from Beijing Hongchang electromechanical equipment Limited company and has the brand number of LDST13002-11 AZ;
the silicone oil particle test performed in the present invention was conducted using an instrument model GWJ-4 purchased from precision instruments of Tianjin university.
The room temperature in the following preparation process means 25. + -. 1 ℃.
Preparation example 1
The material of the non-silicification rubber plug of the embodiment is brominated butyl rubber, and the method comprises the steps of preparing a coating solution from a coating composition, coating the surface of the cleaned and dried rubber plug with the coating solution and curing the coating.
Wherein, the composition of the coating composition is as follows: 100g of hydroxyl-terminated polydimethylsiloxane (viscosity of 5000cSt at 20 ℃), 0.5g of H-type ZSM-5 molecular sieve catalyst (silicon-aluminum molar ratio is 38, cylindrical), 50g of coupling agent (KH-570) and 100g of organic solvent (n-heptane).
The preparation process of the non-siliconized rubber plug of the embodiment comprises the following specific steps:
(1) dissolving the end-capped polydimethylsiloxane, the coupling agent and the catalyst in the organic solvent according to the weight ratio to carry out contact reaction (the contact reaction condition comprises that the temperature is 90 ℃ and the time is 10 hours) to prepare a mixture solution;
(2) centrifuging the mixture solution to obtain a coating solution;
(3) mixing and contacting the mixture solution with 3 wt% (based on the total amount of the prepared coating solution) of photoinitiator 1173 (under the mixing and contacting conditions including temperature of 25 deg.C and time of 40min) to obtain a spray coating solution;
(4) filling the prepared spraying liquid into silicon spraying equipment, and spraying the crown surface of the vulcanized rubber sheet;
(5) carrying out ultraviolet curing treatment on the sprayed rubber plug, wherein the power of a medium-pressure mercury lamp is 1500W, the irradiation distance is 20cm, and the curing time is 180 s;
(6) and performing punching, cleaning and sterilization processes on the treated rubber plug.
Specific process conditions are listed in table 1.
The other preparation examples were carried out by the same procedure as in preparation example 1, and the specific process conditions are shown in Table 1.
Comparative example 1
Comparative example 1 was conducted by the same procedure as in preparation example 1 except that an H-type ZSM-5 molecular sieve catalyst (silica-alumina molar ratio of 38, cylindrical) was replaced with dibutyltin dilaurate (98% concentration, 0.5g by weight, n-heptane as a solvent), and the specific process conditions are shown in Table 1.
Comparative example 2
Comparative example 2 was conducted in a similar manner to preparation example 1, except that the coupling agent (KH-570) was used in an amount of 5g, and the specific process conditions were as shown in Table 1.
Comparative example 3
Comparative example 3 was conducted in a similar manner to preparation example 1, except that the H-type ZSM-5 molecular sieve catalyst (38 mol ratio of Si to Al, cylindrical) was used in an amount of 10g and the specific process conditions were as shown in Table 1.
TABLE 1
Figure BDA0002594179060000111
TABLE 1 (continuation)
Figure BDA0002594179060000121
Test example 1
And (3) detecting the adhesive force of the coating: the adhesive force of the coating is detected by adopting a cross-cut method, and the evaluation criteria are as follows:
Figure BDA0002594179060000131
the test results are shown in Table 2.
Test example 2
The silicone oil particle test is carried out on the rubber plugs prepared in the preparation examples and the comparative examples, and the method comprises the following steps: taking two groups of three batches of injection liquid rubber plug finished products in the same batch, carrying out silicone oil particle test (refer to a light resistance method in a packaging material insoluble particle determination method YBB00272016 issued by the State food and drug administration, wherein according to the requirements of the insoluble particle determination method, for the product with the loading capacity of more than 100mL, the content of insoluble particles with the particle size of more than 10 μm in every 1mL of transfusion is less than 12 particles except for other regulations, the content of insoluble particles with the particle size of more than 25 μm is less than 2 particles), averaging, and obtaining the test results which are listed in Table 2.
Test example 3
The rubber stoppers obtained in the above preparation examples and comparative examples were subjected to a packaging treatment of chlorpromazine hydrochloride placed in an ampoule, inverted, subjected to high temperature tests for 10 days and 30 days under constant temperature and constant humidity conditions (60 ℃, 75% RH), and compared in terms of turbidity (refer to appendix ix of second part of pharmacopoeia of the people's republic of china, 2000 edition), and the test results are shown in table 2.
TABLE 2
Figure BDA0002594179060000141
Note: taking example 1 as an example, 3.4 silicone oil microparticles (. gtoreq.10 μm) indicate that the number of insoluble silicone oil microparticles having a particle size of 10 μm or more contained in 1mL of infusion solution is 3.4;
a turbidity of < 0.5 indicates a turbidity mean value below that of standard solution No. 0.5; a turbidity of 0.5-1 means a mean turbidity value between the turbidity values of the standard solution with turbidity No. 0.5 and the standard solution with turbidity No. 1.
The results in table 2 show that the rubber plug provided by the invention meets the requirements of silicone oil particle tests; compared with the traditional silicone oil silication rubber plug of the comparative example 1, the rubber plug provided by the invention has better adhesive force and better tolerance with chlorpromazine hydrochloride because the silicon-containing compound on the surface of the rubber plug does not fall off.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (18)

1. The coating composition containing the molecular sieve catalyst is characterized by comprising the following components which are stored in a mixing way or independently:
blocked polydimethylsiloxane, catalyst and coupling agent, and optionally containing an organic solvent;
wherein the catalyst is a ZSM-5 molecular sieve catalyst;
relative to 100 parts by weight of the blocked polydimethylsiloxane, the content of the catalyst is 0.01-3 parts by weight, the content of the coupling agent is 20-250 parts by weight, and the content of the organic solvent is 0-2000 parts by weight.
2. The composition as claimed in claim 1, wherein the content of the organic solvent is 100-2000 parts by weight.
3. The composition of claim 1 or 2, wherein the catalyst is an H-type ZSM-5 molecular sieve catalyst;
preferably, the H-type ZSM-5 molecular sieve catalyst has a silica to alumina molar ratio of 25 to 300.
4. The composition of any of claims 1-3, wherein the endblocked polydimethylsiloxane is selected from at least one of amino endblocked polydimethylsiloxane, hydroxy endblocked polydimethylsiloxane, alpha-hydrogen-omega-hydroxy-polydimethylsiloxane, and alkoxy endblocked polydimethylsiloxane;
preferably, the viscosity of the end-capped polydimethylsiloxane is 750-.
5. The composition of any of claims 1-4, wherein the coupling agent is selected from at least one of an aminosilane coupling agent, an epoxy silane coupling agent, and an alkyl alkoxy silane coupling agent; preferably, the coupling agent is selected from at least one of gamma-methacryloxypropyltrimethoxysilane, g-aminopropyltrimethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane;
preferably, the organic solvent is selected from at least one of acetone, butanone, n-hexane, n-heptane, cycloheptane and toluene.
6. A method for preparing a coating solution for a silicone-free rubber plug, which is prepared using the composition of any one of claims 1 to 5, comprising: and (3) carrying out contact reaction on each component in the component A containing the blocked polydimethylsiloxane, the catalyst and the coupling agent in the presence of an organic solvent.
7. The method of claim 6, wherein the conditions of the contact reaction comprise: the temperature is 80-130 ℃ and the time is 2-15 h.
8. The method as claimed in claim 6 or 7, wherein the catalyst is used in an amount of 0.01 to 3 parts by weight, the coupling agent is used in an amount of 20 to 250 parts by weight, and the organic solvent is used in an amount of 100 to 2000 parts by weight, relative to 100 parts by weight of the end-capped polydimethylsiloxane.
9. The method of any of claims 6-8, wherein the method further comprises: carrying out solid-liquid separation on the mixture obtained after the contact reaction to obtain coating liquid for the non-silicification rubber plug;
preferably, the means of solids separation is centrifugation and/or filtration.
10. Coating solution for silicone-free rubber plugs prepared by the method of any one of claims 6 to 9.
11. A method for preparing a silicone-free plug, the method comprising:
(1) mixing and contacting the coating liquid for the siliconized free rubber plug of claim 10 with a curing agent and/or a photoinitiator to obtain a spraying liquid;
(2) coating the spraying liquid on at least part of the area of the rubber plug to be sprayed to obtain the sprayed rubber plug;
(3) and curing the sprayed rubber plug.
12. The method of claim 11, wherein in step (1), the conditions of the mixing contact comprise: the temperature is 20-40 deg.C, and the time is 10-60 min;
preferably, the curing agent is selected from at least one of aromatic polyamine, acid anhydride, resol, amino resin, dicyandiamide, and hydrazide; preferably, the curing agent is selected from at least one of aromatic polyamine and acid anhydride;
preferably, the photoinitiator is selected from at least one of benzoin and derivatives thereof, benzil compounds, alkyl phenone compounds, acyl phosphorus oxide, benzophenone compounds and thioxanthone compounds; preferably, the photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
13. A method according to claim 11 or 12, wherein the curing agent and the photoinitiator are used in amounts such that the total amount of curing agent and photoinitiator in the spray fluid is 1-8 wt%.
14. The method according to any one of claims 11 to 13, wherein the curing treatment is performed by at least one selected from the group consisting of thermal curing and ultraviolet curing.
15. The method according to any one of claims 11-13, wherein the curing process is performed by means of thermal curing;
preferably, the method further comprises: before the thermal curing, the sprayed rubber plug is dried; preferably, the drying temperature is 100-160 ℃;
preferably, the heat curing comprises: sequentially carrying out low-temperature curing at the temperature of 20-40 ℃ and high-temperature curing at the temperature of 150-;
preferably, the time of low-temperature curing is 12-36h, and the time of high-temperature curing is 2-10 min.
16. The method according to any one of claims 11-13, wherein the curing process is performed by means of uv curing;
preferably, the ultraviolet curing is performed using a medium-pressure mercury lamp;
preferably, the conditions of the ultraviolet light curing include: the power of the medium-pressure mercury lamp is 300-2000W, the irradiation distance is 10-50cm, and the curing time is 60-300 s.
17. The method according to any one of claims 11-13, wherein the curing process is performed by a dual curing method of uv curing and thermal curing;
preferably, step (3) comprises: firstly carrying out ultraviolet curing on the sprayed rubber plug, and then carrying out thermal curing;
the ultraviolet curing conditions comprise: the power of the medium-pressure mercury lamp is 300-;
the conditions for the thermal curing include: the temperature is 150 ℃ and 200 ℃, and the curing time is 1-8 min.
18. The method according to any one of claims 11 to 17, wherein the material of the rubber plug to be sprayed is at least one selected from isoprene rubber, butyl rubber and halogenated butyl rubber.
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CN103405335A (en) * 2013-08-02 2013-11-27 山东威高集团医用高分子制品股份有限公司 Surface-modified rubber plug and preparation method thereof
CN104107710A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof
CN105907298A (en) * 2016-05-25 2016-08-31 郑州翱翔医药科技股份有限公司 Grafted rubber plug spraying fluid and treatment method of grafted rubber plug spraying fluid on surface of rubber plug
CN107511169A (en) * 2016-06-18 2017-12-26 中国石油化工股份有限公司 The molecular sieve catalysts of ZSM 5, preparation method and application
CN107629240A (en) * 2017-11-08 2018-01-26 江阴市海华橡塑有限公司 A kind of preparation technology for exempting from silication plug
CN111167509A (en) * 2019-08-20 2020-05-19 中国石油化工股份有限公司 Carbon tetraolefin cracking catalyst, preparation method thereof and catalytic cracking method

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CN101259080A (en) * 2007-03-09 2008-09-10 郑州市翱翔医药包装有限公司 Silicification-free infusion bottle stopper and manufacturing method thereof
CN104107710A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof
CN103405335A (en) * 2013-08-02 2013-11-27 山东威高集团医用高分子制品股份有限公司 Surface-modified rubber plug and preparation method thereof
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