CN115872819B - Lead-free low-temperature starting device and preparation method thereof - Google Patents

Lead-free low-temperature starting device and preparation method thereof Download PDF

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Publication number
CN115872819B
CN115872819B CN202211715866.1A CN202211715866A CN115872819B CN 115872819 B CN115872819 B CN 115872819B CN 202211715866 A CN202211715866 A CN 202211715866A CN 115872819 B CN115872819 B CN 115872819B
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temperature
catalyst
mixture
lead
parts
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CN115872819A (en
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文宝玉
张德明
陈志军
张洁
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Changsha Shixiang Fire Technology Co ltd
Beijing Anxin Tongchuang Technology Co ltd
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Changsha Shixiang Fire Technology Co ltd
Beijing Anxin Tongchuang Technology Co ltd
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Abstract

The invention discloses a lead-free low-temperature starting device which comprises a thermosensitive drug core, wherein the thermosensitive drug core comprises the following components in parts by weight: a temperature sensing agent, an oxidant, a stabilizer, a toughening agent, a catalyst, a catalytic regulator and a solvent; the catalyst is ferrocene; the catalyst regulator is a platinum carbon catalyst. The thermosensitive drug core formula can adjust the temperature-sensing starting temperature and reduce the temperature-sensing starting temperature to 120-150 ℃ (the lowest temperature can be reduced to 120 ℃), so that the fire extinguishing device can be effectively started in a short time at the initial stage of fire occurrence for a small space (such as a battery, particularly an automobile battery, a power distribution cabinet and the like), the aim of initial fire extinguishing is fulfilled, and the safety of equipment can be greatly improved.

Description

Lead-free low-temperature starting device and preparation method thereof
Technical Field
The invention relates to the technical field of fire protection, in particular to a lead-free low-temperature starting device and a preparation method thereof.
Background
In the prior art, the heat-sensitive starting device is a general product of an automatic fire extinguishing device in the fire-fighting industry, the core of the heat-sensitive starting device is the formula of a heat-sensitive medicine core, and the traditional heat-sensitive starting device is formed by coating the medicine core with a layer of PE plastic. The main component of the existing flux core is red lead, the main component of the existing flux core is lead tetraoxide, the temperature-sensing starting temperature of the red lead is low, and the existing flux core is used as an oxidant and a catalyst in the combustion process, has good stability, and is widely applied in the industry. However, the red lead component contains a small amount of lead, and lead is an accumulated poison, which can affect a plurality of systems of the body and particularly has great harm to young children; currently, the world health organization has identified lead as one of ten chemicals that cause significant public health concerns; while products containing lead components have been banned from production and sale by the world health organization and most national directives. Also listed as prohibited materials by the firework and cracker products. Therefore, the fire extinguishing device adopting the lead-containing thermosensitive starting device is greatly influenced in the aspects of export detection, sales and the like.
Therefore, developing a lead-free low-temperature start-up device formula and a preparation method thereof obviously have great social value and economic benefit.
On the other hand, the temperature-sensitive starting temperature of the conventional thermosensitive starting device is generally 170-190 ℃, and for small spaces such as batteries, particularly automobile batteries, power distribution cabinets and the like, a certain time is required for the fire temperature to rise to 170 ℃ (or higher), and if electrolyte leakage occurs during the time, the electrolyte is harmful to human bodies (because the electrolyte is generally a corrosive liquid such as strong acid, strong alkali and the like). Therefore, how to adjust the formulation of the thermosensitive drug core greatly reduces the starting temperature and improves the sensitivity and the effectiveness of the thermosensitive drug core, so that the fire extinguishing device can be effectively started in a short time at the initial stage of fire occurrence, the aim of initial fire extinguishing is achieved, the safety of equipment can be greatly improved, and the thermosensitive drug core has positive practical significance obviously.
Disclosure of Invention
The invention aims to provide a low-temperature starting device without lead and a preparation method thereof.
In order to achieve the above object, the present invention has the technical scheme that: the low-temperature starting device without containing lead comprises a thermosensitive drug core, wherein the thermosensitive drug core comprises the following components in parts by weight:
wherein: the catalyst is ferrocene; the catalyst regulator is a platinum carbon catalyst or a palladium carbon catalyst, and the particle size of the catalyst regulator is 2-200 nanometers; the weight ratio of the two is 4-11: 1, a step of;
the starting temperature of the low-temperature starting device is 120-150 ℃;
the weight ratio of the temperature sensing agent to the oxidant to the catalyst regulator is 80:9 to 21:4 to 11:1 to 2.
Preferably, the weight ratio of the temperature sensing agent, the oxidizing agent, the catalyst and the catalytic regulator is 80: 15-25: 4 to 11:1.
the temperature sensing agent and the oxidant are used for initiating the oxidation-reduction reaction, and the catalyst and the catalytic regulator are matched with the temperature sensing agent and the oxidant to initiate the oxidation-reduction reaction, so that the activation energy is reduced, the ignition temperature is reduced, and the reaction is easy to carry out.
In the invention, the catalyst is ferrocene, and the structure of the ferrocene is that one iron atom is positioned between two parallel cyclopentadiene rings; in a solid state, the two metallocene rings are staggered to form a full-staggered configuration, and can sublimate at the temperature of more than 100 ℃; when the temperature is increased, the two metallocene rings rotate relatively around the vertical axis, so that the molecular movement is further enhanced; meanwhile, the temperature sensing agent (nitrocellulose) is adsorbed on the surface of the nano catalytic regulator, and catalytic oxidation reaction is easier to occur when the temperature is increased and the molecular movement is severe, so that the temperature-sensitive drug core further reduces the ignition temperature, the temperature sensing agent can be ignited at a lower environment temperature, and once part of the temperature sensing agent is ignited, certain heat is released, and other temperature sensing agents are further promoted to undergo oxidation-reduction reaction.
The ferrocene is an organic transition metal compound with aromatic property, and the chemical formula is Fe (C) 5 H 5 ) 2 CAS number 102-54-5.
The platinum carbon catalyst, which is also called platinum carbon or platinum carbon, belongs to noble metal catalysts, is black powder in appearance, has a molecular weight of 195.08 and has a molecular formula of Pt/C. The particle size of the platinum-carbon catalyst is 2-200 nanometers, preferably 2-50 nanometers; more preferably 2 to 20 nm; more preferably 3 to 8 nm.
The ratio of the catalyst to the catalyst regulator is 4-11: 1, a step of; preferably 5 to 8:1, a step of; more preferably 5 to 6:1. the start-up temperature of the lead-free low-temperature start-up device is 120 to 150 degrees, preferably 125 to 145 degrees, more preferably 130 to 135 degrees. But also 121, 122, 123, 124, 126, 127, 128, 129, 131, 132, 133, 134, 136, 137, 138, 139, 141, 142, 143, 144, 148 degrees.
The low-temperature starting device without lead is used for batteries, in particular to an automatic fire extinguishing device for automobile batteries.
Preferably, the temperature sensing agent is a composition of nitrocellulose and nitroglycerin, and the proportion of the nitrocellulose and the nitroglycerin is 70-92: 8-30; wherein the nitrogen content of the nitrocellulose is not less than 12.5% by mass. Preferably 75 to 90:10 to 25, more preferably 80 to 85: 15-20.
Preferably, the oxidant is selected from one or more of potassium perchlorate, ammonium perchlorate, potassium nitrate and potassium chlorate.
Preferably, the stabilizer is selected from one or more of diethyl diphenyl urea, dimethyl diphenyl urea, ethyl methyl diphenyl urea, dibutyl phthalate and diphenyl phthalate.
Preferably, the toughening agent is nano calcium carbonate toughened epoxy resin. The epoxy resin toughened by the nano calcium carbonate is in the prior art, such as research on using the nano calcium carbonate as an epoxy resin toughening material, li Lei, university of Beijing (Nature science edition), and the material is recorded in 2005, volume 32 and 002.
Preferably, the solvent is selected from a mixture of at least two of acetone, ethanol and ethyl acetate.
Preferably, the starting temperature of the low-temperature thermal starting device is 120-140 degrees.
The invention also discloses a preparation method of the lead-free low-temperature starting device, which comprises the following steps:
(1) Dissolving a temperature sensing agent and a stabilizing agent in a solvent, and fully stirring to obtain a jelly A;
(2) Fully mixing an oxidant and a catalyst to obtain a mixture B;
(3) Pouring the mixture B into the jelly A, adding a proper amount of solvent and toughening agent to enable the solvent to completely cover the mixture B, then adding a catalytic regulator, and fully stirring to form a mud mass shape to obtain a mixture C;
(4) Extruding the mixture C into strip leads, and drying to obtain thermosensitive drug core;
(5) Winding a plurality of glass fiber yarns on the outer surface of the thermosensitive drug core to prepare a temperature sensing wire;
one end of the temperature sensing wire is fixed by a connecting terminal or a flame-retardant adhesive tape, and the other end is connected with a section of slow lead wire or a thermosensitive flux core, so that the lead-free low-temperature starting device can be obtained.
Preferably, the slow wire is a slow potassium perchlorate wire.
Preferably, in the step (2): the oxidant, the stabilizer and the catalyst are screened by a 160-mesh screen, and the mixture B is obtained after the mixture is fully mixed.
By adopting the technical scheme, the invention has the following technical effects:
1. the thermosensitive drug core formula of the invention does not contain lead, so the thermosensitive drug core formula has great advantages in the aspects of export detection, sales and the like, and has great social value and economic benefit.
2. The thermosensitive drug core formula can adjust the temperature-sensing starting temperature and reduce the temperature-sensing starting temperature to 120-150 ℃ (the lowest temperature can be reduced to 120 ℃), so that the thermosensitive drug core formula can effectively start a fire extinguishing device in a short time at the initial stage of fire occurrence for a small space (such as a battery, particularly an automobile battery, a power distribution cabinet and the like), and achieves the aim of initial fire extinguishment, thereby greatly improving the safety of equipment and obviously having positive practical significance; meanwhile, the low-temperature starting device has extremely high sensitivity and effectiveness.
3. The preparation method of the invention is simple and easy to implement, has lower cost, greatly saves resources and cost, and is suitable for popularization and application.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention in conjunction with the specific contents of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Examples
The low-temperature starting device without containing lead comprises a thermosensitive drug core, wherein the thermosensitive drug core comprises the following components in parts by weight: a temperature sensing agent, an oxidant, a stabilizer, a toughening agent, a catalyst, a catalytic regulator and a solvent; see the table below for specific formulations;
the preparation method of the lead-free low-temperature starting device comprises the following steps:
(1) Dissolving a temperature sensing agent and a stabilizing agent in a solvent (acetone and ethyl acetate), and fully stirring to obtain a colloid A;
(2) Fully mixing an oxidant and a catalyst to obtain a mixture B;
(3) Pouring the mixture B into the jelly A, adding a proper amount of solvent (ethanol) and a toughening agent to enable the solvent to completely cover the mixture B, then adding a catalytic regulator, and fully stirring to form a mud mass shape to obtain a mixture C;
(4) Extruding the mixture C into strip leads, and drying to obtain thermosensitive drug core;
(5) Winding a plurality of glass fiber yarns on the outer surface of the thermosensitive drug core to prepare a temperature sensing wire;
one end of the temperature sensing wire is fixed by a connecting terminal, the other end of the temperature sensing wire is connected with a section of heat sensitive flux core, and the temperature sensing wire is fixed by an aluminum foil tape, so that the lead-free low-temperature starting device can be obtained.
In the step (2): the oxidant, the stabilizer and the catalyst are screened by a 160-mesh screen, and the mixture B is obtained after the mixture is fully mixed.
Comparative example
The same preparation as in the examples was used with slightly different formulations and contents, see in particular the table below.
In the table above, the temperature sensing agent is a composition of nitrocellulose and nitroglycerin, and the ratio of the nitrocellulose to the nitroglycerin is 70:30; the oxidant is potassium perchlorate; the stabilizer is diethyl diphenyl urea; the toughening agent is epoxy resin toughened by nano calcium carbonate; the solvent is selected from acetone, ethanol and ethyl acetate; the catalyst is ferrocene; the catalyst regulator is a platinum-carbon catalyst, and the particle size of the platinum-carbon catalyst is nano-scale.
As is clear from examples 1 to 5, the following examples: the weight ratio of the catalyst to the catalytic regulator has obvious influence on the ignition temperature of the temperature sensing medicament, and when the weight ratio of the catalyst to the catalytic regulator is 12:2, the best effect, the lowest ignition temperature (up to 120 ℃ C.).
As is clear from the above example 3 and comparative examples 2 to 3: the particle size of the catalytic regulator has obvious influence on the catalytic effect, and the smaller the particle size is, the better the catalytic effect is, but when the particle size of the catalytic regulator is 3 nanometers, the effect is best, and the ignition temperature is the lowest (the lowest can reach 120 ℃).
From the above examples 3, 6, 7, 8 and comparative examples 5 to 6, it is understood that: the weight ratio of the temperature sensing agent, the oxidant, the catalyst and the catalytic regulator also has an effect on the light-off temperature of the temperature sensing agent, and when the ratio of the temperature sensing agent to the catalytic regulator is 80:20:12:2, the light-off temperature is the lowest.
As is clear from the above example 3 and comparative examples 1 and 4: the catalyst and the catalyst regulator have better combined action effect, and when any one of the catalyst and the catalyst regulator is absent, the ignition temperature can be greatly increased.
As can be seen from the above example 3 and comparative example 7: the epoxy resin toughened by nano calcium carbonate has excellent toughening function, can lead the thermosensitive drug core after the component is added to be bent and not easy to break, and can lead the drug core to break easily when the component is not added.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. The low-temperature starting device without containing lead comprises a thermosensitive drug core, and is characterized in that the thermosensitive drug core consists of the following components in parts by weight:
75-85 parts of temperature sensing agent
10-20 parts of oxidant
1-2 parts of stabilizer
4-6 parts of toughening agent
11-20 parts of catalyst
1-5 parts of catalytic regulator
150-170 parts of a solvent;
wherein: the catalyst is ferrocene; the catalyst regulator is a platinum carbon catalyst or a palladium carbon catalyst, and the particle size of the catalyst regulator is 3 nanometers; the weight ratio of the two is 4-8: 1, a step of;
the weight ratio of the temperature sensing agent to the oxidant to the catalyst regulator is 80: 9-21: 4-8: 1, a step of;
the temperature sensing agent is a composition of nitrocellulose and nitroglycerin, and the proportion of the nitrocellulose and the nitroglycerin is 70-92: 8-30 parts; wherein the nitrogen content of the nitrocellulose is not less than 12.5%;
the oxidant is one or more selected from potassium perchlorate, ammonium perchlorate, potassium nitrate and potassium chlorate;
the stabilizer is one or more selected from diethyl diphenyl urea, dimethyl diphenyl urea, ethyl methyl diphenyl urea, dibutyl phthalate and diphenyl phthalate;
the toughening agent is epoxy resin toughened by nano calcium carbonate;
the starting temperature of the low-temperature starting device is 120-140 ℃.
2. The lead-free low temperature thermal start-up device of claim 1, wherein the solvent is selected from the group consisting of a mixture of at least two of acetone, ethanol, and ethyl acetate.
3. Method for preparing a lead-free low temperature thermal start-up device according to any one of claims 1 to 2, characterized in that it comprises the steps of:
(1) Dissolving a temperature sensing agent and a stabilizing agent in a solvent, and fully stirring to obtain a jelly A;
(2) Fully mixing an oxidant and a catalyst to obtain a mixture B;
(3) Pouring the mixture B into the jelly A, adding a proper amount of solvent and toughening agent to enable the solvent to completely cover the mixture B, then adding a catalytic regulator, and fully stirring to form a mud mass shape to obtain a mixture C;
(4) Extruding the mixture C into strip leads, and drying to obtain thermosensitive drug core;
(5) Winding a plurality of glass fiber yarns on the outer surface of the thermosensitive drug core to prepare a temperature sensing wire;
one end of the temperature sensing wire is fixed by a connecting terminal or a flame-retardant adhesive tape, and the other end is connected with a section of slow lead wire or a thermosensitive flux core, so that the lead-free low-temperature starting device can be obtained.
4. The method of claim 3, wherein the slow wire is a slow potassium perchlorate wire.
5. A method according to claim 3, wherein in step (2): the oxidant, the stabilizer and the catalyst are screened by a 160-mesh screen, and the mixture B is obtained after the mixture is fully mixed.
CN202211715866.1A 2022-12-28 2022-12-28 Lead-free low-temperature starting device and preparation method thereof Active CN115872819B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1277192A (en) * 1965-12-30 1972-06-07 Us Gov Sec Army Improvements in and relating to nitrocellulose base propellant compositions
US3689331A (en) * 1964-02-28 1972-09-05 Us Army Nitrocellulose base compositions and method for making same
CN101339999A (en) * 2008-08-12 2009-01-07 浙江大学 Direct sodium borohydride fuel cell using ferrocene as cathode catalyst
CN107670215A (en) * 2017-09-29 2018-02-09 邓筱鲁 A kind of hot-gas sol fire extinguishing agent and preparation method thereof
CN110950724A (en) * 2019-12-10 2020-04-03 江西吉润花炮新材料科技有限公司 Thermal-stable indoor smokeless and sulfur-free cold firework setting-off chemical and preparation method thereof
CN111689824A (en) * 2020-07-08 2020-09-22 泸州北方化学工业有限公司 Thermosensitive wire and preparation method thereof
CN113912465A (en) * 2021-10-14 2022-01-11 长沙士象消防科技有限公司 Moisture-proof and waterproof thermosensitive wire and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689331A (en) * 1964-02-28 1972-09-05 Us Army Nitrocellulose base compositions and method for making same
GB1277192A (en) * 1965-12-30 1972-06-07 Us Gov Sec Army Improvements in and relating to nitrocellulose base propellant compositions
CN101339999A (en) * 2008-08-12 2009-01-07 浙江大学 Direct sodium borohydride fuel cell using ferrocene as cathode catalyst
CN107670215A (en) * 2017-09-29 2018-02-09 邓筱鲁 A kind of hot-gas sol fire extinguishing agent and preparation method thereof
CN110950724A (en) * 2019-12-10 2020-04-03 江西吉润花炮新材料科技有限公司 Thermal-stable indoor smokeless and sulfur-free cold firework setting-off chemical and preparation method thereof
CN111689824A (en) * 2020-07-08 2020-09-22 泸州北方化学工业有限公司 Thermosensitive wire and preparation method thereof
CN113912465A (en) * 2021-10-14 2022-01-11 长沙士象消防科技有限公司 Moisture-proof and waterproof thermosensitive wire and preparation method thereof

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