CN105218967B - A kind of liquid barium/zinc heat stabilizer, its preparation method and the equipment for implementing this method - Google Patents

A kind of liquid barium/zinc heat stabilizer, its preparation method and the equipment for implementing this method Download PDF

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CN105218967B
CN105218967B CN201510573459.5A CN201510573459A CN105218967B CN 105218967 B CN105218967 B CN 105218967B CN 201510573459 A CN201510573459 A CN 201510573459A CN 105218967 B CN105218967 B CN 105218967B
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barium
parts
zinc
acid
reactor
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CN105218967A (en
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李俭
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Guangzhou Yingsu New Material Technology Co Ltd
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Guangzhou Yingsu New Material Technology Co Ltd
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Abstract

The invention discloses a kind of liquid barium/zinc heat stabilizer, the liquid barium/zinc heat stabilizer includes the preparing raw material of following parts by weight:20 30 parts of the hydroxide of barium monoxide and/or barium, 15 20 parts of zinc oxide and/or zinc hydroxide, 30 40 parts of acid solution, 12 parts of azeotropic agent, 5 15 parts of 5 20 parts of saturation cyclic alkane solvents and heat resistance accessory, the hydroxide of barium is at least one of anhydrous barium hydroxide, barium monohydrate and barium hydroxide.The invention also discloses a kind of preparation method of liquid barium/zinc heat stabilizer and the equipment of implementation this method.The liquid barium of the present invention/zinc heat stabilizer properties of product are stable, and product has no irritating odor, and will not produce harm to the body of operator;The preparation method of liquid barium/zinc heat stabilizer of the present invention uses one-step method, simplifies production technology, reduces the unsafe factor of production process, improve production efficiency and output capacity.

Description

A kind of liquid barium/zinc heat stabilizer, its preparation method and the equipment for implementing this method
Technical field
The invention belongs to liquid stabilisers field, more particularly to a kind of liquid barium/zinc heat stabilizer, its preparation method and reality The equipment for applying this method.
Background technology
With the rise of PVC market, revolutionary change is experienced as the heat stabilizer of main processing aid.From industry The liquid barium cadmium zinc and barium cadmium cream heat stabilizer of the high grade of transparency are just widely used in during development, with European Union environmental protection requirement and Sony The rise of electric requirements, increasing country started the limitation to liquid barium cadmium zinc and barium cadmium cream heat stabilizer use or Disabling.So original widely used agricultural film, transparent sole, automatic foot-mat, high transparency toy material, slowly just by liquid Barium zinc heat stabilizer is substituted.
Production liquid barium zinc heat stabilizer typically uses complex multi-step method in the market, including feed intake, into salt, dehydration, These processes such as compound, press filtration, finished product packing.It has the disadvantage:First, production stage is cumbersome, complex process, including feeds intake, into salt, Dehydration, is combined, press filtration, finished product packing process, each process is completed in different equipment, and semi-finished product need to manually shift very numb It is tired;2nd, cycle production time is long, and energy consumption is big, wherein being particularly dehydrated, production process energy consumption is big twice for press filtration;3rd, high temperature production When there is substantial amounts of acid mist to be formed, equipment there is not closing production to endanger big to operating personnel;4th, in new formula new technology, no European Union prohibits The bisphenol-A and nonyl phenol only used, heat-stable time and processing characteristics have clear improvement with technique before.
The content of the invention
An object of the present invention is to provide a kind of liquid barium/zinc heat stabilizer, liquid barium/zinc heat stabilizer of the invention Properties of product are stable, will not have floccule precipitation during placing, product has no irritating odor, will not be to the body of operator Produce harm.
The technical solution adopted by the present invention is:A kind of liquid barium/zinc heat stabilizer, it is characterised in that:Liquid barium/the zinc Heat stabilizer includes the preparing raw material of following parts by weight:20-30 parts of the hydroxide of barium monoxide and/or barium, zinc oxide and/or hydrogen 15-20 parts of zinc oxide, 30-40 parts of acid solution, 1-2 parts of azeotropic agent, 5-20 parts of saturation cyclic alkane solvents and 5-15 parts of heat resistance accessory, barium Hydroxide at least one of for anhydrous barium hydroxide, barium monohydrate and barium hydroxide.
The solvent that existing liquid barium/zinc heat stabilizer is used is usually cycloalkane material, contains a certain amount of insatiable hunger And cycloalkane, this physical property is unstable, can decompose at a certain temperature.The solvent that the inventive method is used is saturation cycloalkanes Hydrocarbon, saturation cyclic alkane solvents can allow product property more to be stablized to a certain extent., will not and the properties of product of manufacture are stable There is floccule precipitation during placing, product has no irritating odor, harm will not be produced to the body of operator.
As the further improvement to above-mentioned technical proposal, the acid solution is oleic acid, and stearic acid, isooctyl acid, benzoic acid is right One or more in p t butylbenzoic acid, m-methyl benzoic acid, certain herbaceous plants with big flowers acid, octanoic acid, citric acid, laurate.As to above-mentioned skill The further improvement of art scheme, the acid solution be isooctyl acid, octanoic acid, aphthenic acids, benzoic acid, p-tert-butyl benzoic acid, oleic acid, At least one of phosphorous acid.Different acid solutions, synthesized monomer performance is also different, and several acid solutions selected above can make The monomer performance that must be synthesized is more preferably.
As the further improvement to above-mentioned technical proposal, the azeotropic agent be in ethylene glycol, methanol and glycerine extremely Few one kind.Azeotropic agent is used to promote moisture evaporation, promotes the progress of reaction.
As the further improvement to above-mentioned technical proposal, the saturation cyclic alkane solvents are glycerine, triethylene glycol, hexamethylene At least one of ketone, butanone, odorless kerosene, albefaction oil, deodorized kerosine.Saturation cyclic alkane solvents cost is than relatively low, with main body Stabilizer compatibility is good.
As the further improvement to above-mentioned technical proposal, the heat resistance accessory in the component of following parts by weight at least Two kinds:3-8 portions of soybean oils, 3-5 parts of phosphite esters, 2-4 parts of antioxidant, 2-4 parts of stearoyl benzoyl methanes, 1-3 parts of hexichol first At least two in acyl methane.Heat resistance accessory selected above, can be according to actual need in the role of PVC process difference Selected.
As the further improvement to above-mentioned technical proposal, the preparing raw material of the liquid barium/zinc heat stabilizer is also included 0.5-1 parts of catalyst, catalyst is at least one of formic acid, acetic acid, propionic acid.Catalyst can promote reaction to carry out, and make reaction More preferably, performance is more stable for finished color and gloss out.
The second object of the present invention is to provide a kind of preparation method of liquid barium/zinc heat stabilizer, and this method passes through simplification Technique, optimization of C/C composites, science control order and temperature of each raw material hybrid reaction etc., can be in short period, the life of Environmental Safety Output product.
The technical solution adopted by the present invention is:A kind of preparation method of liquid barium/zinc heat stabilizer, comprises the following steps:
A, the acid solution is added into reactor, cover reactor lid, agitating and heating acid solution;
B, when acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution The zinc oxide and/or zinc hydroxide and the azeotropic agent are added after thing, 20-30min, while controlling reaction solution in reactor Temperature is 110-120 DEG C of constant temperature;
C, when temperature remains 110-120 DEG C, add the saturation cyclic alkane solvents;
The heat resistance accessory is added after D, reaction completely, that is, the liquid barium/zinc heat stabilizer is made.
In the above-mentioned technical solutions, in step B, why acid liquor temperature rises to 95~100 DEG C, is because only that anti-herein Answer in temperature, the transparency and glossiness that finished product is made are optimal.After the hydroxide that barium monoxide and/or barium are added into acid solution, Because the reaction of acid solution and barium monoxide and/or the hydroxide of barium is exothermic reaction, therefore the temperature of reactor gradually rises, when When temperature rises to more than 120 DEG C, it is unfavorable for zinc oxide and/or zinc hydroxide with acid liquid reaction, it is necessary to condense cooling, finally makes temperature Degree control is at 110-120 DEG C.When temperature is 110-120 DEG C, optimum zinc oxide and/or zinc hydroxide and acid liquid reaction are too high Or too low temperature is unfavorable for this reaction, and at a temperature of this acid solution activity it is most strong, the finished product background color that reflects preferably, Properties of product are most reliable.Preferably, controlled by interior cooling coil and temperature control device built-in in reactor anti-in reactor It is 110-120 DEG C of constant temperature to answer liquid temperature degree.
In the above-mentioned technical solutions, the reaction equation that step B is related to is:
Prepare the metallic soap of barium (by taking barium hydroxide as an example):
Ba(OH)2+ 2RCOOH====Ba (COOH)2R2+H2O
Wherein, RCOOH is probably oleic acid, stearic acid, isooctyl acid, benzoic acid, p-tert-butyl benzoic acid, a methylbenzene first One or more in acid, certain herbaceous plants with big flowers acid, octanoic acid, citric acid, laurate.
Prepare the metallic soap of zinc (by taking zinc oxide as an example):
ZnO+2RCOOH====Zn (COOH)2R2+H2O
Wherein, RCOOH is probably oleic acid, stearic acid, isooctyl acid, benzoic acid, p-tert-butyl benzoic acid, a methylbenzene first One or more in acid, certain herbaceous plants with big flowers acid, octanoic acid, citric acid, laurate.
Existing production method usually first synthesizes each element monomers, is finally combined each composition or semi-finished product, is dehydrated, presses Filter, packaging.And the present invention is then that product can be directly generated in same equipment by Integration Method, it is to avoid half in production process Finished product manually need to be transferred in distinct device.
Prior art needs to be dehydrated and press filtration, the water of reaction generation could be removed, elapsed time is long, and energy consumption is big, and this Inventive method controls to add order and reaction temperature of each raw material progress hybrid reaction etc. by science, coordinates and adds azeotropic agent, Just can be in the short period, Environmental Safety produces finished product.
As the further improvement to above-mentioned technical proposal, the preparation method of the liquid barium/zinc heat stabilizer include with Lower step:
A, into the jacket type stainless steel cauldron provided with heating furnace device, agitator, interior cooling coil and temperature control device The acid solution is added, the thermal medium of kettle outer wall and kettle the inwall formation of reactor, which is held, is contained with oil in area, filled using heating furnace Heating oil is put, kettle inwall transfers heat to acid solution, while stirring acid solution using agitator, mix frequency for 15-20HZ/min;
B, when acid liquor temperature rises to 95-100 DEG C, 25-30 parts of barium monohydrates or eight water are slowly added into acid solution 15-18 parts of zinc oxide and the azeotropic agent are added after barium hydroxide, 30min, while being reacted in temperature control device control reactor Liquid temperature degree is 110-120 DEG C of constant temperature;
C, when temperature remains 110-120 DEG C, add the saturation cyclic alkane solvents;
The heat resistance accessory is added after D, reaction completely, that is, the liquid barium/zinc heat stabilizer is made.
In the step A, oil bath is carried out in jacket type stainless steel cauldron, and because steel plate transfers heat to material, centre has Individual thermal losses, therefore because when temperature must reach certain value, material can be only achieved anti-in the temperature needed for reaction, the present invention Answer kettle oil bath temperature is default to be heated to 135~150 DEG C, preferably 140 DEG C.
As the further improvement to above-mentioned technical proposal, the step B is:
When acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, It is subsequently added after 0.5-1 parts of catalyst, 20-30min and adds the zinc oxide and/or zinc hydroxide and the azeotropic agent, together When control in reactor reacting liquid temperature to be 110-120 DEG C of constant temperature;Or
When acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, The zinc oxide and/or zinc hydroxide and the azeotropic agent are added after 20-30min, continues to heat after 10-15min adding 0.5-1 parts of catalyst, while controlling reacting liquid temperature in reactor to be 110-120 DEG C of constant temperature;Or
When acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, It is subsequently added after 0.3-0.5 parts of catalyst, 20-30min and adds the zinc oxide and/or zinc hydroxide and the azeotropic agent, Continue to heat and 0.2-0.7 parts of catalyst are added after 10-15min, while controlling reacting liquid temperature in reactor to be 110-120 DEG C of perseverance Temperature.
The third object of the present invention is to provide a kind of equipment for the preparation method for implementing liquid barium/zinc heat stabilizer, and this sets It is standby to have significant effect to the control of reaction temperature and the formation of acid mist, directly it can generate product in same equipment.
The technical solution adopted by the present invention is:A kind of equipment for the preparation method for implementing liquid barium/zinc heat stabilizer, including Reactor and lid, lid located at reactor top and with reactor airtight connection;Reactor is jacket structured, and it includes interval The kettle outer wall and kettle inwall of setting, area is held between kettle outer wall and kettle inwall for thermal medium;The inner side of kettle inwall is provided with interior cooling Coil pipe, agitator and temperature element, the axis of agitator are overlapped with the axis of reactor, and agitator is under the drive of motor Rotate;Reactor is externally provided with the heating furnace device for heating thermal medium.
As the further improvement to above-mentioned technical proposal, the reactor is stainless steel cauldron, and use is additionally provided with thereon In the temperature control device of control reactor temperature.
As the further improvement to above-mentioned technical proposal, pressure gauge or rupture disk device are installed on the reactor.
As the further improvement to above-mentioned technical proposal, magnetic coupling is in series between the motor and agitator.
As the further improvement to above-mentioned technical proposal, the agitator is propeller agitator.
Relative to prior art, beneficial effects of the present invention are:
The solvent used in liquid barium/zinc heat stabilizer of the present invention is saturation cycloalkane, and saturation cyclic alkane solvents are one Determine product property can be allowed more to stablize in degree.And the properties of product of manufacture are stable, will not there is floccule analysis during placing Go out, product has no irritating odor, harm will not be produced to the body of operator.
The preparation method of liquid barium/zinc heat stabilizer of the present invention uses one-step method, simplifies production technology, reduces life The unsafe factor of production process, improves production efficiency and output capacity.
The preparation method of liquid barium/zinc heat stabilizer of the present invention is used in totally enclosed reactor and kept the safety in production, production Cycle is short, simple to operate, and due to reducing reaction temperature, the acid mist for reacting generation is small, and energy consumption is small, can reach large-scale production Purpose.
The preparation method of liquid barium/zinc heat stabilizer of the present invention can be generated directly by Integration Method in same equipment Product, it is to avoid semi-finished product manually need to be transferred in distinct device in production process.Each raw material is added by science control to be mixed Order and reaction temperature etc. of reaction are closed, coordinates and adds azeotropic agent, just can be in the short period, Environmental Safety produces finished product.
The equipment of the preparation method of implementation liquid barium/zinc heat stabilizer of the present invention is controlled to reaction temperature can be effective The formation of acid mist is reduced, then coordinates addition azeotropic agent, product can be finally produced within a short period of time, and can be directly same Product is generated in equipment.
Brief description of the drawings
Fig. 1 is the cross section view of the equipment for the preparation method for implementing liquid barium/zinc heat stabilizer.
Embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention It is described further.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention, following reality NM specific experiment method in example is applied, is generally carried out according to normal experiment method.
A kind of equipment of the preparation method of implementation liquid barium/zinc heat stabilizer as shown in Figure 1, including reactor 5 and lid Body 4, lid 4 located at the top of reactor 5 and with the airtight connection of reactor 5;Reactor 5 is that stainless steel is jacket structured, between it includes Every the kettle outer wall and kettle inwall of setting, area is held for thermal medium between kettle outer wall and kettle inwall, thermal medium holds in area and is contained with Oil;The inner side of kettle inwall is provided with interior cooling coil 6, agitator 7 and temperature element 2, axis and the reactor 5 of agitator 7 Axis is overlapped, and agitator 7 is rotated under the drive of motor 9;Reactor 5 is externally provided with the heating furnace device 8 for heating oil;Instead Answer the temperature control device and pressure gauge/rupture disk device 3 being additionally provided with kettle 5 for controlling reactor temperature, motor 9 and agitator Magnetic coupling 1 is in series between 7, agitator 7 is propeller agitator.Liquid barium/zinc heat stabilizer in following examples Preparation method is implemented in this device.
Embodiment 1
A kind of liquid barium/zinc heat stabilizer, includes the preparing raw material of following parts by weight:28 parts of barium monohydrate, oxidation 15 parts of zinc, 33 parts of acid solution, 1 part of catalyst, 2 parts of azeotropic agent, 18 parts of saturation cyclic alkane solvents, 10 parts of heat resistance accessory;
Wherein, acid solution is 5 parts of isooctyl acids, 10 parts of octanoic acids, 5 parts of oleic acid, 10 parts of p-tert-butyl benzoic acids and 3 parts of benzoic acid Mixture, catalyst is the mixture of 0.3 part of acetic acid and 0.7 part of formic acid, and azeotropic agent is the mixing of 1 part of ethylene glycol and 1 part of methanol Thing, saturation cyclic alkane solvents are the mixture of 3 parts of glycerine, 2 parts of butanone, 8 parts of odorless kerosenes and 5 parts of albefaction oil, heat resistance accessory For 5 portions of soybean oils and the mixture of 5 parts of phosphite esters.
A kind of preparation method of liquid barium/zinc heat stabilizer, comprises the following steps:
101st, the oil bath temperature of reactor is preset and is heated to 140 DEG C, 33 parts of acid solutions are added in a kettle., reaction is covered Kettle cover body, opens agitating and heating temperature to 95 DEG C, stirring frequency is 15Hz per minute;
102nd, when being slowly added into 28 parts of barium monohydrates after 95 DEG C of fluid temperature arrival in reactor, reaction is violent, mistake 15 parts of zinc oxide and 2 parts of azeotropic agents are added after 30 minutes;Continue to add 1 part of catalyst, same time control after heating 10 minutes Fluid temperature is 120 DEG C of constant temperature in reactor processed;
103rd, when equitemperature remains 120 DEG C, 18 parts of saturation cyclic alkane solvents are added;
104th, 10 parts of heat resistance accessories are continuously added after the completion of reacting, that is, the liquid barium/zinc heat stabilizer is made.
In a step 101, oil bath is carried out in jacket type stainless steel cauldron, and because steel plate transfers heat to material, centre has Individual thermal losses, therefore because when temperature must reach certain value, material can be only achieved the temperature needed for reaction.
Embodiment 2
A kind of liquid barium/zinc heat stabilizer, includes the preparing raw material of following parts by weight:30 parts of barium monohydrate, oxidation 17 parts of zinc, 38 parts of acid solution, 1 part of catalyst, 1 part of azeotropic agent, 5 parts of saturation cyclic alkane solvents, 5 parts of heat resistance accessory;
Wherein, acid solution is 38 parts of oleic acid, and catalyst is 1 part of propionic acid, and azeotropic agent is 1 part of ethylene glycol, saturation cyclic alkane solvents For 5 parts of deodorized kerosines, heat resistance accessory is 2 parts of SBM and 3 part of DBM mixture.
A kind of preparation method of liquid barium/zinc heat stabilizer, comprises the following steps:
201st, the oil bath temperature of reactor is preset and is heated to 140 DEG C, 38 parts of acid solutions are added in a kettle., reaction is covered Kettle cover body, opens agitating and heating temperature to 95 DEG C, stirring frequency is 18Hz per minute;
202nd, when being slowly added into 30 parts of barium monohydrates after 95 DEG C of fluid temperature arrival in reactor, reaction is violent, with 0.3 part of catalyst is added afterwards, and 17 parts of zinc oxide and 1 part of azeotropic agent are added after spending 20 minutes;Continue after heating 10 minutes Add 0.7 part of catalyst;
203rd, it is 115 DEG C of constant temperature to control fluid temperature in reactor, when equitemperature remains 115 DEG C, adds 5 parts of saturated rings Alkane solvent;
204th, 5 parts of heat resistance accessories are continuously added after the completion of reacting, that is, the liquid barium/zinc heat stabilizer is made.
In step 201, oil bath is carried out in jacket type stainless steel cauldron, and because steel plate transfers heat to material, centre has Individual thermal losses, therefore because when temperature must reach certain value, material can be only achieved the temperature needed for reaction.
Embodiment 3
A kind of liquid barium/zinc heat stabilizer, includes the preparing raw material of following parts by weight:30 parts of barium monohydrate, oxidation 15 parts of zinc, 40 parts of acid solution, 1 part of catalyst, 1 part of azeotropic agent, 8 parts of saturation cyclic alkane solvents, 5 parts of heat resistance accessory;
Wherein, acid solution is the mixture of 18 parts of isooctyl acids and 22 parts of p-tert-butyl benzoic acids, catalyst be 0.5 part of acetic acid, The mixture of 0.2 part of formic acid and 0.3 part of propionic acid, azeotropic agent is 1 part of methanol, and saturation cyclic alkane solvents are 3 parts of triethylene glycols and 5 parts of rings The mixture of hexanone, heat resistance accessory is the mixture of 2 portions of soybean oils and 2 parts of phosphite ester esters and 1 part of antioxidant.
A kind of preparation method of liquid barium/zinc heat stabilizer, comprises the following steps:
301st, the oil bath temperature of reactor is preset and is heated to 140 DEG C, 40 parts of acid solutions are added in a kettle., reaction is covered Kettle cover body, opens agitating and heating temperature to 95 DEG C, stirring frequency is 15Hz per minute;
302nd, when being slowly added into 30 parts of barium monohydrates after 95 DEG C of fluid temperature arrival in reactor, reaction is violent, mistake 15 parts of zinc oxide and 1 part of azeotropic agent are added after 30 minutes;Continue to add 1 part of catalyst after heating 10 minutes;
303rd, it is 120 DEG C of constant temperature to control fluid temperature in reactor, when equitemperature remains 120 DEG C, adds 8 parts of saturated rings Alkane solvent;
304th, 5 parts of heat resistance accessories are continuously added after the completion of reacting, that is, the liquid barium/zinc heat stabilizer is made.
In step 301, oil bath is carried out in jacket type stainless steel cauldron, and because steel plate transfers heat to material, centre has Individual thermal losses, therefore because when temperature must reach certain value, material can be only achieved the temperature needed for reaction.
Embodiment 4
A kind of liquid barium/zinc heat stabilizer, includes the preparing raw material of following parts by weight:20 parts of anhydrous barium hydroxide, oxidation 15 parts of zinc, 32 parts of acid solution, 0.5 part of catalyst, 1.5 parts of azeotropic agent, 20 parts of saturation cyclic alkane solvents, 15 parts of heat resistance accessory;
Wherein, acid solution is 32 parts of octanoic acids, and catalyst is 0.5 part of acetic acid, and azeotropic agent is 1.5 parts of ethylene glycol, saturation cycloalkane Solvent is 20 parts of triethylene glycols, and heat resistance accessory is the mixture of 8 portions of soybean oils, 4 parts of antioxidant and 3 parts of DBM.
A kind of preparation method of liquid barium/zinc heat stabilizer, comprises the following steps:
401st, the oil bath temperature of reactor is preset and is heated to 140 DEG C, 32 parts of acid solutions are added in a kettle., reaction is covered Kettle cover body, opens agitating and heating temperature to 95 DEG C, stirring frequency is 15Hz per minute;
402nd, when being slowly added into 20 parts of anhydrous barium hydroxides after 95 DEG C of fluid temperature arrival in reactor, reaction is violent, mistake 15 parts of zinc oxide and 1.5 parts of azeotropic agents are added after 30 minutes;Continue to add 0.5 part of catalyst after heating 10 minutes;
403rd, it is 120 DEG C of constant temperature to control fluid temperature in reactor, when equitemperature remains 120 DEG C, adds 20 parts of saturations Cyclic alkane solvents;
404th, 15 parts of heat resistance accessories are continuously added after the completion of reacting, that is, the liquid barium/zinc heat stabilizer is made.
In step 401, oil bath is carried out in jacket type stainless steel cauldron, and because steel plate transfers heat to material, centre has Individual thermal losses, therefore because when temperature must reach certain value, material can be only achieved the temperature needed for reaction.
To the liquid barium/zinc heat stabilizer obtained in embodiment 1~4 by the preparation method of liquid barium/zinc heat stabilizer Enter heat-resisting Mobile state, static roasting piece, Congo red test, result of the test is as follows.
Dynamic is heat-resisting The roasting piece of static state It is Congo red
Criterion of acceptability 50min 50min 50min
Embodiment 1 78min 80min 68min
Embodiment 2 70min 75min 65min
Embodiment 3 65min 82min 63min
Embodiment 4 68min 73min 65min
As seen from the above table, the dynamic of liquid barium/zinc heat stabilizer of the invention is heat-resisting, static roasting piece, Congo red test knot Fruit exceedes criterion of acceptability 50min, and performance is stable, superior.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the technical principles of the invention, some improvement and replacement can also be made, these improve and replaced Also it should be regarded as protection scope of the present invention.

Claims (8)

1. a kind of liquid barium/zinc heat stabilizer, it is characterised in that:Liquid barium/the zinc heat stabilizer includes following parts by weight Preparing raw material:15-20 parts of 20-30 parts of the hydroxide of barium monoxide and/or barium, zinc oxide and/or zinc hydroxide, acid solution 30-40 5-15 parts of part, 1-2 parts of azeotropic agent, 5-20 parts of solvent and heat resistance accessory, the hydroxide of barium is anhydrous barium hydroxide, a water hydrogen-oxygen Change at least one of barium and barium hydroxide;The solvent be glycerine, triethylene glycol, cyclohexanone, butanone, odorless kerosene, At least one of deodorized kerosine;The heat resistance accessory is at least two in the component of following parts by weight:2-8 portions of soybean oils, At least two in 2-5 parts of phosphite esters, 1-4 parts of antioxidant, 2-4 parts of stearoyl benzoyl methanes, 1-3 parts of dibenzoyl methanes Kind;
The preparation method of the liquid barium/zinc heat stabilizer, comprises the following steps:
A, the acid solution is added into reactor, cover reactor lid, agitating and heating acid solution;
B, when acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, The zinc oxide and/or zinc hydroxide and the azeotropic agent are added after 20-30min, while controlling to react liquid temperature in reactor Spend for 110-120 DEG C of constant temperature;
C, when temperature remains 110-120 DEG C, add the solvent;
The heat resistance accessory is added after D, reaction completely, that is, the liquid barium/zinc heat stabilizer is made.
2. liquid barium/zinc heat stabilizer as claimed in claim 1, it is characterised in that:The acid solution is isooctyl acid, octanoic acid, ring At least one of alkanoic acid, benzoic acid, p-tert-butyl benzoic acid, oleic acid, phosphorous acid.
3. liquid barium/zinc heat stabilizer as claimed in claim 1, it is characterised in that:The azeotropic agent be ethylene glycol, methanol and At least one of glycerine.
4. liquid barium/zinc heat stabilizer as claimed in claim 1, it is characterised in that:The system of the liquid barium/zinc heat stabilizer Standby raw material is also comprising 0.5-1 parts of catalyst, and catalyst is at least one of formic acid, acetic acid, propionic acid.
5. the preparation method of liquid barium/zinc heat stabilizer as described in any claim in claim 1 ~ 4, its feature exists In:Comprise the following steps:
A, the acid solution is added into reactor, cover reactor lid, agitating and heating acid solution;
B, when acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, The zinc oxide and/or zinc hydroxide and the azeotropic agent are added after 20-30min, while controlling to react liquid temperature in reactor Spend for 110-120 DEG C of constant temperature;
C, when temperature remains 110-120 DEG C, add the solvent;
The heat resistance accessory is added after D, reaction completely, that is, the liquid barium/zinc heat stabilizer is made.
6. the preparation method of liquid barium/zinc heat stabilizer as claimed in claim 5, it is characterised in that:Comprise the following steps:
A, add into the jacket type stainless steel cauldron provided with heating furnace device, agitator, condenser and temperature control device it is described Acid solution, the thermal medium of kettle outer wall and kettle the inwall formation of reactor, which is held, is contained with oil in area, oil is heated using heating furnace device, Kettle inwall transfers heat to acid solution, while stirring acid solution using agitator, stirring frequency is 15-20HZ;
B, when acid liquor temperature rises to 95-100 DEG C, 25-30 parts of barium monohydrates or eight water hydrogen-oxygens are slowly added into acid solution Change 15-18 parts of zinc oxide of addition and the azeotropic agent after barium, 30min, while reacting liquid temperature in temperature control device control reactor Spend for 110-120 DEG C of constant temperature;
C, when temperature remains 110-120 DEG C, add the solvent;
The heat resistance accessory is added after D, reaction completely, that is, the liquid barium/zinc heat stabilizer is made.
7. the preparation method of liquid barium/zinc heat stabilizer as claimed in claim 5, it is characterised in that:The step B is:
When acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, then The zinc oxide and/or zinc hydroxide and the azeotropic agent, same time control are added after 0.5-1 parts of catalyst of addition, 20-30min Reacting liquid temperature is 110-120 DEG C of constant temperature in reactor processed;Or
When acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium, 20- are slowly added into acid solution The zinc oxide and/or zinc hydroxide and the azeotropic agent are added after 30min, continues to add 0.5-1 after heating 10-15min Part catalyst, while controlling reacting liquid temperature in reactor to be 110-120 DEG C of constant temperature;Or
When acid liquor temperature rises to 95-100 DEG C, the hydroxide of the barium monoxide and/or barium is slowly added into acid solution, then The zinc oxide and/or zinc hydroxide and the azeotropic agent are added after 0.3-0.5 parts of catalyst of addition, 20-30min, is continued Heat and 0.2-0.7 parts of catalyst are added after 10-15min, while controlling reacting liquid temperature in reactor to be 110-120 DEG C of constant temperature.
8. the preparation method of liquid barium/zinc heat stabilizer as claimed in claim 5, it is characterised in that:Methods described is by setting Standby to implement, the equipment includes reactor and lid, lid located at reactor top and with reactor airtight connection;Reactor is Jacket structured, it includes spaced kettle outer wall and kettle inwall, and area is held for thermal medium between kettle outer wall and kettle inwall;In kettle The inner side of wall is provided with interior cooling coil, agitator and temperature element, and the axis of agitator overlaps with the axis of reactor, stirred Device is mixed to rotate under the drive of motor;Reactor is externally provided with the heating furnace device for heating thermal medium.
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CN106397831B (en) * 2016-08-31 2019-02-05 湖北犇星化工有限责任公司 A kind of liquid barium zinc heat stabilizer and the preparation method and application thereof
CN107057220B (en) * 2017-04-18 2019-07-30 天津科技大学 A kind of PVC transparent composite thermal stabilizer of liquid barium/zinc
CN107442052A (en) * 2017-08-30 2017-12-08 卢敏 A kind of chemical reaction kettle of high-efficiency stirring
CN107903439A (en) * 2017-11-27 2018-04-13 南通新邦化工科技有限公司 A kind of method of One-step production barium zinc stabilizer
CN109294120A (en) * 2018-10-07 2019-02-01 德清县东来化学有限公司 A kind of compound barium-zinc liquid stabilizer and preparation method thereof
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