CN116693760A - Butyronitrile latex and preparation method and application thereof - Google Patents
Butyronitrile latex and preparation method and application thereof Download PDFInfo
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- CN116693760A CN116693760A CN202310987615.7A CN202310987615A CN116693760A CN 116693760 A CN116693760 A CN 116693760A CN 202310987615 A CN202310987615 A CN 202310987615A CN 116693760 A CN116693760 A CN 116693760A
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- 239000004816 latex Substances 0.000 title claims abstract description 35
- 229920000126 latex Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 179
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 63
- 150000002825 nitriles Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000012544 monitoring process Methods 0.000 claims abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 17
- 239000012498 ultrapure water Substances 0.000 claims description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000012546 transfer Methods 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 37
- 230000008569 process Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 16
- 239000000499 gel Substances 0.000 description 13
- 239000004568 cement Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 230000001133 acceleration Effects 0.000 description 7
- 238000007872 degassing Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a nitrile latex, a preparation method and application thereof, and relates to the technical field of synthetic latex. The preparation method comprises mixing water phase and oil phase in a reaction vessel and heating; when the material is heated to 36-38 ℃, an initiator is added to start the polymerization reaction; monitoring the pressure, temperature and rotating speed in the reaction container, increasing the pressure in the reaction container by 0.01-0.2Mpa, reducing the temperature by 1-3 ℃, increasing the rotating speed by 10-20rpm, carrying out the reaction for 1.5-2.5h, then increasing the polymerization temperature by 1-3 ℃ per hour, reducing the rotating speed by 10-20rpm, keeping the pressure unchanged, continuing the reaction until the target conversion rate is reached, and ending the polymerization. According to the preparation method, the polymerization temperature is reduced, the rotation speed and the pressure are increased in the middle and later stages of polymerization, so that the wall-mounted adhesive of the reaction kettle can be improved, the heat transfer efficiency of the reaction kettle is improved, and the service cycle of the reaction kettle is prolonged; reducing gel generation during polymerization.
Description
Technical Field
The application relates to the technical field of synthetic latex, in particular to a nitrile latex and a preparation method and application thereof.
Background
The carboxylated nitrile latex is a polymer rubber obtained by copolymerizing butadiene, acrylonitrile and methacrylic acid or acrylic acid. Because the carboxyl nitrile rubber molecular chain contains carboxyl and cyano polar groups, the carboxyl nitrile rubber has good mechanical property, heat resistance, wear resistance and good chemical reagent resistance, and is widely applied to the fields of impregnating gloves, carpets, sealing rings, brake pads and the like. However, the production of carboxylated butyronitrile by emulsion polymerization is easy to be in an unstable state, so that wall-hanging glue of a reaction kettle is caused, heat transfer is affected, and adverse effects are caused on the reaction.
Patent CN 113980180A discloses a continuous production process of carboxylated nitrile latex, which adopts a continuous polymerization process, improves the utilization rate of equipment, reduces the times of cleaning a kettle in continuous production, and reduces the generation of waste water and the discharge of waste residues. However, the problem of pot hanging and gelling during batch polymerization has not been solved well. Therefore, it is very significant to solve the problem of gel in the batch polymerization reaction kettle wall-hanging gel and the polymerization process.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a nitrile latex and a preparation method and application thereof.
The application is realized in the following way:
in a first aspect, the present application provides a process for preparing a nitrile latex comprising:
mixing and heating a water phase and an oil phase in a reaction container, wherein the water phase comprises, by weight, 1.2-1.5 parts of sodium dodecyl benzene sulfonate, 0.07-0.12 part of a dispersing agent, 0.02-0.05 part of EDTA-tetrasodium and 15-20 parts of ultrapure water; the oil phase comprises 13-15 parts of acrylonitrile, 2-3 parts of methacrylic acid, 0.2-0.3 part of tertiary dodecyl mercaptan and 32-35 parts of butadiene in parts by weight;
when the material is heated to 36-38 ℃, an initiator is added to start the polymerization reaction;
when the conversion rate of the system reaches 65% -70%, monitoring the pressure, temperature and rotating speed in the reaction vessel, increasing the pressure in the reaction vessel by 0.01-0.2Mpa, reducing the temperature by 1-3 ℃, increasing the rotating speed by 10-20rpm, carrying out reaction for 1.5-2.5h, then increasing the polymerization temperature by 1-3 ℃ per hour, reducing the rotating speed by 10-20rpm, keeping the pressure unchanged, continuing the reaction until the target conversion rate is reached, and ending the polymerization.
In an alternative embodiment, after initiation of the polymerization reaction, the temperature is controlled at 36-38℃and the rotation speed is controlled at 65-75rpm, after 4-6 hours of reaction, the temperature is raised to 39-40℃to continue the reaction.
In an alternative embodiment, when the system conversion rate reaches 65% -70%, the pressure in the reaction vessel is increased by 0.01-0.2Mpa, the reaction is carried out for 1.5-2.5h under the conditions that the polymerization temperature is 36-38 ℃ and the rotating speed is 80-90rpm, then the polymerization temperature is increased by 1-3 ℃ per hour, the rotating speed is adjusted to 65-75rpm, the pressure is kept unchanged, the reaction is continued until the target conversion rate is reached, and the polymerization is ended;
preferably, when the conversion rate of the system reaches 65% -70%, the pressure in the reaction vessel is increased by 0.01-0.2Mpa, the reaction is carried out for 2 hours under the conditions that the polymerization temperature is 36 ℃ and the rotating speed is 80-90rpm, then the polymerization temperature is increased by 2 ℃ per hour, the rotating speed is adjusted to 70rpm, the pressure is kept unchanged, the reaction is continued until the target conversion rate is reached, and the polymerization is ended.
In an alternative embodiment, the step of mixing and heating the aqueous phase and the oil phase within the reaction vessel comprises: firstly, carrying out nitrogen replacement on the reaction vessel, vacuumizing to-0.11 to-0.07 Mpa after the replacement, then adding all components in the water phase and acrylonitrile, methacrylic acid and tert-dodecyl mercaptan in the oil phase, stirring and mixing at the rotating speed of 65-75rpm, then carrying out nitrogen replacement, vacuumizing to-0.11 to-0.07 Mpa after the replacement is completed, and heating after butadiene in the oil phase is added.
In an alternative embodiment, the initiator comprises, in parts by weight, 0.1 to 0.2 parts of potassium persulfate and 4 to 6 parts of ultrapure water.
In a second aspect, the present application provides a nitrile latex prepared by the method for preparing a nitrile latex according to any of the previous embodiments.
In a third aspect, the present application provides the use of the nitrile latex according to the previous embodiments for the preparation of dipped gloves, carpets, sealing rings or brake pads.
The application has the following beneficial effects:
the preparation method of the nitrile latex provided by the application can reduce the automatic acceleration effect by reducing the polymerization temperature by 1-3 ℃ in the middle and later stages of polymerization, can improve the stirring speed by 10-20rpm, can improve the heat transfer effect, and can also reduce the automatic acceleration effect. On the basis of the existing pressure of the reaction kettle, the butadiene can be difficult to gasify by continuously increasing the pressure by 0.01-0.2Mpa, the generation of bubbles is inhibited, and the polymerized gel is reduced. The polymerization temperature, the stirring rate and the reaction pressure are adjusted to have synergistic effect, so that the wall-mounted adhesive of the reaction kettle can be improved, the heat transfer efficiency of the reaction kettle can be improved, and the service life and the service period of the reaction kettle can be prolonged; the gel generation in the polymerization process is reduced, and the reaction yield can be improved. The nitrile latex prepared by the preparation method of the nitrile latex has good stability and can be widely applied to the preparation of impregnated gloves, carpets, sealing rings or brake pads.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The application provides a preparation method of nitrile latex, which comprises the following steps:
s1, feeding.
The aqueous phase and the oil phase are mixed and heated in a reaction vessel.
The water phase comprises 1.2-1.5 parts by weight of sodium dodecyl benzene sulfonate, 0.07-0.12 part by weight of dispersing agent, 0.02-0.05 part by weight of EDTA-tetrasodium and 15-20 parts by weight of ultrapure water.
The oil phase comprises 13-15 parts of acrylonitrile, 2-3 parts of methacrylic acid, 0.2-0.3 part of tertiary dodecyl mercaptan and 32-35 parts of butadiene in parts by weight.
In the application, a reaction vessel (such as a reaction kettle) is firstly subjected to nitrogen replacement, then is vacuumized to-0.11 to-0.07 Mpa, then all components in an aqueous phase and acrylonitrile, methacrylic acid and tert-dodecyl mercaptan in an oil phase are added, stirring and mixing are carried out at the rotating speed of 65-75rpm, then the nitrogen replacement is carried out, after the replacement is completed, the vacuum is pumped to-0.11 to-0.07 Mpa, and the heating is started after butadiene in the oil phase is added.
S2, polymerization.
(1) When the temperature of the material is heated to 36-38 ℃, the pressure is gradually increased to positive pressure, about 0.2-0.25Mpa, and an initiator is added to start the polymerization reaction.
The initiator comprises, by weight, 0.1-0.2 part of potassium persulfate and 4-6 parts of ultrapure water. After initiating polymerization reaction, controlling the temperature to be 36-38 ℃, controlling the rotating speed to be 65-75rpm, reacting for 4-6 hours, and heating to 39-40 ℃ to continue the reaction.
(2) When the conversion rate of the system reaches 65% -70%, detecting the pressure, temperature and rotating speed of the reaction vessel, on the basis, increasing the pressure of the reaction vessel by 0.01-0.2Mpa, reducing the temperature by 1-3 ℃, increasing the rotating speed by 10-20rpm, carrying out the reaction for 1.5-2.5h, then increasing the polymerization temperature by 1-3 ℃ per hour, reducing the rotating speed by 10-20rpm, keeping the pressure unchanged, continuing the reaction until the target conversion rate is reached, and ending the polymerization.
Specifically, the pressure of the reaction vessel is increased by 0.01-0.2Mpa, the reaction is carried out for 1.5-2.5h under the conditions that the polymerization temperature is 36-38 ℃ and the rotating speed is 80-90rpm, then the polymerization temperature is increased by 1-3 ℃ per hour, the rotating speed is adjusted to 65-75rpm, the pressure is kept unchanged, the reaction is continued until the target conversion rate is reached, and the polymerization is ended.
Preferably, when the conversion rate of the system reaches 65% -70%, the pressure of the reaction vessel is detected, on the basis, the pressure of the reaction vessel is increased by 0.01-0.2Mpa, the reaction is carried out for 2 hours under the conditions that the polymerization temperature is 36 ℃ and the rotating speed is 80-90rpm, then the polymerization temperature is increased by 2 ℃ per hour, the rotating speed is adjusted to 70rpm, the pressure is kept unchanged, the reaction is continued until the target conversion rate is reached, and the polymerization is ended.
S3, degassing.
When the reaction reaches the target conversion rate, the polymerization is finished, the latex is transferred into a degassing kettle, and degassing, blending and converting are carried out according to requirements.
The research of the application discovers that the viscosity of the polymer in the middle-late colloidal particles of emulsion polymerization is increased, so that the automatic acceleration effect exists, the reaction rate is fast, and the problem of severe heat release occurs. If the heat can not be timely dispersed, the local heating is uneven, so that butadiene in the system is gasified, a large number of bubbles are generated in the reaction kettle, the generated large number of bubbles can influence the heat transfer efficiency of the reaction kettle, and the problem of reaction runaway is easy to occur. In addition, the generated foam is extremely unstable, and a large amount of gel is generated in the foam breaking process, so that the reaction kettle is coated with the gel.
Therefore, the application reduces the polymerization temperature from the initial 39-40 ℃ to 36-38 ℃ in the middle and later stages of polymerization, can reduce the automatic acceleration effect, and the stirring speed is increased from the initial 65-75rpm to 80-90rpm, so that the heat transfer effect can be improved, and the automatic acceleration effect can also be reduced. On the basis of the existing pressure of the reaction kettle, the pressure is continuously increased by 0.01-0.2Mpa, butadiene can be difficult to gasify through the increase of the pressure, the generation of bubbles is inhibited, and the polymerized gel is reduced. The polymerization temperature, the stirring rate and the reaction pressure are adjusted to have synergistic effect, so that the wall-mounted adhesive of the reaction kettle can be improved, the heat transfer efficiency of the reaction kettle can be improved, and the service life and the service period of the reaction kettle can be prolonged; the gel generation in the polymerization process is reduced, and the reaction yield can be improved.
The nitrile latex prepared by the preparation method of the nitrile latex has good stability and can be widely applied to the preparation of impregnated gloves, carpets, sealing rings or brake pads.
The features and capabilities of the present application are described in further detail below in connection with the examples.
The raw materials used in the examples and comparative examples of the present application were commercially available and had the following concentrations: 100% of ultrapure water, 99.8% of sodium dodecyl benzene sulfonate, 99.7% of dispersant NNO, 99.5% of EDTA-tetrasodium, 100% of ultrapure water, 99.8% of acrylonitrile, 99.6% of methacrylic acid, 99.8% of tertiary dodecyl mercaptan, 99.5% of butadiene and 99.2% of potassium persulfate.
Example 1
The embodiment provides a preparation method of nitrile latex, which comprises the following steps:
s1, proportioning: accurately weighing kettle bottom water, water phase, oil phase and initiator, wherein the kettle bottom water: 30 parts of ultrapure water. Aqueous phase: 1.2 parts of sodium dodecyl benzene sulfonate, 0.07 part of dispersant NNO, 0.02 part of EDTA-tetrasodium and 15 parts of ultrapure water; and (5) uniformly mixing in advance for later use. An oil phase: 13 parts of acrylonitrile, 2 parts of methacrylic acid, 0.2 part of tertiary dodecyl mercaptan and 32 parts of butadiene. And (3) an initiator: 0.1 part of potassium persulfate and 5 parts of ultrapure water are mixed uniformly in advance for standby.
S2, feeding: firstly, nitrogen replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.09 Mpa. Then adding the kettle bottom water into the reaction kettle, and simultaneously adding the acrylonitrile, the methacrylic acid and the tertiary dodecyl mercaptan into the water phase and the oil phase. And (3) starting the reaction kettle to stir, wherein the stirring speed is 70rpm, carrying out nitrogen displacement for three times, and vacuumizing to-0.09 Mpa after the displacement is completed. Butadiene is added into the reaction kettle, and the reaction kettle is heated after butadiene is added.
S3, polymerization: when the temperature of the materials in the reaction kettle reaches 37 ℃, an initiator is added into the reaction kettle to start the polymerization reaction, the temperature is controlled to be 37 ℃, the rotating speed is 70rpm, and the temperature is raised to 39 ℃ after the reaction is carried out for 5 hours to continue the reaction. When the conversion of the system reached 65-70%, the reaction was continued for 2 hours with the process parameters of Table 1, the pressure was maintained, the rotational speed was adjusted down to 70rpm, and the temperature was increased to 2℃per hour until the reaction was completed.
S4, degassing: when the reaction reaches the target conversion rate, the polymerization is finished, the latex is transferred into a degassing kettle, and degassing, blending and converting are carried out according to requirements.
Example 2
This example is essentially identical to example 1, except that the dosage during compounding and the process parameters at which the system conversion reaches 65-70% are different, wherein step S1 in example 2 is as follows, and the process parameters are as described in example 2 of Table 1.
S1, proportioning: accurately weighing kettle bottom water, water phase, oil phase and initiator, wherein the kettle bottom water: 45 parts of ultrapure water. Aqueous phase: 1.5 parts of sodium dodecyl benzene sulfonate, 0.12 part of dispersant NNO, 0.05 part of EDTA-tetrasodium and 20 parts of ultrapure water; and (5) uniformly mixing in advance for later use. An oil phase: 15 parts of acrylonitrile, 3 parts of methacrylic acid, 0.3 part of tertiary dodecyl mercaptan and 35 parts of butadiene. And (3) an initiator: 0.1 part of potassium persulfate and 5 parts of ultrapure water are mixed uniformly in advance for standby.
Example 3
This example is essentially identical to example 1, except that the dosage during the dosing and the process parameters at which the conversion of the system reaches 65 to 70% are different. Step S1 in example 3 is as follows, and the process parameters are shown in example 3 in table 1.
S1, proportioning: accurately weighing kettle bottom water, water phase, oil phase and initiator, wherein the kettle bottom water: 40 parts of ultrapure water. Aqueous phase: 1.3 parts of sodium dodecyl benzene sulfonate, 0.1 part of dispersant NNO, 0.04 part of EDTA-tetrasodium and 18 parts of ultrapure water; and (5) uniformly mixing in advance for later use. An oil phase: 14 parts of acrylonitrile, 2.5 parts of methacrylic acid, 0.25 part of tertiary dodecyl mercaptan and 33 parts of butadiene. And (3) an initiator: 0.1 part of potassium persulfate and 5 parts of ultrapure water are mixed uniformly in advance for standby.
Example 4
This example is essentially the same as example 1, except that the process parameters for achieving a system conversion of 65-70% are different, see example 4 in Table 1.
Example 5
This example is essentially the same as example 2, except that the process parameters are different when the system conversion reaches 65-70%, and the process parameters are shown in example 5 of Table 1.
Examples 6 to 9
This example is essentially the same as example 3, except that the process parameters for achieving a system conversion of 65-70% are different, see examples 6-9 in Table 1.
Example 10
This embodiment is substantially the same as embodiment 1, except that step S2 and step S3 are different.
S2, feeding: firstly, nitrogen replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to minus 0.011Mpa. Then adding the kettle bottom water into the reaction kettle, and simultaneously adding the acrylonitrile, the methacrylic acid and the tertiary dodecyl mercaptan into the water phase and the oil phase. And (3) starting the reaction kettle to stir, wherein the stirring speed is 75rpm, performing nitrogen displacement for three times, and vacuumizing to-0.011 Mpa after the displacement is completed. Butadiene is added into the reaction kettle, and the reaction kettle is heated after butadiene is added.
S3, polymerization: when the temperature of the materials in the reaction kettle reaches 38 ℃, an initiator is added into the reaction kettle to start the polymerization reaction, the temperature is controlled at 38 ℃, the rotating speed is 75rpm, and the temperature is raised to 39 ℃ after the reaction is carried out for 5 hours to continue the reaction. When the system conversion reached 65-70%, the reaction was continued for 2 hours under control of the process parameters of example 1 in Table 1, the pressure was maintained, and the rotation speed was adjusted down to 75rpm, and the temperature was raised to 1℃per hour until the reaction was completed.
Example 11
This embodiment is substantially the same as embodiment 1, except that step S2 and step S3 are different.
S2, feeding: firstly, nitrogen replacement is carried out on the reaction kettle, and after the replacement is finished, the reaction kettle is vacuumized to-0.07 Mpa. Then adding acrylonitrile, methacrylic acid and tertiary dodecyl mercaptan into the water phase and the oil phase. And (3) starting the reaction kettle to stir, wherein the stirring speed is 65 rpm, performing nitrogen displacement for three times, and vacuumizing to-0.07 Mpa after the displacement is completed. Butadiene is added into the reaction kettle, and the reaction kettle is heated after butadiene is added.
S3, polymerization: when the temperature of the materials in the reaction kettle reaches 36 ℃, an initiator is added into the reaction kettle to start the polymerization reaction, the temperature is controlled to 36 ℃, the rotating speed is 65 rpm, and the temperature is raised to 40 ℃ after the reaction is carried out for 5 hours to continue the reaction. When the system conversion reached 65-70%, the reaction was continued for 2 hours under control of the process parameters of example 1 in Table 1, the pressure was maintained, and the rotation speed was adjusted down to 65 rpm, and the temperature was raised to 3℃per hour until the reaction was completed.
TABLE 1 Process parameters Table within 2h after 65-70% conversion of the systems of examples 1-9
Comparative example 1
The comparative example was substantially the same as example 1 except that the process parameters were different when the system conversion reached 65 to 70%, and in the comparative example, when the system conversion reached 65 to 70%, the original pressure and stirring speed were maintained and the temperature was raised by 2℃per hour until the reaction was completed.
Comparative example 2
The comparative example was substantially the same as example 2 except that the process parameters were different when the system conversion reached 65 to 70%, and in the comparative example, when the system conversion reached 65 to 70%, the original pressure and stirring speed were maintained and the temperature was raised by 2℃per hour until the reaction was completed.
Comparative example 3
The comparative example was substantially the same as example 3 except that the process parameters were different when the system conversion reached 65 to 70%, and in the comparative example, when the system conversion reached 65 to 70%, the original pressure and stirring speed were maintained and the temperature was raised by 2℃per hour until the reaction was completed.
Comparative examples 4 to 9
Comparative examples 4 to 9 are substantially identical to example 1, except that the process parameters differ in that the system conversion reaches 65 to 70%, comparative example 4 adjusts only the temperature, comparative example 5 adjusts only the pressure, comparative example 6 adjusts only the rotational speed, comparative example 7 adjusts both the temperature and the pressure, comparative example 8 adjusts both the pressure and the rotational speed, and comparative example 9 adjusts both the temperature and the rotational speed, the adjustment being shown in table 2.
TABLE 2 Process parameters Table within 2h after 65-70% conversion of the systems of comparative examples 4-9
Comparative example 10
This comparative example is substantially identical to example 1, except that in this comparative example, the timing of adjusting the process parameters is changed from when the system conversion reaches 65 to 70% to when the system conversion reaches 50 to 55%.
Comparative example 11
This comparative example is substantially the same as example 1 except that in this comparative example, the timing of adjusting the process parameters is changed from when the system conversion rate reaches 65 to 70% to when the system conversion rate reaches 80 to 85%.
Comparative example 12
This comparative example was substantially the same as example 1 except that in this comparative example, when the conversion of the system reached 65 to 70%, the reaction was conducted at a speed of 150 rpm by adjusting the temperature to 34℃and the pressure to 0.3 MPa for 2 hours.
Experimental example
The preparation method provided by the above examples and comparative examples was carried out in a reaction kettle, and the reaction kettle cleaning cycle and the gum residue yield were tested, wherein the reaction kettle cleaning cycle refers to the number of kettles that can be continuously produced in the same reaction kettle. The gum residue yield refers to the weight of the filtration gel at the end of polymerization as a percentage of the total weight of the formulation, and is the average yield over one cycle. The test results are shown in table 3 below:
TABLE 3 statistical results of reactor cleaning cycle and gum yield for different examples
From the table, the preparation method provided by the application can obviously reduce the wall-mounted adhesive of the reaction kettle, improve the heat transfer efficiency of the reaction kettle and prolong the service life and the service cycle of the reaction kettle by starting the operations of cooling, boosting, increasing the rotating speed and the like of the reaction system at a specific node (when the system conversion rate reaches 65% -70%); the gel generation in the polymerization process is reduced, and the reaction yield can be improved.
Specifically, examples 1-3 show that when the ingredients and the process parameters are within the scope of the application, the service life and the service period of the reaction kettle can be prolonged, the cleaning period of the reaction kettle is longer, the wall-mounted adhesive of the reaction kettle can be obviously reduced, and the adhesive residue yield is low.
Comparing example 1 with example 4, it can be seen that the rotation speed is reduced under the condition of the same temperature and pressure, and this is more beneficial to prolonging the cleaning period of the reaction kettle and reducing the yield of the gumming residue.
Comparing example 2 with example 5, it can be seen that example 5 has a lower temperature drop than example 2, but a higher pressure rise than example 2, and the final reactor cleaning cycle and the cement yield are slightly worse than example 2, thus demonstrating that the change in temperature has a higher effect on the reactor cleaning cycle and cement yield than the change in pressure.
Comparing examples 3 and examples 6-9, it can be seen that excellent pot life and cement paste yield can be obtained by adjusting the temperature, pressure and rotation speed within the scope of the present application, wherein the temperature decrease degree and the rotation speed increase degree of example 6 are slightly lower than those of example 3, and thus the effect thereof is slightly inferior to that of example 3. The temperature decrease and pressure increase for examples 7-9 were both less than example 3, so the reactor cleaning cycle and cement yield were slightly worse than example 3, while the pressure increase for example 9 was slightly better than example 8, and the temperature decrease for example 9 was also slightly higher than example 7, and therefore slightly better than example 7.
Examples 10 and 11 changed the parameters of step S2 and step S3, and still achieved a better reactor cleaning cycle, while the cement yield was substantially identical to example 1.
Comparative examples 1-3 omitted the operations of cooling, boosting and increasing the rotation speed, the reactor cleaning cycle was significantly lower than examples 1-3, and the cement yield was significantly higher than examples 1-3.
Comparative examples 4 to 6, in which only one of the temperature, the pressure and the rotation speed was adjusted, and comparative examples 7 to 9, in which both of the temperature, the pressure and the rotation speed were adjusted, found that the reaction tank washing cycle and the cement yield were not effectively improved, and although the reaction tank washing cycle and the cement yield of comparative examples 7 to 9 were slightly higher than those of corresponding comparative examples 4 to 6, the lifting effect was not obvious, whereas the effect of example 1 of the present application was significantly superior to that of comparative examples 4 to 9, and therefore, it was fully demonstrated that the comprehensive adjustment of the temperature, the pressure and the rotation speed was required to improve the reaction tank washing cycle and the cement yield, and therefore, the adjustment of the temperature, the pressure and the rotation speed in the present application had a synergistic effect. Comparative examples 10-11 showed no improvement in the pot wash cycle and the cement out yield by changing the starting point of the adjustment, indicating that the time point for the temperature pressure and the rotation speed adjustment was important and had no good effect earlier or later than 65-70%.
The parameter range in comparative example 12 is beyond the range of the present application, and the yield of the polymeric cement is rather higher, mainly because the reaction rate is too slow, the reaction period is too long, and the stability of the latex is damaged by long-time stirring, resulting in more gels.
In summary, the preparation method of the nitrile latex provided by the application can reduce the automatic acceleration effect by reducing the polymerization temperature by 1-3 ℃ in the middle and later stages of polymerization, can improve the stirring speed by 10-20rpm, can improve the heat transfer effect, and can also reduce the automatic acceleration effect. On the basis of the existing pressure of the reaction kettle, the butadiene can be difficult to gasify by continuously increasing the pressure by 0.01-0.2Mpa, the generation of bubbles is inhibited, and the polymerized gel is reduced. The polymerization temperature, the stirring rate and the reaction pressure are adjusted to have synergistic effect, so that the wall-mounted adhesive of the reaction kettle can be improved, the heat transfer efficiency of the reaction kettle can be improved, and the service life and the service period of the reaction kettle can be prolonged; the gel generation in the polymerization process is reduced, and the reaction yield can be improved. The nitrile latex prepared by the preparation method of the nitrile latex has good stability and can be widely applied to the preparation of impregnated gloves, carpets, sealing rings or brake pads.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. A method for preparing nitrile latex, which is characterized by comprising the following steps:
mixing and heating a water phase and an oil phase in a reaction container, wherein the water phase comprises, by weight, 1.2-1.5 parts of sodium dodecyl benzene sulfonate, 0.07-0.12 part of a dispersing agent, 0.02-0.05 part of EDTA-tetrasodium and 15-20 parts of ultrapure water; the oil phase comprises 13-15 parts of acrylonitrile, 2-3 parts of methacrylic acid, 0.2-0.3 part of tertiary dodecyl mercaptan and 32-35 parts of butadiene in parts by weight;
when the material is heated to 36-38 ℃, an initiator is added to start the polymerization reaction;
when the conversion rate of the system reaches 65% -70%, monitoring the pressure, temperature and rotating speed in the reaction vessel, increasing the pressure in the reaction vessel by 0.01-0.2Mpa, reducing the temperature by 1-3 ℃, increasing the rotating speed by 10-20rpm, carrying out reaction for 1.5-2.5h, then increasing the polymerization temperature by 1-3 ℃ per hour, reducing the rotating speed by 10-20rpm, keeping the pressure unchanged, continuing the reaction until the target conversion rate is reached, and ending the polymerization.
2. The process for preparing a nitrile latex as claimed in claim 1, wherein after the initiation of the polymerization reaction, the temperature is controlled at 36 to 38℃and the rotation speed is controlled at 65 to 75rpm, the reaction is continued for 4 to 6 hours, and the temperature is raised to 39 to 40 ℃.
3. The process for preparing a nitrile latex as claimed in claim 2, wherein when the system conversion reaches 65% to 70%, the pressure in the reaction vessel is increased by 0.01 to 0.2Mpa, the reaction is carried out for 1.5 to 2.5 hours at a polymerization temperature of 36 to 38 ℃ and a rotation speed of 80 to 90rpm, then the polymerization temperature is increased by 1 to 3 ℃ per hour, the rotation speed is adjusted to 65 to 75rpm, the pressure is kept unchanged, the reaction is continued until the target conversion is reached, and the polymerization is ended.
4. The process for preparing a nitrile latex according to claim 1, wherein when the system conversion reaches 65% -70%, the pressure in the reaction vessel is increased by 0.01-0.2Mpa, the reaction is carried out for 2 hours at a polymerization temperature of 36 ℃ and a rotation speed of 80-90rpm, then the polymerization temperature is increased by 2 ℃ per hour, the rotation speed is adjusted down to 70rpm, the pressure is kept unchanged, the reaction is continued until the target conversion is reached, and the polymerization is ended.
5. The method for preparing nitrile latex according to claim 1, wherein the step of mixing and heating the aqueous phase and the oil phase in the reaction vessel comprises: firstly, carrying out nitrogen replacement on the reaction vessel, vacuumizing to-0.11 to-0.07 Mpa after the replacement, then adding all components in the water phase and acrylonitrile, methacrylic acid and tert-dodecyl mercaptan in the oil phase, stirring and mixing at the rotating speed of 65-75rpm, then carrying out nitrogen replacement, vacuumizing to-0.11 to-0.07 Mpa after the replacement is completed, and heating after butadiene in the oil phase is added.
6. The method for preparing nitrile latex according to claim 1, wherein the initiator comprises 0.1-0.2 parts by weight of potassium persulfate and 4-6 parts by weight of ultrapure water.
7. A nitrile latex prepared by the process for preparing a nitrile latex according to any one of claims 1 to 6.
8. Use of the nitrile latex according to claim 7 for the preparation of dipped gloves, carpets, sealing rings or brake pads.
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| CN117567688A (en) * | 2024-01-15 | 2024-02-20 | 星宇新材料股份有限公司 | Butyronitrile emulsion and synthesis method and application thereof |
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| US5770660A (en) * | 1989-11-27 | 1998-06-23 | Lightsey; John W. | Continuous polymerization process for producing NBR rubber having a high bound content of acrylonitrile |
| EP0955324A1 (en) * | 1998-05-05 | 1999-11-10 | The Goodyear Tire & Rubber Company | Emulsifier-free carboxylated nitrile rubber latex |
| CN103788298A (en) * | 2012-10-30 | 2014-05-14 | 福盈科技化学股份有限公司 | Preparation method of carboxylated nitrile latex and article prepared from carboxylated nitrile latex |
| CN113941174A (en) * | 2021-11-12 | 2022-01-18 | 安庆华兰科技有限公司 | Degassing and concentrating device for butyronitrile latex and degassing and concentrating method thereof |
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| US5770660A (en) * | 1989-11-27 | 1998-06-23 | Lightsey; John W. | Continuous polymerization process for producing NBR rubber having a high bound content of acrylonitrile |
| EP0955324A1 (en) * | 1998-05-05 | 1999-11-10 | The Goodyear Tire & Rubber Company | Emulsifier-free carboxylated nitrile rubber latex |
| CN103788298A (en) * | 2012-10-30 | 2014-05-14 | 福盈科技化学股份有限公司 | Preparation method of carboxylated nitrile latex and article prepared from carboxylated nitrile latex |
| CN113941174A (en) * | 2021-11-12 | 2022-01-18 | 安庆华兰科技有限公司 | Degassing and concentrating device for butyronitrile latex and degassing and concentrating method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117567688A (en) * | 2024-01-15 | 2024-02-20 | 星宇新材料股份有限公司 | Butyronitrile emulsion and synthesis method and application thereof |
| CN117567688B (en) * | 2024-01-15 | 2024-04-05 | 星宇新材料股份有限公司 | Butyronitrile emulsion and synthesis method and application thereof |
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